Surface-Enhanced Raman Spectroscopic Probing in Digital Microfluidics through a Microspray Hole.

We report a novel approach for surface-enhanced Raman spectroscopy (SERS) detection in digital microfluidics (DMF). This is made possible by a microspray hole (μSH) that uses an electrostatic spray (ESTAS) for sample transfer from inside the chip to an external SERS substrate. To realize this, a new ESTAS-compatible stationary SERS substrate was developed and characterized for sensitive and reproducible SERS measurements. In a proof-of-concept study, we successfully applied the approach to detect various analyte molecules using the DMF chip and achieved micro-molar detection limits. Moreover, this technique was exemplarily employed to study an organic reaction occurring in the DMF device, providing vibrational spectroscopic data.

[1]  D. Belder,et al.  On-the-Fly Mass Spectrometry in Digital Microfluidics Enabled by a Microspray Hole: Toward Multidimensional Reaction Monitoring in Automated Synthesis Platforms. , 2022, Journal of the American Chemical Society.

[2]  D. Belder,et al.  Two-photon fluorescence lifetime for label-free microfluidic droplet sorting , 2021, Analytical and Bioanalytical Chemistry.

[3]  V. Brunton,et al.  Detection of Estrogen Receptor Alpha and Assessment of Fulvestrant Activity in MCF-7 Tumor Spheroids Using Microfluidics and SERS , 2021, Analytical chemistry.

[4]  Sujuan Ye,et al.  SERS-Microfluidic Approach for the Quantitative Detection of miRNA Using DNAzyme-Mediated Reciprocal Signal Amplification. , 2021, ACS sensors.

[5]  Zhi Zhu,et al.  Sensitive, Rapid, and Automated Detection of DNA Methylation Based on Digital Microfluidics. , 2021, ACS applied materials & interfaces.

[6]  R. Compton,et al.  A mini-review: How reliable is the drop casting technique? , 2020, Electrochemistry Communications.

[7]  Aaron R Wheeler,et al.  Digital microfluidic isolation of single cells for -Omics , 2020, Nature Communications.

[8]  Y. Ozaki,et al.  An accurate monitoring platform for the surface catalysis of nanozyme validated by surface-enhanced Raman-knietics model. , 2020, Analytical chemistry.

[9]  T. Pradeep,et al.  Probing Subtle Changes in Molecular Orientations Using Ambient Electrospray Deposition Raman Spectroscopy (AESD RS) , 2020 .

[10]  Yi-ping Cui,et al.  Quaternary Ammonium-modulated SERS Effect: Discovery, Mechanism and Application for Highly-sensitive in-vitro Sensing Acetylcholine. , 2020, Analytical chemistry.

[11]  Christian Dusny,et al.  Microfluidic device for concentration and SERS‐based detection of bacteria in drinking water , 2020, Electrophoresis.

[12]  William L. Fatigante,et al.  Integrating SERS and PSI-MS with Dual Purpose Plasmonic Paper Substrates for On-Site Illicit Drug Confirmation. , 2020, Analytical chemistry.

[13]  Yong‐Lai Zhang,et al.  In Situ Integration of SERS Sensors for On‐Chip Catalytic Reactions , 2020, Advanced Materials Technologies.

[14]  A. Nathan,et al.  An Impedance Sensing Platform for Monitoring Heterogeneous Connectivity and Diagnostics in Lab-on-a-Chip Systems , 2019, ACS omega.

[15]  D. Belder,et al.  A microfluidic device enabling surface-enhanced Raman spectroscopy at chip-integrated multifunctional nanoporous membranes , 2019, Analytical and Bioanalytical Chemistry.

[16]  Rebecca L. M. Gieseking,et al.  Molecular engineering of organic semiconductors enables noble metal-comparable SERS enhancement and sensitivity , 2019, Nature Communications.

[17]  Yingzhou Huang,et al.  Organic Molecule Detection Based on SERS in Microfluidics , 2019, Scientific Reports.

[18]  A. Wheeler,et al.  Rapid Chemical Reaction Monitoring by Digital Microfluidics-NMR: Proof of Principle Towards an Automated Synthetic Discovery Platform. , 2019, Angewandte Chemie.

[19]  J. Sangshetti,et al.  Synthesis and biological activity of structurally diverse phthalazine derivatives: A systematic review. , 2019, Bioorganic & medicinal chemistry.

