KR102399647B1 - Metal complex based on gallic acid-introduced copolymer and electrode comprising the same - Google Patents

Abstract

The present invention relates to a gallic acid-introduced copolymer-based metal complex and an electrode comprising the same. When the gallic acid-introduced copolymer-based metal complex according to the present invention is used as an electron transfer medium applied to electrodes such as biosensors and biofuel cells, Compared to the conventional polymer-based metal complex in which gallic acid is not introduced, it has an increased signal, stable current flow, and improved adhesion stability with an electrode, so it can be applied to a biosensor, a biofuel cell, and the like.

Description

Metal complex based on gallic acid-introduced copolymer and electrode comprising the same

The present invention relates to a gallic acid-introduced copolymer-based metal complex and an electrode comprising the same, and the electrode may be used in a biosensor, a biofuel cell, and the like.

The electrochemical biosensor generally refers to a device that detects various analytes in the field of environment, biology, medicine, etc., and there is a biosensor that detects analytes such as glucose, cholesterol, and amino acids from human body fluid. do.

Currently, a commercialized electrochemical biosensor has a structure in which a glucose oxidase is immobilized on an electrode capable of converting an electrical signal by a chemical or physical method.

This electrochemical biosensor is based on the principle of measuring the concentration of glucose in the analyte by measuring the current generated by transferring electrons generated when glucose in the analyte is oxidized by an enzyme to the electrode.

However, in the case of a biosensor using an enzyme electrode, since the distance from the active center of the enzyme is too far, it is not easy to directly transfer electrons generated by oxidation of the substrate to the electrode. Therefore, an oxidation/reduction mediator, that is, an electron transport mediator, is essential to facilitate this electron transport reaction.

Recently, the conversion of a disposable biosensor to a multi-use biosensor for real-time monitoring has been in the spotlight. In order to realize this, a polymer-based electron transporter should be used instead of the conventional monomeric electron transport mediator.

Osmium polymer is known as a suitable candidate for a multi-use biosensor, and many researchers are researching new osmium polymers, but technology development is required for increased signal, stable current flow, and improved adhesion stability with electrodes. there is.

Patent Publication No. 10-2020-0011110

It is an object of the present invention to provide a metal complex based on a gallic acid introduced copolymer or a chloride thereof.

Another object of the present invention is to provide a method for preparing the gallic acid-introduced copolymer-based metal complex.

Another object of the present invention is to provide a reagent composition for redox reaction comprising the gallic acid-introduced copolymer-based metal complex.

Another object of the present invention is to provide an electrode coated with a reagent composition for redox reaction.

Another object of the present invention is to provide a biosensor including the electrode.

Another object of the present invention is to provide a biofuel cell including the electrode.

Another object of the present invention is to provide a cell culture device including the biofuel cell.

Gallic acid introduced copolymer based metal complex or chloride thereof

The present invention relates to a first monomer having a functional group capable of forming a bond by condensation reaction with a carboxyl group;

a second monomer having a functional group capable of forming a coordination bond with the metal complex;

a gallic acid moiety represented by the following Chemical Formula 1, which is bound to a functional group of the first monomer; and

and a metal complex moiety represented by the following formula 2A, which is bonded to the functional group of the second monomer;

wherein the gallic acid moiety is introduced into some of the repeating units of the first monomer,

The metal complex moiety is characterized in that it is introduced into some of the repeating units of the second monomer,

The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.05-50,

A metal complex based on a gallic acid introduced copolymer or a chloride thereof is provided.

[Formula 1]

[Formula 2A]

(In Formula 2A,

R ¹ to R ⁴ are independently hydrogen, C _1-10 linear or branched alkyl, C _1-10 straight or branched alkoxy, halogen, carboxyl or amine, preferably R ¹ to R ⁴ are independently hydrogen , C _1-5 straight-chain or branched alkyl, C _1-5 straight-chain or branched alkoxy, halogen, carboxyl or amine;

M is osmium (Os), ruthenium (Ru) or iron (Fe);

X is halogen.)

The gallic acid-introduced copolymer-based metal complex according to the present invention can be used as an electron transport medium for redox reactions, and an important factor in electrochemical properties is the equivalent ratio of the metal complex moiety to the gallic acid moiety.

The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.05-50, preferably 1:0.1-30, 1:0.1-20, 1:0.2-10, 1:0.25-5, particularly preferably 1 :0.3-0.7. If the equivalent of the gallic acid moiety is excessive compared to the metal complex moiety, the signal strength of the current increases but there may be a problem that current stability is lowered. The effect of increase of , increase of current stability, and improvement of adhesion with the electrode may be insignificant.

