WO2013081442A1 - Dispositif de détection de calcium et procédé pour sa préparation - Google Patents

Dispositif de détection de calcium et procédé pour sa préparation Download PDF

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Publication number
WO2013081442A1
WO2013081442A1 PCT/MY2012/000177 MY2012000177W WO2013081442A1 WO 2013081442 A1 WO2013081442 A1 WO 2013081442A1 MY 2012000177 W MY2012000177 W MY 2012000177W WO 2013081442 A1 WO2013081442 A1 WO 2013081442A1
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WO
WIPO (PCT)
Prior art keywords
calcium
transducer
self
sensor
doped
Prior art date
Application number
PCT/MY2012/000177
Other languages
English (en)
Inventor
Alva Sagir
Rais Ahmad Mohd
Original Assignee
Mimos Berhad
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mimos Berhad filed Critical Mimos Berhad
Publication of WO2013081442A1 publication Critical patent/WO2013081442A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • G01N27/333—Ion-selective electrodes or membranes
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/122—Copolymers statistical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/514—Electron transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors

Definitions

  • the present invention relates generally to beneficial compound detection device and methods, and more particularly to calcium detection device and methods.
  • calcium is the fifth element and the third most abundant metal in the earth's crust whereby it accounts for 3.64% of the earth's ' crust.
  • the distribution of calcium is very wide; it is found in almost every terrestrial area in the world. This element is essential for the life of plants and animals, as it plays a major role the growth of the animal's skeleton, in tooth, in the egg's shell, in the coral and in many soils. Seawater contains 0.15% of calcium chloride. Nevertheless, calcium cannot be found alone in nature. Calcium is found mostly as limestone, gypsum and fluorite. Stalagmites and stalactites contain calcium carbonate.
  • calcium is always present in every plant, as it is essential for its growth. It is contained in the soft tissue, in fluids within the tissue and in the structure of every animal's skeleton.
  • the vertebrate's bones contain calcium in the form of calcium fluoride, calcium carbonate and calcium phosphate.
  • EDTA ethylenediaminetetraacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • the ability of EDTA to potentially donate its six lone pairs of electrons for the formation of coordinate covalent bonds to metal cations like calcium makes EDTA a hexadentate ligand.
  • it measurement and detection of calcium ions in practice EDTA is usually only partially ionized, and thus forms fewer than six coordinate covalent bonds with metal cations.
  • EDTA forms an octahedral complex with most 2+ metal, cations, M 2+ , in aqueous solution.
  • the main reason that EDTA is used so extensively in the standardization of calcium solutions is that the formation constant for most calcium-EDTA complexes is very high, meaning that the equilibrium for the reaction:
  • methods use to determine the calcium ion concentration further includes atomic absorption spectroscopy (AAS) or inductively coupled plasma atomic emission spectroscopy (ICP-AES) .
  • AAS atomic absorption spectroscopy
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • titration or spectroscopy exhibits its own disadvatanges particulary when used for field adjations, because request more reagent, sample and big tools.
  • Ca-ISE Calcium ion-selective electrode
  • Ca-ISE Calcium ion-selective electrode
  • the application of Ca-ISE has evolved to a well establish routine analytical technique in ' many fields, including clinical, precision agriculture and environmental analysis.
  • Most of calcium ion-selective electrode used Ag/AgCl as transducer, but there are many disadvantages to decreased performance of Ca-ISE.
  • Dissolved carbon dioxide (C0 2 ) can react with water in the membrane to produced carbonic acid (H 2 C0 3 ) and oxidized Ag/AgCl electrode to make silver oxide layer. Silver oxide can prohibited electron transfer to Ag/AgCl surface and make electrode become unstable. The complete reaction following:
  • a calcium sensor electrode with self-doped polythiophene as a transducer layer Furthermore, we have demonstrated good responses and good linearity on miniaturized planar electrode. The results indicate that the disclosed can be deployed for detecting a wide range of calcium species in the fields. Calcium ion selective with polythiophenes layer can be packaged into a small wireless system and deployed for in-situ measurement of the analytes.
  • a calcium ion sensor with self- doped polythiophene nano-composite transducer comprising: at least one substrate for conductor layer seeding; at least one conductor to function as an electrical contact; a self-doped polythiophene transducer that functions as transducer layer for electron transfer; a carbon layer to function as a seeding substrate for the self-doped polythiophenes transducer layer; a calcium sensing membrane as a polymeric membrane and to function as calcium detector; and a retaining dam to hold calcium sensing membrane to not flood and carried out from surface area.
