ABSTRACT
Electrochemical methods are combined with shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) for a comprehensive study of pyridine adsorption on Au(111), Au(100) and Au(110) single crystal electrode surfaces. The effects of crystallographic orientation, pyridine concentration, and applied potential are elucidated, and the formation of a second pyridine adlayer on Au(111) is observed spectroscopically for the first time. Electrochemical and SHINERS results correlate extremely well throughout this study, and we demonstrate the potential of EC-SHINERS for thorough characterization of processes occurring on single crystal surfaces. Our method is expected to open up many new possibilities in surface science, electrochemistry and catalysis. Analytical figures of merit are discussed.
ABSTRACT
In this work, a cylindrical-substrate array for surface-enhanced Raman scattering (SERS) measurements was developed to enable analysis of nucleobases in a few microliters of liquid. To eliminate uncertainties associated with SERS detection of aqueous samples, a new type of cylindrical SERS substrate was designed to confine the aqueous sample at the tip of the SERS probe. Poly(methyl methacrylate) (PMMA) optical fibers in a series of different diameters were used as the basic substrate. A solution of poly(vinylidene fluoride)/dimethylformamide (PVDF/DMF) was used to coat the tip of each fiber to increase the surface roughness and facilitate adsorption of silver nanoparticles (AgNPs) for enhancing Raman signals. A chemical reduction method was used to form AgNPs in and on the PVDF coating layer. The reagents and reaction conditions were systematically examined with the aim of estimating the optimum parameters. Unlike the spreading of aqueous sample on most SERS substrates, particularly flat ones, the new SERS substrates showed enough hydrophobicity to restrict aqueous sample to the tip area, thus enabling quantitative analysis. The required volume of sample could be as low as 1 µL with no need for a drying step in the procedure. By aligning the cylindrical SERS substrates into a solid holder, an array of cylindrical substrates was produced for mass analysis of aqueous samples. This new substrate improves both reproducibility and sensitivity for detection in aqueous samples. The enhancement factor approaches 7 orders in magnitude with a relative standard error close to 8%. Using the optimized conditions, nucleobases of adenine, cytosine, thymine, and uracil could be detected with limits approaching a few hundreds nanomolar in only a few microliters of solution.
