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WO2018039585A1 - Polymère soluble dans l'eau fonctionnalisé par un médiateur redox - Google Patents

Polymère soluble dans l'eau fonctionnalisé par un médiateur redox Download PDF

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Publication number
WO2018039585A1
WO2018039585A1 PCT/US2017/048655 US2017048655W WO2018039585A1 WO 2018039585 A1 WO2018039585 A1 WO 2018039585A1 US 2017048655 W US2017048655 W US 2017048655W WO 2018039585 A1 WO2018039585 A1 WO 2018039585A1
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Prior art keywords
polymer
group
repeating unit
ferrocene
side chain
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Inventor
Cuihua Xue
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Resonac Corp
Resonac America Inc
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Hitachi Chemical Co Ltd
Hitachi Chemical Co America Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G61/126—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 sulfur atom in the ring
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    • C08G2261/10—Definition of the polymer structure
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    • 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
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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    • C08G2261/10—Definition of the polymer structure
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    • 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
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/14—Side-groups
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    • 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
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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    • 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
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    • 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
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
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    • 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
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/64—Solubility

Definitions

  • the present invention relates to, in general, water-soluble conjugated polymers having redox mediators and functional groups on flexible side chains, methods of manufacturing such water-soluble conjugated polymers, and applications thereof.
  • Redox mediators that assist in transferring electrons are a necessary component in the fabrication of electrochemical sensors and bio-sensors.
  • Mediators are often small molecules that leach easily from the sensor interface, which affects the stability and durability of the sensors and also has potential harmful effects if the sensor (e.g., a wearable sensor) makes contact with the body.
  • Polymers are macromolecules and covalent attachment of mediators onto the polymers prevents leaching of the mediators.
  • Ferrocene is a redox mediator with reversible redox properties and polythiophenes are well-known conducting polymers. Both ferrocene and
  • polythiophenes have been used separately or together in many sensing applications.
  • the ferrocene-polythiophene films are formed directly on the electrode surface by electrochemically co-polymerizing small thiophenes and ferrocene-containing thiophenes, and the ferrocene-polythiophenes are not isolated materials.
  • Such ferrocene-polythiophenes are limited when used in sensor mass production due to the lack of control of the ferrocene number in the sensor film.
  • the ferrocene-polythiophenes are mostly hydrophobic, which lacks compatibility with biological species for biosensor development.
  • the present invention may address one or more of the problems and deficiencies of the prior art discussed above. However, it is contemplated that the invention may prove useful in addressing other problems and deficiencies, or provide benefits and advantages, in a number of technical areas. Therefore the invention should not necessarily be construed as being limited to addressing only the particular problems or deficiencies discussed herein.
  • the redox mediator macromolecular materials have potential reactive sites for further modification with other functional species, which may lead to further fabrication of versatile sensor platforms, and can be used in many other applications like medical detections, targeting etc. Furthermore, due to the redox activity, the materials can be used as semiconducting materials in organic photovoltaic cells, organic light-emitting diodes, field-effect transistors, organic semiconductors, electronic optical sensors and other opto-electronic devices, and the like.
  • the present invention provides a polymer comprising at least one repeating unit selected from repeating unit (A), repeating unit (B) and repeating unit (C).
  • the present invention provides a polymer comprising at least one repeating unit (A) and at least one repeating unit (B) or a polymer comprising at least one repeating unit (A) and at least one repeating unit (C).
  • the present invention provides a polymer comprising at least one repeating unit (A), at least one repeating unit (B) and at least one repeating unit (C).
  • Repeating unit (A) is one or more monomers represented by the following
  • Repeating unit (B) is one or more monomers represented by the following
  • Repeating unit (C) is one or more monomers represented by the following
  • X is a single bond, C1 -C20 alkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl,
  • n is 0, 1 or an integer greater than 1
  • M is substituted ferrocene or ferrocene derivatives
  • R is OH, Br, I, CI, SH, COOH, SO 3 H, NH 2 , ⁇ + (R 1 ) 3 , YRiCOOH, YRTSOSH, maleimide, NHS ester, YR ⁇ , COONa, SO 3 Na, COOK, SO 3 K, YR ⁇ OONa, YR ⁇ OsNa, YR ⁇ OOK or YR ⁇ OsK;
  • Y is C, O, S or N;
  • R-i is alkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl, and can be the same or different;
  • L is selected from carbohydrates, proteins, peptides, DNA, RNA, antibodies, antigens, enzymes, bacteria, redox molecules, host molecules, guest molecules, haptens, lipids, microbes, sugars and aptamers, maleimide and NHS ester.
