Fully Inkjet-Printed Paper-Based Potentiometric Ion-Sensing Devices

Article
Fully inkjet-printed paper-based potentiometric ion-sensing devices

Nipapan Ruecha, Orawon Chailapakul, Koji Suzuki, and Daniel Citterio
Anal. Chem., Just Accepted Manuscript DOI: 10.1021/acs.analchem.7b03177 Publication Date (Web): 29 Aug 2017
Downloaded from http://pubs.acs.org on September 11, 2017
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Page 1 of 31 Analytical Chemistry
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6 Fully inkjet-printed paper-based potentiometric ion-sensing
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9 devices
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Nipapan Ruecha, Orawon Chailapakul, Koji Suzuki, Daniel Citterio*
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15 Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-
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18 14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan
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20 Electrochemistry and Optical Spectroscopy Research Unit (EOSRU), Department of
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22 Chemistry, Faculty of Science, Chulalongkorn University, Patumwan, Bangkok 10330,
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24 Thailand
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*Corresponding author. E-mail: citterio@applc.keio.ac.jp, Phone: +81 45 566 1568, Fax: +81
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29 45 566 1568
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ACS Paragon Plus Environment
Analytical Chemistry Page 2 of 31
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3 Abstract
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6 A fully inkjet printed disposable and low cost paper-based device for potentiometric Na+- or
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8 K+-ion sensing has been developed. A printed ionophore-based all-solid-state ion selective
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10 electrode on a graphene/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
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(G/PEDOT:PSS) nanocomposite solid contact, and a printed all-solid state reference
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15 electrode consisting of a pseudo-silver/silver chloride electrode coated by a lipophilic salt-
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17 incorporating poly(vinyl chloride) membrane overprinted with potassium chloride, have been
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19 combined on a microfluidically patterned paper substrate. Devices are built on standard filter
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paper using off-the-shelf materials. Ion sensing has been achieved within 180 s by simple
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24 addition of 20 L sample solution without electrode preconditioning. The limits of detection
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26 were 32 M and 101 M for Na+ and K+, respectively. The individual single-use sensing
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28 devices showed near Nernstian response of 62.5 2.1 mV/decade (Na+) and 62.9 1.1
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mV/decade (K+) with excellent standard potential (E0) reproducibilities of 455.7 5.1 mV
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33 (Na+) and 433.9 2.8 mV (K+). The current work demonstrates the promising possibility to
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35 obtain low-cost and disposable paper-based potentiometric sensing devices potentially
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manufacturable at large scales with industrial inkjet printing technology.
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43 Keywords: paper-based device, inkjet printing, ion sensing, potentiometric sensor, sodium,
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45 potassium, all-solid-state electrode
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3 Introduction
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6 Potentiometric ion sensing is one of the most important electrochemical detection
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8 methods and is widely used for selective quantitative analysis of target ions in both clinical
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10 and environmental settings.1-2 Originally developed measurement systems required bulky,
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maintenance-intensive macro electrodes and conventional reference electrodes to be paired
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15 with ISEs.3-5 Therefore, overall system miniaturization and the introduction of all-solid-state
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17 potentiometric sensors have become attractive approaches to low-cost and portable
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19 alternatives.6-8
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22 Although the overall performance of a potentiometric ion sensing device also depends
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24 on the potential stability of the reference electrode, all-solid-state reference electrodes2, 9-10
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have been given much less attention than the ISEs themselves. Colloid imprinted mesoporous
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29 (CIM) carbon9, 11 coupled with a hydrophobic redox buffer has recently been introduced as a
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31 solid contact for all-solid-state reference electrodes with outstanding potential stability and
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33 applied to a paper platform. Unfortunately however, the fabrication of this type of reference
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electrode requires significant efforts for the synthesis of the redox couple system.11-12 In
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38 another approach to paper-based all-solid-state reference electrodes, the use of traditional
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40 plasticized PVC membranes doped with a lipophilic salt13-14 resulted in good potential
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42 stability, while being easy to prepare.10
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45 Paper substrates have been introduced as simple and cost-effective analytical
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47 platforms for quantitative colorimetric15-16 and electrochemical17-18 analyte detection in many
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fields including clinical19-21 and environmental monitoring.15, 22 It has been demonstrated that
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52 paper-based devices coupled with electrochemical detection show similarly high performance
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54 to conventional electrochemical sensors.23 Therefore, the development of paper-based
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56 electrochemical analytical devices has become a very attractive research area.24-25 Not
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3 surprisingly, paper-based approaches are recently also drawing attention for the development
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5 of potentiometric ion sensing devices.4, 10, 26-33 The first paper-based ISE was introduced by
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Novell et al..30 A carbon nanotube (CNT) modified conductive paper was used as both ion-to-
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10 electron transducer and electric conductor in an all-solid-state ISE. There are many reports
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12 focusing on the development of potentiometric sensors on paper platforms using various
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14 materials to create all-solid-state ISEs, including CNTs, graphene33 and gold
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16 nanoparticles (AuNPs).10
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19 Recently, the interest in the development of fully integrated paper-based
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potentiometric sensing devices including ion selective and reference electrodes to achieve
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24 self-standing miniaturized potentiometric ion sensing devices has grown. Conductive
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26 papers based on carbon nanotubes used as solid contacts for separated strip-type ISE and
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28 reference electrode31, as well as inkjet-printed gold electrodes on recyclable paper as solid
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30 contacts for PVC membrane-based ISE and reference electrode10 have been reported.
