Marios Constantinou1,Sotirios Christodoulou1,Agapios Agapiou1,Chrysafis Andreou1
University of Cyprus1
Marios Constantinou1,Sotirios Christodoulou1,Agapios Agapiou1,Chrysafis Andreou1
University of Cyprus1
Nanomaterials, such as nanowires (NWs), are enabling new directions in nanotechnology with significant applications in the biomedical sector. With the use of Surface-Enhanced Raman Spectroscopy (SERS) as an analytical technique for rapid biomarker identification, nanomaterials can play a pivotal role in shaping the next generation of non-invasive, rapid, and pain-free diagnostic devices. Potential applications include breath analysis for cancer screening.<br/>SERS is an ultrasensitive vibrational spectroscopic technique used as a tool to detect volatile organic compounds (VOCs) near the surface of plasmonic metal nanoparticles with sharp features (‘hot spots’). Conventional bottom-up approaches for sensing applications are based on the self-assembly of nanoparticles, which offers a simplistic, quick, and low-cost SERS substrate preparation. However, this approach demonstrates low reproducibility, hampering the sensor’s performance. Top-down approaches use micro- and nanofabrication techniques with better uniformity and reproducibility, but with higher manufacturing costs.<br/>We present a hybrid approach using NWs as the backbone of the SERS sensor – decorated with nanoparticles (NPs) – acting as 3D ‘hot-spot’ network for maximizing the available SERS-active surface of the device while achieving signal reliability and reproducibility.<br/>We employed this new architecture for SERS-based gas sensing. The NWs are derived from fast and cost-effective solution processing, and form higher-order structures via dielectrophoresis (DEP)-based self-assembly. DEP offers unique features, including NW alignment on predefined locations, preferential orientation, and most importantly, controllable deposition and NW densities for precise ‘hot-spot’ distribution. The self-assembly technique will be discussed and compared to conventional SERS-sensor approaches. Our solution-based technique for the rapid gold (Au) nanoparticle decoration of the 1D titanium oxide (TiO<sub>2</sub>) NWs will be described. This novel architecture further increases the overall ‘hot-spot’ availability, and combines strong SERS signal amplification with increased sample capture, allowing the detection of analytes at low concentrations.<br/>The performance of the developed sensor was assessed by investigating the SERS signal of 4-aminothiophenol (4-ATP) in gas phase, at concentrations as low as 10 parts-per-billion (ppbv), and in liquid phase down to 24 picomolar (pM). Additionally, the SERS signals successfully separated - using the principal components analysis (PCA) – samples of exhaled breath from healthy volunteers. These findings demonstrate the applicability and potential of 1D nanomaterials in conjunction with state-of-the-art solution-processed techniques for the development of breath analysis platforms for cancer screening.<br/>The developed non-invasive NW-based breath sensor platform can provide mobile, low-cost, miniaturized, and rapid breath analysis, making it suitable for clinical deployment. The sensor is suitable for real-time point-of-care (PoC) diagnosis and can significantly improve the understanding of the complex relationship between the exhaled VOC profile and disease, and lead the way to a new clinical breath-based diagnostic tests.