The surface-enhanced Raman scattering detection of N-nitrosodimethylamine and N-nitrosodiethylamine via gold nanorod arrays with a chemical linkage of zwitterionic copolymer.

Due to the emerging issue of the contamination of sartan medicines and drinking water with N-nitrosodimethylamine (NDMA) and/or N-nitrosodiethylamine (NDEA), the detection of NDMA/NDEA has become an important theme. In this study, we utilized the focused ion beam (FIB) technique to fabricate gold nanorods (Au NRs) and Surface-enhanced Raman Scattering (SERS) substrates and modified them with 1,2-ethanedithiol to quench the high luminescence excitation background signals derived from the high density of localized surface plasmon resonance. To improve the surface hydrophilicity, zwitterionic copolymer PGMA-r-PSBMA was grafted onto the nanosurface of Au NRs, which was confirmed by contact angle analysis and AFM. Raman spectra of the copolymer were observed to confirm the successful grafting of Au NRs, which was also corroborated by TEM and SEM. The Au NRs could easily trap the small polar NDMA and NDEA molecules in aqueous solution due to strong zwitterionic hydrophilicity. Furthermore, the self-association of the anions and cations of the polymeric chain grafted in the hot spot zone assisted in trapping the NDMA/NDEA polar molecules. The Raman scattering cross-section of NDMA/NDEA molecules could be enhanced through the chemical linkage of 1,2-ethanedithiol and the self-association behavior of the zwitterionic copolymer. Accordingly, for the first time, we detected the characteristic peaks of NDMA/NDEA through SERS with detection limit of 10-8 M for both molecules.

[1]  B. Rodriguez,et al.  Enhanced photocatalysis and biomolecular sensing with field-activated nanotube-nanoparticle templates , 2019, Nature Communications.

[2]  Lingling Wang,et al.  Unexpected large nanoparticle size of single dimer hotspot systems for broadband SERS enhancement. , 2018, Optics letters.

[3]  L. Lagae,et al.  High spatial resolution nanoslit SERS for single-molecule nucleobase sensing , 2018, Nature Communications.

[4]  Manish K Jaiswal,et al.  Vacancy‐Driven Gelation Using Defect‐Rich Nanoassemblies of 2D Transition Metal Dichalcogenides and Polymeric Binder for Biomedical Applications , 2017, Advanced materials.

[5]  Hyunook Kim,et al.  Simple quantification method for N-nitrosamines in atmospheric particulates based on facile pretreatment and GC-MS/MS. , 2017, Environmental pollution.

[6]  T. Wen,et al.  An anti-fouling nanoplasmonic SERS substrate for trapping and releasing a cationic fluorescent tag from human blood solution. , 2017, Nanoscale.

[7]  F. Breider,et al.  Quantification of Total N-Nitrosamine Concentrations in Aqueous Samples via UV-Photolysis and Chemiluminescence Detection of Nitric Oxide. , 2017, Analytical Chemistry.

[8]  G. Fanchini,et al.  In situ Raman spectroscopy distinguishes between reversible and irreversible thiol modifications in L-cysteine , 2017 .

[9]  T. Wen,et al.  The size effect of silver nanocubes on gap-mode surface enhanced Raman scattering substrate , 2016 .

[10]  Shaoyi Jiang,et al.  Hierarchical zwitterionic modification of a SERS substrate enables real-time drug monitoring in blood plasma , 2016, Nature Communications.

[11]  T. Wen,et al.  Zwitterionic surface grafting of epoxylated sulfobetaine copolymers for the development of stealth biomaterial interfaces. , 2016, Acta biomaterialia.

[12]  Xiao-jian Zhang,et al.  Occurrence of nitrosamines and their precursors in drinking water systems around mainland China. , 2016, Water research.

[13]  C. Höppener,et al.  Impact of the Nanoscale Gap Morphology on the Plasmon Coupling in Asymmetric Nanoparticle Dimer Antennas. , 2016, Small.

[14]  Liguang Xu,et al.  SERS-active silver nanoparticle trimers for sub-attomolar detection of alpha fetoprotein , 2015 .

[15]  Peng Zhang,et al.  Stealth surface modification of surface-enhanced Raman scattering substrates for sensitive and accurate detection in protein solutions. , 2015, ACS nano.

[16]  T. Karanfil,et al.  Assessing trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment plants using fluorescence spectroscopy and parallel factor analysis. , 2015, Chemosphere.

[17]  M. Aydin.  Comparative Study of the Structural and Vibroelectronic Properties of Porphyrin and Its Derivatives , 2014, Molecules.

[18]  J. Liao,et al.  Focused-ion-beam-fabricated Au/Ag multilayered nanorod array as SERS-active substrate for virus strain detection , 2013 .

[19]  J. V. Sancho,et al.  Determination of eight nitrosamines in water at the ng L(-1) levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry. , 2011, Analytica chimica acta.

[20]  Naomi J Halas,et al.  Nanosphere arrays with controlled sub-10-nm gaps as surface-enhanced raman spectroscopy substrates. , 2005, Journal of the American Chemical Society.

[21]  Zhiping Zhou,et al.  In situ FTIR investigation on the adsorption of nitrosamines in zeolites , 2004 .

[22]  D. Wiersma,et al.  Photodissociation dynamics of dimethylnitrosamine studied by resonance Raman spectroscopy , 1994 .

[23]  Shaoyi Jiang,et al.  Molecular Understanding and Design of Zwitterionic Materials , 2015, Advanced materials.