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However, both systems require customized paper substrates. Ordinary filter paper-based
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35 potentiometric ion sensing devices based on simple stencil-printed Ag/AgCl electrodes have
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37 been reported.26, 29
The unmodified Ag/AgCl electrodes have been applied for chloride
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39 sensing, while modification with ionophore doped PVC membranes allowed the detection of
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other ions (e.g. sodium,26 calcium,26 potassium26, 29). In all cases however, the user is required
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44 to apply a reference electrolyte (aqueous KCl solution) besides the actual sample solution to
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46 be measured.
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49 Finally, one limiting step in terms of fabrication effort and reproducibility of all-solid-
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51 state ISEs is the modification of the solid contact with the ion selective membrane layer.2-4, 14,
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53 26, 30, 34
Inkjet printing technology is an ideal candidate to overcome this limitation and
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effectively used for potentiometric sensor fabrication,10, 35 because it allows creation of well-
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3 defined patterns with precise control and enables the deposition of several materials onto an
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5 identical area in a layer-by-layer structure.10, 36-37
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8 Herein, the reproducible fabrication of fully inkjet printed single-use paper-based
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10 potentiometric ion sensing devices combining an all-solid-state ISE and a reference electrode
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on conventional filter paper is presented. The present devices require no reagent handling and
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15 no preconditioning before sample measurements. As a proof of principle, the developed
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17 paper-based potentiometric ion sensing devices were applied for sodium and potassium ion
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19 determination. The observed good analytical performance and the fabrication reproducibility
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confirms the potential of inkjet printing technology for the large-scale production of low-cost,
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24 user-friendly potentiometric ion sensing devices.
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Experimental Section
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32 Chemicals: Didecalino-16-crown-5 (DD16C5) and o-nitrophenyl octyl ether (o-NPOE,
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>99%) were purchased from Dojindo laboratories (Kumamoto, Japan). Potassium tetrakis
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37 (4chlorophenyl) borate (KTpClPB, >97%) and high molecular weight poly vinyl chloride
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39 (PVC) were obtained from TCI chemicals (Tokyo, Japan). Poly(3,4-ethylenedioxythiophene)
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41 polystyrene sulfonate (PEDOT:PSS, 0.8 wt% in water) and 30 wt% silver nanoparticle
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dispersion in ethylene glycol (Ag ink) were obtained from Sigma-Aldrich (St. Louis, MO,
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46 USA). Valinomycin (potassium ionophore I), bis(2-ethylhexyl) sebacate (DOS, >97%),
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48 sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl2), calcium
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50 chloride (CaCl2), zinc chloride (ZnCl2), ferric chloride (FeCl3), tetrabutylammonium
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tetrabutylborate (TBA-TBB) (97%), cyclohexanone and ethylene glycol were purchased from
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55 Wako Pure Chemical Industrials, Ltd. (Osaka, Japan). Graphene (G) nanopowder with an
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3 average size of 6-8 nm was purchased from SkySpring Nanomaterials, Inc. (Houston, TX,
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5 USA).
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8 G/PEDOT:PSS ink preparation: G/PEDOT:PSS ink was prepared by adding the graphene
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10 nanopowder into 0.8 wt% PEDOT:PSS aqueous solution. A concentration of 2 mg/mL of
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graphene was selected, since it was well dispersible in the PEDOT:PSS solution. Graphene
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15 was successfully dispersed using an Iuchi ultrasonic bath (Osaka, Japan) for 4 h with 38 kHz
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17 frequency. The prepared G/PEDOT:PSS ink was filtered through a 0.45 m polypropylene
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19 syringe filter before use.
