Plasma Parameters During Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) in the Presence of Nanoparticle-Protein Conjugates.

Nanoparticle-enhanced laser-induced breakdown spectroscopy (NELIBS) is an optical emission technique based on the laser-induced plasma (LIP) on a sample after the deposition of plasmonic nanoparticles (NPs) on its surface. The employment of the NPs allows an enhancement of the signal with respect to the one obtained with the conventional laser-induced breakdown spectroscopy (LIBS) enabling an extremely high sensitivity and very low limits of detection compared with the LIBS performance. Recently, NELIBS was used for monitoring the NP protein corona formation. As a matter of fact, the NPs in the presence of proteins adsorbed on the surface change their surface properties, therefore the sensing of protein corona formation was possible because of the strong dependence of NELIBS effects on the NP organization on the substrate, which in turn is deeply affected by the surface properties of the NPs. A correlation was found between NELIBS enhancement and the structure of the NP-protein conjugate in terms of protein content absorbed on the NP surface. An interesting question that was not yet exploited regards the role of LIP during the NELIBS when the NPs are covered with proteins. Since the presence of organic matter can strongly quench the LIP emission, the study of the LIP properties during protein corona sensing by NELIBS is of interest for two main reasons: (i) to understand whether the plasma parameters can vary in the presence of proteins adsorbed on the NP surface and (ii) to investigate how and if the plasma parameters themselves can influence the NELIBS processes. With this aim, the study of plasma parameters, i.e., electron densities and temperatures, during the sensing of NP protein corona by NELIBS is presented and discussed. The NPs used during these experiments were ultrapure gold NPs (AuNPs) produced by pulsed laser ablation in liquid, which are stable without any stabilizer. The human serum albumin protein is used to form AuNP-protein conjugates further deposited on a titanium target in NELIBS measurements. Dynamic light scattering, surface plasmon resonance spectroscopy, and laser Doppler electrophoresis for ζ-potential determination were employed to monitor the protein coverage of NP surface in the conjugate solutions before the NELIBS measurements.