Aggregation of Ag nanoparticle based on surface acoustic wave for surface-enhanced Raman spectroscopy detection of dopamine.

BACKGROUND: Dopamine (DA), a vital neurotransmitter, plays a critical role in the human brain and relates to neuropsychiatric disorders such as Parkinson's disease and schizophrenia. Numerous studies have explored detection of such biomarkers through surface-enhanced Raman spectroscopy (SERS). However, most of the studies focused on SERS detection face significant challenges with plasmonic nanostructure development. Such challenges often include time-consuming processes, complex fabrication, specialized chemical labeling, poor reproducibility, and random hotspot generation. Therefore, the need for simple and rapid nanostructure development is evident in SERS. RESULTS: We propose an innovative SERS-active sensing technique for 50 nm silver nanoparticle (AgNP) clustering based on surface acoustic wave (SAW). When a 1 µL droplet of AgNP colloid is dispensed onto the SAW-propagation zone, the AgNP cluster is deposited after the droplet completely evaporates, developing plasmonic nanogaps for SERS hotspot caused by spherical AgNP aggregation. By optimizing the SAW system through the hydrophobic treatment and modulation of the operational power, the SAW-induced AgNP clustering showed densely packed AgNP within a dot-like configuration (∼2200 AgNP µm-2), effectively preventing particle welding. The characterization of 4-mercaptobenzoic acid as a probe analyte revealed that concentrations as low as 1.14 pM was detected using our SAW-SERS system under 785 nm laser excitation. Moreover, DA was detected up to 4.28 nM with a determination of 0.99 (R2). SIGNIFICANCE: This technique for AgNP clustering induced by SAW provides a rapid, in situ, label-free SERS sensing method with outstanding sensitivity and linearity. A mere act of dropping can create extensive plasmonic hotspots featuring nanogap of ∼1.5 nm. The SAW-induced AgNP clustering can serve as an ultrasensitive SERS-active substrate for diverse molecular detections, including neurotransmitter detection.

Quantitative detection of dopamine in human serum with surface-enhanced Raman scattering (SERS) of constrained vibrational mode.

Dopamine (DA) is a crucial neurotransmitter involved in the hormonal, nervous, and vascular systems being considered as an index to diagnose neurodegenerative diseases, including Parkinson's and Alzheimer's disease. Herein, we demonstrate the quantitative sensing of DA using the peak shift in surface-enhanced Raman scattering (SERS) of 4-mercaptophenylboronic acid (4-MPBA), resulting from the concentration of DA. To enable the signal enhancement of Raman scattering, Ag nanostructure was built with one-step gas-flow sputtering. 4-MPBA was then introduced using vapor-based deposition, acting as a reporter molecule for bonding with DA. The gradual peak-shift from 1075.6 cm-1 to 1084.7 cm-1 was observed with the increasing concentration of DA from 1 pM to 100nM. The numerical simulation revealed that DA bonding induced a constrained vibrational mode corresponding to 1084.7 cm-1 instead of a C-S-coupled C-ring in-plane bending mode of 4-MPBA corresponding to 1075.6 cm-1. Proposed SERS sensors depicted reliable DA detection in human serum and good selectivity against other analytes, including glucose, creatinine, and uric acid.