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22 Preparation of reference and sodium and potassium ion selective membranes: The ion-
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24 selective membranes for the solid contact electrode modification contained 1.0% of
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ionophore valinomycin for K+ or DD16C5 for Na+, 0.5% (for K+ ion sensors) or 1.0% (for
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29 Na+ ion sensors) of KTpClPB, 65.0% of NPOE for K+ ion sensors or DOS for Na+ ion
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31 sensors and 32.0-33.0% of PVC (all wt%). The reference membrane for the solid contact
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33 reference electrode contained 12.0% of TBA-TBB, 58.0 % NPOE and 30.0 % of PVC (all
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wt%). The membrane solutions were prepared with a solute content of 5 wt% using
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38 cyclohexanone as the solvent.
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Patterning of paper substrates: The fabrication procedure of paper-based potentiometric
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43 devices is schematically shown in Scheme 1. Firstly, the wax-printing technique was used to
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45 fabricate the flow channel pattern on Whatman grade 1 filter paper (GE Healthcare,
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47 Buckinghamshire, UK). The flow channel template was printed on one side of the filter paper
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by a wax printer (Xerox Phaser 8570, Xerox, Norwalk, CT, USA), followed by placing on a
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52 hot plate at 150 C for 240 s to create a hydrophobic wall. Then, the paper was subjected to
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54 Ag ink printing described in the next section, before a rectangular (18 cm 25 cm) shape was
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56 printed on the backside of the paper in a second wax printing step. The double-side wax
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3 patterned paper was then inserted between two sheets of lamination film (refer also to next
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5 section), and passed through a hot laminator (QHE325, Meikoshokai Co., Ltd., Tokyo,
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Japan).
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10 Inkjet printing of potentiometric devices: The two-electrode system for potentiometric
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detection was fabricated using a piezoelectric DimatixTM material printer (DMP 2800,
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15 FUJIFILM Dimatix, Inc., Santa Clara, CA, USA). A cartridge (DMC-11610) with a nominal
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17 droplet volume of 10 pL and 16 nozzles was used for all inkjet printing experiments. For all
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19 printing steps, 7 nozzles were selected. The printing parameters for all inks deposited are
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shown in Table S-1 of the supporting information. Silver (Ag) nanoparticle ink for the
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24 reference electrode and for the ion selective electrode connector was printed on the single
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26 side wax-patterned paper and sintered at 120 C for 10 min. This step was followed by
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28 backside wax printing and hot lamination between two sheets of lamination film, with a
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rectangular area (18 cm 25 cm) cut out of the top sheet to allow further inkjet modification.
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33 After that, freshly prepared 10 mM FeCl3 solution and the reference membrane (REM) ink
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35 were subsequently printed on top of the Ag reference electrode structure, to obtain the REM-
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37 coated pseudo silver/silver chloride electrode (REM-coated p-Ag/AgCl). Finally, a 3 M KCl
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39 solution was printed on top of the REM-coated p-Ag/AgCl electrode. For the ion selective
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42 electrode fabrication, the G/PEDOT:PSS ink (or only PEDOT:PSS solution for comparative
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44 purposes) was printed as the solid-state contact and finally overprinted with the ion selective
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46 membrane ink for sodium or potassium, respectively. The resistance of printed solid contacts
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48 for the ion-selective (G/PEDOT:PSS) and reference (Ag/AgCl) electrodes was measured over
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a distance of 9 mm for 10 individually printed electrodes using a digital multimeter
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53 (KEW1012, Kyoritsu, Japan).
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56 Electroanalytical measurements: All potentiometric and cyclic voltammetric measurements
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58 were performed using a potentiostat (CHI 660A, CH Instruments, Austin, TX). For cyclic
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3 voltammetry, a three-electrode system was used. The printed PEDOT:PSS and
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5 G/PEDOT:PSS electrodes were used as working electrodes. A stencil-screen printed carbon
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electrode on a PVC substrate and a conventional double junction-type Ag/AgCl electrode
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10 were used as the counter and reference electrodes, respectively. For potentiometric
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12 measurement, the printed silver electrodes acting as electrical contacts for ion selective and
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14 reference electrodes were connected to the potentiostat by copper wire. 20.0 L of sample
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16 solution was dropped on the sample reservoir (center square area of the device shown in
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19 Scheme 1) and potentiometric measurements initiated 20 s after sample introduction.
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21 Potentials were constantly monitored and recorded over 180 s. All experiments with sodium
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23 and potassium were performed using NaCl and KCl standard solutions, respectively. To
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25 obtain a calibration curve, three individual paper-based potentiometric sensing devices were
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used for each concentration of standard solution. Therefore, 21 individual single-use devices
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30 were used for each calibration curve for sodium and potassium ions in the concentration
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32 range of 106 to 1 M. Single ion activity coefficients were estimated according to a Debye-
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34 Hckel approximation.38 Potentiometric selectivity coefficients for Na+, K+, NH4+, Ca2+ and
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Mg2+ were estimated according to the separate solution method (SSM) using 0.1 M chloride
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39 salt solutions of the respective cations.