For reference, the ratio of the first monomer and the second monomer constituting the main chain of the copolymer does not significantly affect the electrochemical properties even if freely set, which is a gallic acid moiety only in part of the repeating unit of the first monomer This is because the t is introduced, and also the metal complex moiety is introduced into only a portion of the repeating units of the second monomer. Accordingly, the ratio of the first monomer and the second monomer may be appropriately set by those skilled in the art in consideration of the yield and the like.

The first monomer may be acrylamide, acrylic acid, methacrylic acid, vinyl acetate, or the like.

The second monomer may be vinylimidazole, vinylpyrrolidone, vinylpyridine, acrylic acid-aminomethylpyridine, allylamine-bromomethylpyridine (allylamine)-bromomethylpyridine) or the like.

The metal complex represented by Formula 2 acts as an electron transfer mediator reacting with an enzyme for an anode or an enzyme for a cathode, and osmium complex, ruthenium complex, iron complex, etc. commonly used in the art may be used. Specifically, Os(dimethoxy-bipyridine) ₂ Cl ₂ , Os(dichloro-bipyridine) ₂ Cl ₂ , Os(dimethyl-bipyridine) ₂ Cl ₂ , Os(dicarboxyl-bipyridine) ₂ Cl ₂ , Os(diamine-bipyridine) ₂ Cl ₂ , Ru(dimethoxy-bipyridine) ₂ Cl ₂ , Ru(dichloro-bipyridine) ₂ Cl ₂ , Ru(dimethyl-bipyridine) ₂ Cl ₂ , Ru(dicarboxyl -bipyridine) ₂ Cl ₂ , Ru (diamine-bipyridine) ₂ Cl ₂ , Fe (dimethoxy-bipyridine) ₂ Cl ₂ , Fe (dichloro-bipyridine) ₂ Cl ₂ , Fe (dimethyl-bipyridine) ₂ Cl ₂ , Fe (dicarboxyl-bipyridine) ₂ Cl ₂ , Fe (diamine-bipyridine) ₂ Cl ₂ and the like can be used, and in the present invention, as an example, Os (dimethoxy-bipyridine) ₂ Cl ₂ is used did In the metal complex, a functional group of the second monomer may form a coordination bond at a position where one chlorine (Cl) is omitted.

Preferably, the gallic acid-introduced copolymer-based metal complex may be a compound represented by the following formula (3).

[Formula 3]

(In Formula 3,

n and m are each an integer from 1-100,000;

또는

이고;Fn ¹ is

or

ego;

또는

이고,Fn ² is

or

ego,

R ¹ to R ⁴ are each hydrogen, C _1-10 linear or branched alkyl, C _1-10 straight or branched alkoxy, halogen, carboxyl or amine, preferably R ¹ to R ⁴ are independently hydrogen, C _1-5 straight-chain or branched alkyl, C _1-5 straight-chain or branched alkoxy, halogen, carboxyl or amine;

M is osmium (Os), ruthenium (Ru) or iron (Fe),

X is halogen).

Manufacturing method

The present invention comprises the steps of polymerizing a first monomer having a functional group capable of forming a bond by condensation reaction with a carboxyl group and a second monomer having a functional group capable of forming a coordination bond with a metal complex to obtain a copolymer (step 1);

reacting the copolymer obtained in step 1 with the metal complex represented by the following formula 2B (step 2); and

Including; reacting the reactant obtained in step 2 with gallic acid (step 3);

The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.05-50,

Provided is a method for preparing a metal complex based on a gallic acid-introduced copolymer.

[Formula 2B]

(In Formula 2B,

R ¹ to R ⁴ are independently hydrogen, C _1-10 linear or branched alkyl, C _1-10 straight or branched alkoxy, halogen, carboxyl or amine, preferably R ¹ to R ⁴ are independently hydrogen , C _1-5 straight-chain or branched alkyl, C _1-5 straight-chain or branched alkoxy, halogen, carboxyl or amine;

M is osmium (Os), ruthenium (Ru) or iron (Fe);

X is halogen.)

In step 1, water, C _1-3 alcohol, ethylene glycol, a mixture thereof, etc. may be used as a solvent,

In step 2, water, C _1-3 alcohol, ethylene glycol, a mixture thereof, etc. may be used as a solvent,

In step 3, MES (2-(N-morpholino)ethanesulfonic acid) buffer, PBS (Phosphate buffered saline), Tris ((hydroxymethyl)aminomethane) buffer, a mixture thereof, etc. may be used as a solvent.

In step 1, TEME (N,N,N',N'-tetramethyl ethylenediamin), ammonium persulfate, etc. may be additionally used as a catalyst,

In step 2, hydrochloric acid (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), etc. may be additionally used as a catalyst,

In step 3, EDC (1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide), NHS (N-hydroxy succinimide), etc. may be additionally used as a catalyst.

Reagent composition for redox reaction

The present invention relates to a metal complex or a chloride thereof based on the gallic acid introduced copolymer of claim 1 as an electron transport medium; and an oxidoreductase; provides a reagent composition for a redox reaction, including.