  • the present invention provides a polymer comprising: a structural unit (A), a structural unit ( ⁇ '), and a structural unit (C).
  • the polymer comprises 20-40 mol% of structural unit (A), 20-40 mol% of structural unit ( ⁇ '), and 20-40 mol% of structural unit (C).
  • the structural unit (A), structural unit ( ⁇ '), and structural unit (C) have a composition represented by the following formulas, respectively:
  • Y ferrocene or its derivatives
  • Z a carboxylic acid group, a carboxylate group, a sulfonic group or a sulfonate group
  • R 2 a divalent organic group
  • R 4 a divalent organic group
  • m 1 or 2
  • n 1 or 2
  • p 2 to 20
  • q 2 to 20.
  • the divalent organic group referenced above may be a 1 -10C alkylene group, which may contain one or more hetero atoms or one or more unsaturated bonds,
  • p may further optionally be of 2 to 5, and/or q may optionally be 2 to 5.
  • the polymer may comprise 25-35 mol% of structural unit ( ⁇ '), 25-35 mol% of structural unit ( ⁇ '), and 25-35 mol% of structural unit (C), according to optional embodiments.
  • the present invention provides a polymer comprising: a backbone having a conjugated polymer; a first side chain attached to the backbone, the first side chain having a ferrocene group or a derivative thereof; a second side chain attached to the backbone, the second side chain having an organic acid, a salt of an organic acid, or quaternary ammonium; and at least one of the first and second side chains having at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the conjugated polymer may optionally comprise at least one of: a polythiophene, a polyaniline, a polyacetylene, a poly(p-phenylene), a polypyrrole or derivatives thereof.
  • the first chain can optionally include 5 to 40 atoms between the ferrocene group or derivative thereof and the conjugated polymer backbone.
  • the first chain may further optionally comprise 10 to 30 atoms between the ferrocene group or derivative thereof and the conjugated polymer backbone.
  • the first side chain can optionally include 5 to 40 atoms between the organic acid, salt of an organic acid or quaternary ammonium and the conjugated polymer backbone.
  • the first side chain may further optionally comprise 10 to 30 atoms between the organic acid, salt of an organic acid or quaternary ammonium and the conjugated polymer backbone.
  • Fig. 1 A is an initial cyclic voltammetry curve for 2.5 mg of Polymer 1 in 1 ml_ of 0.1 M PBS buffer, measured using a glassy carbon electrode.
  • Fig. 1 B are cyclic voltammetry curves for a Polymer 1 film formed on a glassy carbon electrode in 0.1 M PBS buffer, where the two curves correspond to a CV scan before sonication (solid line) and a CV scan after 10 minutes of sonication (broken line) in the PBS buffer.
  • Fig. 2 is a cyclic voltammetry curve for 1 .5 mg of Polymer 2 in 1 mL of 0.1 M KCIO 4 .
  • Fig. 3A is an initial cyclic voltammetry curve for Polymer 3 in PBS buffer (2.5 mg/ml), measured using a glassy carbon electrode.
  • Fig. 3B is a cyclic voltammetry curve for a Polymer 3 film formed on a glassy carbon electrode in 0.1 M PBS buffer.
  • Fig. 4 is a cyclic voltammetry curve for 2 mg of Polymer 4 in 10 mL of 0.1 M PBS buffer, measured using a glassy carbon electrode.
  • Fig.5 is a cyclic voltammetry (CV) curve of Polymer 5 in 0.1 M PBS buffer ( ⁇ 2mg/1 ml_) using glassy carbon electrode, which shows its redox activity in a low potential range (0-0.2V).
  • redox mediator refers to a chemical moiety capable of undergoing oxidation or reduction through electron transfer with an electrode and with a redox enzyme.
  • redox mediator macromolecular materials refers to a polymer modified with a redox mediator.
  • reactive site refers to a functional group capable of reacting with another functional group.
  • An exemplary embodiment of the invention described in the application is a series of water-soluble conjugated polymers having redox mediators and functional groups on flexible side chains.
  • the present invention provides a polymer comprising at least one repeating unit selected from repeating unit (A), repeating unit (B) and repeating unit (C).
  • the present invention provides a polymer comprising at least one repeating unit (A) and at least one repeating unit (B) or a polymer comprising at least one repeating unit (A) and at least one repeating unit (C).
