Creation of novel gold-nanorod-based localized surface plasmon resonance biosensors

Starting with a comprehensive review of both surface plasmon resonance (SPR) based and localized surface plasmon resonance (LSPR) based sensors, this thesis reports the studies on the development of a novel sensitive gold nanorod (GNR) based label-free LSPR optical fibre biosensor, and the development of a novel robust method for effectively modifying the surface of cetyl-trimethyl ammonium bromide (CTAB) capped GNRs and their LSPR biosensing applications. A novel GNR-based LSPR optical fibre sensor was fabricated and evaluated in this work. The sensor probe was prepared by covalently immobilizing GNRs, synthesized using a seed-mediated growth method, on the decladed surface of a piece of multimode optical fibre. In order to operate the LSPR sensor as a reflective sensor, a silver mirror was also coated at one distal end of the sensor probe by a dip coating method. In the refractive index sensitivity test, it was found that the longitudinal plasmon band (LPB) of GNRs is highly sensitive to the refractive index change close to the GNRs surface, and the sensitivity of the LSPR optical fibre sensor increases with the increase of the aspect ratio of GNRs. The results showed that the GNR-based LSPR optical fibre sensors prepared in this work have linear and high refract index sensitivities. For sensors based on GNRs with aspect ratios of 2.6, 3.1, 3.7 and 4.3, their refractive index sensitivities were found to be 269, 401, 506 and 766 nm/RIU (RIU = refractive index unit), respectively, in the refractive index range from 1.34 to 1.41. In order to evaluate the biosensing performance, the GNR-based LSPR optical fibre sensor with aspect ratio of 4.1 and a 2 cm sensing length was further functionalized with human IgG to detect the specific target — anti-human IgG, and a detection limit of 1.6 nM was observed using a wavelength-based interrogation approach. In another study, in order to overcome the drawbacks of the CTAB-capped GNRs found in biosensing and biomedical applications, a simple yet robust pH-mediated method for effectively modifying the surface of CTAB-capped GNRs synthesized by the seed-mediated growth method was developed. This method allows the complete replacement of the CTAB molecules attached on the GNRs surface with the 11-mercaptoundecaonic acid (MUA) molecules to take place in a total aqueous environment by controlling the pH of the MUA aqueous solution, thus avoiding the irreversible aggregation of GNRs during the complex surface modification process observed in the previous reported methods. The success of the complete replacement of CTAB with MUA was confirmed by the surface elemental analysis using an X-ray photoelectron spectroscopy (XPS), and the MUA-modified GNRs created in this work demonstrated a high stability up to 4 months at least when stored in a buffer solution at pH 9 at 4°C. The MUA-modified GNRs with an aspect ratio of 3.9 were furthered developed as a solution-phase-based label-free LSPR biosensor by functionalizing the GNRs with human IgG. A detection limit as low as 0.4 nM for detecting anti-human IgG was achieved by this sensor. The achievements of this work are concluded and the directions of future work are also pointed out.