The oxidoreductase is

glucose oxidase (GOX or GOD), glucose dehydrogenase (GDH), lactate oxidase (uricase; UOX), lactate dehydrogenase (LDH), galactose oxidase; GAOX), cellobiose dehydrogenase (CDH), fructose dehydrogenase, alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH), formic acid dehydrogenase enzymes for oxidation electrodes, such as formate dehydrogenase, oxalate oxidase, pyruvate dehydrogenase (PDH), and membrane-bound hydrogenase (MBH); and

Bilirubin oxidase (BOD), Laccase, horseradish peroxidase (HRP), catalase (CAT), cytochrome c (CYCS), cytochrome oxidase; COX) and enzymes for reduction electrodes, such as microperoxidase (MP-11); It can be used individually or in mixture of 2 or more types.

The composition is polyethylene glycol diglycidyl ether, poly (dopamine), poly (vinyl pyridine), poly (vinylimidazole), poly (acrylamide), poly (ethylene glycol), poly (ethyleneimine), poly A crosslinking agent such as vinylpyrrolidone or Nafion may be further included alone or in a mixture of two or more.

electrode

The present invention provides an electrode, characterized in that the reagent composition for redox reaction is applied.

The electrode may be an anode or a cathode.

The electrode may be an electrode including carbon black, carbon nanotubes, graphene, graphite, gold, silver, copper, platinum, iron, or a composite thereof.

biosensor

The present invention provides a biosensor comprising the electrode.

The biosensor may use any known configuration, and only the electrode is replaced with the electrode according to the present invention.

The biosensor can sense glucose, cholesterol, dopamine, DNA, RNA, amino acids, etc. alone or two or more types simultaneously in the sample.

biofuel cell

The present invention provides a biofuel cell comprising the electrode.

The biofuel cell can use any known configuration, and is characterized in that only the electrode is replaced with the electrode according to the present invention.

cell culture device

The present invention provides a cell culture device comprising the biofuel cell.

The cell culture apparatus can use any known configuration, it is characterized in that only the electrode is replaced with the electrode according to the present invention.

When the gallic acid-introduced copolymer-based metal complex according to the present invention is used as an electron transport medium applied to electrodes such as biosensors and biofuel cells, increased signal strength and stable There is an effect of improving the stability of the current flow and adhesion to the electrode.

1 is a reaction scheme for the preparation of a gallic acid-introduced copolymer-based osmium complex according to Example 1 of the present invention.
Figure 2 is ¹ H NMR data according to the PAA ratio in the PAA-PVI copolymer, it appears that as the PAA monomer ratio increases, the hydrogen ratio near 6.4 ppm compared to the ratio near 6.8 ppm increases, the hydrogen concentration due to the increase in the PAA monomer ratio It can be seen that the ratio increases.
3 is a cyclic voltammetry result confirming the redox potential of the PAA-PVI copolymer-based osmium complex in the state before the introduction of gallic acid, it can be confirmed that it has the characteristics of the redox potential at 0.0V (vs. Ag/AgCl). .
4 is a cyclic voltammetry result confirming the oxidation-reduction potential of the gallic acid-introduced copolymer-based osmium complex according to the Example, confirming that it has a characteristic of the redox potential at 0.0 V (vs. Ag/AgCl), compared with FIG. 3 It can be seen that there is no potential change due to the introduction of gallic acid.
5 is ¹ H NMR data of a copolymer-based osmium complex prepared by varying the gallic acid (GA) introduction ratio. As the ratio of gallic acid (GA) to 1 equivalent of the osmium complex increases from 0 to 0.5 to 50 equivalents, the NMR peak It can be confirmed that gallic acid formed a covalent bond in the PAA monomer of the PAA-PVI copolymer by seeing that the difference in hydrogen ratio around 1.6 and 2.2 ppm changes sequentially.
6 is FT-IR data of a copolymer-based osmium complex prepared by varying the gallic acid (GA) introduction ratio. A broad band of OH appearing in 3300 to 3400 shows that the ratio of gallic acid (GA) to 1 equivalent of the osmium complex is 0 to It can be confirmed that gallic acid forms a covalent bond in the PAA monomer of the PAA-PVI copolymer by looking at the increase as it increases to 0.5 and 50 equivalents.
7 to 9 show the linearity of the response according to the glucose concentration in the electrode coated with the gallic acid-introduced copolymer-based osmium complex of Example 1, wherein the ratio of gallic acid (GA) to 1 equivalent of the osmium complex is 0 to 0.5 and 50 equivalents. is the indicated result.
10 is a current-time amperometry result comparing the current value change for 1 hour in order to evaluate the current signal increase and stability according to the gallic acid introduction ratio, a copolymer-based osmium complex (conventional material) in which gallic acid (GA) is not introduced. Corresponding to), it can be confirmed that the electrode coated with the osmium complex based on the gallic acid-introduced copolymer of 0.5 equivalent ratio exhibits about twice the current signal intensity and at the same time the intensity of the current is constantly stable for 1 hour, and also the 50 equivalent ratio of gallic acid The electrode coated with the introduced copolymer-based osmium complex showed a high signal, but the current signal continuously decreased for 1 hour and showed unstable results, suggesting that an appropriate gallic acid (GA) concentration is important.
11 is a result of measuring the current signal after washing the electrode with water in order to evaluate the electrode adhesion stability according to the gallic acid introduction ratio, a copolymer-based osmium complex (corresponding to the conventional material) in which gallic acid (GA) is not introduced is applied The current strength of the electrode coated with the gallic acid-introduced copolymer-based osmium complex of 0.5 equivalent ratio compared to that of the used electrode was about 10% higher or more, confirming that the electrode attachment stability was improved.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited by the following examples.

