Enhancing the electrocatalytic activity and stability of Prussian blue analogues by increasing their electroactive sites through the introduction of Au nanoparticles.

Prussian blue analogues (PBAs) have been proven as excellent Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) in acidic, neutral and alkaline media. Further improvements can be achieved by increasing their electrical conductivity, but scarce attention has been paid to quantify the electroactive sites of the electrocatalyst when this enhancement occurs. In this work, we have studied how the chemical design influences the specific density of electroactive sites in different Au-PBA nanostructures. Thus, we have first obtained and fully characterized a variety of monodisperse core@shell hybrid nanoparticles of Au@PBA (PBA of NiIIFeII and CoIIFeII) with different shell sizes. Their catalytic activity is evaluated by studying the OER, which is compared to pristine PBAs and other Au-PBA heterostructures. By using the coulovoltammetric technique, we have demonstrated that the introduction of 5-10% of Au in weight in the core@shell leads to an increase in the electroactive mass and thus, to a higher density of active sites capable of taking part in the OER. This increase leads to a significant decrease in the onset potential (up to 100 mV) and an increase (up to 420%) in the current density recorded at an overpotential of 350 mV. However, the Tafel slope remains unchanged, suggesting that Au reduces the limiting potential of the catalyst with no variation in the reaction kinetics. These improvements are not observed in other Au-PBA nanostructures mainly due to a lower contact between both compounds and the Au oxidation. Hence, an Au core activates the PBA shell and increases the conductivity of the resulting hybrid, while the PBA shell prevents Au oxidation. The strong synergistic effect existing in the core@shell structure evidences the importance of the chemical design for preparing PBA-based nanostructures exhibiting better electrocatalytic performances and higher electrochemical stabilities.

The design of magneto-plasmonic nanostructures formed by magnetic Prussian Blue-type nanocrystals decorated with Au nanoparticles.

We have developed a general protocol for the preparation of hybrid nanostructures formed by nanoparticles (NPs) of molecule-based magnets based on Prussian Blue Analogues (PBAs) decorated with plasmonic Au NPs of different shapes. By adjusting the pH, Au NPs can be attached preferentially along the edges of the PBA or randomly on the surface. The protocol allows tuning the plasmonic properties of the hybrids in the whole visible spectrum.

Plasmon-assisted spin transition in gold nanostar@spin crossover heterostructures.

Herein we report the design of core@shell nanoparticles formed by a metallic Au nanostar core and a spin-crossover shell based on the coordination polymer [Fe(Htrz)2(trz)](BF4). This procedure is general and has been extended to other metallic morphologies (nanorods, nanotriangles). Thanks to the photothermal effect arising from the plasmonic properties of the Au nanostar, 60% of iron centers undergo a thermal spin transition inside the thermal hysteresis triggered by a 808 nm laser low intensity irradiation. Compared to other Au morphologies, the great advantage of the nanostar shape arises from the hot spots created at the branches of the nanostar. These hot spots give rise to large NIR absorptions, making them ideal nanostructures for efficiently converting light into heat using low energy light, like that provided by a 808 nm laser.

Design of Bistable Gold@Spin-Crossover Core-Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching.

A simple chemical protocol to prepare core-shell gold@spin-crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin-crossover [Fe(Htrz)2 (trz)](BF4 ) coordination polymer is reported. The synthesis relies on a two-step approach consisting of a partial surface ligand substitution of the citrate-stabilized Au NPs followed by the controlled growth of a very thin layer of the SCO polymer. As a result, colloidally stable core@shell spherical NPs with a Au core of ca. 12 nm and a thin SCO shell 4 nm thick, are obtained, exhibiting a narrow distribution in sizes. Differential scanning calorimetry proves that a cooperative spin transition in the range 340-360 K is maintained in these Au@SCO NPs, in full agreement with the values reported for pristine 4 nm SCO NPs. Temperature-dependent charge-transport measurements of an electrical device based on assemblies of these Au@SCO NPs also support this spin transition. Thus, a large change in conductance upon spin state switching, as compared with other memory devices based on the pristine SCO NPs, is detected. This results in a large improvement in the sensitivity of the device to the spin transition, with values for the ON/OFF ratio which are an order of magnitude better than the best ones obtained in previous SCO devices.

Tunable porous nanoallotropes prepared by post-assembly etching of binary nanoparticle superlattices.

