A new method based on the coffee
ring effect was developed for
improving the sensitivity, simplicity, and robustness of surface-enhanced
Raman scattering (SERS) in determining trace levels of analytes. In
this method, a polyvinylpyrrolidone (PVP)-stabilized silver colloidal
(AgC) solution was first prepared and mixed with a sample solution.
Following deposition of the mixture solution on a solid substrate
with a rough surface, a coffee ring was formed once the solvent had
evaporated. The formation of a coffee ring not only concentrated the
analyte but also reduced the space between silver nanoparticles (AgNPs)
to strengthen the hotspot effect, thereby considerably improving SERS
sensitivity. To strengthen the coffee ring effect further, the surface
roughness of the solid support and PVP content of the AgC solution
were investigated. The results indicated that an increase in surface
roughness reduced the size of the coffee rings, whereas the addition
of PVP not only stabilized the AgNPs but also improved the compactness
of the coffee rings. When applying the proposed method to determine
the phenylalanine (Phe) level in urine for rapid screening of the
phenylketonuria disorder, strong chemical interference from uric acid
(UA), which is a major component in urine, was observed. To minimize
the interference from UA, ZnO powder was applied to the urine sample
to adsorb UA prior to SERS detection. After cleaning by using ZnO,
the SERS signals of Phe were revealed for quantitative purposes. Under
the optimized conditions, both the sensitivity and reproducibility
of SERS measurement considerably improved. Quantitative analyses revealed
that the developed method is highly feasible for the rapid determination
of Phe in real samples.