Waveguide enhanced Raman spectroscopy (WERS) utilizes simple, robust, high-index contrast dielectric waveguides to generate a strong evanescent field, through which laser light interacts with analytes residing on the surface of the waveguide. It offers a powerful tool for the direct identification and reproducible quantification of biochemical species and an alternative to surface enhanced Raman spectroscopy (SERS) without reliance on fragile noble metal nanostructures. The advent of low-cost laser diodes, compact spectrometers, and recent progress in material engineering, nanofabrication techniques, and software modeling tools have made realizing portable and cheap WERS Raman systems with high sensitivity a realistic possibility. This review highlights the latest progress in WERS technology and summarizes recent demonstrations and applications. Following an introduction to the fundamentals of WERS, the theoretical framework that underpins the WERS principles is presented. The main WERS design considerations are then discussed, and a review of the available approaches for the modification of waveguide surfaces for the attachment of different biorecognition elements is provided. The review concludes by discussing and contrasting the performance of recent WERS implementations, thereby providing a future roadmap of WERS technology where the key opportunities and challenges are highlighted.
The enormous complexity of a typical heterogeneous catalyst makes understanding the development and properties of any active nanoparticles present extremely challenging.In the case of carbon based catalysts that difficulty is compounded by the variability of the carbon powders used. We have previously developed a strategy that addresses these problems by mimicking the catalyst preparation conditions very closely but using highly ordered pyrolytic graphite crystals (HOPG) as a model surface. This enables us to examine the effects of specific functional groups on nanoparticle formation. We report here an extension of our work characterising functional groups on the HOPG surface, using XPS and AFM to explore the deposition of gold from aqueous solution onto HOPG surfaces treated in a variety of ways to alter the surface functionality. The structure and oxidation state of the resulting nanoparticles depend critically on the nature of the functional groups present and offers some insight into the development of catalysts based on these materials. Hydroxyls are identified as key functional species, reducing gold ions to their metallic state whilst being oxidised themselves to carbonyls.Carbonyls meanwhile promote the nucleation of Au 3+ , creating a network of islands at the HOPG surface. The results have relevance not only to catalysts using activated carbons but also the new generation of materials based on graphene and carbon nanotubes.
Particle in cavity nanostructures were produced by sedimentation of silver nanostars (AgNSs) onto sphere segment void (SSV) cavity structures produced by electrodeposition of gold around templates formed by assembling close packed monolayer arrays of 220 or 600 nm diameter polystyrene spheres. The resulting AgNS@SSV nanostructures were characterized by scanning electron microscopy and their performance as substrates for surface enhanced Raman spectroscopy (SERS) was examined. The enhancement factors obtained for the different structures were evaluated using benzenethiol as Raman probe, which adsorbs on Ag and Au to form a monolayer with uniform coverage, so allowing the enhancement to be quantified. Higher enhancements were obtained for the AgNSs@SSV substrates as compared with the gold SSV structures. The greatest enhancements were obtained when matching cavity and nanostar dimension so that only one nanostar could be accommodated in the cavity. The AgNS@SSV substrates were then shown to be promising substrates for the highly sensitive detection of dyes and, particularly, for the lake‐pigment cochineal lake, providing useful information and novel analytical tool for application in the field of cultural heritage diagnostics and conservation.
Surface functional groups have a strong influence on the deposition and final state of nanoparticles adsorbed on to the surface, a role discussed by Professor Spencer in his work. This tribute to Spencer explores the formation of hydroxyls, thiosulfates, sulfites and sulfur atoms on carbon (HOPG) surfaces and their effect on the deposition of gold and palladium from aqueous solutions. Hydroxyls formed from ammonium hydroxide treatment have identical behaviour to those formed by acid treatment, and gold adsorption from Au3+ solutions gives Au0 initially, with Au3+ formed at higher concentrations on these surfaces. In contrast, palladium adsorption is hindered by the presence of the hydroxyls and there is no indication of any reduction to the metallic state. Ammonium thiosulfate adsorbs dissociatively from aqueous solutions on HOPG if the surface is pre-activated by the presence of surface hydroxyls. At low concentrations of ammonium thiosulfate, adsorbed sulfite and sulfur are formed in equimolar concentrations whereas adsorption of high concentrations of ammonium thiosulfate gives some degree of molecular adsorption, with evidence in XP spectra for an ammonium ion and a sulfur 2p peak at 282.9 eV attributed to the undissociated thiosulfate ion. Both sulfur and the sulfite are stable at the surface in neutral solutions but the sulfite desorbs when treated with acidified solutions (~ pH ≤ 6). These two groups are also stable at 373 K but begin to desorb by 473 K. Exposure to a weak chloroauric acid solution causes the desorption of the sulfite and formation of a gold species with an XP binding energy of 84.6 eV; we cannot determine from the present data whether this peak is due to a Au(I) state or very small nanoparticles of Au(0). Graphic Abstract
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