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42 Urine sample preparation: Diluted human urine samples were prepared by mixing
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44 collected urine with deionized water in a 1:1 ratio. Samples were analyzed on individual
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46 single-use paper-based potentiometric ion sensing devices, and results were compared to
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48 those obtained with compact ISE-based sodium and potassium meters (LAQUAtwin compact
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B-722 and B-731 ion meters; Horiba, Kyoto, Japan).
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56 Results and Discussion
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3 Electrode characterization
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6 Inkjet printing allows to directly and precisely deposit ink materials with high speed, low cost
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8 and high reproducibility, without the need for specifically designed masks or screens. The
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10 fabrication process for conductive electrodes on filter paper is simpler than on other flat
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substrates such as transparency films and glass,27, 30 since the paper substrate readily absorbs
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15 the hydrophilic printing ink resulting in high shape fidelity, while droplet aggregation and
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17 surface de-wetting frequently occur on non-ink absorbing materials. Filter paper is inherently
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19 non-conductive, but the printing of a conductive ink onto the porous structure produces large
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active electrode surface areas. The poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
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24 (PEDOT:PSS) conducting polymer was selected as the base material for the ion selective
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26 electrode, due to its known compatibility with the inkjet printing process.39 It has been
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28 widely used as conducting polymer material to obtain an electron-conducting substrate10, 40
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30 by techniques such as electrochemical polymerization, drop-casting and printing,41 since it
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exhibits extraordinary electrical conductivity. However, the hydrophilicity of PEDOT:PSS
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35 potentially promotes the formation of a water layer at the electrode substrate/sensing
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37 membrane interface, which is known to decrease the sensitivity of the resulting ISEs.24, 42-43
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39 Therefore, the use of nanocomposites of PEDOT:PSS with hydrophobic graphene is a good
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strategy for avoiding the accumulation of water at the interface of solid-contact ISEs. The
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44 presence of graphene not only increases the hydrophobicity of the electrode surface, but also
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46 provides a high surface area, excellent conductivity and electrocatalytic activity. Moreover, it
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48 has been reported that graphene/PEDOT:PSS nanocomposites (G/PEDOT:PSS) show higher
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50 sensitivity and conductivity than PEDOT:PSS alone, due to electron hopping at the interface
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53 of graphene and PEDOT:PSS.39, 44
Therefore, the electrochemical behavior of printed
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55 electrodes obtained from PEDOT:PSS ink or from a G/PEDOT:PSS nanocomposite ink were
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57 investigated. The effect of graphene addition could be observed by cyclic voltammetry and
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3 electrochemical impedance spectroscopy. Figure S-1a shows cyclic voltammograms recorded
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5 with the resulting filter paper-based electrodes in the absence (PEDOT:PSS) and presence
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(G/PEDOT:PSS) of graphene in 2 mM ferri/ferrocyanide solution. The use of the
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10 graphene/polymer composite material resulted in increased anodic and cathodic peak currents
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12 compared to the conducting polymer alone. The presence of graphene is assumed to
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14 accelerate the electron transfer kinetics on the electrode. The peak-to-peak separation (Ep)
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observed with the G/PEDOT:PSS paper electrode significantly decreased compared to the
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19 PEDOT:PSS system. The Nyquist plots of impedance data for G/PEDOT:PSS and
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21 PEDOT:PSS solid contacts in the 100 kHz to 10 mHz frequency range are shown in Figure
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23 S-1b. In contrast to the data obtained for the solid contact consisting of PEDOT:PSS alone,
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25 the impedance spectrum of inkjet deposited G/PEDOT:PSS has the shape of a near vertical
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28 line due to the bulk redox capacitance of G/PEDOT:PSS. This implies a very low transfer
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30 resistance, which is in accordance with the results obtained through cyclic voltammetry.
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32 Therefore, the G/PEDOT:PSS electrode was chosen as electric contact and ion-to-electron
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34 transducer on which to build the ion selective electrode. The electrical resistance measured
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over a 9 mm electrode trace in dry state was found to be 13.7 0.8 k (n=10). For specific
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39 ion measurements, the G/PEDOT:PSS electrode was subsequently inkjet modified by a
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41 polyvinyl chloride (PVC)-based ion selective membrane (ISM). The surface of the
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43 G/PEDOT:PSS modified paper and of the additionally ISM coated electrodes was observed
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45 by SEM shown in Figure 1. In all cases the cellulosic fiber structure of the underlying paper
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48 remains visible, indicating the penetration of the electrode ink into the paper substrate.
