Amplifying Sensing Capabilities: Combining Plasmonic Resonances and Fresnel Reflections through Multivariate Analysis.

Multivariate analysis applied in biosensing greatly improves analytical performance by extracting relevant information or bypassing confounding factors such as nonlinear responses or experimental errors and noise. Plasmonic sensors based on various light coupling mechanisms have shown impressive performance in biosensing by detecting dielectric changes with high sensitivity. In this study, gold nanodiscs are used as metasurface in a Kretschmann setup, and a variety of features from the reflectance curve are used by machine learning to improve sensing performance. The nanostructures of the metasurface generate new plasmonic features, apart from the typical resonance that occurs in the classical Kretschmann mode of a gold thin film, related to the evanescent field beyond total internal reflection. When the engineered metasurface is integrated into a microfluidic chamber, the device provides additional spectral features generated by Fresnel reflections at all dielectric interfaces. The increased number of features results in greatly improved detection. Here, multivariate analysis enhances analytical sensitivity and sensor resolution by 200% and more than 20%, respectively, and reduces prediction errors by almost 40% compared to a standard plasmonic sensor. The combination of plasmonic metasurfaces and Fresnel reflections thus offers the possibility of improving sensing capabilities even in commonly available setups.

Ultrathin films of variable polarity and crystallinity obtained from 1,2-polybutadiene nanoparticle dispersions.

Characterization of ultrathin films of different polymer nanoparticles obtained at room temperature via spin-coating of aqueous dispersions and their morphology are described. Very small nanoparticles of semicrystalline 1,2-polybutadiene (PB), noncrystalline poly(1-butene) (PH), and poly(1-butenal) (PHF) were prepared via catalytic emulsion polymerization and subsequent hydrogenation or hydroformylation. The prefabricated nanoparticles were used as building blocks. The thin films obtained are continuous and transparent (n=1.5; κ=0). The properties of these films, formed from different constituents, are analyzed. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) images show that the PB-films are very smooth (rms roughness=10 nm) and polycrystalline. Recrystallization of these PB films reveals that edge-on lamellae are the constituent units. Films with very low roughness values (rms roughness <2 nm) are obtained with PH nanoparticles, due to the soft character of the nanoparticles. The AFM profile of the PHF films reveals that the surface remains structured after drying due to the high degree of the internal cross-linking that occurs in the nanoparticles. Quantification of the films' polarity (I(3)/I(1)=0.89, 1.3, and 2.1 for PHF, PB, and PH, respectively) agrees well with the previous values obtained for the polymer dispersions. Surfactant molecules are desorbed during the film formation; however, these aggregates can be removed by rinsing with water with no undesirable effects observed on the films.

Conveniently accessible polymer nanoparticles of adjustable polarity.

The postpolymerization modification by hydroformylation of 1,2-polybutadiene nanoparticles provides access to colloidally stable aqueous dispersions of <20 nm particles. Their polarity can be adjusted via the degree of conversion of double bonds over a broad range. Fluorescence studies illustrate the polarity of the environment experienced by pyrene as a probe molecule.