In-Situ Immobilization of Silver Nanoparticles on Self-Assembled Honeycomb-Patterned Films Enables Surface-Enhanced Raman Scattering (SERS) Substrates

Surface-enhanced Raman scattering (SERS) is an important sustainable technique because of its ability to detect trace-level analytes including pesticides, heavy metals, explosives, proteins, pathogens, and other chemical and biological contaminants. In this paper, we report a facile approach to highly sensitive SERS substrates by combining hierarchically patterned micro- and nanostructures with silver nanoparticles (Ag NPs) adsorbed on poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) surface. The patterned structures were fabricated using breath figures as dynamic templates in which polar block enriches at the rim of the pores. This characteristic of the breath figure method makes it possible to employ a simple coating technique to construct substrates decorated with Ag NPs, which have a diameter mostly ranging from 18 to 30 nm. Results indicate that the hierarchically ordered substrates show enhancement factors as high as 4 × 108. It is also found that the enhancement factors are concentration-depende...

[1]  P. Hildebrandt,et al.  Surface-enhanced resonance Raman spectroscopy of Rhodamine 6G adsorbed on colloidal silver , 1984 .

[2]  Bernard François,et al.  Self-organized honeycomb morphology of star-polymer polystyrene films , 1994, Nature.

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

[4]  Mohan Srinivasarao,et al.  Three-Dimensionally Ordered Array of Air Bubbles in a Polymer Film , 2001, Science.

[5]  M. Ghosh,et al.  Concentration-dependent surface-enhanced Raman scattering of 2-benzoylpyridine adsorbed on colloidal silver particles. , 2004, Journal of colloid and interface science.

[6]  Vladimir M. Shalaev,et al.  Resonant Field Enhancements from Metal Nanoparticle Arrays , 2004 .

[7]  G. Schatz,et al.  Electromagnetic fields around silver nanoparticles and dimers. , 2004, The Journal of chemical physics.

[8]  R. Singh,et al.  Concentration‐dependent surface‐enhanced Raman scattering and molecular dynamic study of dimethyl formamide , 2007 .

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

[10]  Jian-Feng Li,et al.  Expanding generality of surface-enhanced Raman spectroscopy with borrowing SERS activity strategy. , 2007, Chemical communications.

[11]  Marc D Porter,et al.  SERS as a bioassay platform: fundamentals, design, and applications. , 2008, Chemical Society reviews.

[12]  Yiping Zhao,et al.  Novel nanostructures for SERS biosensing , 2008 .

[13]  J. Homola.  Surface plasmon resonance sensors for detection of chemical and biological species. , 2008, Chemical reviews.

[14]  Hyunhyub Ko,et al.  Nanostructured surfaces and assemblies as SERS media. , 2008, Small.

[15]  G. Franks,et al.  Photochromic, metal-absorbing honeycomb structures. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[16]  Frank Simon,et al.  Poly(2‐(dimethylamino)ethyl methacrylate) Brushes with Incorporated Nanoparticles as a SERS Active Sensing Layer , 2010 .

[17]  Masatsugu Shimomura,et al.  Arrays of triangular shaped pincushions for SERS substrates prepared by using self-organization and vapor deposition. , 2010, Chemical communications.

[18]  Ning Gu,et al.  Interfacial effects of in situ-synthesized Ag nanoparticles on breath figures. , 2010, Langmuir : the ACS journal of surfaces and colloids.

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

[20]  Zhi‐Kang Xu,et al.  Facilitated and site-specific assembly of functional polystyrene microspheres on patterned porous films. , 2010, ACS applied materials & interfaces.

[21]  Zhi‐Kang Xu,et al.  Tunable assembly of nanoparticles on patterned porous film. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[22]  Zhi‐Kang Xu,et al.  Controllable construction of carbohydrate microarrays by site-directed grafting on self-organized porous films. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  J. Hao,et al.  Directionally electrodeposited gold nanoparticles into honeycomb macropores and their surface-enhanced Raman scattering , 2010 .

[24]  N. Gu,et al.  Surfactant-induced formation of honeycomb pattern on micropipette with curvature gradient. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[25]  Xuewang Zhu,et al.  Self-assembly and morphology control of new L-glutamic acid-based amphiphilic random copolymers: giant vesicles, vesicles, spheres, and honeycomb film. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[26]  Hongmin Ma,et al.  Dimensional architecture of ferrocenyl-based oligomer honeycomb-patterned films: from monolayer to multilayer. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[27]  James E Hutchison,et al.  Generation of metal nanoparticles from silver and copper objects: nanoparticle dynamics on surfaces and potential sources of nanoparticles in the environment. , 2011, ACS nano.

[28]  Zhi-Kang Xu,et al.  Honeycomb-patterned film segregated with phenylboronic acid for glucose sensing. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[29]  Zhi‐Kang Xu,et al.  Pore shape of honeycomb-patterned films: modulation and interfacial behavior. , 2012, The journal of physical chemistry. B.

