All-solid-state reference electrodes based on colloid-imprinted mesoporous carbon and their application in disposable paper-based potentiometric sensing devices.

Reference electrodes are used in almost every electroanalytical measurement. Here, all-solid-state reference electrodes are described that employ colloid-imprinted mesoporous (CIM) carbon as solid contact and a poly(vinyl chloride) reference membrane to contact the sample. Such a reference membrane is doped with a moderately hydrophilic ionic liquid and a hydrophobic redox couple, leading to well-defined constant potentials at the interfaces of this membrane to the sample and to the solid contact, respectively. Due to the intrinsic properties of CIM carbon, reference electrodes with a CIM carbon solid contact exhibit excellent resistance to common interfering agents such as light and O2, with outstanding potential stability in continuous potentiometric measurements. The potential drift of CIM carbon-based reference electrodes without redox couple is as low as 1.7 μV/h over 110 h, making them the most stable all-solid-state reference electrodes reported so far. To demonstrate the compatibility of CIM carbon-based reference electrodes with miniaturized potentiometric systems, these reference electrodes were integrated into paper-based potentiometric sensing devices, successfully replacing the conventional reference electrode with its reference electrolyte solution. As a proof of concept, disposable paper-based Cl(-) sensing devices that contain stencil-printed Ag/AgCl-based Cl(-) selective electrodes and CIM carbon-based reference electrodes were constructed. These sensing devices are inexpensive, easy to use, and offer highly reproducible Cl(-) measurements with sample volumes as low as 10 μL.

[1]  Andreas Stein,et al.  Advantages and limitations of reference electrodes with an ionic liquid junction and three-dimensionally ordered macroporous carbon as solid contact. , 2012, Analytical chemistry.

[2]  N. D. de Rooij,et al.  Potential Drifts of Solid‐Contacted Ion‐Selective Electrodes Due to Zero‐Current Ion Fluxes Through the Sensor Membrane , 2000 .

[3]  Philippe Bühlmann,et al.  Calibration-free ionophore-based ion-selective electrodes with a Co(II)/Co(III) redox couple-based solid contact. , 2014, Analytical chemistry.

[4]  E. Hall,et al.  All‐Solid‐State Reference Electrodes with Poly(n‐butyl acrylate) Based Membranes , 2008 .

[5]  Dermot Diamond,et al.  A liquid-junction-free reference electrode based on a PEDOT solid-contact and ionogel capping membrane. , 2014, Talanta.

[6]  A. Kisiel,et al.  All-solid-state reference electrodes based on conducting polymers. , 2005, The Analyst.

[7]  A. Stein,et al.  Effects of architecture and surface chemistry of three-dimensionally ordered macroporous carbon solid contacts on performance of ion-selective electrodes. , 2010, Analytical chemistry.

[8]  J. Riu,et al.  Potentiometric strip cell based on carbon nanotubes as transducer layer: toward low-cost decentralized measurements. , 2011, Analytical chemistry.

[9]  Werner E. Morf,et al.  Reference electrode with free-flowing free-diffusion liquid junction , 1986 .

[10]  B. Buckley,et al.  Protein Interference with Ion-Selective Electrode Measurement Depends on Reference Electrode Composition and Design , 1991, Annals of clinical biochemistry.

[11]  F. Rius,et al.  Ion-selective electrodes using carbon nanotubes as ion-to-electron transducers. , 2008, Analytical chemistry.

[12]  T. Kakiuchi,et al.  A new salt bridge based on the hydrophobic room-temperature molten salt , 2006 .

[13]  A. Stein,et al.  Ion-selective electrodes with three-dimensionally ordered macroporous carbon as the solid contact. , 2007, Analytical chemistry.

[14]  Jordi Riu,et al.  Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane. , 2011, Analytical chemistry.

[15]  George M. Whitesides,et al.  Paper-based electroanalytical devices for accessible diagnostic testing , 2013 .

[16]  Dermot Diamond,et al.  Ionic Liquid-Based, Liquid-Junction-Free Reference Electrode , 2011 .

