Raman Spectroscopic Detection in Continuous Micro-Flow Using a Chip-Integrated Silver Electrode as Electrically Regenerable SERS Substrate.

An electrochemical approach to enable surface-enhanced Raman spectroscopy (SERS) detection in continuous microflow is presented. This is achieved by the integration of a silver electrode as SERS-substrate in a microfluidic chip device. By the application of actuation pulses of about 4 V otherwise irreversibly adsorbed analytes are stripped off, which enables quasi-realtime SERS-detection in a continuous microflow. The approach opens up a way for in situ SERS monitoring of com-pounds in microflow with high application potential in micro separation techniques like HPLC and lab-on-a-chip devices.

[1]  Dusan Losic,et al.  Nanoporous anodic aluminium oxide: Advances in surface engineering and emerging applications , 2013 .

[2]  Jaebum Choo,et al.  A portable surface-enhanced Raman scattering sensor integrated with a lab-on-a-chip for field analysis. , 2008, Lab on a chip.

[3]  J. Popp,et al.  Quantitative SERS studies by combining LOC-SERS with the standard addition method , 2015, Analytical and Bioanalytical Chemistry.

[4]  Duncan Graham,et al.  Chemical and bioanalytical applications of surface enhanced Raman scattering spectroscopy. , 2008, Chemical Society reviews.

[5]  Alexei Lapkin,et al.  SE(R)RS devices fabricated by a laser electrodispersion method. , 2011, The Analyst.

[6]  Bernhard Lendl,et al.  A New Method for Fast Preparation of Highly Surface-Enhanced Raman Scattering (SERS) Active Silver Colloids at Room Temperature by Reduction of Silver Nitrate with Hydroxylamine Hydrochloride , 2003 .

[7]  Matt Trau,et al.  Enabling Rapid and Specific Surface-Enhanced Raman Scattering Immunoassay Using Nanoscaled Surface Shear Forces. , 2015, ACS nano.

[8]  A. Morschhauser,et al.  Microfluidic setup for on-line SERS monitoring using laser induced nanoparticle spots as SERS active substrate , 2017, Beilstein journal of nanotechnology.

[9]  Gas removal in free-flow electrophoresis using an integrated nanoporous membrane , 2015, Microchimica Acta.

[10]  D. Belder,et al.  Catalysis by Metal Nanoparticles in a Plug-In Optofluidic Platform: Redox Reactions of p-Nitrobenzenethiol and p-Aminothiophenol , 2018 .

[11]  Luis M Liz-Marzán,et al.  SERS detection of small inorganic molecules and ions. , 2012, Angewandte Chemie.

[12]  Jürgen Popp,et al.  Label-free SERS in biological and biomedical applications: Recent progress, current challenges and opportunities. , 2018, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[13]  B. Man,et al.  Roles of graphene nanogap for the AgNFs electrodeposition on the woven Cu net as flexible substrate and its application in SERS , 2018, Carbon.

[14]  Ivano Alessandri,et al.  Recyclable SERS substrates based on Au-coated ZnO nanorods. , 2011, ACS applied materials & interfaces.

[15]  X. Lv,et al.  Preparation of sensitive and recyclable porous Ag/TiO 2 composite films for SERS detection , 2015 .

[16]  B. Ren,et al.  Clean and modified substrates for direct detection of living cells by surface-enhanced Raman spectroscopy. , 2011, Chemical communications.

[17]  Michael Sepaniak,et al.  Chemical and biochemical analysis using microfluidic-localized field platforms , 2007, SPIE Optics East.

[18]  Zhong-Qun Tian,et al.  Surface-enhanced Raman spectroscopy: substrate-related issues , 2009, Analytical and bioanalytical chemistry.

[19]  Jürgen Popp,et al.  Droplet formation via flow-through microdevices in Raman and surface enhanced Raman spectroscopy--concepts and applications. , 2011, Lab on a chip.

[20]  Eun Kyu Lee,et al.  Fast and sensitive trace analysis of malachite green using a surface-enhanced Raman microfluidic sensor. , 2007, Analytica chimica acta.

[21]  Jürgen Popp,et al.  Probing innovative microfabricated substrates for their reproducible SERS activity. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[22]  Jürgen Popp,et al.  Towards a fast, high specific and reliable discrimination of bacteria on strain level by means of SERS in a microfluidic device. , 2011, Lab on a chip.

