NIR dye‐encoded nanotags for biosensing: Role of functional groups on sensitivity and performance in SERRS‐based LFA

Abstract

Surface‐enhanced resonance Raman scattering (SERRS) is based on nanostructures supporting localized surface plasmon resonances as well as electronic resonances of the molecular adsorbate. Bright NIR‐SERRS nanotags require dyes with high Raman scattering cross‐sections upon NIR laser excitation in combination with functional groups for chemisorption. Here, we report on the role of isothiocyanate (ITC) and sulfonate (SO) groups in five cyanine dyes on sensitivity and performance of nanotags in SERRS‐based LFA. Dye concentration‐dependent SERRS and zeta potential measurements on bare gold nanostars (AuNS) revealed strong differences in their sensitivity and stability as a function of the number of ITC and SO groups. A positive correlation with the number of ITC groups due to stronger chemisorption and a negative correlation with the number of SO groups due to stronger desorption because of higher water solubility was observed. The application in SERRS‐based biosensing requires additional functionalization steps, for example, co‐adsorption of PEG with the NIR dye. The comparison of the Raman intensities before and after bioconjugation showed that the presence of at least one ITC group is necessary for minimizing Raman signal losses, irrespective of the additional presence of SO groups. In a SERRS‐based lateral flow assay (LFA) for sensing the pregnancy marker beta‐hCG, the two dyes NIR 4f and NIR 5e (both ITC = 2, SO = 0) showed the best performance. In contrast, we do not recommend to use IR‐783 (ITC = 0, SO = 2) for SERRS‐based biosensing. Overall, this study highlights the importance of surface‐seeking moieties such as the common ITC group for optimal performance in SERRS‐based biosensing platforms.

SERS-based microdevices for use as in vitro diagnostic biosensors

“…As SERS nanotags, both gold (Au) and silver (Ag) nanomaterials with unique and fascinating properties have been extensively used in bioassays. 39–51 Plasmonics is a subfield of photonics that addresses the interaction between light and metallic nanoparticles with particular emphasis on the excitation of oscillating electrons at the surface of nanoparticles. Au and Ag exhibit a resonance phenomenon known as LSPR.…”

Introduction to the Journal of Raman Spectroscopy Emerging Investigators Special Issue

“…As shown in this work, the enhancement due to the plasmonic effects of Au nanoparticles allows determinations at physiologically relevant concentrations in biological fluids. N. Choi et al 6 (University of Duisburg‐Essen, Germany) report on the development of an optimized SERRS (surface‐enhanced resonance Raman scattering)‐based lateral flow assay strip to improve the detection sensitivity of beta‐hCG, a pregnancy diagnostic biomarker. For this purpose, Au nanostars act as the highly sensitive SERS nanotag combined with the electronically and plasmonically enhanced 785 nm excited NIR dyes.…”