Tips and tricks for the surface engineering of well‐ordered morphologically driven silver‐based nanomaterials

Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighte

SERS-active metal-dielectric nanostructures integrated in microfluidic devices for ultra-sensitive label-free miRNA detection

In this work, silver decorated porous silicon membranes integrated in a polydimethylsiloxane multi-chamber microfluidic chip were functionalized with DNA-probes and used for the detection of miRNA by Surface-enhanced Raman Scattering analysis. An innovative biological protocol has been designed: the probe was divided in two short pieces that interact before and after the miRNA incubation. The optofluidic biosensor was applied for the label-free detection of miRNA sequences at in vivo concentrations

Graphene-metal nanostructures as surface enhanced Raman scattering substrates for biosensing

Multilayered structures composed by Single Layer Graphene (SLG), silver nanoparticles and polydimethylsiloxane membranes were used as SERS substrates for the analysis of porphyrins and hemoproteins (e.g. Myoglobin). The transfer process of SLG from its Cu growth substrate to the Ag-decorated polydimethylsiloxane membrane was optimized. A Limit of Detection (LOD) of 10^-8 M was found for ethanolic solutions of Rhodamine 6G and the efficient detection of porphyrins and Myoglobin, adsorbed on SLG surface, was achieved. This study evidenced the potentialities of plasmonic graphene-based chips for biosensing

Edge-Grafted Molecular Junctions between Graphene Nanoplatelets: Applied Chemistry to Enhance Heat Transfer in Nanomaterials

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 application

Bispyrene Functionalization Drives Self-Assembly of Graphite Nanoplates into Highly Efficient Heat Spreader Foils

Thermally conductive nanopapers fabricated from graphene and related materials are currently showing 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 a defect-free sp2 structure, non-covalent functionalization with bispyrene compounds, synthesized 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 diffusivities. 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

Bloch surface waves-controlled fluorescence emission: coupling into nanometer-sized polymeric waveguides

The lateral confinement of Bloch surface waves on a patterned multilayer is investigated by means of leakage radiation microscopy (LRM). Arrays of nanometric polymeric waveguides are fabricated on a proper silicon-nitride/silicon-oxide multilayer grown on a standard glass coverslip. By exploiting the functional properties of the polymer, fluorescent proteins are grafted onto the waveguides. A fluorescence LRM analysis of both the direct and the Fourier image plane reveals that a substantial amount of emitted radiation couples into a guided mode and then propagates into the nanometric waveguide. The observations of the mode are supported by numerical simulations

Role of probe design and bioassay configuration in surface enhanced Raman scattering based biosensors for miRNA detection

The 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 bioassays relying on a one-step or two-step hybridization of the target miRNA with DNA probes. Then, the detection configuration is varied to evaluate the impact of different Raman reporters and their labelling position along the oligo sequence on bioassay sensitivity. At high miRNA concentration (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 different configurations is recorded at low miRNA concentration. Such effect is attributed to the increased relative contribution of Raman hot-spots to the whole SERS signal, in line with the electric near field distribution simulated for a simplified model of the Ag nanostructures. However, the beneficial effect of reducing the reporter-to-surface distance is partially retained for a two-step hybridization assay thanks to the less sterically hindered environment in which the second hybridization occurs. The study thus demonstrates an improvement of the detection limit of the two-step assay by tuning the probe labelling position, but sheds at the same time light on the multiple factors affecting the sensitivity of SERS-based bioassays