SERS characterization of dopamine and in situ dopamine polymerization on silver nanoparticles

Dopamine (DA) regulates several functions in the central nervous system and its depletion is responsible for psychological disorders like Parkinson's disease. Several analytical approaches have been presented for DA detection in pathological diagnosis. SERS spectroscopy is a highly promising technique for the sensitive detection of DA. However, an improvement in its detection in aqueous solution is highly desirable for reliable quantification in biological fluids. In this work, we explored a label-free SERS approach for DA detection, employing two conventional methods to synthesize Ag colloids: reduction via citrates (c-AgNPs) and reduction via hydroxylamine (h-AgNPs), and SERS measurements were performed with a laser at 488 nm wavelength. Under these conditions, DA was identified through reproducible SERS spectra in the c-AgNP medium; however, the SERS spectra of DA in h-AgNP solution showed a completely different SERS profile. SERS band analysis revealed that DA in h-AgNPs was oxidized and converted into polydopamine (PDA), which was triggered after exposure to laser radiation. DA oxidation and PDA formation were followed over time through the SERS band profile at pH 7, 9 and 12. We found that in situ PDA formation started after 50 min of laser irradiation of DA at pH 7, while DA was quickly oxidized at pH 9 and 12. Here, we present a detailed SERS band analysis of PDA, which sheds light on the molecular steps in the pathway formation of the PDA structure. Spectroscopic analysis and characterization revealed that a long laser exposure time led to the formation of stable PDA complexes with AgNPs, which allowed us to propose a novel approach for synthesis of AgNP-PDA composites. In conclusion, to detect DA through a label-free SERS approach, c-AgNPs must be employed, while stable AgNP-PDA materials can be achieved with h-AgNPs and 488 nm laser excitation.