Highly Sensitive and Selective Surface-Enhanced Raman Spectroscopy Label-free Detection of 3,3′,4,4′-Tetrachlorobiphenyl Using DNA Aptamer-Modified Ag-Nanorod Arrays

An improved label-free approach for highly sensitive and selective detection of 3,3',4,4'-tetrachlorobiphenyl (PCB-77), a type of polychlorinated biphenyl, via surface-enhanced Raman spectroscopy (SERS) using DNA aptamer-modified Ag-nanorod arrays as the effective substrate is reported. The devised system consists of Ag-nanorod (Ag-NR) arrays with the PCB-77 binding aptamers anchored covalently to the Ag surfaces through a thiol linker. The aptamers are made of single-stranded DNA (ssDNA) oligomers, with one end standing on the Ag surface, and upon conjugation with PCB-77, the ssDNA molecules can change their conformation to hairpin loops, so that the Raman intensity of guanines at the other end of the DNA strand increases accordingly. As such, the intensity ratio I(656 cm(-1))/I(733 cm(-1)) increases concomitantly with the increase of the concentration of PCB-77, making the quantitative evaluation of trace amounts of PCB-77 attainable. Moreover, it is found that the DNA aptamer-based Ag-NR arrays can be more responsive with a lower and optimal density of the DNA molecules modified on the substrate surface, and the best sensitivity for detection of PCB-77 can be achieved with the lower detection limit approaching 3.3 × 10(-8) M. This work therefore demonstrates that the design of aptamer-modified Ag-NRs can be used as a practically promising SERS substrate for label-free trace detection of persistent organic pollutants (POPs) in the environment.