  • a method of preparing the calcium sensor with cast self- doped polythiophene nanocomposite transducer comprising the steps of: depositing carbon on electrode; preparing self-doped polythiophene nanocomposite casting solution; preparing calcium sensor cocktail composition; coating self-doped polythiophene nanocomposite solution on carbon electrode surface; coating calcium sensor cocktail on self-doped polythiophene transducer layer; and characterizing calcium sensor response.
  • FIG 1 shows a flowchart on the steps involved for preparing the ) sensor in accordance with the preferred embodiments of the present invention
  • FIG 2 shows the sensor in accordance with a preferred embodiment of the present invention.
  • FIG 3 shows the response versus activity of calcium ion shows good Nernstian response and good linearity, using the sensor of the present invention.
  • the present invention provides a calcium ion sensor. Furthermore,
  • the senor of the present invention shows good responses and good linearity on miniaturized planar electrode.
  • the results indicate that the disclosed can be deployed for detecting a wide range of calcium species in the fields.
  • Calcium ion selective with polythiophenes layer can be packaged into a small wireless system and deployed for in-situ measurement of the analytes.
  • FIG. 1 A schematic view of the method involved in preparing the calcium ion i sensor in accordance with the preferred embodiments of the present invention is shown in FIG 1.
  • I steps are: preparation of carbon electrode, preferably via screen printing method, that functions as a seeding substrate for self- doped polythiophenes transducer layer; preparation of self-doped polythiophenes conducting layer, preferably via chemically process, that functions as transducer layer for electron transfer;
  • the calcium ion sensor in accordance with the preferred embodiments of the i present invention comprises the following layers; at least one substrate which is preferably an inert material for conductor layer seeding; at least ' one conductor preferably metal and function as electrical contact; at least one carbon layer to function as a seeding substrate for self-doped polythiophenes transducer layer; a self-Doped polythiophene transducer that functions as transducer layer for electron transfer; a calcium sensing membrane is polymeric membrane and function as calcium detector; and a retaining dam formed as inert material and function to hold calcium sensing membrane to not flood and carried out from surface area.
  • the calcium sensor with cast self-doped polythiophene nanocomposite transducer preferably comprises 0.1 to 20% polythiophene, 0.1 to 20% dopant, 40 to 90% binder and 0.1 to 20% carbon nanotubes, all by weight; and the conducting polythiophene having the following structure:
  • R H, methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl
  • the dopant is at least one or combination of the following dopants; chloride, tetrafluoroborate, iodide, para- toluene sulfonate, trifluoromethane sulfonate, camphor sulfonate, poly styrene sulfonate, nafion, hexafluorophosphate .
  • calcium sensing membrane comprises; acrylic copolymer adhesive; forms homogenous blend with high molecular weight polymer and functions as adhesion promoter to solid electrode surface; high molecular weight polymer; functions as lipophilic polymeric matrix to allow transport of ionic species to electrochemical transducer surface; plasticizer; to soften the high molecular weight polymer in order to give flexible characteristic to the matrix; lipophilic additive; to create ionic sites within the polymer matrix to allow transport of ionic species; ion-recognizing molecule; to selectively bind with the analyte and to transport it across the membrane; at least one type of solvent; to homogenously dissolve all solid materials and for casting the cocktail composition on electrode surface.
  • the copolymer adhesive it is preferred that it comprises one part of methyl methacrylate monomer and at least one part of tetrahydrofurfuryl acrylate monomer by volume.
  • the copolymer may comprise of one part methyl methacrylate monomer and at least one part of n-butyl acrylate monomer by volume.
  • Carbon paste is screen printed on copper-gold or prefabricated screen printed silver.
  • printed carbon and silver are 100 micrometer.
  • the circular shaped electrodes with 3mm diameter is printed on polyester or printed circuit board substrate and separated by 2mm spacing from each other for integrated multi-sensor application.
  • the printed paste was cured at 120 °C to give the desired dry thickness.
  • Solder mask i insulating layer was also screen printed to define the electrode window, separate the wells and protect the printed conducting wires.
  • Calcium ion selective composition was prepared by mixing 28.2 mg poly (vinyl) chloride (PVC) , 3.1 mg copolymer methyl metha acrylate- n-butyl acrylate (MB28), 0.7 mg sodium tetrakis [bis
  • This calcium sensor was tested using commercial Ag/AgCl double junction reference electrode with 0.1M LiOAc as outer solution and calcium standard calibration solution at pH 6. Before tested, calcium sensor was soaked into 0.1 M calcium chloride at pH 6 until overnight to conditioning. The results were shown in TABLE 1 below and plotted in FIG 3. The plot of emf response versus activity of calcium ion shows good Nernstian response and good linearity.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Light Receiving Elements (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

