Search

Accurate design of labelled oligo probes for the detection of miRNA biomarkers by Surface Enhanced Raman Scattering (SERS) may improve the exploitation of the plasmonic enhancement. This work, thus, critically investigates the role of probe labelling configuration on the performance of SERS based bioassays for miRNA quantitation. To this aim, highly efficient SERS substrates based on Ag-decorated porous silicon/PDMS membranes are functionalized according to two different bioassays relying on a one-step or two-step hybridization of the target miRNA with oligonucleotide probes. The detection configuration is varied, exploring the impact of the position of the Raman reporter along the oligo sequence and of the reporter identity on bioassay sensitivity. In the high miRNA concentration regime(100-10 nM), a significantly increased SERS intensity is detected when the reporters are located closer to the plasmonic surface compared to farther probe labelling positions. Counterintuitively, a levelling-off of the SERS intensity from the two configuration is instead recorded at low miRNA concentration. Such effect is explained by an increased contribution of Raman hot spot to the whole SERS signal, as confirmed by simulations of the electric near field for a simplified model of the Ag nanostructures. The beneficial effect of reducing the reporter-to-surface distance is however partially retained for the two-step hybridization assay thanks to the less sterically hindered environment in which the second hybridization occurs. The study thus demonstrates that the limit of detection of the assay can be lowered by tuning the probe labelling position, but sheds at the same time light on the complexity of the bionanointerfaces in SERS and on the multiple factors affecting bioassay sensitivity.

Thermally conductive nanopapers fabricated from graphene and related materials are currently showing a great potential in thermal management applications. However, thermal contacts between conductive plates represent the bottleneck for thermal conductivity of nanopapers prepared in the absence of a high temperature step for graphitization. In this work, the problem of ineffective thermal contacts is addressed by the use of bifunctional polyaromatic molecules designed to drive self-assembly of graphite nanoplates (GnP) and establish thermal bridges between them. To preserve the high conductivity associated to defect-free sp2 structure, non-covalent functionalization with bispyrene compounds, synthesised on purpose with variable tethering chain length, was exploited. Pyrene terminal groups granted for a strong {\pi}-{\pi} interaction with graphene surface, as demonstrated by UV-Vis, fluorescence and Raman spectroscopies. Bispyrene molecular junctions between GnP were found to control GnP organization and orientation within the nanopaper, delivering significant enhancement in both in-plane and cross-plane thermal diffusivity. Finally, nanopapers were validated as heat spreader devices for electronic components, evidencing comparable or better thermal dissipation performance than conventional Cu foil, while delivering over 90% weight reduction.

The edge-functionalization of graphene nanoplatelets (GnP) was carried out exploiting diazonium chemistry, aiming at the synthesis of edge decorated nanoparticles to be used as building blocks in the preparation of engineered nanostructured materials for enhanced heat transfer. Indeed, both phenol functionalized and dianiline-bridged GnP (GnP-OH and E-GnP, respectively) were assembled in nanopapers exploiting the formation of non-covalent and covalent molecular junctions, respectively. Molecular dynamics allowed to estimate the thermal conductance for the two different types of molecular junction, suggesting a factor 6 between conductance of covalent vs. non-covalent junctions. Furthermore, the chemical functionalization was observed to drive the self-organization of the nanoflakes into the nanopapers, leading to a 20% enhancement of the thermal conductivity for GnP-OH and E-GnP while the cross plane thermal conductivity was boosted by 150% in the case of E-GnP. The application of chemical functionalization to the engineering of contact resistance in nanoparticles network was therefore validated as a fascinating route for the enhancement of heat exchange efficiency on nanoparticle networks, with great potential impact in low-temperature heat exchange and recovery applications

Er-doped phosphate glasses were fabricated by melt-quenching technique. The changes in their thermal, structural and luminescence properties with the addition of Al2O3, TiO2 or ZnO were studied. Physical and thermal properties were investigated through density measurement and differential thermal analysis. Structural characterization was performed using the Raman and Infrared spectroscopy. In order to study the influence of the composition on the luminescence properties of the glasses, the refractive index, the luminescence spectra and the lifetime values were measured. The results show that with the addition of Al2O3 and TiO2 the phosphate network becomes more connected increasing the glass transition temperature, whereas the addition of ZnO does not show significant changes in the optical, thermal and structural properties but it leads to a larger emission cross-section at 1540 nm as compared to the other glasses. As the site of the Er3+ is not strongly affected by the change in the glass composition, we think that the emission properties of the glasses depend on the glass structure connectivity, which has an impact on the Er3+ ions solubility., Comment: 32 pages, 9 figures, 1 table