Flexible membranes of Ag-nanosheet-grafted polyamide-nanofibers as effective 3D SERS substrates.

We report on a synthetic approach to produce self-supported flexible surface-enhanced Raman scattering (SERS) active membranes consisting of polyamide (PA) nanofibers grafted with vertical Ag-nanosheets, via a combinatorial process of electrospinning PA-nanofiber membranes, assembling Au-nanoparticles on the PA-nanofibers as seeds for subsequent growth of Ag-nanosheets, and electrodepositing Ag-nanosheets on the electrospun PA-nanofibers. As a high density of Ag-nanosheets are vertically grown around each PA-nanofiber in the three-dimensional (3D) networked PA-nanofiber membranes, homogeneous nano-scaled gaps between the neighboring Ag-nanosheets are formed, leading to a high density of 3D SERS "hot spots" within the Ag-nanosheet-grafted PA-nanofiber membranes. The Ag-nanosheet-grafted PA-nanofiber membranes demonstrate high SERS activity with excellent Raman signal reproducibility for rhodamine 6G over the whole membrane. For a SERS-based trial analysis of polychlorinated biphenyls (PCBs, a kind of global environmental hazard), the 3D SERS substrate membranes are modified with mono-6-β-cychlodextrin to effectively capture PCB molecules. As a result, not only a low concentration down to 10(-6) M is reached, but also two congeners of PCBs in their mixed solution are identified, showing promising potential in SERS-based rapid detection of trace organic pollutants such as PCBs in the environment.

[1]  G. Meng,et al.  Ag nanosheet-assembled micro-hemispheres as effective SERS substrates. , 2011, Chemical communications.

[2]  Combined antenna and localized plasmon resonance in Raman scattering from random arrays of silver-coated, vertically aligned multiwalled carbon nanotubes. , 2011, Nano letters.

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

[4]  K. Kneipp,et al.  Surface-enhanced Raman scattering in local optical fields of silver and gold nanoaggregates-from single-molecule Raman spectroscopy to ultrasensitive probing in live cells. , 2006, Accounts of chemical research.

[5]  L. Liz‐Marzán,et al.  Reversible assembly of metal nanoparticles induced by penicillamine. Dynamic formation of SERS hot spots , 2011 .

[6]  H. Fong,et al.  SERS-active silver nanoparticles on electrospun nanofibers facilitated via oxygen plasma etching , 2013 .

[7]  Limei Tian,et al.  Paper-based SERS swab for rapid trace detection on real-world surfaces. , 2010, ACS applied materials & interfaces.

[8]  G. Meng,et al.  Vertically aligned Ag nanoplate-assembled film as a sensitive and reproducible SERS substrate for the detection of PCB-77. , 2012, Journal of hazardous materials.

[9]  Baohua Zhang,et al.  Large‐Area Silver‐Coated Silicon Nanowire Arrays for Molecular Sensing Using Surface‐Enhanced Raman Spectroscopy , 2008 .

[10]  Xu,et al.  Electromagnetic contributions to single-molecule sensitivity in surface-enhanced raman scattering , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[11]  Lifeng Zhang,et al.  Electrospun nanofibrous membranes surface-decorated with silver nanoparticles as flexible and active/sensitive substrates for surface-enhanced Raman scattering. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[12]  Younan Xia,et al.  Electrospinning of Nanofibers: Reinventing the Wheel? , 2004 .

[13]  G. Meng,et al.  Electrospun 1,4-DHAQ-doped cellulose nanofiber films for reusable fluorescence detection of trace Cu2+ and further for Cr3+. , 2012, Environmental science & technology.

[14]  Shuhong Yu,et al.  Co-assembly of Au nanorods with Ag nanowires within polymer nanofiber matrix for enhanced SERS property by electrospinning. , 2012, Nanoscale.

[15]  C. Haynes,et al.  Surface-enhanced Raman scattering detection and discrimination of polychlorinated biphenyls , 2009 .

[16]  Alexei A Kornyshev,et al.  Self-assembled nanoparticle arrays for multiphase trace analyte detection. , 2013, Nature materials.

[17]  G. Wiederrecht,et al.  Surfactantless synthesis of silver nanoplates and their application in SERS. , 2007, Small.

[18]  L. Liz‐Marzán,et al.  SERS-based diagnosis and biodetection. , 2010, Small.

[19]  Y. Cho,et al.  Charge-selective surface-enhanced Raman scattering using silver and gold nanoparticles deposited on silicon-carbon core-shell nanowires. , 2012, ACS nano.

