EP1448670A1 - Selektives verfahren zur detektion, identifikation und dosierung eines divalenten metallischen ions in einer probe - Google Patents

Selektives verfahren zur detektion, identifikation und dosierung eines divalenten metallischen ions in einer probe

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Publication number
EP1448670A1
EP1448670A1 EP02796891A EP02796891A EP1448670A1 EP 1448670 A1 EP1448670 A1 EP 1448670A1 EP 02796891 A EP02796891 A EP 02796891A EP 02796891 A EP02796891 A EP 02796891A EP 1448670 A1 EP1448670 A1 EP 1448670A1
Authority
EP
European Patent Office
Prior art keywords
polymer
nta
poly
electroactive
monomers
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02796891A
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English (en)
French (fr)
Inventor
Francis Garnier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Biomerieux SA
Original Assignee
Biomerieux SA
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 Biomerieux SA filed Critical Biomerieux SA
Publication of EP1448670A1 publication Critical patent/EP1448670A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • the invention relates to organic electrodes produced from electroactive polymers functionalized by agents capable of interacting with chemical species and thus allowing their detection, assay and identification by measuring sensitive and selective variations in the electrochemical properties of the electroactive polymer.
  • the aforementioned variations are of potentiometric type, such as a variation of the oxidation potential of the electroactive polymer before and after interaction, or of amperometric type, such as a variation of the oxidation or reduction current of the polymer before and after interaction , determined at a determined potential.
  • Conjugated polymers such as polypyrroles, polythiophenes, polyanilines, polyphenylenes and their derivatives are known for their electroactive nature and authors have been interested in the use of these polymers by functionalizing them to develop analyte sensors.
  • EP-B-0314009 discloses thienylpyrroles grafted in position 3 of the pyrrole nucleus capable of covalently binding to an organic molecule, but these products, because of their hydrophobicity, are not suitable for detection in an aqueous medium.
  • a polypyrrole is known, consisting of monomers each consisting of a pyrrole nucleus covalently substituted on the carbon in position 3 of the pyrrole nucleus, by a probe polynucleotide.
  • the polypyrrole thus obtained is applied to the detection, and optionally the determination, of ligands, in vitro or in vivo.
  • chelating agents such as NTA (nitrilotriacetate) or IDA (iminodiacetate)
  • IMAC immobilized metal affinity chromatography
  • IDA was loaded with metal ions, such as Zn 2+ , Cu 2+ or Ni 2+ and was used to purify proteins or peptides.
  • Patent application WO90 / 02829 describes microelectrodes coated with electropolymers such as in particular an electroactive polymer film in which EDTA is incorporated.
  • This electropolymer has for disadvantage a resistance problem when subsequently binding to any analyte.
  • the Applicant has surprisingly found that the detection of potentially toxic metal ions in a sample capable of containing them has been greatly improved by the use of an electroactive probe consisting of an electroactive polymer to which is covalently bonded a chelating agent.
  • a first object of the invention is an electroactive probe, characterized in that it comprises a homopolymer or electroactive copolymer polymer of at least two monomers, functionalized with a chelating agent.
  • the electroactive polymer which is suitable for the purposes of the invention is an electroactive polymer in water.
  • the electroactive polymer is chosen from polypyrrole, polyacetylene, polyazine, poly (p-phenylene), poly (p-phenylene vinylene), polypyrene, polythiophene, polyethylenedioxythiophene , polyfuran, polyselenophene, polypyridazine, polycarbazole and polyaniline.
  • the chelating agent used in the probe of the invention is any non-specific chelating agent, that is to say capable of multidetection.
  • the chelating agent is chosen from iminodiacetic acid, nitrilotriacetic acid and ethylene diamine tetraacetic acid.
  • NTA is a tetradendate agent that binds metal ions more stably than other resins available for chelation.
  • EDTA is a hexadentate complexing agent in its ionic form.
  • the probe of the invention as defined above has a structure such that the electroactive polymer of the invention is functionalized with a chelating agent.
  • the structure is such that the chelating agent is linked directly to the conductive polymer covalently via a linking group.
  • a linking group according to the invention connects, by covalent bond, two chemical entities, at least one having previously been activated or activatable, with a view to this interaction, by an activated or activatable group.
  • the linking group can therefore result from the reaction of an activated group or activatable of an entity on a reactive function of the other entity, and vice-versa, or of the reaction of a said activated or activatable group of one entity to another said activated or activatable group of the other entity.
  • activated group is meant a group allowing, through its intermediary, the interaction of the entity on which it is fixed with another entity.
  • it may be an activated ester group such as the group -CO- [ON-phthalimide].