[20]  Weihua Li,et al.  Rapid, one-step preparation of SERS substrate in microfluidic channel for detection of molecules and heavy metal ions. , 2019, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[21]  Anish Das,et al.  Raman Spectroscopic Detection in Continuous Micro-Flow Using a Chip-Integrated Silver Electrode as Electrically Regenerable SERS Substrate. , 2019, Analytical chemistry.

[22]  L. Diéguez,et al.  Microfluidics-Driven Fabrication of a Low Cost and Ultrasensitive SERS-Based Paper Biosensor , 2019, Applied Sciences.

[23]  Ankur Gupta,et al.  Design Automation for Dilution of a Fluid Using Programmable Microfluidic Device--Based Biochips , 2019, ACM Trans. Design Autom. Electr. Syst..

[24]  Tai-Lin Chen,et al.  Design and Synthesis of 1,2-Bis(hydroxymethyl)pyrrolo[2,1- a]phthalazine Hybrids as Potent Anticancer Agents that Inhibit Angiogenesis and Induce DNA Interstrand Cross-links. , 2019, Journal of medicinal chemistry.

[25]  Shyh‐Chyang Luo,et al.  Electrochemical SERS for in Situ Monitoring the Redox States of PEDOT and Its Potential Application in Oxidant Detection. , 2019, ACS applied materials & interfaces.

[26]  Weiqiang Wang,et al.  Driving and sorting of the fluorescent droplets on digital microfluidic platform , 2018, Microfluidics and Nanofluidics.

[27]  R. Panneerselvam,et al.  A rapid and simple chemical method for the preparation of Ag colloids for surface-enhanced Raman spectroscopy using the Ag mirror reaction. , 2018, Vibrational Spectroscopy.

[28]  Dominique Langevin,et al.  Characterization of Nanoparticle Batch-To-Batch Variability , 2018, Nanomaterials.

[29]  Ren Hu,et al.  Surface-Enhanced Raman Spectroscopy for Bioanalysis: Reliability and Challenges. , 2018, Chemical reviews.

[30]  Zhi Zhu,et al.  Facile fabrication of microfluidic surface-enhanced Raman scattering devices via lift-up lithography , 2018, Royal Society Open Science.

[31]  Zhi Zhu,et al.  Highly Sensitive and Automated Surface Enhanced Raman Scattering-based Immunoassay for H5N1 Detection with Digital Microfluidics. , 2018, Analytical chemistry.

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

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

[34]  M. Rahman,et al.  A systematic review on silver nanoparticles-induced cytotoxicity: Physicochemical properties and perspectives , 2017, Journal of Advanced Research.

[35]  C. Chan,et al.  Electrospray surface-enhanced Raman spectroscopy (ES-SERS) for probing surface chemical compositions of atmospherically relevant particles , 2017 .

[36]  Liguo Chen,et al.  Digital microfluidics: A promising technique for biochemical applications , 2017 .

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

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

[39]  M. O'connell,et al.  Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces , 2017 .

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

[41]  J. Masson,et al.  Dynamic-SERS Optophysiology: A Nanosensor for Monitoring Cell Secretion Events. , 2016, Nano letters.

[42]  J. Pawliszyn,et al.  A digital microfluidic interface between solid-phase microextraction and liquid chromatography-mass spectrometry. , 2016, Journal of chromatography. A.

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

[44]  A. Wheeler,et al.  Direct Interface between Digital Microfluidics and High Performance Liquid Chromatography-Mass Spectrometry. , 2015, Analytical chemistry.

[45]  Q. Cong,et al.  Charge-Transfer Effect on Surface-Enhanced Raman Scattering (SERS) in an Ordered Ag NPs/4-Mercaptobenzoic Acid/TiO2 System , 2015 .

[46]  Jon P Camden,et al.  Surface-Enhanced Raman Spectroscopy-Based Approach for Ultrasensitive and Selective Detection of Hydrazine. , 2015, Analytical chemistry.

[47]  Yukihiro Ozaki,et al.  Recent progress and frontiers in the electromagnetic mechanism of surface-enhanced Raman scattering , 2014 .

[48]  R. Cooks,et al.  Using ambient ion beams to write nanostructured patterns for surface enhanced Raman spectroscopy. , 2014, Angewandte Chemie.

[49]  R. Cooks,et al.  Analysis on the go: quantitation of drugs of abuse in dried urine with digital microfluidics and miniature mass spectrometry. , 2014, Analytical chemistry.