  • the present invention provides a polymer comprising at least one repeating unit (A), at least one repeating unit (B) and at least one repeating unit (C).
  • the repeating units may be conjugated via a single, double or triple bond.
  • Repeating unit (A) is one or more monomers selected from Table 1 ;
  • repeating unit (B) is one or more monomers selected from Table 2; and repeating unit (C) is one or more monomers selected from Table 3.
  • R OH, Br, I, CI, SH, COOH, SO 3 H, NH 2 , ⁇ + (R 1 ) 3 , YRiCOOH, YRTSOSH, maleimide, NHS ester, YF ⁇ L, COONa, SO 3 Na, COOK, SO 3 K, YF ⁇ COONa, YR1 SO 3 Na, YRTCOOK or YF ⁇ SC ⁇ K;
  • Y C, O, S or N;
  • Ri alkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl, and Ri can be the same or different;
  • L carbohydrates, proteins, peptides, DNA, RNA, antibodies, antigens, enzymes, bacteria, redox molecules, host molecules, guest molecules, haptens, lipids, microbes, sugars and aptamers, maleimide or NHS ester.
  • R OH, Br, I, CI, SH, COOH, SO 3 H, NH 2 , ⁇ + (R 1 ) 3 , YRiCOOH, YRTSOSH, maleimide, NHS ester, YR 1 L, COONa, SO 3 Na, COOK, SO 3 K, YF ⁇ COONa, YR1 SO 3 Na, YRTCOOK or YR ⁇ O 3 K;
  • Y C, O, S or N;
  • X a single bond, C1 -C20 alkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl;
  • M substituted ferrocene or ferrocene derivatives
  • R OH, Br, I, CI, SH, COOH, SO 3 H, NH 2 , ⁇ + (R 1 ) 3 , YR1COOH, YRTSOSH, maleimide, NHS ester, YR ⁇ , COONa, SO 3 Na, COOK, SO 3 K, YR ⁇ OONa,
  • R-i an alkyl, aryl, substituted aryl, heteroaryl or substituted heteroaryl, and R-i can be the same or different;
  • L carbohydrates, proteins, peptides, DNA, RNA, antibodies, antigens, enzymes, bacteria, redox molecules, host molecules, guest molecules, haptens, lipids, microbes, sugars and aptamers, maleimide or NHS ester.
  • the present invention provides a polymer comprising: a backbone having a conjugated polymer; a first side chain attached to the backbone, the first side chain having a ferrocene group or a derivative thereof; a second side chain attached to the backbone, the second side chain having an organic acid, a salt of an organic acid, or quaternary ammonium; and at least one of the first and second side chains having at least one of a caron atom, a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the conjugated polymer may comprise at least one of: a polythiophene, a polyaniline, a polyacetylene, a poly(p-phenylene), a polypyrrole, or derivatives thereof.
  • the first chain may have 5 to 40 atoms between the ferrocene group and the conjugated polymer backbone. At least one of the first and second side chains can optionally comprise an ethylene oxide group.
  • the second side chain may optionally comprise a carboxylic acid group, a carboxylate group, a sulfonic acid group or a sulfonate group.
  • the versatile ferrocene-functionalized water-soluble polythiophenes can be obtained after post-functionalizing polymer precursors with functional molecules.
  • the polymers are soluble in water and various buffers and show good redox activity in various detection buffers.
  • the solubility of the polymers in water may be more than 0.8 g/100 g at 25°C, preferably more than 1 .0 g/100 g at 25°C, more preferably more than 2.0 g/100 g at 25°C, and still more preferably more than 3.0 g/100 g at 25°C, where the concentration is a measure of the amount of polymer with respect to the amount of water.
  • the solubility of the polymer in water may be less than 100 g /100 g at 25°C.
  • Synthesis Example 1 Synthesis of Polymer 1 , which is represented by the following structural formula, is shown in Schemes 1 to 3:
  • Scheme 1 illustrates the synthesis of monomer 1 : 2,5-dibromo (2-(2-(2-bromoethoxy)ethoxy)ethoxy)thiophene.
  • Scheme 3 shows the co-polymerization of monomer 1 , thiophene- 2,5-diboronic acid and monomer 2 to produce polymer 1 precursor and polymer 1.
  • the polymer 1 precursor was then dissolved in anhydrous DMF, and 2 equivalents of K2CO3 and 2 equivalents of sodium 2-mercaptoethanesulfonate were added. The mixture was stirred at room temperature for about 16 hrs, and transferred into a dialysis tube (CO 12,000) for dialysis against water. After dialysis, the solution in the dialysis tube was filtered to remove insoluble impurities and then freeze-dried to give polymer 1 .