  • activatable group includes a group which can be transformed into an activated group, for example under certain reaction conditions or during contact with an activated group capable of interacting with it such as the group -CH 2 -COOH or -CH 2 -CH 2 -OH.
  • the invention also relates to the electroactive homopolymer or copolymer polymer, characterized in that it comprises at least two monomers functionalized by a chelating agent.
  • the electroactive polymer of the invention advantageously meets the following characteristics considered alone or in combination:
  • the monomers are chosen from pyrrole, acetylene, azine, p-phenylene, p-phenylene vinylene, pyrene, thiophene, polyethylenedioxythiophene, furan, selenophene, pyridazine, carbazole and l 'aniline and,
  • the chelating agent is chosen from iminodiacetic acid, nitrilotriacetic acid and ethylene diamine tetraacetic acid.
  • the electroactive polymer of the invention as such or in the electroactive probe is a polypyrrole consisting of at least two monomers and the chelate is an IDA or an NTA, said chelate being fixed by a covalent bond in position 3 of the pyrrole ring via a caerboxymethyl residue.
  • the invention also relates to a process for the preparation of a conductive polymer functionalized with a chelating agent.
  • This process comprises the following stages: a) synthesis of the monomers substituted by an activated group, by the conventional methods of esterification, b) polymerization and deposition by coulometry in the form of films on electrodes, c) functionalization by the chelating agent by hydrolysis of the activated group.
  • the functionalization of the conductive polymer with a chelating agent can be carried out by two routes, the first by functionalization of the monomer followed by polymerization and the second by functionalization after formation of the polymeric film.
  • the monomers substituted by an activated group are synthesized by conventional methods of esterification, for example of a carboxylic acid such as 3-pyrrole acetic acid with N-hydroxyphthalimide.
  • the monomers obtained are then polymerized and deposited by coulometry in the form of films on electrodes, and the functionalization by the chelating agent is then carried out by hydrolysis of the activated group.
  • the probes of the invention find utility in the detection of potentially toxic metal ions, and in particular of divalent metal cations.
  • metals giving cations capable of being the subject of such detection are for example cadmium, zinc, copper, nickel, mercury, lead, chromium, cobalt and silver which depending on their oxidation numbers may give rise to cations, for example divalent, monovalent, trivalent or tetravalent.
  • the invention also relates to a selective method of detection, identification and determination of a potentially toxic metal ion in a sample capable of containing a plurality of metal ions, characterized in that one implements a probe according to the invention and in that a potential difference characteristic of the redox potential of the cation (s) present in the sample is observed and / or measured. This difference in potential or this variation in current is observed and / or measured before complexing and after complexing, that is to say between the electroactive polymer functionalized without metal complex formed and the same polymer after chelation with a metal cation.
  • the present invention relates to an electrode in which all or part of the contact surface with the electrolyte is coated with a probe such as defined above.
  • Such an electrode can be obtained by any conventional technique well known to those skilled in the art.
  • a preparation can be carried out by depositing the functionalized polymer on the surface of a conventional electrode.
  • the deposits of conductive polymers can be carried out by coulometry by controlling the current charge on the surface of an electrode of platinum, gold or any other metal or alloy well known in these techniques.
  • Example 1 preparation of films based on electroconductive polymers. Pyrrole monomers functionalized in position 3 with an N-hydroxyphthalimide (NHP) were synthesized and then polymerized to obtain a poly (3- (carboxymethylpyrrole) -NHP) polymer film carrying active ester groups.
  • N-hydroxyphthalimide N-hydroxyphthalimide
  • a solution of 0.1 M 3-carboxymethylpyrrole-NHP monomer is prepared in anhydrous acetonitrile freshly distilled in the presence of an electrolyte (LiCO 4 , 0.5 M).
  • This monomer is polymerized in a four-compartment cell, using a 0.7 cm 2 platinum electrode, a platinum auxiliary electrode and a saturated calomel electrode as reference electrode, with the controlled potential of 0.9 V to obtain Poly (3 carboxymethylpyrrole-NHP) film.
  • the film obtained is washed with acetone and dried.
  • the electroactivity is then measured in an acetonitrile medium containing 0.1 M LiCl0 4 as an electrolyte after purging with argon to remove the oxygen.
  • the cyclic voltammetry is recorded at the speed of 20 mV / s.
  • the electrode is washed with acetone and dried.
  • Example 2 grafting of imino-diacetic acid (IDA) or of N- (5-amino-1-carboxypentyl) imino-diacetic acid (NTA) on conductive 3-carboxymethylpyrrole polymer films.
  • IDA imino-diacetic acid
  • NTA N- (5-amino-1-carboxypentyl) imino-diacetic acid
  • Example 2 grafting of imino-diacetic acid (IDA) or of N- (5-amino-1-carboxypentyl) imino-diacetic acid (NTA) on conductive 3-carboxymethylpyrrole polymer films.
  • the electrode obtained is washed with ultra pure water, dried and the electroactivity is checked in an aqueous medium containing 0.5 M NaCl.
