SERS-encoded nanogapped plasmonic nanoparticles: growth of metallic nanoshell by templating redox-active polymer brushes.

We report a new strategy to synthesize core-shell metal nanoparticles with an interior, Raman tag-encoded nanogap by taking advantage of nanoparticle-templated self-assembly of amphiphilic block copolymers and localized metal precursor reduction by redox-active polymer brushes. Of particular interest for surface-enhanced Raman scattering (SERS) is that the nanogap size can be tailored flexibly, with the sub-2 nm nanogap leading to the highest SERS enhancement. Our results have further demonstrated that surface functionalization of the nanogapped Au nanoparticles with aptamer targeting ligands allows for specific recognition and ultrasensitive detection of cancer cells. The general applicability of this new synthetic strategy, coupled with recent advances in controlled wet-chemical synthesis of functional nanocrystals, opens new avenues to multifunctional core-shell nanoparticles with integrated optical, electronic, and magnetic properties.

[1]  Jiajing Zhou,et al.  Biodegradable theranostic plasmonic vesicles of amphiphilic gold nanorods. , 2013, ACS nano.

[2]  E. Zubarev.  Nanoparticle synthesis: any way you want it. , 2013, Nature nanotechnology.

[3]  Zhiqun Lin,et al.  A general and robust strategy for the synthesis of nearly monodisperse colloidal nanocrystals. , 2013, Nature nanotechnology.

[4]  Jiajing Zhou,et al.  Stimuli-responsive plasmonic core-satellite assemblies: i-motif DNA linker enabled intracellular pH sensing. , 2013, Chemical communications.

[5]  E. Zubarev,et al.  Therapeutic platforms based on gold nanoparticles and their covalent conjugates with drug molecules. , 2013, Advanced drug delivery reviews.

[6]  Shuling Shen,et al.  Rational Tuning the Optical Properties of Metal Sulfide Nanocrystals and Their Applications , 2013 .

[7]  J. Irudayaraj,et al.  Surface-enhanced Raman spectroscopy applied to food safety. , 2013, Annual review of food science and technology.

[8]  Peter Nordlander,et al.  A Plethora of Plasmonics from the Laboratory for Nanophotonics at Rice University , 2012, Advanced materials.

[9]  Ping Wu,et al.  Aptamer-guided silver-gold bimetallic nanostructures with highly active surface-enhanced Raman scattering for specific detection and near-infrared photothermal therapy of human breast cancer cells. , 2012, Analytical chemistry.

[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]  G. Arya,et al.  Self-orienting nanocubes for the assembly of plasmonic nanojunctions. , 2012, Nature nanotechnology.

[12]  George C Schatz,et al.  Dispersible gold nanorod dimers with sub-5 nm gaps as local amplifiers for surface-enhanced Raman scattering. , 2012, Nano letters.

[13]  Taeghwan Hyeon,et al.  Designed synthesis of uniformly sized iron oxide nanoparticles for efficient magnetic resonance imaging contrast agents. , 2012, Chemical Society reviews.

[14]  Xin Lu,et al.  Novel MUC1 Aptamer Selectively Delivers Cytotoxic Agent to Cancer Cells In Vitro , 2012, PloS one.

[15]  Jibin Song,et al.  SERS-Active Nanoparticles for Sensitive and Selective Detection of Cadmium Ion (Cd2+) , 2011 .

[16]  Yong Wang,et al.  Assembly of colloidal nanoparticles directed by the microstructures of polycrystalline ice. , 2011, ACS nano.

[17]  S. Gambhir,et al.  Gold nanoparticles: a revival in precious metal administration to patients. , 2011, Nano letters.

[18]  H. Duan,et al.  Self-Assembled Plasmonic Dimers of Amphiphilic Gold Nanocrystals , 2011 .

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

[20]  Xiaolian Sun,et al.  Monodisperse magnetic nanoparticles for theranostic applications. , 2011, Accounts of chemical research.

[21]  A. Agarwal,et al.  Gold nanorods 3D-supercrystals as surface enhanced Raman scattering spectroscopy substrates for the rapid detection of scrambled prions , 2011, Proceedings of the National Academy of Sciences.

[22]  Ximei Qian,et al.  Detection of circulating tumor cells in human peripheral blood using surface-enhanced Raman scattering nanoparticles. , 2011, Cancer research.

[23]  Tal Dvir,et al.  Nanotechnological strategies for engineering complex tissues. , 2020, Nature nanotechnology.

[24]  Sadia Afrin Khan,et al.  Gold nano-popcorn-based targeted diagnosis, nanotherapy treatment, and in situ monitoring of photothermal therapy response of prostate cancer cells using surface-enhanced Raman spectroscopy. , 2010, Journal of the American Chemical Society.

