Optimizing Upconversion Nanoparticles for FRET Biosensing.

Upconversion nanoparticles (UCNPs) are some of the most promising nanomaterials for bioanalytical and biomedical applications. One important challenge to be still solved is how UCNPs can be optimally implemented into Förster resonance energy transfer (FRET) biosensing and bioimaging for highly sensitive, wash-free, multiplexed, accurate, and precise quantitative analysis of biomolecules and biomolecular interactions. The many possible UCNP architectures composed of a core and multiple shells doped with different lanthanoid ions at different ratios, the interaction with FRET acceptors at different possible distances and orientations via biomolecular interaction, and the many and long-lasting energy transfer pathways from the initial UCNP excitation to the final FRET process and acceptor emission make the experimental determination of the ideal UCNP-FRET configuration for optimal analytical performance a real challenge. To overcome this issue, we have developed a fully analytical model that requires only a few experimental configurations to determine the ideal UCNP-FRET system within a few minutes. We verified our model via experiments using nine different Nd-, Yb-, and Er-doped core-shell-shell UCNP architectures within a prototypical DNA hybridization assay using Cy3.5 as an acceptor dye. Using the selected experimental input, the model determined the optimal UCNP out of all theoretically possible combinatorial configurations. An extreme economy of time, effort, and material was accompanied by a significant sensitivity increase, which demonstrated the powerful feat of combining a few selected experiments with sophisticated but rapid modeling to accomplish an ideal FRET biosensor.

Au-Ag Alloy Nanocorals with Optimal Broadband Absorption for Sunlight-Driven Thermoplasmonic Applications.

Noble metal nanoparticles are efficient converters of light into heat but typically cover a limited spectral range or have intense light scattering, resulting in unsuited for broadband thermoplasmonic applications and sunlight-driven heat generation. Here, Au-Ag alloy nanoparticles were deliberately molded with an irregular nanocoral (NC) shape to obtain broadband plasmon absorption from the visible to the near-infrared yet at a lower cost compared to pure Au nanostructures. The Au-Ag NCs are produced through a green and scalable methodology that relies on pulsed laser fragmentation in a liquid, without chemicals or capping molecules, leaving the particles surface free for conjugation with thiolated molecules and enabling full processability and easy inclusion in various matrixes. Numerical calculations showed that panchromism, i.e., the occurrence of a broadband absorption from the visible to the near-infrared region, is due to the special morphology of Au-Ag alloy NCs and consists of a purely absorptive behavior superior to monometallic Au or Ag NCs. The thermoplasmonic properties were assessed by multiwavelength light-to-heat conversion experiments and exploited for the realization of a cellulose-based solar-steam generation device with low-cost, simple design but competitive performances. Overall, here it is shown how laser light can be used to harvest solar light. Besides, the optimized broadband plasmon absorption, the green synthetic procedure, and the other set of positive features for thermoplasmonic applications of Au-Ag NCs will contribute to the development of environmentally friendly devices of practical utility in a sustainable world.

Spatial and Temporal Resolution of Luminescence Quenching in Small Upconversion Nanocrystals.

Luminescent upconversion nanocrystals (UCNCs) have become one of the most promising nanomaterials for biosensing, imaging, and theranostics. However, their ultimate translation into robust luminescent probes for daily use in biological and medical laboratories requires comprehension and control of the many possible deactivation pathways that cause upconversion luminescence (UCL) quenching. Here, we demonstrate that thorough modeling of UCL rise and decay kinetics using a freely accessible software can identify the UCL quenching mechanisms in small (<40 nm) UCNCs with spatial and temporal resolution. Applied to the most relevant ß-NaYF4:Yb3+,Er3+ UCNCs, our model showed that only a few distinct nonradiative low-energy transitions were deactivated via specific solvent and ligand vibrations with a strong downstream effect on the population and depopulation dynamics of the emitting states. UCL quenching could penetrate ca. 4 nm inside the UCNC, which resulted in significant size-dependent changes of UCL intensities and spectra. Despite the large surface-to-volume ratios and UCL quenching via the UCNC surface, we found strong contributions of the outer layers to the overall UCL, which will be highly important for the design of UCNPs to investigate biomolecular interactions via distance-dependent energy transfer methods. Our advanced kinetic model is easily scalable to different UCNC architectures, environments, and energy transfer interactions such that relatively simple modeling of UCL kinetics can be used for efficiently optimizing UCNCs for their final application as practical luminescent probes.