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50 Among all reference electrode systems, the silver/silver chloride (Ag/AgCl) electrode
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52 is one of the most commonly used in miniaturization approaches.27 Recently, all-solid-state
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54 reference electrodes without liquid junction have been fabricated by inkjet printing of silver
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nanoparticle ink, followed by the formation of a silver chloride layer using chemical
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3 oxidation with ferric chloride45 or bleach solution.27 In this work, a pseudo-silver/silver
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5 chloride (p-Ag/AgCl) reference electrode was fabricated by inkjet printing of ferric chloride
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solution on a printed silver trace on filter paper. The formation of silver chloride was visually
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10 confirmed by the color change from silver to a dark surface. Moreover, the presence of
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12 chloride on the reference electrode was characterized by SEM and energy dispersive X-ray
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14 spectroscopy (EDX). The SEM images of silver and pseudo-Ag/AgCl (p-Ag/AgCl) paper
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16 electrodes are presented in Figure 2. Upon initial inkjet printing of silver nanoparticle ink
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19 onto filter paper and 10 min drying at 120 C, a homogeneous silver layer was formed on the
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21 cellulose fibers (Figure 2a). After chemical oxidation by inkjet deposited ferric chloride, the
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23 surface morphology change and the appearance of a solid crystalline-like precipitation on the
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25 cellulose fibers indicated the formation of an AgCl coating (Figure 2b). The electrical
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28 resistance measured over a 9 mm electrode trace in dry state was found to be 5.5 0.3 k
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30 (n=10). In addition, the presence of AgCl on the paper electrode was also confirmed by EDX.
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32 The Ag electrode shows only the signals relative to Ag particles, but the additional peak of
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34 chloride was observed on p-Ag/AgCl. For a potentiometric sensing device, a stable and
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reliable reference electrode with a sample independent potential response is required.9, 32 For
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39 this reason, the p-Ag/AgCl electrode was inkjet coated with a reference membrane (REM)
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41 composed of PVC incorporating a lipophilic salt, tetrabutylammonium tetrabutylborate
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43 (TBA-TBB)10, 14 (Figure 2c). The potential stability of the unmodified p-Ag/AgCl and the
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45 REM-coated reference electrodes was individually tested against a conventional double
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48 junction-type Ag/AgCl reference electrode by applying KCl solutions of various
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50 concentrations (Figure S-2). Although to a lesser degree than the uncoated pseudo reference
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52 electrode, the REM-modified p-Ag/AgCl still responded to changes in chloride anion
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54 concentrations. This might be caused by the high surface area to volume ratio of filter paper,
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making the complete coverage of the p-Ag/AgCl electrode with the REM difficult. To obtain
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3 a well-defined constant potential of the reference system, 3 M KCl solution was inkjet
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5 deposited on the top of the REM-modified p-Ag/AgCl. The crystalline deposit of KCl on the
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REM-p-Ag/AgCl electrode was clearly observed by SEM (Figure 2d). The finalized all-
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10 inkjet-printed reference electrode system with KCl coverage exhibited stable potential values
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12 (40.4 5.1mV) upon exposure to KCl solutions in a concentration range of 106 M to 1 M
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14 (Figure 3). Therefore, the fabrication of reliable all-solid-state reference electrodes for
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disposable paper-based potentiometric devices on filter paper using inkjet printing technology
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19 was successfully achieved. The small error bars representing the standard deviation of
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21 measurements obtained with three individual single-use electrodes clearly demonstrate the
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23 reproducibility of the inkjet-based fabrication approach and its potential suitability for high
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25 throughput electrode manufacturing.
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31 Paper-based potentiometric sensing device design
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34 The paper-based potentiometric sensing devices were fabricated by inkjet printing of
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36 electrodes onto wax patterned filter paper. The design included a central sample inlet zone,
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from where the applied sample liquid (20 L) wicks towards the separated ion selective
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41 electrode and reference electrode zones (Figure 4). This arrangement, which gives rise to a
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43 split capillary flow-driven passive sample transport from the sample inlet in opposite
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45 directions, prevents the contamination of the ISE zone with potassium chloride from the
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47 reference electrode zone during the duration of potentiometric measurements (generally 3
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50 min). Figure S-3 shows a cross section (along the dotted line indicated in Figure 4) through a
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52 paper-based ion sensing device after application of an aqueous red dye solution to visualize
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54 the hydrophilic areas. The wax layer deposited on the backside of the paper surface serves to
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56 prevent the access of the aqueous sample liquid to uncoated areas of the p-Ag/AgCl and the
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3 G/PEDOT:PSS electrodes in the reference and ion selective electrode zones. The lamination
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5 film on the backside of the devices provides additional mechanical stability to the system. In
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addition, the hot lamination process results in vertical compression of the filter paper
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10 accompanied by increased wax penetration46 and therefore, the closure of any gaps between
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12 the backside deposited wax and the printed electrodes. The hydrophilic flow channel inside
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14 the backside wax printed and laminated paper devices had a depth of 81.2 5.1 m (n=10)
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16 (Figure S-3b and 3c). With this device design, an electrical contact between reference and ion
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19 selective electrodes was found to be established within 30 s of sample application to the
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21 central inlet zone.
