A cyclo olefin polymer microfluidic chip with integrated gold microelectrodes for aqueous and non-aqueous electrochemistry.

This paper presents an entirely polymeric microfluidic system, made of cyclo olefin polymer (COP), with integrated gold microband electrodes for electrochemical applications in organic media. In the present work, we take advantage of the COP's high chemical stability to polar organic solvents in two different ways: (i) to fabricate gold microelectrodes using COP as a substrate by standard lithographic and lift-off techniques; and (ii) to perform electrochemical experiments in organic media. In particular, fourteen parallel gold microelectrodes with a width of 14 microm and separated from their closest neighbour by 16 microm were fabricated by lithographic and lift-off techniques on a 188 microm thick COP sheet. A closed channel configuration was obtained by pressure-assisted thermal bonding between the COP sheet containing the microelectrodes and a microstructured COP sheet, where a 3 cm long, 50 microm wide and 24 microm deep channel was fabricated via hot embossing. Cyclic voltammetric measurements were carried out in aqueous and organic media, using a solution consisting of 5 mM ferrocyanide/ferricyanide in 0.5 M KNO(3) and 5 mM ferrocene in 0.1 M TBAP/acetonitrile, respectively. Experimental currents obtained for different flow rates ranging from 1 to 10 microL min(-1) were compared to the theoretical steady state currents calculated by the Levich equation for a band electrode (R. G. Compton, A. C. Fisher, R. G. Wellington, P. J. Dobson and P. A. Leigh, J. Phys. Chem., 1993, 97, 10410-10415). In both cases, the difference between the experimental and the predicted data is less than 5%, thus validating the behaviour of the fabricated device. This result opens the possibility to use a microfluidic system made entirely from COP with integrated microband electrodes in organic electroanalysis and in electrosynthesis.

[1]  Champak Das,et al.  Dynamic coating for protein separation in cyclic olefin copolymer microfluidic devices , 2008 .

[2]  Douglas J Jackson,et al.  Fully integrated on-chip electrochemical detection for capillary electrophoresis in a microfabricated device. , 2002, Analytical chemistry.

[3]  C. Ahn,et al.  Functionalized nano interdigitated electrodes arrays on polymer with integrated microfluidics for direct bio-affinity sensing using impedimetric measurement , 2007 .

[4]  F. Marken,et al.  Electrochemical processes at a flowing organic solvent∣aqueous electrolyte phase boundary , 2007 .

[5]  R. Compton,et al.  Voltammetry in the presence of ultrasound: mass transport effects , 1996 .

[6]  R. Compton,et al.  Hydrodynamic voltammetry with channel microband electrodes : axial diffusion effects , 1996 .

[7]  Richard G Compton,et al.  Microelectrode arrays for electrochemistry: approaches to fabrication. , 2009, Small.

[8]  Jun Kameoka,et al.  Quantitative mass spectrometric determination of methylphenidate concentration in urine using an electrospray ionization source integrated with a polymer microchip. , 2004, Analytical chemistry.

[9]  R. Compton,et al.  Channel Microband Electrode Arrays for Mechanistic Electrochemistry. Two-Dimensional Voltammetry: Electrode Kinetics , 1999 .

[10]  D. Knapp,et al.  Plastic microchip liquid chromatography-matrix-assisted laser desorption/ionization mass spectrometry using monolithic columns. , 2006, Journal of chromatography. A.

[11]  Holger Becker,et al.  Polymer microfabrication technologies for microfluidic systems , 2008, Analytical and bioanalytical chemistry.

[12]  R. Zengerle,et al.  Sensitivity enhancement for colorimetric glucose assays on whole blood by on-chip beam-guidance , 2006, Biomedical microdevices.

[13]  Anders Kristensen,et al.  Nanoimprint lithography in the cyclic olefin copolymer, Topas®, a highly ultraviolet-transparent and chemically resistant thermoplast , 2004 .

[14]  Janko Auerswald,et al.  Fabrication of metallic patterns by microstencil lithography on polymer surfaces suitable as microelectrodes in integrated microfluidic systems , 2006 .

[15]  S. Shoji,et al.  Polymer microchip integrated with nano-electrospray tip for electrophoresis–mass spectrometry , 2008 .

[16]  Leif Nyholm,et al.  Electrochemical techniques for lab-on-a-chip applications. , 2005, The Analyst.

[17]  Xavi Illa,et al.  An array of ordered pillars with retentive properties for pressure-driven liquid chromatography fabricated directly from an unmodified cyclo olefin polymer. , 2009, Lab on a chip.

[18]  P. Renaud,et al.  Polyimide-based microfluidic devices. , 2001, Lab on a Chip.

[19]  S. Lunte,et al.  Fabrication and evaluation of a carbon‐based dual‐electrode detector for poly(dimethylsiloxane) electrophoresis chips , 2001, Electrophoresis.

[20]  Francesc Xavier Muñoz,et al.  On-chip electric field driven electrochemical detection using a poly(dimethylsiloxane) microchannel with gold microband electrodes. , 2008, Analytical chemistry.

[21]  C. E. Walker,et al.  Investigation of Airbrushing for Fabricating Microelectrodes in Microfluidic Devices , 2008 .

[22]  Mandy B Esch,et al.  Influence of master fabrication techniques on the characteristics of embossed microfluidic channels. , 2003, Lab on a chip.