  • the electrochemical analysis is shown in Figure 2.
  • the electrochemical signal is stable and reversible in an aqueous medium.
  • Poly (3-carboxymethylpyrrole-NHP) films of different thicknesses were prepared and the films obtained were grafted with NTA.
  • the electrochemical response recorded in an aqueous medium in the presence of 0.5 M NaCl confirms the presence of an electrochemically active film in an aqueous medium.
  • the comparison of the charge of Poly (3-carboxymethylpyrrole-NHP) deposited at the start on the electrode and the calculated charge of NTA grafted on the film suggests that the grafting yield of NTA or IDA on the film of 100 %.
  • the quantity of NTA or IDA grafted onto the poly (3-carboxy) pyrrole film depends on the quantity of 3-carboxymethylpyrrole-NHP units present on the electrodes, as illustrated by the curves of Figure 3.
  • Example 3 Detection of metals by modified conductive polymer films.
  • the electrode comprising the poly (3-carboxymethylpyrrole-NTA) film was electrochemically analyzed in an aqueous medium, washed with deionized water, dried and then immersed in an aqueous solution of
  • the electrode is then rinsed in deionized water, dried and analyzed electrochemically in an aqueous solution containing 0.5M NaCl.
  • the amount of copper complexed with the Poly (3-carboxymethylpyrrole-NTA) film depends on the amount of NTA on the polymer film, which depends on the amount of functionalized pyrrole monomer units which have been polymerized on the platinum electrodes . In other words, this means that the amount of copper complexes on the polymer films depends on the thickness of the polymer films. This is shown in FIG. 5 in which it is observed that two electrodes of different thicknesses complex different amounts of copper.
  • FIG. 6 shows the effect of the concentration of Cu 2+ on the electrochemical response of Cu 2+ .
  • Figure 6 shows that the electrochemical signal is stable and reversible.
  • Example 6 Electrochemical reversibility of the electrodes.
  • the diagram below shows the complexation and decomplexation of copper and mercury with the Poly (3-carboxymethylpyrrole-NTA) film on the electrode.
  • the electrodes comprising the poly (3-carboxymethylpyrroIe-NTA) polymer film complexed with Cu 2+ were immersed in a 0.1 M solution of EDTA (ethylene diamine tetracetic acid) for 15 minutes. The electrodes are then rinsed with water, dried and analyzed. Analysis of the initial poly (3-carboxymethylpyrrole-NTA) voltammograms shows that the electrochemical signal is reversible and stable.
  • Example 7 Mercury complexation with the Poly film (3-carboxymethylpyrrole-NTA) on the electrode.
  • the complexation of mercury with the Poly (3-carboxymethylpyrrole-NTA) film is shown in the diagram below.
  • the film of Poly (3-carboxymethylpyrrole-NTA) was was washed with deionized water, dried and the electrode was immersed in a saturated aqueous solution (deionized water) of HgCl 2 containing 0.5 M NaCl, at room temperature for 3 hours.
  • the electrode was then analyzed in an aqueous solution which contains 0.5 M NaCl.
  • Example 9 Selectivity of the electrodes.
  • Copper is characterized by redox potentials for the Cu "/ Cu 'and Cu' / Cu ° transitions.
  • the metals each have their specific oxidation potential.
  • the oxidation potentials given in the literature for different metals are summarized in Table 3 below.
  • the characteristic oxidation peak for Cu 2+ / Cu + is -0.1 V / SCE, while for mercury for Hg 2+ / Hg + it is 0.1 V / SCE by Poly film electrode (3-carboxymethylpyrrole-NTA).
  • Example 10 Detection limit for copper and mercury for an electrode modified with conductive polymers functionalized with chelates.
  • an electrochemical analysis of a solution containing the minimum quantity of copper and mercury detectable by the electrodes of Poly (3-carboxymethylpyrrole-NTA) was carried out.
  • Figure 10 highlights the electrochemical response for the Poly (3-carboxymethylpyrrole-NTA) film complexed with copper at a copper concentration of 2.10 "7 M / L and the comparison with a reference voltamograme of a Poly electrode (3- carboxymethylpyrrole-NTA) without complexing with copper, which only highlights the effect of 0.5 M NaCl in water on the polymer film.
  • the effect of the concentration of bivalent metals on the electrochemical response made it possible to show that the sensitivity of these electrodes is of the order of 2 ⁇ A / 2.10 "7 M / L of Cu 2+ in solution, which corresponds to 3.10 " 8 ⁇ A / ML for Cu 2+ in the aqueous solution.
  • the detection limit for Cu 2+ is 4 PPB in aqueous solution.
  • the sensitivity of the electrodes is of the order of 0.3 ⁇ A / 2.10 "7 M / L in solution, which corresponds to 1.10 " 8 ⁇ A / ML of Hg 2+ in the aqueous solution.
  • the detection limit for Hg 2+ is around 4 PPB in aqueous solution.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Medicinal Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
EP02796891A 2001-11-30 2002-12-02 Selektives verfahren zur detektion, identifikation und dosierung eines divalenten metallischen ions in einer probe Withdrawn EP1448670A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0115669 2001-11-30
FR0115669A FR2833014B1 (fr) 2001-11-30 2001-11-30 Procede selectif de detection, d'identification et de dosage d'un cation metallique divalent dans un echantillon
PCT/FR2002/004135 WO2003046051A1 (fr) 2001-11-30 2002-12-02 Procede selectif de detection, d'identification et de dosage d'un ion metallique divalent dans un echantillon

