Macroscopical monolayer films of ordered arrays of gold nanoparticles as SERS substrates for in situ quantitative detection in aqueous solutions

In this work, macroscopical monolayer films of ordered arrays of gold nanoparticles (MMF-OA-Au NPs) are successfully prepared at the interfaces of toluene-diethylene glycol (DEG) with a water volume fraction of 10% (no more than 25%), which can greatly reduce the electrostatic repulsion among NPs during the self-assembly due to the quick transfer of the remaining citrate ions into the DEG solutions containing water. Thanks to the uniformity in the intensity of SERS signals, the as-prepared MMF-OA-Au NPs transferred onto polydimethylsiloxane (PDMS) as SERS substrates (MMF-OA-Au NP@PDMS) can achieve in situ quantitative detection of the analytes (such as crystal violet and malachite green) in aqueous solutions. Moreover, MMF-OA-Au NP@PDMS as SERS-based pH sensors can directly determine the pH value of the aqueous solution in the range of 3 to 10 by means of the established well-defined linear relationship with the intensity of the peak of νCOO^- without any calibration, instead of the intensity ratio of the Raman peaks of νCOO^- to ν8a with further calculation. In addition, the as-prepared SERS-based pH sensors can still have excellent long-term durability.