  • Polymer 1 is highly soluble in water, and also soluble in various buffers. Solubility in water of Polymer 1 is more than 3 g/100g.
  • cyclic voltammetry was carried out in a solution of 2.5 mg of Polymer 1 dissolved in 1 mL 0.1 M PBS buffer using a glassy carbon electrode.
  • Fig. 1 A is a first CV scan for Polymer 1 , which shows the redox peaks of the mediator ferrocenes. After the CV scans, a Polymer 1 film was formed on the electrode surface.
  • Fig. 1 B are the CV curves of the Polymer 1 film before (solid line) and after 10 minutes of sonication in PBS buffer (broken line), which shows the Polymer 1 film is quite stable and also has good redox activity.
  • the polymer 1 precursor was dissolved in anhydrous DMF, and then 2 equivalents of K2CO3 and 2 equivalents of sodium 2-mercaptoacetate were added. The mixture was stirred at room temperature for about 16 hrs, and then transferred into a dialysis tube (CO 12,000) for dialysis against water. After dialysis, the solution in the dialysis tube was filtered to remove insoluble impurities and then freeze-dried to give polymer 2.
  • Polymer 2 is highly soluble in water, and various buffers.
  • the solubility of Polymer 2 in water is more than 3 g/100 g.
  • the cyclic voltammetry curve of Polymer 2 is similar to that of polymer 1 in a 0.1 M PBS buffer, as shown in Fig. 2.
  • Polymer 2 also has reactive sites (-COOH), which can be used to further couple with other substrates like enzymes.
  • Scheme 7 shows the co-polymerization of monomer 3, thiophene- 2,5-diboronic acid and monomer 4 to produce polymer 3 precursor and polymer 3.
  • the polymer 3 precursor was then dissolved in anhydrous DMF, and 2 equivalents of K 2 C0 3 and 2 equivalents of sodium 2-mercaptoethanesulfonate were added. The mixture was stirred at room temperature for about 16 hrs, and then transferred into a dialysis tube (CO 12,000) for dialysis against water. After dialysis, the solution in the dialysis tube was filtered to remove insoluble impurities and then freeze-dried to give polymer 3.
  • Polymer 3 is highly soluble in water, and also soluble in various buffers. Solubility of Polymer 3 in water is more than 3 g/100 g.
  • cyclic voltammetry was carried out in a solution of 2.5 mg of Polymer 3 in 1 ml_ of 0.1 M PBS buffer using a glassy carbon electrode.
  • Fig. 3A is the initial CV curve for Polymer 3, which shows the redox peaks of the mediator ferrocenes. After CV scans, a Polymer 3 film was formed on an electrode surface.
  • Fig. 3B shows the CV curves of the Polymer 3 film in PBS buffer, which shows Polymer 3 film has good redox activity.
  • the polymer 3 precursor was dissolved in anhydrous DMF, and 2 equivalents of K 2 CO 3 and 2 equivalents of sodium 2-mercaptoacetate were added. The mixture was stirred at room temperature for about 16 hrs, and then transferred into a dialysis tube (CO 12,000) for dialysis against water. After dialysis, the solution in the dialysis tube was filtered to remove insoluble impurities and then freeze-dried to give Polymer 4.
  • Polymer 4 is highly soluble in water and various buffers, and its cyclic voltammetry curve is similar to that of polymers 1 , 2 and 3 in buffer, as shown in Fig. 4. Polymer 4 also has reactive sites (-COOH), which can be used to couple with other substrates, e.g., enzymes.
  • -COOH reactive sites
  • Scheme 1 1 shows the synthesis of polymer 5 precursor.
  • mercaptoethanesulfonate (1 .Og, 6.1 mmol) was added a solution of polymer 5 precursor (1.5g) in anhydrous DMF (10ml) under N 2 atmosphere and the mixture was stirred at room temperature for about 24 hrs. Then, a small amount of water (5ml) was added into the mixture and the whole mixture was transferred into dialysis tube (CO 12,000) to perform dialysis in deionized (“Dl”) water. After dialysis, the clear water solution (about 1 .5g polymer 5 in 20ml Dl H 2 O) in the dialysis tube went through a filter (0.1 pm) and the filtered solution was then freeze-dried to give polymer 5.
  • Polymer 5 is highly soluble in water and various buffers, for example 50mg polymer 5 can easily dissolve in 1 ml Dl water or 0.1 M PBS buffer to give a clear yellow solution.
