Charge-driven arrested phase-separation of polyelectrolyte-gold nanoparticle assemblies leading to plasmonic oligomers.

Aggregates of charged metal particles obtained by electrostatic coupling with a compound of opposite charge in the vicinity of the net zero charge ratio are of interest in the field of plasmonics because the inter-particle distance is minimal, which favours plasmonic coupling. However, these structures present a low colloidal stability limiting the development of applications. In this article we show that globally neutral aggregates formed by electrostatic complexation of citrate-stabilized gold particles and a quaternized chitosan (i.e., polycation) around the net zero charge ratio could be stabilized at a nanometric size by the subsequent addition of polyelectrolyte chains. Furthermore, the sign of the charge carried by the stabilizing chains determines the sign of the global charge carried by the stabilized complexes. The stabilization is demonstrated in saline environment on a broad pH range as well as in a cell culture media over periods of several days. Contrarily to stabilization by charged particles, our stabilized complexes are found to retain their initial characteristics (i.e. shape, size, internal structure and optical properties) after stabilization. Hence, the plasmonic coupling allows to maximize the optical absorption around the 800 nm wavelength at which the lasers used for thermoplasmonic and surface enhanced Raman scattering analysis operate.

Self-assembly of gold nanoparticles by chitosan for improved epinephrine detection using a portable surface enhanced Raman scattering device.

Surface enhanced Raman scattering (SERS) has become widely used for identification, quantification and providing structural information about molecular structure in low concentrations as it allows signal Raman enhancement using metallic nanoparticles (NPs). Controlling interaction between analyte and NPs is a major point for the optimization of signal exaltation in SERS analysis. The objective of this study is the improvement and the control of SERS analysis by aggregation/self-assembly optimization of AuNPs using quaternized chitosan. The interest of this approach is to allow stable and reliable measurements with a simple and low cost approach compatible with a massive use in the field. In this work, we used design of experiments by Box-Behnken design to fix optimized conditions to increase signal sensibility of epinephrine water solutions. We also tested SERS signal stability in isotonic sodium chloride 0.9% and glucose 5% matrices. Our results demonstrate that globally neutral AuNPs aggregates were stabilized at a nanometric size by the subsequent addition of polyelectrolyte chains and allows for significant Raman signal enhancement of epinephrine. We succeed to prepare the SERS active material and measure a stable signal of epinephrine at a concentration as down as 0.1 µg mL-1 in less than 5 min. The signal remained stable and exploitable for at least 2 h. Our results reveal a strong correlation between intensity and logarithm of the concentration (concentration before dilution from 0.1 to 10 µg mL-1) suggesting a possible quantification. Furthermore, the signal of epinephrine at 10 µg mL-1 were also exploitable and stable in complex media as isotonic sodium chloride 0.9% and glucose 5%. This represents a particularly interesting application that would allow direct analysis of drugs complex media and open the way to analysis in biological samples.