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27 Potentiometric measurement of sodium and potassium ions
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29 The ion selective membrane (ISM) was deposited on top of the G/PEDOT:PSS paper
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32 electrodes by inkjet printing. The amount of ISM ink applied was optimized by varying the
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34 number of printing cycles between 1 and 20, while observing the potentiometric response of
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36 the resulting paper-based ISEs measured against a conventional double junction-type
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38 Ag/AgCl reference electrode (data not shown). Since inkjet printing relies on the deposition
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of pL-volume ink droplets, a single print cycle, even performed at low drop spacing of 25 m
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43 (Table S-1) is insufficient to obtain full coverage of the high surface area of the cellulose
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45 fiber network in filter paper. The slopes (sensitivity) of the ion activity-dependent calibration
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47 curves recorded with the printed paper-based ISEs increased by increasing the number of
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ISM printing cycles up to 10 cycles for Na+ and 15 cycles for K+ (data not shown).
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52 Potentiometric ion sensing for characterization of printed electrodes was performed in the
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54 concentration range of 106 M to 1 M. The electrode response curves of the optimized printed
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56 ion-selective electrodes tested against a conventional double junction-type Ag/AgCl
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1
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3 reference electrode are shown in Figure S-4. A separate single-use paper electrode was used
4
5 for every measurement. The printed ISEs showed a slightly super-Nernstian response with
6
7
electrode function slopes of 61.6 mV/decade for both the sodium- and potassium-selective
8
9
10 sensors. The optimized printing conditions were then applied to the fabrication of the paper-
11
12 based sensing devices with integrated pseudo-reference electrodes. For the fully integrated
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14 ion sensing devices, a stable potential signal was observed a short time after the sample
15
16 solution reached the ion selective electrode and reference electrode zones, closing the
17
18
19 electrical circuit. Figure S-5 shows a set of representative time-dependent potential response
20
21 curves. This data demonstrates, that the single-use disposable paper-based potentiometric
22
23 sensing devices do not require any sensor conditioning before sample analysis to achieve a
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25 stable potential value within a short sample contact time. The stable signal observed in Figure
26
27
S-5b also clearly indicates that during the 3 min measurement time, diffusion of K+ ions from
28
29
30 the reference electrode zone to the ISE zone is not an issue, since otherwise a significant
31
32 increase of the potential value over time would be observed for the potassium sensing device.
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34 The unidirectional capillary force-driven sample liquid wicking from the central inlet zone to
35
36 the respective electrode zones efficiently prevents diffusion-based mixing. The potential
37
38
39 values measured at 3 min into the electrode response were used to draw the ion activity-
40
41 dependent response curves shown in Figure 5. A linear response range for sodium and
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43 potassium ions was observed in between 104 M and 1 M ion concentrations, with a slope of
44
45 62.5 mV/decade for sodium (Figure 5a) and 62.9 mV/decade for potassium (Figure 5b).
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47
These values are close to the theoretical slope of 59.2 mV/decade according to the Nernst
48
49
50 equation at 25C, but super-Nernstian in all cases. No active temperature control was
51
52 performed during measurements at room temperature. As mentioned above, the paper-based
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54 ion sensing devices are not pre-conditioned before potentiometric measurements. It has been
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56 previously reported that super-Nernstian response is a common phenomenon for
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58
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60
1
2
3 unconditioned membranes.47 Due to the use of KTpClPB as the anionic additive, K+-
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5 electrode membranes incorporate an initial amount of primary (K+) ions, whereas Na+-
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7
electrode membranes are essentially free of primary ion before contact with sample solution.
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9
10 In the case of the Na+-electrode system (Fig. 5a) the point of highest ion activity is slightly
11
12 deviating from linearity. A similar experimental result is not observed for the K+ sensing
13
14 devices (Fig. 5b). It is therefore assumed that the unconditioned Na+-electrodes are
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16 particularly prone to super-Nernstian response. The detection limits estimated from the cross-
17
18
19 section of an extrapolated horizontal line in the non-responsive activity range and the linear
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21 section of the calibration curve (Figure 5) were found to be 32 M and 101 M for sodium
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23 and potassium, respectively (Table 1). The linear dynamic response range observed for the
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25 paper-based sensing devices is narrower and the detection limits are higher than for
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27
28 conventional ISEs based on the same ionophores. The reason for this phenomenon, which has
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30 also been reported for other paper-based ISE approaches,29 is currently unknown, but it is
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32 attributed to the presence of anionic carboxylate groups on paper cellulose fibers, originating
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34 from the paper making process.48 Nevertheless, the linear response range covers the
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36
37
physiologically relevant concentrations of sodium and potassium in biological samples (e.g.
