Reversible Association of Nitro Compounds with p-Nitrothiophenol Modified on Ag Nanoparticles/Graphene Oxide Nanocomposites through Plasmon Mediated Photochemical Reaction.

Because localized surface plasmon resonance in nanostructures of noble metals is accompanied by interesting physical effects such as optical near-field enhancement, heat release, and the generation of hot electrons, it has been employed in a wide range of applications, including plasmon-assisted chemical reactions. Here, we use a composite of silver nanoparticles and graphene oxide (Ag@GO) as the catalytic as well as the analytic platform for plasmon-assisted chemical reactions. Through time-dependent surface-enhanced Raman scattering experiments, it is found that p-nitrothiophenol (pNTP) molecules on Ag@GO can be associated with nitro compounds such as nitrobenzene and 1-nitropropane to form azo compounds when aided by the plasmons. Furthermore, the reaction rate can be modulated by varying the wavelength and power of the excitation laser as well as the nitro compounds used. In addition, the aforementioned coupling reaction can be reversed. We demonstrate that the oxidation of azo compounds on Ag@GO using KMnO4 leads to the dissociation of the N═N double bond in the azo compounds and that the rate of bond dissociation can be accelerated significantly via laser irradiation. Furthermore, the pNTP molecules on Ag@GO can be recovered after the oxidation reaction. Finally, we demonstrate that the plasmon-assisted coupling reaction allows for the immobilization of nitro-group-containing fluorophores at specific locations on Ag@GO.

Surface-enhanced Raman spectroscopy for DNA detection by the self-assembly of Ag nanoparticles onto Ag nanoparticle-graphene oxide nanocomposites.

A novel surface-enhanced Raman scattering (SERS) sensing system which operates by the self-assembly of Ag nanoparticles (AgNPs) onto the nanocomposite of AgNPs and graphene oxide (AgNP-GO) in the presence of two complementary DNAs has been developed. In this system, AgNP-GO serves as a SERS-active substrate. The AgNPs with the modification of non-fluorescent 4-mercaptobenzoic acid (4-MBA) act as highly efficient Raman probes for DNA hybridization. When probe DNAs on AgNP-GO are complementary to target DNAs on AgNPs functionalized with 4-MBA, the DNA hybridization occurring directs the self-assembly of AgNPs onto AgNP-GO, leading to the creation of SERS hot spots. Due to the fact that partial 4-MBA molecules are located in the region of the hot spots, their SERS signals are greatly enhanced, indicating successful DNA hybridization. It is noteworthy that the size of AgNPs contributes significantly to the enhancement of SERS activity. The detection limit of the target DNAs at the pM level can be achieved through the self-assembly of large sized AgNPs onto AgNP-GO. More importantly, the AgNP-AgNP-GO system shows reproducible SERS signals in proportion to the logarithm of the target DNA concentrations spanning from 10(-6) to 10(-12) M and the excellent capability for multiplex DNA detection.