[17]  Ulrich S Schubert,et al.  Inkjet printing of polyurethane colloidal suspensions. , 2007, Soft matter.

[18]  P. Bühlmann,et al.  Glass and polymeric membrane electrodes for the measurement of pH in milk and cheese. , 2004, Talanta.

[19]  T. Kakiuchi,et al.  Determination of the activity of hydrogen ions in dilute sulfuric acids by use of an ionic liquid salt bridge sandwiched by two hydrogen electrodes. , 2011, Analytical chemistry.

[20]  Philip A. Gale,et al.  Supramolecular Chemistry: From Molecules to Nanomaterials , 2012 .

[21]  A. Michalska.  All‐Solid‐State Ion Selective and All‐Solid‐State Reference Electrodes , 2012 .

[22]  Grzegorz Lisak,et al.  Potentiometric sensing utilizing paper-based microfluidic sampling. , 2014, The Analyst.

[23]  Dermot Diamond,et al.  All-solid-state sodium-selective electrode based on a calixarene ionophore in a poly(vinyl chloride) membrane with a polypyrrole solid contact , 1992 .

[24]  P. D'Orazio,et al.  Hypertonic versus Isotonic Salt Bridges in Ion-Selective Electrode Based Clinical Analysers , 1991, Annals of clinical biochemistry.

[25]  Ernö Pretsch,et al.  Carrier-Based Ion-Selective Electrodes and Bulk Optodes. 1. General Characteristics. , 1997, Chemical reviews.

[26]  A. Ivaska,et al.  Potentiometric ion sensors. , 2008, Chemical reviews.

[27]  A. Ivaska,et al.  Influence of oxygen and carbon dioxide on the electrochemical stability of poly(3,4-ethylenedioxythiophene) used as ion-to-electron transducer in all-solid-state ion-selective electrodes , 2002 .

[28]  G. Whitesides,et al.  Understanding wax printing: a simple micropatterning process for paper-based microfluidics. , 2009, Analytical chemistry.

[29]  Yixian Wang,et al.  High-performance flexible potentiometric sensing devices using free-standing graphene paper. , 2013, Journal of materials chemistry. B.

[30]  E. Bakker,et al.  Polyion Sensors as Liquid Junction‐Free Reference Electrodes , 1999 .

[31]  P. C. Meier.  Two-parameter debye-hückel approximation for the evaluation of mean activity coefficients of 109 electrolytes , 1982 .

[32]  F. Rius,et al.  A paper-based potentiometric cell for decentralized monitoring of Li levels in whole blood. , 2014, Lab on a chip.

[33]  A. Lewenstam,et al.  An analytical quality solid-state composite reference electrode. , 2013, The Analyst.

[34]  Róbert E. Gyurcsányi,et al.  Quality control criteria for solid-contact, solvent polymeric membrane ion-selective electrodes , 2009 .

[35]  Yixian Wang,et al.  Development of an all-solid-state potassium ion-selective electrode using graphene as the solid-contact transducer , 2011 .

[36]  M. Jaroniec,et al.  Colloidal imprinting: a novel approach to the synthesis of mesoporous carbons. , 2001, Journal of the American Chemical Society.

[37]  R. Johnson,et al.  Ionophore-based ion-selective potentiometric and optical sensors , 2003, Analytical and bioanalytical chemistry.

[38]  G. Whitesides,et al.  Diagnostics for the developing world: microfluidic paper-based analytical devices. , 2010, Analytical chemistry.

[39]  Jaclyn A. Adkins,et al.  Recent developments in paper-based microfluidic devices. , 2015, Analytical chemistry.

[40]  G. Whitesides,et al.  Paper-based potentiometric ion sensing. , 2014, Analytical chemistry.

[41]  Andreas Stein,et al.  Ion-selective electrodes with colloid-imprinted mesoporous carbon as solid contact. , 2014, Analytical chemistry.

[42]  W. E. Morf.  The Principles of Ion-Selective Electrodes and of Membrane Transport , 2012 .