Large-area Ag nanorod array substrates for SERS: AAO template-assisted fabrication, functionalization, and application in detection PCBs

Highly ordered arrays of thiolated β-cyclodextrin (HS-β-CD) functionalized Ag-nanorods (Ag-NRs) with plasmonic antennae enhancement of electrical field have been achieved for encapsulation and rapid detection of polychlorinated biphenyls (PCBs). The large-area ordered arrays of rigid Ag-NRs supported on copper base were fabricated via porous anodic aluminum oxide (AAO) template-assisted electrochemical deposition. The inter-nanorod gaps between the neighboring Ag-NRs were tuned to sub-10 nm by thinning the pore-wall thickness of the AAO template using diluted H3PO4. The nearly perfect large-area ordered arrays of Ag-NRs supported on copper base render these systems excellent in surface-enhanced Raman scattering (SERS) performance with uniform electric field enhancement, as testified by the SERS spectra and Raman mappings of rhodamine 6 G. Furthermore, the Ag-NRs were functionalized with HS-β-CD molecules so as to capture the apolar PCB molecules in the hydrophobic cavity of the CD. Compared to the ordinary undecorated SERS substrates, the HS-β-CD modified Ag-NR arrays exhibit better capture ability and higher sensitivity in rapid detection of PCBs. Copyright © 2012 John Wiley & Sons, Ltd.

[1]  Jung Sang Suh,et al.  Optimum Length of Silver Nanorods for Fabrication of Hot Spots , 2007 .

[2]  M. Romkes,et al.  High-resolution PCB analysis: synthesis and chromatographic properties of all 209 PCB congeners. , 1984, Environmental science & technology.

[3]  R. Dasari,et al.  Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS) , 1997 .

[4]  P. Shields.  Understanding Population and Individual Risk Assessment: The Case of Polychlorinated Biphenyls , 2006, Cancer Epidemiology Biomarkers & Prevention.

[5]  Pablo G. Etchegoin,et al.  Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study , 2007 .

[6]  K. Wommack,et al.  Influence of environmental changes on degradation of chiral pollutants in soils , 1999, Nature.

[7]  G. Meng,et al.  Large-scale well-separated Ag nanosheet-assembled micro-hemispheres modified with HS-β-CD as effective SERS substrates for trace detection of PCBs , 2012 .

[8]  M. Brewster,et al.  Pharmaceutical applications of cyclodextrins. 1. Drug solubilization and stabilization. , 1996, Journal of pharmaceutical sciences.

[9]  Peidong Yang,et al.  Surface-enhanced Raman spectroscopy for trace arsenic detection in contaminated water. , 2008, Angewandte Chemie.

[10]  G. Meng,et al.  Improved SERS Performance from Au Nanopillar Arrays by Abridging the Pillar Tip Spacing by Ag Sputtering , 2010, Advanced materials.

[11]  R Stanley Williams,et al.  Gold nanofingers for molecule trapping and detection. , 2010, Journal of the American Chemical Society.

[12]  O. Schrems,et al.  Theoretical Study of the Reaction Mechanism and Role of Water Clusters in the Gas-Phase Hydrolysis of SiCl4 , 2003 .

[13]  E. Laginestra,et al.  Distribution of inorganic and organic contaminants in sediments from Sydney Olympic Park and the surrounding Sydney metropolitan area. , 2009, Journal of environmental monitoring : JEM.

[14]  Katsuhiro Ajito,et al.  Observation of a small number of molecules at a metal nanogap arrayed on a solid surface using surface-enhanced Raman scattering. , 2007, Journal of the American Chemical Society.

[15]  K. Carron,et al.  Octadecylthiol-modified surface-enhanced Raman spectroscopy substrates: a new method for the detection of aromatic compounds , 1992 .

[16]  Christy L Haynes,et al.  Partition layer-modified substrates for reversible surface-enhanced Raman scattering detection of polycyclic aromatic hydrocarbons , 2009, Analytical and bioanalytical chemistry.

[17]  Samuel S. R. Dasary,et al.  Gold nanoparticle based label-free SERS probe for ultrasensitive and selective detection of trinitrotoluene. , 2009, Journal of the American Chemical Society.

