WO2020245312A1 - Dispositif de mesure de ph comportant un composé composite à base de cnc-pan i et procédés correspondants - Google Patents

Dispositif de mesure de ph comportant un composé composite à base de cnc-pan i et procédés correspondants Download PDF

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Publication number
WO2020245312A1
WO2020245312A1 PCT/EP2020/065548 EP2020065548W WO2020245312A1 WO 2020245312 A1 WO2020245312 A1 WO 2020245312A1 EP 2020065548 W EP2020065548 W EP 2020065548W WO 2020245312 A1 WO2020245312 A1 WO 2020245312A1
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WO
WIPO (PCT)
Prior art keywords
cnc
electrode
pani
working electrode
composite compound
Prior art date
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PCT/EP2020/065548
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English (en)
Inventor
Davide MIGLIORELLI
Ye TANG
Reufa JUNUZOVIC
Lea MÜHLEBACH
Konstantinos PETROPOULOS
Silvia GENERELLI
Hui Chai-Gao
Original Assignee
CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement
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Publication of WO2020245312A1 publication Critical patent/WO2020245312A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/4035—Combination of a single ion-sensing electrode and a single reference electrode
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention concerns a device for pH measurement comprising a reference electrode and a working electrode, wherein the working electrode exhibits a free area, intended to be brought into contact with a liquid composition, together with the reference electrode, in order to measure the pH of the liquid composition.
  • the invention also concerns a method for manufacturing such a device for measuring pH, as well as a process for conducting pH measurements with such a device, and a use of such a device for measuring pH.
  • the standard device for pH measurement has been for a long time, and is still, the combination of a reference electrode with a working glass electrode.
  • these two electrodes might be kept distinct from one another or, in alternative, they might be combined into each other so as to finally constitute one sensor enclosing both electrodes.
  • the reference electrode might comprise a wire made of silver and immersed in a saturated solution of AgCI and KCI
  • the working electrode comprises a silver wire immersed in a pH 7 buffer solution containing AgCI and enclosed in a pH sensitive glass.
  • This standard glass electrode has an excellent sensitivity, selectivity, stability, and long lifetime. It is the gold standard used in laboratory settings to determine the pH of an aqueous solution. However, the semi-permeable glass membrane that gives the probe these properties is very fragile, expensive to fabricate, and difficult to miniaturize for point of care (POC) applications.
  • POC point of care
  • SPE Screen-Printed Electrode
  • electrodes which are specifically functionalized to be able to sense predefined biological or biochemical entities.
  • the sensor might be based on a commercially available carbon SPE and might comprise a PANI/CNC layer, itself covered with a first layer of IL (ionic liquid) and with a second layer of GLU (glutaraldehyde).
  • IL ionic liquid
  • GLU glycolhyde
  • a ChOx enzyme solution is drop casted on the GLU layer in order to immobilize the ChOx enzyme on the electrode and complete the fabrication of this cholesterol biosensor.
  • this biosensor is clearly tailored for a very specific application, which is dosing cholesterol, and is not suited at all for measuring pH, the function of the PANI/CNC consisting here in improving transmission of charges between the two adjacent layers.
  • publication US2016/235347A1 is directed to the fabrication of sensors of different kinds, for sensing many different types of species.
  • this publication teaches how to modify a SPE by covering its working electrode with a PANI/CNC compound, for instance as an intermediate layer designed to support a functional outer sensing layer including metal particles.
  • the function of the PANI/CNC layer is to improve the transfer of charges between two adjacent layers, while the corresponding sensor is not suited at all for measuring pH.
  • An aim of the invention is to propose a device for pH measurement fulfilling the above-mentioned requirements in terms of ease of use, sensitivity, selectivity, stability, long lifetime, and limited dimensions, as well as a method for manufacturing such a device in the field of large scale manufacturing, and a process for measuring pH with such a device.
  • the invention relates to a device for pH measurement according to the above mentioned features and wherein the free area of the working electrode is integrally covered with a composite compound comprising crystal of nanocellulose (CNC) and PANI.
  • CNC nanocellulose
  • the device according to the invention exhibits all the previously mentioned required features, while its manufacturing process is suitable for mass production, offering significant advantage over the state of the art.
  • the composite compound when using a CNC available at Blue Goose (under the trademark BGB Ultra, https://bluegoosebiorefineries.com/product/), the composite compound features a PANI/CNC mass ratio comprised between 0.95/0.05 and 0.75/0.25, more preferably between 0.95/0.05 and 0.88/0.12. According to the Applicant's experimentations, these ranges lead to the most efficient devices.
  • the device according to the invention is based on a Screen- Printed Electrode, having for instance a working electrode essentially made of carbon, and integrally covered by the PANI/CNC composite compound.
  • the device might further comprise a counter electrode.