L'invention concerne un détecteur de calcium comportant une couche de transducteur ; ledit détecteur comportant en outre ; au moins un substrat pour ensemencement de couche de conducteurs ; au moins un conducteur destiné à faire fonction de contact électrique ; un transducteur au polythiophène auto-dopé faisant fonction de couche de transducteur pour le transfert d'électrons ; une couche de carbone destinée à faire fonction de substrat d'ensemencement pour la couche de transducteur au polythiophène auto-dopé ; une membrane de détection de calcium sous la forme d'une membrane polymérique et destinée à faire fonction de détecteur de calcium ; et un barrage de retenue servant à maintenir une membrane de détection de calcium pour éviter qu'elle ne soit inondée et entraînée hors de la zone de surface.
PCT/MY2012/000177 2011-12-01 2012-06-29 Dispositif de détection de calcium et procédé pour sa préparation WO2013081442A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2011005813 2011-12-01
MYPI2011005813A MY169834A (en) 2011-12-01 2011-12-01 Calcium sensing device and method of preparing thereof

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WO2013081442A1 true WO2013081442A1 (fr) 2013-06-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014092543A1 (fr) * 2012-12-11 2014-06-19 Mimos Berhad Capteur sélectif d'ions calcium
CN104849335A (zh) * 2015-05-29 2015-08-19 李宏奎 一种检测血样离子钙含量的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1634922A1 (fr) * 2003-06-18 2006-03-15 Shin-Etsu Polymer Co., Ltd. Composition conductrice, enduit conducteur, resine conductrice, condensateur, element convertisseur photo-electrique et procede de production associe
US20060065527A1 (en) * 2004-09-24 2006-03-30 Sendx Medical, Inc. Polymeric reference electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1634922A1 (fr) * 2003-06-18 2006-03-15 Shin-Etsu Polymer Co., Ltd. Composition conductrice, enduit conducteur, resine conductrice, condensateur, element convertisseur photo-electrique et procede de production associe
US20060065527A1 (en) * 2004-09-24 2006-03-30 Sendx Medical, Inc. Polymeric reference electrode

Non-Patent Citations (4)

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Title
BENDIKOV T A ET AL: "Development and environmental application of a nitrate selective microsensor based on doped polypyrrole films", SENSORS AND ACTUATORS B: CHEMICAL: INTERNATIONAL JOURNAL DEVOTED TO RESEARCH AND DEVELOPMENT OF PHYSICAL AND CHEMICAL TRANSDUCERS, ELSEVIER S.A, SWITZERLAND, vol. 106, no. 2, 13 May 2005 (2005-05-13), pages 512 - 517, XP027810284, ISSN: 0925-4005, [retrieved on 20050513] *
BOBACKA J: "Conducting Rolymer-Based Solid-State Ion-Selective Electrodes", ELECTROANALYSIS, VHC PUBLISHERS, INC, US, vol. 18, no. 1, 1 January 2006 (2006-01-01), pages 7 - 18, XP002478091, ISSN: 1040-0397, DOI: 10.1002/ELAN.200503384 *
MICHALSKA A ET AL: "ALL-SOLID-STATE CALCIUM SOLVENT POLYMERIC MEMBRANE ELECTRODE FOR LOW-LEVEL CONCENTRATION MEASUREMENTS", ANALYTICAL CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 75, no. 1, 1 January 2003 (2003-01-01), pages 141 - 144, XP001161587, ISSN: 0003-2700, DOI: 10.1021/AC025916Y *
MOUSAVI Z ET AL: "Poly(3,4-ethylenedioxythiophene) (PEDOT) doped with carbon nanotubes as ion-to-electron transducer in polymer membrane-based potassium ion-selective electrodes", JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTRO CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 633, no. 1, 1 August 2009 (2009-08-01), pages 246 - 252, XP026349168, ISSN: 0022-0728, [retrieved on 20090613] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014092543A1 (fr) * 2012-12-11 2014-06-19 Mimos Berhad Capteur sélectif d'ions calcium
CN104849335A (zh) * 2015-05-29 2015-08-19 李宏奎 一种检测血样离子钙含量的方法

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