[25]  N. Halas,et al.  Metallic nanoshells with semiconductor cores: optical characteristics modified by core medium properties. , 2010, ACS nano.

[26]  P. Vikesland,et al.  Surface-enhanced Raman spectroscopy (SERS) for environmental analyses. , 2010, Environmental science & technology.

[27]  Shuo Peng,et al.  Responsive plasmonic assemblies of amphiphilic nanocrystals at oil-water interfaces. , 2010, ACS nano.

[28]  George C Schatz,et al.  Structure-activity relationships in gold nanoparticle dimers and trimers for surface-enhanced Raman spectroscopy. , 2010, Journal of the American Chemical Society.

[29]  Yong Wang,et al.  Hotspot-induced transformation of surface-enhanced Raman scattering fingerprints. , 2010, ACS nano.

[30]  Naomi J. Halas,et al.  Nanosphere-in-a-Nanoshell: A Simple Nanomatryushka† , 2010 .

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

[32]  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.

[33]  Christine H. Moran,et al.  Understanding the SERS Effects of Single Silver Nanoparticles and Their Dimers, One at a Time. , 2010, The journal of physical chemistry letters.

[34]  Shuming Nie,et al.  Semiconductor nanocrystals: structure, properties, and band gap engineering. , 2010, Accounts of chemical research.

[35]  Yung Doug Suh,et al.  Nanogap-engineerable Raman-active nanodumbbells for single-molecule detection. , 2010, Nature materials.

[36]  Chi‐Kuang Sun,et al.  Efficient near-IR hyperthermia and intense nonlinear optical imaging contrast on the gold nanorod-in-shell nanostructures. , 2009, Journal of the American Chemical Society.

[37]  Xiaohu Gao,et al.  Plasmonic fluorescent quantum dots. , 2009, Nature nanotechnology.

[38]  Jianping Xie,et al.  Protein-directed synthesis of highly fluorescent gold nanoclusters. , 2009, Journal of the American Chemical Society.

[39]  Weiyang Li,et al.  Dimers of silver nanospheres: facile synthesis and their use as hot spots for surface-enhanced Raman scattering. , 2009, Nano letters.

[40]  Shuming Nie,et al.  Bioconjugated quantum dots for in vivo molecular and cellular imaging. , 2008, Advanced drug delivery reviews.

[41]  T. Chen,et al.  Controlled assembly of eccentrically encapsulated gold nanoparticles. , 2008, Journal of the American Chemical Society.

[42]  J. Zhao,et al.  Controlled plasmonic nanostructures for surface-enhanced spectroscopy and sensing. , 2008, Accounts of chemical research.

[43]  Jeffrey N. Anker,et al.  Biosensing with plasmonic nanosensors. , 2008, Nature materials.

[44]  Xiaohua Huang,et al.  Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine. , 2008, Accounts of chemical research.

[45]  Chad A Mirkin,et al.  Rationally designed nanostructures for surface-enhanced Raman spectroscopy. , 2008, Chemical Society reviews.

[46]  S. Nie,et al.  Single-molecule and single-nanoparticle SERS: from fundamental mechanisms to biomedical applications. , 2008, Chemical Society reviews.

[47]  Daniele Fava,et al.  "Supramolecular" assembly of gold nanorods end-terminated with polymer "pom-poms": effect of pom-pom structure on the association modes. , 2008, Journal of the American Chemical Society.

[48]  Peter Nordlander,et al.  Plasmonic nanostructures: artificial molecules. , 2007, Accounts of chemical research.

[49]  V. Backman,et al.  Engineering sub-100 nm multi-layer nanoshells , 2006 .

[50]  Thomas R Huser,et al.  Surface-enhanced Raman scattering from individual au nanoparticles and nanoparticle dimer substrates. , 2005, Nano letters.

[51]  T. A. Taton,et al.  Controlling Shell Thickness in Core−Shell Gold Nanoparticles via Surface-Templated Adsorption of Block Copolymer Surfactants , 2005 .

[52]  T. A. Taton,et al.  Core/Shell gold nanoparticles by self-assembly and crosslinking of micellar, block-copolymer shells. , 2005, Angewandte Chemie.

[53]  Taeghwan Hyeon,et al.  Ultra-large-scale syntheses of monodisperse nanocrystals , 2004, Nature materials.

[54]  C. Mirkin,et al.  Nanoparticle-Based Bio-Bar Codes for the Ultrasensitive Detection of Proteins , 2003, Science.

[55]  T. Klar,et al.  Biomolecular Recognition Based on Single Gold Nanoparticle Light Scattering , 2003 .

[56]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[57]  Naomi J. Halas,et al.  Nanoengineering of optical resonances , 1998 .