Decoupling Individual Optical Nanosensor Responses Using a Spin-Coated Hydrogel Platform.

Abstract

Significant advances have been made in fields such as nanotechnology and biomedicine using the unique properties of single-walled carbon nanotubes (SWCNTs). Specifically, SWCNTs are used as near-infrared fluorescence sensors in the solution phase to detect a wide array of biologically relevant analytes. However, solution-based sensing has several limitations, including limited sensitivity and poor spatial resolution. We have therefore devised a new spin-coated poly(ethylene glycol) diacrylate (PEG-DA) hydrogel platform to examine individual DNA-functionalized SWCNTs (DNA-SWCNTs) in their native aqueous state and have subsequently used this platform to investigate the temporal modulations of each SWCNT in response to a model analyte. A strong surfactant, sodium deoxycholate (SDC), was chosen as the model analyte as it rapidly exchanges with DNA oligonucleotides on the SWCNT surface, modulating several optical properties of the SWCNTs and demonstrating multiparameter analyte detection. Upon addition of SDC, we observed time-dependent spectral modulations in the emission center wavelengths and peak intensities of the individual SWCNTs, indicative of a DNA-to-surfactant exchange process. Interestingly, we found that the modulations in the peak intensities, as determined by kinetic data, were significantly delayed when compared to their center wavelength counterparts, suggesting a potential decoupling of the response of these two spectral features. We used a 1-D diffusion model to relate the local SDC concentration to the spectral response of each SWCNT and created dose-response curves. The peak intensity shifts at a higher SDC concentration than the center wavelength, indicating a potential change in the conformation of the surfactant molecules adsorbed to the SWCNT sidewall after the initial exchange process. This platform allows for a unique single-molecule analysis technique that is significantly more sensitive and modifiable than utilizing SWCNTs in the solution phase.