[18]  M. Moskovits.  Surface‐enhanced Raman spectroscopy: a brief retrospective , 2005 .

[19]  M. Moskovits,et al.  Hot spots in silver nanowire bundles for surface-enhanced Raman spectroscopy. , 2006, Journal of the American Chemical Society.

[20]  R. V. Van Duyne,et al.  Toward a glucose biosensor based on surface-enhanced Raman scattering. , 2003, Journal of the American Chemical Society.

[21]  Martin Moskovits,et al.  Surface-enhanced Raman spectroscopy for DNA detection by nanoparticle assembly onto smooth metal films. , 2007, Journal of the American Chemical Society.

[22]  R. J. Bell,et al.  Optical properties of the metals Al, Co, Cu, Au, Fe, Pb, Ni, Pd, Pt, Ag, Ti, and W in the infrared and far infrared. , 1983, Applied optics.

[23]  Steven R. Emory,et al.  Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering , 1997, Science.

[24]  Hugo A. Jiménez-Vázquez,et al.  Binding Energy in and Equilibrium Constant of Formation for the Dodecahedrane Compounds He@C20H20 and Ne@C20H20 , 2001 .

[25]  P. Liu,et al.  Investigation on the inclusions of PCB52 with cyclodextrins by performing DFT calculations and molecular dynamics simulations. , 2010, The journal of physical chemistry. A.

[26]  A. Kaifer,et al.  Metal Nanoparticles with a Knack for Molecular Recognition , 2000 .

[27]  C. Domingo,et al.  Sensing polycyclic aromatic hydrocarbons with dithiocarbamate-functionalized ag nanoparticles by surface-enhanced Raman scattering. , 2009, Analytical chemistry.

[28]  Nicholas A. Klymyshyn,et al.  Finite Element Method Simulation of the Field Distribution for AFM Tip-Enhanced Surface-Enhanced Raman Scanning Microscopy , 2003 .

[29]  J. Szejtli,et al.  Past, present and futute of cyclodextrin research , 2004 .

[30]  S. Retterer,et al.  Free-standing optical gold bowtie nanoantenna with variable gap size for enhanced Raman spectroscopy. , 2010, Nano letters.

[31]  Luis M Liz-Marzán,et al.  Recyclable molecular trapping and SERS detection in silver-loaded agarose gels with dynamic hot spots. , 2009, Analytical chemistry.

[32]  R. Muller,et al.  Plasmonic nanoparticle arrays with nanometer separation for high-performance SERS substrates. , 2010, Nano letters.

[33]  G. Meng,et al.  Ag dendritic nanostructures for rapid detection of polychlorinated biphenyls based on surface-enhanced Raman scattering effect , 2010 .

[34]  Luis M Liz-Marzán,et al.  Loading of exponentially grown LBL films with silver nanoparticles and their application to generalized SERS detection. , 2009, Angewandte Chemie.

[35]  C. Guinet,et al.  Persistent organic pollutants (POPs) in killer whales (Orcinus orca) from the Crozet Archipelago, southern Indian Ocean. , 2009, Marine environmental research.

[36]  Wei Wang,et al.  Controlled fabrication of nanopillar arrays as active substrates for surface-enhanced Raman spectroscopy. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[37]  Sarah M. Stranahan,et al.  Super-resolution optical imaging of single-molecule SERS hot spots. , 2010, Nano letters.

[38]  Shr-Bin Wu,et al.  Highly Raman‐Enhancing Substrates Based on Silver Nanoparticle Arrays with Tunable Sub‐10 nm Gaps , 2006 .

[39]  G. Meng,et al.  Size-tunable nano-dots and nano-rings from nanochannel-confined electrodeposition. , 2009, Chemical communications.

[40]  Magnus Willander,et al.  Theory of surface-plasmon resonance optical-field enhancement at prolate spheroids , 2002 .

[41]  Zheng Guo,et al.  Synthesis of novel decorated one-dimensional gold nanoparticle and its application in ultrasensitive detection of insecticide , 2010 .

[42]  J. Pendry,et al.  Collective Theory for Surface Enhanced Raman Scattering. , 1996, Physical review letters.