Porous Au-Ag Nanospheres with High-Density and Highly Accessible Hotspots for SERS Analysis.

Colloidal plasmonic metal nanoparticles have enabled surface-enhanced Raman scattering (SERS) for a variety of analytical applications. While great efforts have been made to create hotspots for amplifying Raman signals, it remains a great challenge to ensure their high density and accessibility for improved sensitivity of the analysis. Here we report a dealloying process for the fabrication of porous Au-Ag alloy nanoparticles containing abundant inherent hotspots, which were encased in ultrathin hollow silica shells so that the need of conventional organic capping ligands for stabilization is eliminated, producing colloidal plasmonic nanoparticles with clean surface and thus high accessibility of the hotspots. As a result, these novel nanostructures show excellent SERS activity with an enhancement factor of ∼1.3 × 10(7) on a single particle basis (off-resonant condition), promising high applicability in many SERS-based analytical and biomedical applications.

[1]  Q. Cao,et al.  Porous Au-Ag Alloy Particles Inlaid AgCl Membranes As Versatile Plasmonic Catalytic Interfaces with Simultaneous, in Situ SERS Monitoring. , 2015, ACS applied materials & interfaces.

[2]  Mingwei Chen,et al.  Nanoporous Metals for Catalytic and Optical Applications , 2009 .

[3]  Hongyu Chen,et al.  Measuring ensemble-averaged surface-enhanced Raman scattering in the hotspots of colloidal nanoparticle dimers and trimers. , 2010, Journal of the American Chemical Society.

[4]  Mathieu Kociak,et al.  Zeptomol detection through controlled ultrasensitive surface-enhanced Raman scattering. , 2009, Journal of the American Chemical Society.

[5]  N. Halas,et al.  Mesoscopic Au “Meatball” Particles , 2008 .

[6]  Chien-Hung Li,et al.  Morphological control and plasmonic tuning of nanoporous gold disks by surface modifications , 2015 .

[7]  Wenzheng Li,et al.  “Re-growth Etching” to Large-sized Porous Gold Nanostructures , 2013, Scientific Reports.

[8]  Chao Zhang,et al.  Highly Sensitive, Uniform, and Reproducible Surface‐Enhanced Raman Spectroscopy from Hollow Au‐Ag Alloy Nanourchins , 2014, Advanced materials.

[9]  Xiaoping Song,et al.  Interface synthesis of gold mesocrystals with highly roughened surfaces for surface-enhanced Raman spectroscopy , 2012 .

[10]  Jibin Song,et al.  Self-assembled plasmonic vesicles of SERS-encoded amphiphilic gold nanoparticles for cancer cell targeting and traceable intracellular drug delivery. , 2012, Journal of the American Chemical Society.

[11]  Wei-Chuan Shih,et al.  Surface-enhanced Raman spectroscopy with monolithic nanoporous gold disk substrates. , 2013, Nanoscale.

[12]  Nobuo Tanaka,et al.  Atomic origins of the high catalytic activity of nanoporous gold. , 2012, Nature materials.

[13]  Joseph M. McLellan,et al.  Fabrication of cubic nanocages and nanoframes by dealloying Au/Ag alloy nanoboxes with an aqueous etchant based on Fe(NO3)3 or NH4OH. , 2007, Nano letters.

[14]  Kevin L. Shuford,et al.  Multiple surface plasmon modes for a colloidal solution of nanoporous gold nanorods and their comparison to smooth gold nanorods. , 2008, Nano letters.

[15]  Jin-Seung Jung,et al.  Bimodal porous gold opals for molecular sensing , 2013, Electronic Materials Letters.

[16]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[17]  G. Yi,et al.  Surfactant size effect on surface-enhanced Raman scattering intensity from silver nanoparticles. , 2013, Journal of nanoscience and nanotechnology.

[18]  Miaofang Chi,et al.  Fully alloyed Ag/Au nanospheres: combining the plasmonic property of Ag with the stability of Au. , 2014, Journal of the American Chemical Society.

[19]  T. Klar,et al.  Optical Plasmons of Individual Gold Nanosponges , 2015, ACS photonics.

[20]  Dong Wang,et al.  Nanoporous gold nanoparticles , 2012 .

[21]  Akihiko Hirata,et al.  Wrinkled nanoporous gold films with ultrahigh surface-enhanced Raman scattering enhancement. , 2011, ACS nano.

[22]  Yadong Li,et al.  Single-crystalline octahedral Au-Ag nanoframes. , 2012, Journal of the American Chemical Society.

[23]  Yung Doug Suh,et al.  Thiolated DNA-based chemistry and control in the structure and optical properties of plasmonic nanoparticles with ultrasmall interior nanogap. , 2014, Journal of the American Chemical Society.