[50]  J. Lammertyn,et al.  A highly efficient extraction protocol for magnetic particles on a digital microfluidic chip , 2014 .

[51]  J. Weibel,et al.  Effect of superhydrophobic surface morphology on evaporative deposition patterns , 2014 .

[52]  Yang Ou,et al.  In-Situ Immobilization of Silver Nanoparticles on Self-Assembled Honeycomb-Patterned Films Enables Surface-Enhanced Raman Scattering (SERS) Substrates , 2014 .

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

[54]  Hongxing Xu,et al.  Nanogaps for SERS applications , 2014 .

[55]  I. White,et al.  Multiplexed detection of DNA sequences using a competitive displacement assay in a microfluidic SERRS-based device. , 2013, Analytical chemistry.

[56]  Michael D M Dryden,et al.  Integrated digital microfluidic platform for voltammetric analysis. , 2013, Analytical chemistry.

[57]  A. Wheeler,et al.  Microfluidic origami: a new device format for in-line reaction monitoring by nanoelectrospray ionization mass spectrometry. , 2013, Lab on a chip.

[58]  Bing Yan,et al.  SERS tags: novel optical nanoprobes for bioanalysis. , 2013, Chemical reviews.

[59]  H. B. Eral,et al.  Contact angle hysteresis: a review of fundamentals and applications , 2013, Colloid and Polymer Science.

[60]  Wenhui He,et al.  Engineering natural materials as surface-enhanced Raman spectroscopy substrates for in situ molecular sensing. , 2012, ACS applied materials & interfaces.

[61]  Bai Yang,et al.  Avoiding coffee ring structure based on hydrophobic silicon pillar arrays during single-drop evaporation , 2012 .

[62]  Michael G. Roper,et al.  Online coupling of digital microfluidic devices with mass spectrometry detection using an eductor with electrospray ionization. , 2012, Analytical chemistry.

[63]  Steve C. C. Shih,et al.  Dried blood spot analysis by digital microfluidics coupled to nanoelectrospray ionization mass spectrometry. , 2012, Analytical chemistry.

[64]  K. Audus,et al.  Digital microfluidics. , 2012, Annual review of analytical chemistry.

[65]  Saman Sadeghi,et al.  Micro-chemical synthesis of molecular probes on an electronic microfluidic device , 2011, Proceedings of the National Academy of Sciences.

[66]  Adisorn Tuantranont,et al.  Electrochemical detection on electrowetting-on-dielectric digital microfluidic chip. , 2011, Talanta.

[67]  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.

[68]  J. Lammertyn,et al.  A versatile electrowetting-based digital microfluidic platform for quantitative homogeneous and heterogeneous bio-assays , 2011 .

[69]  A. Goudah,et al.  Synthesis and anti-inflammatory evaluation of some condensed [4-(3,4-dimethylphenyl)-1(2H)-oxo-phthalazin-2-yl]acetic acid hydrazide. , 2010, European journal of medicinal chemistry.

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

[71]  A. Zecchina,et al.  Gold Nanoparticle Aggregates Immobilized on High Surface Area Silica Substrate for Efficient and Clean SERS Applications , 2010 .

[72]  M. Çulha,et al.  Surface-Enhanced Raman Scattering on Aggregates of Silver Nanoparticles with Definite Size , 2008 .

[73]  N. Shah,et al.  Surface-enhanced Raman spectroscopy. , 2008, Annual review of analytical chemistry.

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

[75]  N. Halas,et al.  Tailoring plasmonic substrates for surface enhanced spectroscopies. , 2008, Chemical Society reviews.

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

[77]  J. Solla-Gullón,et al.  A combination of SERS and electrochemistry in Pt nanoparticle electrocatalysis: Promotion of formic acid oxidation by ethylidyne , 2008 .

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

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

[80]  M. Haaf,et al.  Solving the clogging problem: precipitate-forming reactions in flow. , 2006, Angewandte Chemie.

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

[82]  Glen McHale,et al.  The use of high aspect ratio photoresist (SU-8) for super-hydrophobic pattern prototyping , 2004 .

[83]  Duncan Graham,et al.  SERRS. In situ substrate formation and improved detection using microfluidics. , 2002, Analytical chemistry.

[84]  Y. Shen,et al.  Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains. , 2001, Journal of the American Chemical Society.

[85]  T. Dupont,et al.  Capillary flow as the cause of ring stains from dried liquid drops , 1997, Nature.

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

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