  • the invention also concerns a method for manufacturing a device according to the above mentioned features.
  • the method of the invention comprises the steps consisting in:
  • a bare sensor comprising a working electrode essentially made of carbon and a reference electrode;
  • the device is advantageously based on a bare sensor which is a Screen-Printed Electrode, commercially available.
  • a bare sensor which is a Screen-Printed Electrode, commercially available.
  • step b) may comprise operations consisting in: - preparing an acid solution of aniline in an ice bath,
  • step b) may further comprise an operation consisting in drying the obtained composite compound precipitate.
  • step b) may comprise additional operations consisting in reducing the composite compound precipitate to a fine powder and dissolving the fine powder in water so as to define the suspension comprising the PANI/CNC composite compound.
  • the fine powder Preferably, between 0.1 and 8 mg of the fine powder, more preferably between 2 and 6 mg, is dissolved per ml_ of water so as to define the suspension comprising the PANI/CNC composite compound.
  • step c) may be carried out by dispensing at least one drop of the suspension comprising the PANI/CNC composite compound on the free area of the working electrode.
  • the present invention further relates to a process for conducting pH measurement comprising steps consisting in:
  • a measuring device comprising a reference electrode and a working electrode, wherein the working electrode exhibits a free area intended to be brought into contact with a liquid composition together with the reference electrode, in order to measure the pH of the liquid composition, and wherein the free area of the working electrode is integrally covered with a composite compound comprising CNC and PANI,
  • the process according to the invention might further include one or more of the above-mentioned additional features of the device for pH measurement, taken either singly or in combination.
  • the present invention further relates to the use of a device to conduct pH measurement, this device comprising a reference electrode and a working electrode,
  • the working electrode exhibits a free area intended to be brought into contact with a liquid composition together with the reference electrode, in order to measure the pH of the liquid composition
  • FIG. 1 schematic illustration of a SPE
  • FIG. 2 schematic illustration of a method for manufacturing a device for pH measurement according to the invention
  • Figs. 3a-3b diagrams corresponding to tests conducted on devices manufactured by implementation of the method of Fig. 2, and
  • Fig. 4a-4b diagrams corresponding to additional tests conducted on devices manufactured by implementation of the method of Fig. 2.
  • FIG. 1 is a schematic illustration of a standard sensor 1 of the Screen-Printed Electrode (SPE) type which might be used as a basis to implement the manufacturing method of the invention.
  • the sensor 1 comprises, in a known manner, a substrate 2 bearing, on one side, electrical contacts 4 to be connected to a measuring apparatus such as a voltmeter or a potentiometer, and, on the other side, a reference electrode 6, a working electrode 8 and, in the present case, an optional counter electrode 10, each of these electrodes being connected to one of the electrical contacts 4.
  • a measuring apparatus such as a voltmeter or a potentiometer
  • references DRP-110 and DRP-C110 of Dropsens might be used
  • each of the working electrode 8 and the counter electrode 10 is essentially made of carbon, while the reference electrode 6 might be made of silver/silver chloride.
  • This type of bare sensors can be customised in many different ways so as to be usable in connection with many different electrochemical or biological applications.
  • PANI is one of the well-known conducting polymers that has been widely used in numerous applications including supercapacitors, batteries, chemical and biological sensors, electrical conductors and in anti-static coatings. Nonetheless, PANI has some disadvantages such as low dispersibility and solubility in most solvents and low electron transfer rates and conductivity in solutions with a higher pH, which have limited its performance in biosensors and electrical devices.
  • CNC can vary from 10 to 50 nm in diameter and 100 to 500 nm in length depending on the starting material.
  • the high surface area of the CNC induces great mechanical properties and offers a good surface reactivity, allowing the introduction of functional groups by the mean of grafting or oxidation.
  • the corresponding preparation process comprises operations consisting in:
  • the composite compound can simply be centrifuged and washed until the pH of the corresponding supernatant is between 6 and 7.
  • the solution must be sonicated with Ultrasonic processor for at most 3 minutes (for instance, an Ultrasonic processor HP 200 st from Hielscher Ultrasonic GmbH might be used, with 500 W Power, 80% Amplitude, 20% Pulse).
  • Ultrasonic processor HP 200 st from Hielscher Ultrasonic GmbH might be used, with 500 W Power, 80% Amplitude, 20% Pulse.
  • the suspension of PANI/CNC composite compound can be further diluted in order to obtain lower concentration of the PANI/CNC composite compound.
  • the suspension should preferably be sonicated under the same conditions as mentioned above for at least 1 minute.
  • the suspension can be dispensed on the working electrode of a bare sensor or SPE. It is recommended to provide that the SPE is pre treated, for instance by using plasma treatment (applicable on a batch of electrodes) or amperometric techniques, such that its surface becomes more hydrophilic to improve the spreading out of the suspension.
