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.
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.
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.
Materials scientists have performed exceptional accomplishments in the design of various types of materials that can be directly used for biomedical research. In particular, nanomaterials (including plasmonic nanoparticles) have become forefront scaffolds for designing bioactive materials. The application of such materials in biomedicine however requires a directed design providing actuation and stability in a particularly complex environment such as living organisms. Enhanced diagnostic tools for diseases such as cancer and HIV are pursued, and in this context nanoparticles offer exclusive physicochemical features for accurate biosensing, as well as actuation. We discuss the biosensing capabilities of plasmonic nanoparticles, in connection with SERS imaging. Novel therapies based on local drug delivery and photothermal therapy activated by nanoparticles are being explored. These applications are briefly discussed in this article, considering the actual biological problems faced by materials scientists and highlighting the beneficial interactions between materials science and biomedicine, which lead to novel routes in biomedical research and practice.
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.
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