[24]  N. Kotov,et al.  SERS-active gold lace nanoshells with built-in hotspots. , 2010, Nano letters.

[25]  J. Erlebacher,et al.  Dealloying of noble-metal alloy nanoparticles. , 2014, Nano letters.

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

[27]  Xiaohong Xu,et al.  Low temperature CO oxidation over unsupported nanoporous gold. , 2007, Journal of the American Chemical Society.

[28]  Younan Xia,et al.  Synthesis and optical properties of cubic gold nanoframes , 2008, Nano research.

[29]  Zhuang Liu,et al.  Noble metal coated single-walled carbon nanotubes for applications in surface enhanced Raman scattering imaging and photothermal therapy. , 2012, Journal of the American Chemical Society.

[30]  Lidong Li,et al.  Uniform arrays of gold nanoparticles with different surface roughness for surface enhanced Raman scattering , 2015 .

[31]  Karren L. More,et al.  Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces , 2014, Science.

[32]  Zhong Lin Wang,et al.  Shell-isolated nanoparticle-enhanced Raman spectroscopy , 2010, Nature.

[33]  A. El Mel,et al.  Planar Arrays of Nanoporous Gold Nanowires: When Electrochemical Dealloying Meets Nanopatterning. , 2016, ACS applied materials & interfaces.

[34]  Rene Lopez,et al.  Tunable SERS in gold nanorod dimers through strain control on an elastomeric substrate. , 2010, Nano letters.

[35]  P. Nordlander,et al.  Porous Au Nanoparticles with Tunable Plasmon Resonances and Intense Field Enhancements for Single-Particle SERS. , 2014, The journal of physical chemistry letters.

[36]  Peidong Yang,et al.  Anisotropic etching of silver nanoparticles for plasmonic structures capable of single-particle SERS. , 2010, Journal of the American Chemical Society.

[37]  Xiaojun Wu,et al.  Integration of Kinetic Control and Lattice Mismatch To Synthesize Pd@AuCu Core-Shell Planar Tetrapods with Size-Dependent Optical Properties. , 2016, Nano letters.

[38]  M. Kappes,et al.  Gold mesostructures with tailored surface topography and their self-assembly arrays for surface-enhanced Raman spectroscopy. , 2010, Nano letters.

[39]  S. Schlücker Surface-enhanced Raman spectroscopy: concepts and chemical applications. , 2014, Angewandte Chemie.

[40]  Wee Chew,et al.  Nanoporous Gold Nanoframes with Minimalistic Architectures: Lower Porosity Generates Stronger Surface-Enhanced Raman Scattering Capabilities , 2015 .

[41]  Jiajing Zhou,et al.  SERS-encoded nanogapped plasmonic nanoparticles: growth of metallic nanoshell by templating redox-active polymer brushes. , 2014, Journal of the American Chemical Society.

[42]  Yadong Yin,et al.  Seeded growth route to noble metal nanostructures , 2013 .

[43]  Yadong Li,et al.  Sophisticated construction of Au islands on Pt-Ni: an ideal trimetallic nanoframe catalyst. , 2014, Journal of the American Chemical Society.

[44]  Tuan Vo-Dinh,et al.  Gold nanostars: surfactant-free synthesis, 3D modelling, and two-photon photoluminescence imaging , 2012, Nanotechnology.

[45]  Yadong Yin,et al.  Size-tailored synthesis of silver quasi-nanospheres by kinetically controlled seeded growth. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[46]  Dingsheng Wang,et al.  General preparation for Pt-based alloy nanoporous nanoparticles as potential nanocatalysts , 2011, Scientific reports.

[47]  Sunghoon Kwon,et al.  Highly uniform and reproducible surface-enhanced Raman scattering from DNA-tailorable nanoparticles with 1-nm interior gap. , 2011, Nature nanotechnology.

[48]  P. Vikesland,et al.  Facile, tunable, and SERS-enhanced HEPES gold nanostars , 2016 .

[49]  Jaebum Choo,et al.  Gold nanoparticle silica nanopeapods. , 2014, Journal of the American Chemical Society.

[50]  Yugang Sun,et al.  Tailored Synthesis of Superparamagnetic Gold Nanoshells with Tunable Optical Properties , 2010, Advanced materials.

[51]  Lu Han,et al.  Gold Nanoframes by Nonepitaxial Growth of Au on AgI Nanocrystals for Surface-Enhanced Raman Spectroscopy. , 2015, Nano letters.

[52]  A. Karma,et al.  Evolution of nanoporosity in dealloying , 2001, Nature.

[53]  Jonah Erlebacher,et al.  Nanoporous Gold Leaf: “Ancient Technology”/Advanced Material , 2004 .