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39 blood serum or urine). The individually inkjet printed devices show very good
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41 reproducibilities with electrode function slope and E0 values of 62.5 2.1 mV/decade and
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43 455.7 5.1 mV for sodium sensing devices, and 62.9 1.1 mV/decade and 433.9 2.8 mV
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45
46 for potassium sensing devices.
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48
49
The PEDOT:PSS and G/PEDOT:PSS solid contacts were also compared in terms of
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51 analytical performance of the resulting ion selective electrodes. The relevant parameters are
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53 summarized in Table 1 and the ion activity-dependent response curves are shown in Figure S-
54
55 6. The use of the graphene/polymer composite material showed significant improvements in
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57
ISE sensitivity and slightly lower detection limits. The combination of graphene and
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60
1
2
3 PEDOT:PSS results in a very effective ion-to-electron transducer and electrical conductor for
4
5 potentiometric sensing devices, presumably due to the high conductivity and the large surface
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7
area of the graphene nanomaterial. In addition, graphene is a highly hydrophobic material
8
9
10 that can prevent the formation of a water layer at the interface of the ion selective membrane
11
12 and the underlying contact electrode, which is important for the performance of all-solid-state
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14 ISEs.
15
16
17 The selectivity of the paper-based potentiometric ion sensing devices was evaluated
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19 by measuring the potentiometric response in separate solutions of 6 potentially interfering
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21
cations consisting of Na+, K+, Ca2+, Cu2+, Zn2+, Mg2+, and NH4+. As summarized in Figure S-
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23
24 7a-b, the paper-based sensing devices showed negligible response for all interfering ions
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26 investigated up to concentrations of 10 mM, while a potential increase was observed at
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28 concentrations of 100 mM and higher. Potentiometric selectivity coefficients for Na+, K+,
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30 NH4+, Ca2+ and Mg2+ were experimentally determined according to the separate solution
31
32
33
method. The results are summarized in Table S-2. Based on these values, it must be
34
35 concluded that the selectivity of the paper-based sensing device is not as high as in the case
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37 of conventional ISEs using the same ionophores. Although the reason for this decrease in
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39 selectivity can currently not be explained, it is most likely caused by the fact that cellulosic
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41
filter paper is not a completely chemically inert substrate material, but can show some
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43
44 general cation exchange properties caused by the presence of carboxylate groups as already
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46 mentioned earlier.
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49 The shelf storage time-dependent stability of the paper-based potentiometric sensing
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51 devices was studied over a period of two weeks (Figure S-8). Printed devices were kept at
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53 ambient condition for one or two weeks, and then used to acquire calibration curves for
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55
sodium and potassium ions. The observed changes in the slopes of the response curves were
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58 below 5 mV/decade, indicating a reasonably good storage stability of the devices.
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60
1
2
3 The fully inkjet-printed paper-based potentiometric ion-sensing devices developed in
4
5 the current work show characteristics and performance comparable to previously reported
6
7
ion-selective electrode sensing devices with integrated reference electrodes implemented on
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9
10 filter paper platforms.26, 29 In terms of practical application however, the current device is
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12 characterized by a high degree of user-friendliness. No electrolyte solution addition is
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14 required before sample analysis.
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19 Sodium and potassium ion sensing in human urine sample
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22 The applicability of the developed paper-based ISE sensing devices was investigated
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24 by measuring the concentration of sodium and potassium ions in human urine. Samples were
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26
27
diluted with deionized water (1:1) before analysis with the developed devices to reduce
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29 interference by potassium (for sodium ISE) and by sodium (for potassium ISE). The results
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31 were validated against commercialized sodium and potassium ion sensing devices. The
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33 measured concentrations were not statistically different from those obtained by the validation
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35
method (Table 2), confirming the possibility of accurate measurements of ion concentrations
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38 with the paper-based potentiometric sensing device.