[30]  Zhi-Kang Xu,et al.  Ordered microporous membranes templated by breath figures for size-selective separation. , 2012, Journal of the American Chemical Society.

[31]  Tony S. Yu,et al.  Fog deposition and accumulation on smooth and textured hydrophobic surfaces. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[32]  Annemarie Pucci,et al.  Angstrom-scale distance dependence of antenna-enhanced vibrational signals. , 2012, ACS nano.

[33]  A. Wark,et al.  Tuning the interparticle distance in nanoparticle assemblies in suspension via DNA-triplex formation : correlation between plasmonic and surface-enhanced Raman scattering responses , 2012 .

[34]  Zhi‐Kang Xu,et al.  Patterned biocatalytic films via one-step self-assembly. , 2012, Chemical communications.

[35]  J. Rodríguez-Hernández,et al.  Hierarchically structured multifunctional porous interfaces through water templated self-assembly of ternary systems. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[36]  Martina H. Stenzel,et al.  Honeycomb structured polymer films via breath figures , 2012 .

[37]  C. Bain,et al.  Superhydrophobic hierarchical honeycomb surfaces. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[38]  J. Hao,et al.  Preparation and functions of hybrid membranes with rings of Ag NPs anchored at the edges of highly ordered honeycomb-patterned pores. , 2013, Chemistry.

[39]  Lei Jiang,et al.  Bioinspired design of honeycomb structure interfaces with controllable water adhesion. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[40]  J. Hao,et al.  Au NP honeycomb-patterned films with controllable pore size and their surface-enhanced Raman scattering. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[41]  B. Reinhard,et al.  Generation of scalable quasi-3D metallo-dielectric SERS substrates through orthogonal reactive ion etching , 2013 .

[42]  Ross Brown,et al.  Photoactive, porous honeycomb films prepared from Rose Bengal-grafted polystyrene. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[43]  Aijuan Zhang,et al.  Breath figure arrays: unconventional fabrications, functionalizations, and applications. , 2013, Angewandte Chemie.

[44]  Zhi‐Kang Xu,et al.  Honeycomb Porous Films Prepared from Porphyrin-Cored Star Polymers: Submicrometer Pores Induced by Transition of Monolayer into Multilayer Structures , 2013 .

[45]  Zhi‐Kang Xu,et al.  Nonlithographic Fabrication of Nanostructured Micropatterns via Breath Figures and Solution Growth , 2014 .

[46]  Ting-Yu Liu,et al.  Selective SERS detecting of hydrophobic microorganisms by tricomponent nanohybrids of silver-silicate-platelet-surfactant. , 2014, ACS applied materials & interfaces.

[47]  Zhi‐Kang Xu,et al.  Polystyrenes with hydrophilic end groups: synthesis, characterization, and effects on the self-assembly of breath figure arrays. , 2014, The journal of physical chemistry. B.

[48]  Reinhard Niessner,et al.  SERS detection of bacteria in water by in situ coating with Ag nanoparticles. , 2014, Analytical chemistry.

[49]  Zhi‐Kang Xu,et al.  Multiple interfaces in self-assembled breath figures. , 2014, Chemical communications.

[50]  Jing-fu Liu,et al.  Submonolayer-Pt-Coated Ultrathin Au Nanowires and Their Self-Organized Nanoporous Film: SERS and Catalysis Active Substrates for Operando SERS Monitoring of Catalytic Reactions. , 2014, The journal of physical chemistry letters.

[51]  Galo J. A. A. Soler-Illia,et al.  Silver nanoparticle-mesoporous oxide nanocomposite thin films: a platform for spatially homogeneous SERS-active substrates with enhanced stability. , 2014, ACS applied materials & interfaces.

[52]  Zhi‐Kang Xu,et al.  Synthesis of polystyrene with cyclic, ionized and neutralized end groups and the self-assemblies templated by breath figures , 2014 .

[53]  P. Netti,et al.  Highly efficient surface-enhanced Raman scattering substrate formulation by self-assembled gold nanoparticles physisorbed on poly(N-isopropylacrylamide) thermoresponsive hydrogels. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[54]  N. Gu,et al.  Controllable preparation of core-shell Au-Ag nanoshuttles with improved refractive index sensitivity and SERS activity. , 2014, ACS applied materials & interfaces.

[55]  K. Thurecht,et al.  Hyperbranched polymer-gold nanoparticle assemblies: role of polymer architecture in hybrid assembly formation and SERS activity. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[56]  Jinhuai Liu,et al.  Three-dimensional and time-ordered surface-enhanced Raman scattering hotspot matrix. , 2014, Journal of the American Chemical Society.

[57]  Marta Fernández-García,et al.  Towards hierarchically ordered functional porous polymeric surfaces prepared by the breath figures approach , 2014 .

[58]  I. Chourpa,et al.  Polyethylene-glycol-Stabilized Ag Nanoparticles for Surface-Enhanced Raman Scattering Spectroscopy: Ag Surface Accessibility Studied Using Metalation of Free-Base Porphyrins , 2014 .