  • plasma treatment applicable on a batch of electrodes
  • amperometric techniques such that its surface becomes more hydrophilic to improve the spreading out of the suspension.
  • a drop having a predefined volume is dispensed on the free area of the SPE working electrode 8 such that the free area is integrally covered.
  • several smaller drops can be dispensed so as to integrally cover the free area of the working electrode 8.
  • the dispensed composite compound is then dried up, either by being kept more or less at room temperature or by suitable heating means.
  • the dispensing step can be conducted through an automatic dispenser such that the whole manufacturing process might be suited for mass production.
  • an automatic dispenser such that the whole manufacturing process might be suited for mass production.
  • it is possible to dispense the composite compound by means of a Biodot dispenser see https://www.biodot.com/).
  • the ratio (in weight) between PANI and CNC in the composite PANI/CNC compound has been optimized, with the suspension featuring a PANI/CNC mass ratio comprised between 0.95/0.05 and 0.75/0.25, more preferably between 0.95/0.05 and 0.88/0.12, when BGB Ultra (trademark) commercially available at Blue Goose is used, as a non-limiting example.
  • the suspension has been optimized as far as the concentration of the composite PANI/CNC compound is concerned. Indeed, between 0.1 and 8 mg of the composite PANI/CNC compound, more preferably between 2 and 6 mg, is dissolved per ml_ of water so as to define the suspension to be dispensed on the bare SPEs.
  • Aniline available at SIGMA-ALDRICH, was used together with ammonium persulfate (APS), available at SIGMA, and 1 mol.L ⁇ 1 hydrochloric acid (HCI), available at MERCK.
  • APS ammonium persulfate
  • HCI hydrochloric acid
  • CNC cellulose nanocrystals at 8% weight in water (BGB Ultra - trademark - available at Blue Goose) were used, as well as standard deionized water (DIW) and bare carbon based SPEs (as mentioned above).
  • Example 1 Preparation of PANI/CNC with a mass ratio of 0.84/0.16
  • Example 2 Preparation of PANI/CNC with a mass ratio of 0.6/0.4
  • Example 3 Preparation of PANI/CNC with a mass ratio of 0.92/0.08
  • a pure PAN I sample was also prepared for comparison purposes, by preparing a 0.2 mol.L 1 of Aniline in HCI as described above, before dissolving 0.92 g (0.004 mol) of APS in 9 mL of HCI 1 mol.L 1 and adding this solution dropwise into the Ani solution. Steps 5/ and 6/ of the preceding examples were also implemented then.
  • the nanocomposite stock powder might preferably be milled in fine powder, for instance by means of a pestle and mortar.
  • the nanocomposite suspensions were let cooled down before being dispensed on the bare carbon based SPEs.
  • the bare SPEs were pre-treated, before application of the suspensions, preferably by plasma treatment.
  • the electrodes might be pre treated by using amperometric techniques. For instance, a 1.5 V potential might be applied on each SPE for 180 seconds while it is immersed in a 0.05 mmol.L ⁇ 1 phosphate buffer solution (with 0.1 mol.L ⁇ 1 of KCI).
  • FIG. 3a illustrates the experimental protocol implemented for testing the selectivity of the devices according to the invention.
  • the measuring devices were submitted in continuous to the following solutions:
  • a preliminary calibration curve was made to check the device functionality, in steps a to c, before the device was stabilized in the phosphate buffer solution in step d.
  • NaCI was added to reach a final concentration of 0.1 mol.L ⁇ 1 .
  • two calibration points were measured again, in steps f and g, to check the device functionality before the latter was stabilized again in the phosphate buffer solution in step h.
  • KCI was added to reach a final concentration of 0.1 mol.L ⁇ 1 .
  • two calibration points were finally measured, in steps j and k, to check the device functionality.
  • Figure 3b illustrates the great stability in the results of measures taken with one given device in each of the three cycles illustrated in Figure 3a, i.e. a first line abc corresponds to the first cycle (a, b, c) of Figure 3a, a second line efg corresponds to the second cycle (e, f, g) of Figure 3a and a third line ijk corresponds to the third cycle (I, j, k) of Figure 3a.
  • the device used in these measures was obtained by dispensing a 4 mg.mL ⁇ 1 nanocomposite suspension having a PANI/CNC mass ratio of 0.92/0.08 on bare SPEs.
  • Figures 4a and 4b are diagrams illustrating the results of additional measurements carried out in connection with the devices obtained through implementation of the manufacturing process of the present invention.
  • the measuring devices of the invention were tested while immersed in cutting fluids, a type of coolant and lubricant designed specifically for metalworking processes (oil based), which provide a bad environment for the sensors in general. Some measures were carried out with a protective membrane on the pH sensitive area and some other measures were carried out without the protective membrane. Nafion 5% was used here as the protective membrane in a non-limiting illustrative way.