Publications (1)

Publication Number Publication Date
EP1448670A1 true EP1448670A1 (de) 2004-08-25

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EP02796891A Withdrawn EP1448670A1 (de) 2001-11-30 2002-12-02 Selektives verfahren zur detektion, identifikation und dosierung eines divalenten metallischen ions in einer probe

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US (1) US20050008860A1 (de)
EP (1) EP1448670A1 (de)
JP (1) JP2005513423A (de)
AU (1) AU2002361361A1 (de)
FR (1) FR2833014B1 (de)
WO (1) WO2003046051A1 (de)

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US20080220465A1 (en) * 2007-03-05 2008-09-11 Pocared Diagnostics, Inc. Antibiotic Sensitivity Testing Method
EP2162736B1 (de) 2007-06-29 2018-12-26 Arizona Board of Regents, acting for and on behalf of Arizona State University Vorrichtung und verfahren zum elektrochemischen nachweis von siliziumdioxid-spezies
WO2011090793A2 (en) * 2010-01-20 2011-07-28 Customarray, Inc. Multiplex microarray of serially deposited biomolecules on a microarray
US20120193240A1 (en) * 2011-01-21 2012-08-02 Clark Sue B Electrochemical Concentration of Lanthanide and Actinide Elements
US20160025678A1 (en) * 2013-04-03 2016-01-28 University Of Massachusetts Electrochemical Tongue
CN108110256B (zh) * 2017-12-07 2020-07-03 成都新柯力化工科技有限公司 一种锂电池的金属-氨三乙酸复合负极材料及制备方法
CN111936846B (zh) 2018-06-14 2022-12-20 Nok株式会社 银-氯化银电极的制造方法
CN112225880B (zh) * 2020-09-21 2023-02-17 新疆农业大学 一种Hg2+荧光探针及制备方法
US12496612B2 (en) 2021-01-08 2025-12-16 Surmodics, Inc. Coating application system and methods for coating rotatable medical devices

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WO1990002829A1 (en) * 1988-09-07 1990-03-22 Wollongong Uniadvice Limited Electropolymer coated microelectrodes
US5312762A (en) * 1989-03-13 1994-05-17 Guiseppi Elie Anthony Method of measuring an analyte by measuring electrical resistance of a polymer film reacting with the analyte
JPH03205422A (ja) * 1990-01-08 1991-09-06 Nippon Oil Co Ltd ポリ［（３―ピロリル）酢酸］
FR2707642B1 (fr) * 1993-07-16 1995-10-13 Electricite De France Dérivés de polyéthers et d'hétérocycles pentacycliques, leurs polymères et leurs applications, notamment à la complexation d'ions métalliques.
FR2720832A1 (fr) * 1994-04-22 1995-12-08 Francis Garnier Electrodes et membranes électroactives à base de peptides bioactifs, pour la reconnaissance, l'extraction ou le relargage d'espèces biologiquement actives.
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JP2005513423A (ja) 2005-05-12
FR2833014A1 (fr) 2003-06-06
WO2003046051A1 (fr) 2003-06-05
AU2002361361A1 (en) 2003-06-10
FR2833014B1 (fr) 2005-07-08
US20050008860A1 (en) 2005-01-13

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