  • Fig.5 is a cyclic voltammetry (CV) curve of Polymer 5 in 0.1 M PBS buffer ( ⁇ 2mg/1 ml_) using glassy carbon electrode, which shows its redox activity in a low potential range (0-0.2V).
  • the polymers discussed in this application can be used as sensor interface materials for various biosensor developments. Also, due to their easy processibility in water and buffers, the sensors can be fabricated using already established drop casting or printing technology, and thus, these sensors can be mass produced easily.
  • the redox mediator macromolecular materials of this application can also be used to functionalize other electro-conductive materials to create new materials with functional surfaces for other applications like implantable materials.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne une série de polymères conjugués solubles dans l'eau présentant des médiateurs redox et des groupes fonctionnels sur des chaînes latérales flexibles. Les polymères peuvent comprendre un squelette présentant un polymère conjugué ; une première chaîne latérale fixée au squelette, la première chaîne latérale présentant un groupe ferrocène ou un dérivé correspondant ; une deuxième chaîne latérale fixée au squelette, la deuxième chaîne latérale présentant un acide organique, un sel d'un acide organique ou un ammonium quaternaire ; et au moins l'une parmi la première et la deuxième chaîne latérale présentant au moins l'un parmi un atome de carbone, un atome d'azote, un atome d'oxygène et un atome de soufre. Du fait de leur activité redox, de la solubilité dans l'eau et de la facilité d'autres couplages avec des espèces fonctionnelles polyvalentes, les polymères discutés dans cette demande peuvent être utilisés en tant que matériaux d'interface de capteur pour diverses mises au point de biocapteurs.
PCT/US2017/048655 2016-08-25 2017-08-25 Polymère soluble dans l'eau fonctionnalisé par un médiateur redox Ceased WO2018039585A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113423755A (zh) * 2019-02-07 2021-09-21 马丁·舍丁 导电氧化还原低聚物
WO2024165749A1 (fr) * 2023-02-10 2024-08-15 N-Ink Ab Synthèse d'un polymère donneur de type p à base d'eau

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020040805A1 (en) * 2000-02-04 2002-04-11 Swager Timothy M. Insulated nanoscopic pathways, compositions and devices of the same
US20070105119A1 (en) * 2003-10-29 2007-05-10 Zhinqiang Gao Method for detecting analytes by means of an analyte/polymeric activator bilayer arrangement
US20120322944A1 (en) * 2010-03-26 2012-12-20 Hitachi Chemical Research Center, Inc. Water soluble near infrared sensing polymers with low band gaps

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020040805A1 (en) * 2000-02-04 2002-04-11 Swager Timothy M. Insulated nanoscopic pathways, compositions and devices of the same
US20070105119A1 (en) * 2003-10-29 2007-05-10 Zhinqiang Gao Method for detecting analytes by means of an analyte/polymeric activator bilayer arrangement
US20120322944A1 (en) * 2010-03-26 2012-12-20 Hitachi Chemical Research Center, Inc. Water soluble near infrared sensing polymers with low band gaps

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MISHRA ET AL.: "Functional Oligothiophenes: Molecular Design for Multidimensional Nanoarchitectures and Their Applications", CHEM. REV., vol. 109, 2009, pages 1141 - 1276, XP055012790 *
VAN STAVEREN ET AL.: "Bioorganometallic Chemistry of Ferrocene", CHEM. REV., vol. 104, 2004, pages 5931 - 5985, XP001217792 *
VELAYUDHAM ET AL.: "Noncovalent Functionalization of Boron Nitride Nanotubes with Poly(p- phenylene-ethynylene)s and Polythiophene", APPLIED MATERIALS AND INTERFACES, vol. 2, 2010, pages 104 - 110, XP055467979 *
ZOTTI ET AL.: "Surface Initiated Polymerization of Thiophene and Pyrrole Monomers on Poly(terthiophene) Films and Ollgothlophene Monolayers", CHEM. MATER., vol. 17, 2005, pages 3681 - 3694, XP055467976 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113423755A (zh) * 2019-02-07 2021-09-21 马丁·舍丁 导电氧化还原低聚物
WO2024165749A1 (fr) * 2023-02-10 2024-08-15 N-Ink Ab Synthèse d'un polymère donneur de type p à base d'eau
WO2024165176A1 (fr) * 2023-02-10 2024-08-15 N-Ink Ab Synthèse d'un polymère donneur de type p à base d'eau

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