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43 Conclusion
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46 The aim of this work was the development of fully inkjet-printed disposable single-
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48
use paper-based potentiometric ion sensing devices that are suitable for future mass
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51 production. For this purpose, an all-solid-state ISE and a reference electrode were
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53 successfully constructed. Sensing devices were realized on common filter paper using
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55 commercially available and relatively low cost off-the-shelf components not requiring any in-
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57 house synthesized materials. Despite of the simple electrode compositions relying on
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60
1
2
3 standard materials, astonishingly high reproducibility in both electrode calibration function
4
5 slopes and E0 values has been achieved, which is attributed to the liquid dispensing precision
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7
and reproducibility of the inkjet printing method. For practical measurements, user
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10 interaction is limited to the addition of the sample solution alone, with no requirement of
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12 sensor preconditioning or any further liquid handling. The printed devices are applicable to
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14 the quantification of sodium and potassium in aqueous solutions over concentration ranges
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16
that are biologically and environmentally relevant (1041 M). By making use of the large
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19 choice of ionophores presented in the literature until now, it is believed that the concept
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21 demonstrated here can be adapted to further low-cost and disposable paper-based
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23 potentiometric sensing devices produced at large scales with high-speed and reproducible
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25 inkjet printing technology.
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27
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29
30
31 Acknowledgements
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33
34 This work was supported by Medical Research and Development Programs Focused
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36 on Technology Transfer: Development of Advanced Measurement and Analysis Systems
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38
(SENTAN) (Japan Agency for Medical Research and Development; AMED).
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44 Supporting Information
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47 The Supporting Information is available free of charge on the ACS Publications
48
49 website: Printing parameters for all inks; selectivity coefficients of potentiometric ion sensing
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51
devices; cyclic voltammograms and Nyquist plots of printed solid contacts; reference
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53
54 electrode test setup; cross section through a paper-based potentiometric ion sensing device;
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56 calibration curves of printed ISEs measured against commercial Ag/AgCl reference
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60
1
2
3 electrode; time-dependent potential response curves; calibration curves of ISEs with
4
5 PEDOT:PSS solid contact; potentiometric response to primary and interfering ions; short-
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7
term storage stability of devices.
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9
10
11
12
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3 Table 1 Analytical performance of paper-based potentiometric sensing devices for sodium
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5 and potassium ions relying on PEDOT:PSS and G/PEDOT:PSS solid-state electrodes.
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7
8 PEDOT:PSS G/PEDOT:PSS
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10
Na+ K+ Na+ K+
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13 Sensitivity (mV/dec) 43.6 46.1 62.5 62.9
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15 Linear range 104 1 M 104 1 M 104 1 M 104 1 M
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17 LOD 42.2106 M 108.8106 M 32.3106 M 100.8106 M
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3 Table 2 Determination of sodium and potassium ion concentrations in diluted human urine
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5 samples.
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8 Sample no. Concentration of Na+ %Error Concentration of K+ %Error
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10 (mM) (mM)
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13 Paper- Paper-
14 Horiba Horiba
15 based ISE based ISE
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17 1 104.227.8 100.07 4.1 54.094.2 53.79 0.5
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2 126.075.5 121.44 3.8 47.804.1 50.47 5.3
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22 3 97.826.9 100.70 2.9 41.645.2 39.8 4.6
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31 Scheme 1 Schematic of the fabrication process of paper-based potentiometric devices by
32 inkjet printing.
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31 Figure 1 SEM images of (a) G/PEDOT:PSS; (b) ISM coated G/PEDOT:PSS for sodium; and
32 (c) potassium ion sensing (10 and 15 printed layers of ISM ink for Na+ and K+ selective
33 electrode, respectively).
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31 Figure 2 SEM images of (a) filter paper with inkjet deposited Ag nanoparticle ink; (b) p-
32 Ag/AgCl electrode after AgCl layer formation by printing of ferric chloride solution on Ag
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paper electrode; (c) reference membrane-modified p-Ag/AgCl electrode; and (d) finalized
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35 KCl-coated REM-p-Ag/AgCl reference electrode; insets show the results of EDX analysis.
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31 Figure 3 Potentiometric response of p-Ag/AgCl (), REM- p-Ag/AgCl (), KCl coated p-
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Ag/AgCl () and commercial double junction-type Ag/AgCl () reference electrodes in
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34 aqueous KCl solutions (106 M to 1 M) measured against a conventional double junction-type
35 Ag/AgCl reference electrode; each data point has been obtained by measurements with 3
36 individual single-use electrodes (inkjet printed electrodes) or 3 consecutively performed
37 measurements (conventional reference electrode); error bars indicate the standard deviations.
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31 Figure 4 Photograph of a single paper-based potentiometric ion sensing device and schematic
32 of the measurement procedure; the dotted line indicates the cross-section through the device
33 shown in Figure S-3.
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31 Figure 5 Calibration curves obtained with paper-based (a) sodium and (b) potassium ion
32 sensing devices; each data point has been obtained by measurements with 3 individual single-
33 use devices; error bars indicate the standard deviations.
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Fully Inkjet-Printed Paper-Based Potentiometric Ion-Sensing Devices

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Fully inkjet-printed paper-based potentiometric ion-sensing devices

Analytical Chemistry is published by the American Chemical Society. 1155 Sixteenth

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