On-chip monitoring of toxic gases: capture and label-free SERS detection with plasmonic mesoporous sorbents.

The detection of the spread of toxic gas molecules in the air at low concentration in the field requires a robust miniaturized system combined with an analytical technique that is portable and able to detect and identify the molecules, as is the case with surface enhanced Raman scattering (SERS). This work aims to address capability gaps faced by first responders in real-time detection, identification and monitoring of neurotoxic gases by developing robust, reliable and reusable SERS microfluidic chips. Thus, the key performance attributes of a portable SERS detection system that must be addressed in detail are its limit of detection, response time and reusability. To this purpose, we integrate a 3D plasmonic architecture based on closely packed mesoporous silica (MCM48) nanospheres decorated with Au nanoparticle arrays, denoted as MCM48@Au, into a Si microfluidic chip designed and used for preconcentration and label-free detection of gases at a trace concentration level. The SERS performance of the plasmonic platform is thoroughly analyzed using DMMP as a model neurotoxic simulant over a 1 cm2 SERS active area and over a range of concentrations from 100 ppbV to 2.5 ppmV. The preconcentration-based SERS signal amplification by the mesoporous silica moieties is evaluated against dense silica counterparts, denoted as Stöber@Au. To assess the potential for applications in the field, the microfluidic SERS chip has been interrogated with a portable Raman spectrometer, evaluated with temporal and spatial resolution and subjected to several gas detection/regeneration cycles. The reusable SERS chip shows exceptional performance for the label-free monitoring of 2.5 ppmV gaseous DMMP.

In Situ Synthesis of SERS-Active Au@POM Nanostructures in a Microfluidic Device for Real-Time Detection of Water Pollutants.

We present a simple, versatile, and low-cost approach for the preparation of surface-enhanced Raman spectroscopy (SERS)-active regions within a microfluidic channel 50 cm in length. The approach involves the UV-light-driven formation of polyoxometalate-decorated gold nanostructures, Au@POM (POM: H3PW12O40 (PW) and H3PMo12O40 (PMo)), that self-assemble in situ on the surface of the polydimethylsiloxane (PDMS) microchannels without any extra functionalization procedure. The fabricated LoCs were characterized by scanning electron microscopy (SEM), UV-vis, Raman, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) techniques. The SERS activity of the resulting Au@POM-coated lab-on-a-chip (LoC) devices was evaluated in both static and flow conditions using rhodamine R6G. The SERS response of Au@PW-based LoCs was found to be superior to Au@PMo counterparts and outstanding when compared to reported data on metal@POM nanocomposites. We demonstrate the potentialities of both Au@POM-coated LoCs as analytical platforms for real-time detection of the organophosphorous pesticide paraoxon-methyl at 10-6 M concentration level.

Attomolar SERS detection of organophosphorous pesticides using silver mirror-like micro-pyramids as active substrate.

Surface-enhanced Raman spectroscopy (SERS) is gaining importance as an ultrasensitive analytical tool for routine high-throughput analysis of a variety of molecular compounds. One of the main challenges is the development of robust, reproducible and cost-effective SERS substrates. In this work, we study the SERS activity of 3D silver mirror-like micro-pyramid structures extended in the z-direction up to 3.7 µm (G0 type substrate) or 7.7 µm (G1 type substrate), prepared by Si-based microfabrication technologies, for trace detection of organophosphorous pesticides, using paraoxon-methyl as probe molecule. The average relative standard deviation (RSD) for the SERS intensity of the peak displayed at 1338 cm-1 recorded over a centimetre scale area of the substrate is below 13% for pesticide concentrations in the range 10-6 to 10-15 mol L-1. This data underlies the spatial uniformity of the SERS response provided by the microfabrication approach. According to finite-difference time-domain (FDTD) simulations, such remarkable feature is mainly due to the contribution on electromagnetic field enhancement of edge plasmon polaritons (EPPs), propagating along the pyramid edges where the pesticide molecules are preferentially adsorbed. Graphical abstract.

3D Fractals as SERS Active Platforms: Preparation and Evaluation for Gas Phase Detection of G-Nerve Agents.

One of the main limitations of the technique surface-enhanced Raman scattering (SERS) for chemical detection relies on the homogeneity, reproducibility and reusability of the substrates. In this work, SERS active platforms based on 3D-fractal microstructures is developed by combining corner lithography and anisotropic wet etching of silicon, to extend the SERS-active area into 3D, with electrostatically driven Au@citrate nanoparticles (NPs) assembly, to ensure homogeneous coating of SERS active NPs over the entire microstructured platforms. Strong SERS intensities are achieved using 3D-fractal structures compared to 2D-planar structures; leading to SERS enhancement factors for R6G superior than those merely predicted by the enlarged area effect. The SERS performance of Au monolayer-over-mirror configuration is demonstrated for the label-free real-time gas phase detection of 1.2 ppmV of dimethyl methylphosphonate (DMMP), a common surrogate of G-nerve agents. Thanks to the hot spot accumulation on the corners and tips of the 3D-fractal microstructures, the main vibrational modes of DMMP are clearly identified underlying the spectral selectivity of the SERS technique. The Raman acquisition conditions for SERS detection in gas phase have to be carefully chosen to avoid photo-thermal effects on the irradiated area.