Self-assembly of inorganic nanoparticles has been used to prepare hundreds of different colloidal crystals, but almost invariably with the restriction that the particles must be densely packed. Here, we show that non-close-packed nanoparticle arrays can be fabricated through the selective removal of one of two components comprising binary nanoparticle superlattices. First, a variety of binary nanoparticle superlattices were prepared at the liquid-air interface, including several arrangements that were previously unknown. Molecular dynamics simulations revealed the particular role of the liquid in templating the formation of superlattices not achievable through self-assembly in bulk solution. Second, upon stabilization, all of these binary superlattices could be transformed into distinct "nanoallotropes"-nanoporous materials having the same chemical composition but differing in their nanoscale architectures.

Surface Enhanced Raman Scattering and Gated Materials for Sensing Applications: The Ultrasensitive Detection of Mycoplasma and Cocaine.

We present herein a novel combination of gated mesoporous silica nanoparticles (MSNs) and surface-enhanced Raman scattering (SERS) for sensing applications. As a proof-of-concept, we show the design of a system comprising MSNs loaded with crystal violet (CV), a molecule with high Raman cross section acting as SERS reporter, and capped with either a suitable DNA sequence for the detection of Mycoplasma genomic DNA or with an aptamer that selectively coordinates cocaine. In both cases the presence of the corresponding target analyte in solution (i.e., genomic DNA or cocaine) resulted in the release of CV. CV delivery was detected by SERS upon adsorption on gold nanotriangles (AuNTs), which display an efficient electromagnetic field enhancement and a high colloidal stability. By using this novel procedure a limit of detection of at least 30 copies DNA per µL was determined for the detection of Mycoplasma genomic DNA, whereas cocaine was detected at concentrations as low as 10 nm.

Enzymatic etching of gold nanorods by horseradish peroxidase and application to blood glucose detection.

Gold nanorods (AuNRs) have become some of the most used nanostructures for biosensing and imaging applications due to their plasmon-related optical response, which is highly sensitive toward minute changes in the AuNR aspect ratio. In this context, H2O2 has been used to trigger the chemical etching of AuNRs, thereby inducing a decrease of their aspect ratio. However, special conditions and relatively high concentrations of H2O2 are usually required, preventing the applicability of the system for biodetection purposes. To overcome this limitation we have introduced a biocatalytic species, the enzyme horseradish peroxidase (HRP) that is able to induce a gradual oxidation of AuNRs in the presence of trace concentrations of H2O2. Interestingly, the presence of halide ions has also been found to be essential for this process. As a consequence, other enzymatic reactions, such as those catalyzed by glucose oxidase, can be easily coupled to HRP activity, allowing the detection of different amounts of glucose. On the basis of these findings, we developed a highly sensitive and simple colorimetric assay that can be read out by the naked eye and allows the detection of physiological glucose concentrations in human serum.

Monodisperse gold nanotriangles: size control, large-scale self-assembly, and performance in surface-enhanced Raman scattering.

Au nanotriangles display interesting nanoplasmonic features with potential application in various fields. However, such applications have been hindered by the lack of efficient synthetic methods yielding sufficient size and shape monodispersity, as well as by insufficient morphological stability. We present here a synthesis and purification protocol that efficiently addresses these issues. The size of the nanotriangles can be tuned within a wide range by simply changing the experimental parameters. The obtained monodispersity leads to extended self-assembly, not only on electron microscopy grids but also at the air-liquid interface, allowing transfer onto centimeter-size substrates. These extended monolayers show promising performance as surface-enhanced Raman scattering substrates, as demonstrated for thiophenol detection.

Pen-on-paper approach toward the design of universal surface enhanced Raman scattering substrates.

The translation of a technology from the laboratory into the real world should meet the demand of economic viability and operational simplicity. Inspired by recent advances in conductive ink pens for electronic devices on paper, we present a "pen-on-paper" approach for making surface enhanced Raman scattering (SERS) substrates. Through this approach, no professional training is required to create SERS arrays on paper using an ordinary fountain pen filled with plasmonic inks comprising metal nanoparticles of arbitrary shape and size. We demonstrate the use of plasmonic inks made of gold nanospheres, silver nanospheres and gold nanorods, to write SERS arrays that can be used with various excitation wavelengths. The strong SERS activity of these features allowed us to reach detection limits down to 10 attomoles of dye molecules in a sample volume of 10 µL, depending on the excitation wavelength, dye molecule and type of nanoparticles. Furthermore, such simple substrates were applied to pesticide detection down to 20 ppb. This universal approach offers portable, cost effective fabrication of efficient SERS substrates at the point of care. This approach should bring SERS closer to the real world through ink cartridges to be fixed to a pen to create plasmonic sensors at will.