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Replacement of Cetyltrimethylammoniumbromide Bilayer on
Gold Nanorod by Alkanethiol Crosslinker for Enhanced Plasmon
Resonance Sensitivity
Justin Casas, Meenakshi Venkataramasubramani, Yanyan Wang, and Liang Tang*
Department of Biomedical Engineering, University of Texas at San Antonio, San Antonio, TX
78249, U.S.A
Abstract
Surface modification of gold nanorods (GNRs) is often problematic due to tightly packed
cetyltrimethylammoniumbromide (CTAB) bilayer. Herein, we performed a double phase transfer
ligand exchange to achieve displacement of CTAB on nanorods. During the removal, 11-
mercaptoundecanoic acid (MUDA) crosslinker is simultaneously assembled on nanorod surfaces
to prevent aggregation. The resulting MUDA-GNRs retain the shape and position of plasmon
peaks similar to CTAB-capped GNRs. The introduction of carboxyl groups allows covalent
conjugation of biological receptors in a facile fashion to construct a robust, label-free biosensor
based on localized surface plasmon resonance (LSPR) transduction of biomolecular interaction.
More importantly, smaller MUDA layer on the GNRs reduces the distance of target binding to the
plasmonic nanostructure interface, leading to a significant enhancement in LSPR assay sensitivity
and specificity. Compared to modification using conventional electropolymer adsorption, MUDA-
coated gold nanosensor exhibits five times lower detection limit for cardiac troponin I assay with a
high selectivity.
Keywords
Gold nanorod; Surface modification; Functionalization; Biosensing; Surface plasmon resonance
1. Introduction
In sensor applications, the optical transduction by gold nanoparticles is based upon the
phenomenon of localized surface plasmon resonance, i.e. LSPR (Lee and El-Sayed 2006).
According to the plasmon hybridization mode (Prodan et al. 2003), the plasmon resonance
frequency is largely determined by the geometry of the colloidal metal structure, as a result
of electrostatic interactions between confined electrons distributed
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