  • Figure 4a illustrates the measuring results of a pure PAN I device while figure 4b illustrates the measuring results of a 4 mg.mL ⁇ 1 PANI/CNC with a mass ratio of 0.92/0.08 device, both devices without the protective membrane here.
  • devices for measuring pH according to the present invention can be manufactured, more generally, as long as value ranges are respected in terms of PANI/CNC mass ratio and of concentration of the nanocomposite compound in the suspension which is dispensed on the working electrode of the bare SPE, when BGB Ultra (trademark) is used.
  • a device according to the invention can be manufactured on the basis of a composite compound featuring a PANI/CNC mass ratio comprised between 0.95/0.05 and 0.75/0.25, more preferably between 0.95/0.05 and 0.88/0.12.
  • a device according to the invention can be manufactured as long as between 0.1 and 8 mg of the fine powder (the dry PANI/CNC nanocomposite compound), more preferably between 2 and 6 mg, is dissolved per ml_ of water so as to define the suspension to be dispensed on the working electrode of the bare SPE.
  • the molar weight of CNC may substantially vary depending on its source (so, on its structure), the one skilled in the art will be able to adapt the ratio ranges accordingly without going beyond the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Molecular Biology (AREA)
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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

L'invention concerne un dispositif de mesure du pH qui comporte une électrode de référence (6) et une électrode de travail (8), l'électrode de travail (8) présentant une zone libre, destinée à être mise en contact avec une composition liquide conjointement avec l'électrode de référence (6), afin de mesurer le pH de la composition liquide. La zone libre de l'électrode de travail (8) est intégralement recouverte d'un composé composite comportant du CMC et du PAN I.
PCT/EP2020/065548 2019-06-05 2020-06-04 Dispositif de mesure de ph comportant un composé composite à base de cnc-pan i et procédés correspondants WO2020245312A1 (fr)

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EP19178351 2019-06-05

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120298530A1 (en) 2010-01-07 2012-11-29 Universite Catholique De Louvain Smart sensor system using an electroactive polymer
US20160235347A1 (en) 2015-02-13 2016-08-18 Maarij Baig Artificial sensors and methods of manufacture thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120298530A1 (en) 2010-01-07 2012-11-29 Universite Catholique De Louvain Smart sensor system using an electroactive polymer
US20160235347A1 (en) 2015-02-13 2016-08-18 Maarij Baig Artificial sensors and methods of manufacture thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
..:: METROHM DROPSENS ::..: "Screen-printed electrodes", 6 November 2019 (2019-11-06), XP055639754, Retrieved from the Internet <URL:http://www.dropsens.com/en/screen_printed_electrodes_pag.html> [retrieved on 20191106] *
ABDI MAHNAZ M ET AL.: "Optimized fabrication of newly cholesterol biosensor based on nanocellulose", INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, vol. 126, 3 January 2019 (2019-01-03)
ABDI MAHNAZ M ET AL: "Optimized fabrication of newly cholesterol biosensor based on nanocellulose", INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, vol. 126, 3 January 2019 (2019-01-03), pages 1213 - 1222, XP085602114, ISSN: 0141-8130, DOI: 10.1016/J.IJBIOMAC.2019.01.001 *
KAEMPGEN M ET AL: "Transparent and flexible carbon nanotube/polyaniline pH sensors", JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 586, no. 1, 2 November 2005 (2005-11-02), pages 72 - 76, XP028017038, ISSN: 0022-0728, [retrieved on 20060101], DOI: 10.1016/J.JELECHEM.2005.09.009 *
RAWAIDA LIYANA RAZALLI ET AL: "Polyaniline-modified nanocellulose prepared from Semantan bamboo by chemical polymerization: preparation and characterization", RSC ADVANCES, vol. 7, no. 41, 10 May 2017 (2017-05-10), pages 25191 - 25198, XP055639742, DOI: 10.1039/C7RA03379F *
SHA RINKY ET AL: "Amperometric pH Sensor Based on Graphene-Polyaniline Composite", IEEE SENSORS JOURNAL, IEEE SERVICE CENTER, NEW YORK, NY, US, vol. 17, no. 16, 27 June 2017 (2017-06-27), pages 5038 - 5043, XP011657415, ISSN: 1530-437X, [retrieved on 20170721], DOI: 10.1109/JSEN.2017.2720634 *
SIXIANG LI ET AL: "Fabrication of pH-electroactive Bacterial Cellulose/Polyaniline Hydrogel for the Development of a Controlled Drug Release System", ES MATERIALS & MANUFACTURING, 11 October 2018 (2018-10-11), XP055725292, ISSN: 2578-0611, DOI: 10.30919/esmm5f120 *

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