[23]  Jin Wang,et al.  Gold nanorod@nanoparticle seed-SERSnanotags/graphene oxide plasmonic superstructured nanocomposities as an “on-off” SERS aptasensor , 2018, Carbon.

[24]  Jürgen Popp,et al.  A droplet-based microfluidic chip as a platform for leukemia cell lysate identification using surface-enhanced Raman scattering , 2017, Analytical and Bioanalytical Chemistry.

[25]  Andrew J. deMello,et al.  Surface-enhanced Raman scattering in nanoliter droplets: towards high-sensitivity detection of mercury (II) ions , 2009, Analytical and bioanalytical chemistry.

[26]  R. Álvarez-Puebla,et al.  Surface-enhanced Raman scattering on colloidal nanostructures. , 2005, Advances in colloid and interface science.

[27]  Gerhard Werner,et al.  Lehrbuch der Quantitativen Analyse , 1998 .

[28]  Steven G. Bratsch,et al.  Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K , 1989 .

[29]  Quan Feng,et al.  Electrospun TiO₂ nanofelt surface-decorated with Ag nanoparticles as sensitive and UV-cleanable substrate for surface enhanced Raman scattering. , 2014, ACS applied materials & interfaces.

[30]  A. Campion,et al.  Surface-enhanced Raman scattering , 1998 .

[31]  Meikun Fan,et al.  A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry. , 2011, Analytica chimica acta.

[32]  Wamadeva Balachandran,et al.  Chemically Roughened Solid Silver: A Simple, Robust and Broadband SERS Substrate , 2016, Sensors.

[33]  A. Ozbay,et al.  Tunable Plasmonic Silver Nanodomes for Surface-Enhanced Raman Scattering , 2017, Plasmonics.

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

[35]  A. deMello,et al.  Ultrafast surface enhanced resonance Raman scattering detection in droplet-based microfluidic systems. , 2011, Analytical chemistry.

[36]  Jyisy Yang,et al.  Photochemical method for decoration of silver nanoparticles on filter paper substrate for SERS application , 2014 .

[37]  J. Popp,et al.  Copper nanostructures for chemical analysis using surface-enhanced Raman spectroscopy , 2018, TrAC Trends in Analytical Chemistry.

[38]  De‐Yin Wu,et al.  Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials , 2016 .

[39]  V. Beushausen,et al.  Implementation of substrates for surface-enhanced Raman spectroscopy for continuous analysis in an optofluidic device , 2012 .

[40]  B. Rasco,et al.  Detection of triphenylmethane drugs in fish muscle by surface-enhanced raman spectroscopy coupled with Au-Ag core-shell nanoparticles , 2014 .

[41]  M. Fleischmann,et al.  Raman spectra of pyridine adsorbed at a silver electrode , 1974 .

[42]  D. Lim,et al.  Nanoscale graphene oxide-induced metallic nanoparticle clustering for surface-enhanced Raman scattering-based IgG detection , 2018 .

[43]  Jürgen Popp,et al.  A reproducible surface-enhanced raman spectroscopy approach. Online SERS measurements in a segmented microfluidic system. , 2007, Analytical chemistry.

[44]  Jürgen Popp,et al.  SERS: a versatile tool in chemical and biochemical diagnostics , 2008, Analytical and bioanalytical chemistry.

[45]  K. Kant,et al.  Surface-Enhanced Raman Scattering Spectroscopy and Microfluidics: Towards Ultrasensitive Label-Free Sensing , 2018, Biosensors.

[46]  K. S. Krishnan,et al.  A New Type of Secondary Radiation , 1928, Nature.

[47]  Liangbao Yang,et al.  Multifunctional Au‐Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants Detection , 2010 .

[48]  D. Belder,et al.  Surface enhanced Raman spectroscopy in microchip electrophoresis. , 2018, Journal of chromatography. A.

[49]  Martin Moskovits,et al.  Rapid identification by surface-enhanced Raman spectroscopy of cancer cells at low concentrations flowing in a microfluidic channel. , 2015, ACS nano.

[50]  Yaping Hu,et al.  Universal surface-enhanced Raman scattering amplification detector for ultrasensitive detection of multiple target analytes. , 2014, Analytical chemistry.

[51]  P. Ajayan,et al.  Gold Nanoparticles and g‐C3N4‐Intercalated Graphene Oxide Membrane for Recyclable Surface Enhanced Raman Scattering , 2017 .