[20]  M. H. Yeung,et al.  Formation of Gold and Silver Nanoparticle Arrays and Thin Shells on Mesostructured Silica Nanofibers , 2007 .

[21]  G. Meng,et al.  Arrays of Cone‐Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface‐Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls , 2012 .

[22]  Minhua Cao,et al.  Preparation and surface-enhanced Raman performance of electrospun poly(vinyl alcohol)/ high-concentration-gold nanofibers , 2011, Journal of Polymer Research.

[23]  Kan Wang,et al.  Large-scale synthesis of flexible free-standing SERS substrates with high sensitivity: electrospun PVA nanofibers embedded with controlled alignment of silver nanoparticles. , 2009, ACS nano.

[24]  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 .

[25]  Qing Huang,et al.  Large-area Ag nanorod array substrates for SERS: AAO template-assisted fabrication, functionalization, and application in detection PCBs , 2013 .

[26]  Jing-fu Liu,et al.  Fabrication of a Au nanoporous film by self-organization of networked ultrathin nanowires and its application as a surface-enhanced Raman scattering substrate for single-molecule detection. , 2011, Analytical chemistry.

[27]  Hsing-lin Wang,et al.  Synthesis of homogeneous silver nanosheet assemblies for surface enhanced Raman scattering applications , 2010 .

[28]  Younan Xia,et al.  A mechanistic study on the formation of silver nanoplates in the presence of silver seeds and citric acid or citrate ions. , 2011, Chemistry, an Asian journal.

[29]  Younan Xia,et al.  Functionalization of electrospun TiO2 nanofibers with Pt nanoparticles and nanowires for catalytic applications. , 2008, Nano letters.

[30]  G. Meng,et al.  Galvanic-cell-induced growth of Ag nanosheet-assembled structures as sensitive and reproducible SERS substrates. , 2012, Chemistry.

[31]  G. Frens Controlled Nucleation for the Regulation of the Particle Size in Monodisperse Gold Suspensions , 1973 .

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

[33]  E. Wang,et al.  Fabrication, characterization, and application in SERS of self-assembled polyelectrolyte-gold nanorod multilayered films. , 2005, The journal of physical chemistry. B.

[34]  Yiping Zhao,et al.  Surface-enhanced Raman scattering from helical silver nanorod arrays. , 2011, Chemical communications.

[35]  Quanqin Zhao,et al.  Synthesis of a β-cyclodextrin-modified Ag film by the galvanic displacement on copper foil for SERS detection of PCBs. , 2012, Journal of colloid and interface science.

[36]  Hong Dong,et al.  Assembly of Metal Nanoparticles on Electrospun Nylon 6 Nanofibers by Control of Interfacial Hydrogen-Bonding Interactions , 2008 .

[37]  Siew Yee Wong,et al.  Electrospinning-derived “Hairy Seaweed” and its photoelectrochemical properties , 2013 .

[38]  Bin Yan,et al.  Fabrication and SERS performance of silver-nanoparticle-decorated Si/ZnO nanotrees in ordered arrays. , 2010, ACS applied materials & interfaces.

[39]  S. Singamaneni,et al.  Directed assembly of gold nanorods using aligned electrospun polymer nanofibers for highly efficient SERS substrates , 2011, Nanotechnology.

[40]  C. Mirkin,et al.  Controlling anisotropic nanoparticle growth through plasmon excitation , 2003, Nature.

[41]  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.

[42]  M. Delville,et al.  Gold Nanoparticle Deposition on Silica Nanohelices: A New Controllable 3D Substrate in Aqueous Suspension for Optical Sensing , 2012 .

[43]  W. Cai,et al.  Standing Ag nanoplate-built hollow microsphere arrays: Controllable structural parameters and strong SERS performances , 2012 .

[44]  Z. Chang,et al.  "Firecracker-shaped" ZnO/polyimide hybrid nanofibers via electrospinning and hydrothermal process. , 2011, Chemical communications.

[45]  Enhanced Raman scattering from nanoparticle-decorated nanocone substrates: a practical approach to harness in-plane excitation. , 2010, ACS nano.

[46]  J. Rabolt,et al.  Immobilization of gold nanorods onto electrospun polycaprolactone fibers via polyelectrolyte decoration--a 3D SERS substrate. , 2013, Analytical chemistry.

[47]  Luis M Liz-Marzán,et al.  Towards low-cost flexible substrates for nanoplasmonic sensing. , 2013, Physical chemistry chemical physics : PCCP.

[48]  G. Frens Controlled nucleation for the regulation of the particle size in monodisperse gold solutions , 1973 .