Light-enhanced catalytic activity of stable and large gold nanoparticles in homocoupling reactions.

Validating the direct photocatalytic activity of colloidal plasmonic nanoparticles is challenging due to their limited stability and needed support materials that can often contribute to the chemical reactions. Stable gold nanoparticles (AuNPs) with tunable sizes are prepared across porous polymer particles without any chemical bonds where the resulting composite particles exhibit intense surface plasmon resonances (SPRs) in the visible region. These composite particles are then tested as photocatalysts under a broadband solar-simulated light source to examine the contribution degree of photothermal heating and SPR coming from the incorporated AuNPs in the C-C bond forming homocoupling reaction. Generally, the thermal and photothermal heating are the main driving force to increase the reactivity of relatively smaller AuNPs (~ 44 nm in diameter) with a narrower SPR band. However, the SPR-induced catalytic activity is much greater for the composite particles containing larger AuNPs (~ 87 nm in diameter) with a broader SPR. As the polymer particle matrix does not influence the catalytic activity (e.g., inducing charge delocalization and/or separation), the unique SPR role of the colloidal AuNPs in the catalytic reaction is assessable under light irradiation. This study experimentally demonstrates the possibility of evaluating the direct contribution of SPRs to photocatalytic chemical reactions.

Integrating SERS and PSI-MS with Dual Purpose Plasmonic Paper Substrates for On-Site Illicit Drug Confirmation.

Forensic laboratory backlogs are replete with suspected drug samples. Shifting analysis toward the point of seizure would save significant time and public funds. Moreover, a two-tiered identification strategy for controlled substance testing that relies on two independent, discerning methods could entirely circumvent the need for forensic laboratory testing. To this end, we coupled Raman spectroscopy and paper spray ionization mass spectrometry (PSI-MS) on a single instrumental platform. Both methods are capable of ambient analysis with fieldable instruments, yet Raman is often limited to bulk analysis. Critical to this work is the development of a gold nanoparticle (AuNP)-embedded paper swab to extend the capability of Raman spectroscopy to trace evidence via surface-enhanced Raman scattering (SERS). Plasmonic papers are characterized with respect to SERS signals and compatibility with PSI-MS analysis. Proof-of-principle is established with the identification of five representative drugs, and detection limits on the scale of 1-100 ng are achieved for both PSI-MS and SERS. The integrated SERS-PSI-MS system achieved 99.8% accurate chemical identification in a blind study consisting of 500 samples. Additionally, we demonstrate facile discrimination of several JWH-018 isomers via SERS even when MS and MS2 spectra are indistinguishable. Successful coupling of SERS and PSI-MS to enable on-site chemical analysis by two independent methods can potentially lead to a desirable paradigm shift in the handling of drug evidence.

Sandwiching analytes with structurally diverse plasmonic nanoparticles on paper substrates for surface enhanced Raman spectroscopy.

This report describes the systematic combination of structurally diverse plasmonic metal nanoparticles (AgNPs, AuNPs, Ag core-Au shell NPs, and anisotropic AuNPs) on flexible paper-based materials to induce signal-enhancing environments for surface enhanced Raman spectroscopy (SERS) applications. The anisotropic AuNP-modified paper exhibits the highest SERS response due to the surface area and the nature of the broad surface plasmon resonance (SPR) neighboring the Raman excitation wavelength. The subsequent addition of a second layer with these four NPs (e.g., sandwich arrangement) leads to the notable increase of the SERS signals by inducing a high probability of electromagnetic field environments associated with the interparticle SPR coupling and hot spots. After examining sixteen total combinations, the highest SERS response is obtained from the second layer with AgNPs on the anisotropic AuNP paper substrate, which allows for a higher calibration sensitivity and wider dynamic range than those of typical AuNP-AuNP arrangement. The variation of the SERS signals is also found to be below 20% based on multiple measurements (both intra-sample and inter-sample). Furthermore, the degree of SERS signal reductions for the sandwiched analytes is notably slow, indicating their increased long-term stability. The optimized combination is then employed in the detection of let-7f microRNA to demonstrate their practicability as SERS substrates. Precisely introducing interparticle coupling and hot spots with readily available plasmonic NPs still allows for the design of inexpensive and practical signal enhancing substrates that are capable of increasing the calibration sensitivity, extending the dynamic range, and lowering the detection limit of various organic and biological molecules.