[23]  Andreas Neyer,et al.  A new PMMA-microchip device for isotachophoresis with integrated conductivity detector , 2001 .

[24]  Timothy D. Goodman Advancements in polymer optics design, fabrication, and materials : 31 July 2005, San Diego, California, USA , 2005 .

[25]  Suyeon Cho,et al.  Micro-scale metallization of high aspect-ratio Cu and Au lines on flexible polyimide substrate by electroplating using SU-8 photoresist mask , 2005 .

[26]  P. Bartlett,et al.  An accurate microdisc simulation model for recessed microdisc electrodes , 1998 .

[27]  M. T. Fernández-Abedul,et al.  Electroactive intercalators for DNA analysis on microchip electrophoresis , 2007, Electrophoresis.

[28]  Hyeon-Bong Pyo,et al.  Wafer-scale fabrication of polymer-based microdevices via injection molding and photolithographic micropatterning protocols. , 2005, Analytical chemistry.

[29]  Martin Dufva,et al.  Pinched flow fractionation devices for detection of single nucleotide polymorphisms. , 2008, Lab on a chip.

[30]  D. J. Harrison,et al.  Capillary electrophoresis and sample injection systems integrated on a planar glass chip , 1992 .

[31]  C. Henry,et al.  Dual-electrode electrochemical detection for poly(dimethylsiloxane)-fabricated capillary electrophoresis microchips. , 2000, Analytical chemistry.

[32]  Eivind Hovig,et al.  Parallel nanoliter detection of cancer markers using polymer microchips. , 2005, Lab on a chip.

[33]  J. Henion,et al.  A polymeric microfluidic chip for CE/MS determination of small molecules. , 2001, Analytical chemistry.

[34]  Yu-Cheng Lin,et al.  Electroporation microchips for continuous gene transfection , 2001 .

[35]  P. Dobson,et al.  Hydrodynamic voltammetry with microelectrodes. Channel microband electrodes : theory and experiment , 1993 .

[36]  Agustín Costa-García,et al.  Poly(methylmethacrylate) and Topas capillary electrophoresis microchip performance with electrochemical detection , 2005, Electrophoresis.

[37]  Craig E. Banks,et al.  Characterization and fabrication of disposable screen printed microelectrodes , 2009 .

[38]  Junshan Liu,et al.  Plasma assisted thermal bonding for PMMA microfluidic chips with integrated metal microelectrodes , 2009 .

[39]  M. Sharp Determination of the charge-transfer kinetics of ferrocene at platinum and vitreous carbon electrodes by potential steps chronocoulometry , 1983 .

[40]  S. Soper,et al.  Fabrication of a gold microelectrode for amperometric detection on a polycarbonate electrophoresis chip by photodirected electroless plating , 2006, Electrophoresis.

[41]  J. Zen,et al.  A new fabrication process for a microchip electrophoresis device integrated with a three‐electrode electrochemical detector , 2005, Electrophoresis.

[42]  Changgeng Liu,et al.  Multichannel microchip electrophoresis device fabricated in polycarbonate with an integrated contact conductivity sensor array. , 2007, Analytical chemistry.

[43]  James P Landers,et al.  A simple PDMS-based electro-fluidic interface for microchip electrophoretic separations. , 2002, The Analyst.

[44]  R A Mathies,et al.  Capillary electrophoresis chips with integrated electrochemical detection. , 1998, Analytical chemistry.

[45]  Joseph Wang,et al.  Electrochemical detection for microscale analytical systems: a review. , 2002, Talanta.

[46]  Martin Pumera,et al.  New materials for electrochemical sensing VII. Microfluidic chip platforms , 2006 .

[47]  Gavin Conibeer,et al.  Structural studies of SnS films prepared by thermal evaporation , 2006, SPIE Micro + Nano Materials, Devices, and Applications.

[48]  F. Marken,et al.  Two-phase flow electrosynthesis: Comparing N-octyl-2-pyrrolidone-aqueous and acetonitrile-aqueous three-phase boundary reactions , 2009 .

[49]  Champak Das,et al.  Integration of isoelectric focusing with multi-channel gel electrophoresis by using microfluidic pseudo-valves. , 2007, Lab on a chip.

[50]  R. Compton,et al.  A general computational approach to linear sweep voltammetry at channel electrodes , 1992 .

[51]  Jörg P Kutter,et al.  Underivatized cyclic olefin copolymer as substrate material and stationary phase for capillary and microchip electrochromatography , 2008, Electrophoresis.

[52]  J. Rossier,et al.  Electrochemical detection in polymer microchannels. , 1999, Analytical chemistry.

[53]  J Wang,et al.  Micromachined electrophoresis chips with thick-film electrochemical detectors. , 1999, Analytical chemistry.

[54]  W. Xiaodong,et al.  Microfluidic chip made of COP (cyclo-olefin polymer) and comparion to PMMA (polymethylmethacrylate) microfluidic chip , 2008 .

[55]  R. Compton,et al.  Linear sweep voltammetry at channel electrodes , 1986 .

[56]  P. Dobson,et al.  Channel microband electrode arrays for mechanistic electrochemistry. Two-dimensional voltammetry:  transport-limited currents. , 1998, Analytical chemistry.

[57]  Richard G. Compton,et al.  Channel Electrodes — A Review , 1998 .