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

[53]  Haiyang Mao,et al.  Microfluidic surface-enhanced Raman scattering sensors based on nanopillar forests realized by an oxygen-plasma-stripping-of-photoresist technique. , 2014, Small.

[54]  Jürgen Popp,et al.  Quantitative online detection of low-concentrated drugs via a SERS microfluidic system. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[55]  Zachary D. Schultz,et al.  Ultrasensitive surface-enhanced Raman scattering flow detector using hydrodynamic focusing. , 2013, Analytical chemistry.

[56]  Sudip Malik,et al.  Facile Decoration of Polyaniline Fiber with Ag Nanoparticles for Recyclable SERS Substrate. , 2015, ACS applied materials & interfaces.

[57]  Neil J. Pothier,et al.  Surface-Enhanced Raman Spectroscopy at a Silver Electrode as a Real-Time Detector in Flowing Streams , 1992 .

[58]  Y. Ozaki,et al.  Recent Developments in Plasmon-Supported Raman Spectroscopy:45 Years of Enhanced Raman Signals , 2017 .

[59]  J. Popp,et al.  SERS as an analytical tool in environmental science: The detection of sulfamethoxazole in the nanomolar range by applying a microfluidic cartridge setup. , 2017, Analytica chimica acta.

[60]  Neil J. Pothier,et al.  Surface-enhanced Raman spectroscopy at a silver electrode as a detection system in flowing streams , 1990 .

[61]  Zhipeng Li,et al.  In Situ Two‐Step Photoreduced SERS Materials for On‐Chip Single‐Molecule Spectroscopy with High Reproducibility , 2017, Advanced materials.

[62]  Zachary D. Schultz,et al.  Bioanalytical applications of surface-enhanced Raman spectroscopy: de novo molecular identification , 2017, Reviews in analytical chemistry.

[63]  Yiping Cui,et al.  Mixing Assisted "Hot Spots" Occupying SERS Strategy for Highly Sensitive In Situ Study. , 2018, Analytical chemistry.

[64]  Jian-Feng Li,et al.  Electrochemical surface-enhanced Raman spectroscopy of nanostructures. , 2008, Chemical Society reviews.

[65]  A. deMello,et al.  Integrated SERS-Based Microdroplet Platform for the Automated Immunoassay of F1 Antigens in Yersinia pestis. , 2017, Analytical chemistry.

[66]  Cole,et al.  On-column surface-enhanced Raman spectroscopy detection in capillary electrophoresis using running buffers containing silver colloidal solutions , 2000, Analytical chemistry.

[67]  F. Long,et al.  Reusable nanosilver-coated magnetic particles for ultrasensitive SERS-based detection of malachite green in water samples , 2016, Scientific Reports.

[68]  Lars Montelius,et al.  Photoconjugation of Molecularly Imprinted Polymer Nanoparticles for Surface-Enhanced Raman Detection of Propranolol. , 2015, ACS applied materials & interfaces.

[69]  J. Köhler,et al.  Microflow SERS Measurements Using Sensing Particles of Polyacrylamide/Silver Composite Materials , 2015 .

[70]  Lei Wu,et al.  Simultaneous and highly sensitive detection of multiple breast cancer biomarkers in real samples using a SERS microfluidic chip. , 2018, Talanta.

[71]  C. Min,et al.  Sensitive Gap-Enhanced Raman Spectroscopy with a Perfect Radially Polarized Beam , 2018, Plasmonics.

[72]  M. Fiałkowski,et al.  Highly reproducible, stable and multiply regenerated surface-enhanced Raman scattering substrate for biomedical applications , 2011 .

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

[74]  M. Albrecht,et al.  Anomalously intense Raman spectra of pyridine at a silver electrode , 1977 .

[75]  K. Kneipp,et al.  SERS--a single-molecule and nanoscale tool for bioanalytics. , 2008, Chemical Society reviews.

[76]  D. Belder,et al.  Seamless Combination of High-Pressure Chip-HPLC and Droplet Microfluidics on an Integrated Microfluidic Glass Chip. , 2017, Analytical chemistry.

[77]  K. Faulds,et al.  Surface-enhanced Raman spectroscopy for in vivo biosensing , 2017 .

[78]  Zhangrun Xu,et al.  Highly reproducible and fast detection of 6-thioguanine in human serum using a droplet-based microfluidic SERS system , 2019, Sensors and Actuators B: Chemical.