<Example 1> Preparation of osmium complex based on gallic acid introduced copolymer

As shown in the reaction scheme shown in FIG. 1, a gallic acid-introduced copolymer-based osmium complex corresponding to the final compound was synthesized through a three-step reaction.

[Step 1] is 1:1, 1:3, 1:5, 1:7, 1:10, 1:15, 1:20, 1 of vinyl imidazole (monomer of PVI) and acrylamide (monomer of PAA), respectively. It was synthesized in a ratio of :30, 1:50, and 1:100.

The copolymer used in the experimental example of the present invention was used to prepare PAA-PVI (10:1 ratio). Hereinafter, all of the PAA-PVI copolymers refer to those prepared in a ratio of 10:1. Specifically, 0.509 mL of vinyl imidazole was placed in a round flask with 3.9907 g of acylamide and dissolved in 15 mL of water. For the reaction, 0.069 mL of catalyst TEME (N,N,N',N'-tetramethyl ethylenediamin) and 0.06 g of ammonium persulfate were mixed with 20 mL of DW and added to a round flask. The reaction was stirred for about 30 minutes, and the compound was precipitated in methanol and then vacuum dried at 60° C. to obtain a PAA-PVI copolymer in powder form (4.0943 g, 90.6%). ¹ H NMR data of the PAA-PVI copolymer prepared in step 1 is shown in FIG. 2 .

Figure 2 is ¹ H NMR data according to the PAA ratio in the PAA-PVI copolymer, it appears that as the PAA monomer ratio increases, the hydrogen ratio near 6.4 ppm compared to the ratio near 6.8 ppm increases, the hydrogen concentration due to the increase in the PAA monomer ratio It can be seen that the ratio increases.

In [Step 2], 10 mg of PAA-PVI and 5 mg of the osmium complex (Os(dimethoxy-bipyridine) ₂ Cl ₂ ) were added to 5 mL of ethylene glycol and reacted at 180° C. for 10 minutes. The synthesized solution was re-precipitated in 300 mL of ethyl ether to obtain a powder through a nylon filter.

3 is a cyclic voltammetry result confirming the redox potential of the PAA-PVI copolymer-based osmium complex in the state before the introduction of gallic acid, it can be confirmed that it has the characteristics of the redox potential at 0.0V (vs. Ag/AgCl). .

[Step 3] Put the compound of step 2 (based on 1 equivalent of the osmium complex) and gallic acid (0, 0.5, 50 equivalents) into a round flask, pour 1mL of 50mM MES buffer, and then add 40mM EDC and 20mM NHS for 24 hours reacted. The final compound was obtained through a polymer filter (10,000 molecular weight).

4 is a cyclic voltammetry result confirming the oxidation-reduction potential of the gallic acid-introduced copolymer-based osmium complex according to the Example, confirming that it has a characteristic of the redox potential at 0.0 V (vs. Ag/AgCl), compared with FIG. 3 It can be seen that there is no potential change due to the introduction of gallic acid.

5 is ¹ H NMR data of a copolymer-based osmium complex prepared by varying the gallic acid (GA) introduction ratio. As the ratio of gallic acid (GA) to 1 equivalent of the osmium complex increases from 0 to 0.5 to 50 equivalents, the NMR peak It can be confirmed that gallic acid formed a covalent bond in the PAA monomer of the PAA-PVI copolymer by seeing that the difference in hydrogen ratio around 1.6 and 2.2 ppm changes sequentially.

6 is FT-IR data of a copolymer-based osmium complex prepared by varying the gallic acid (GA) introduction ratio, in which a wide band of OH appearing in 3300 to 3400 shows that the ratio of gallic acid (GA) to 1 equivalent of the osmium complex is 0 It can be confirmed that gallic acid forms a covalent bond in the PAA monomer of the PAA-PVI copolymer by looking at the increase as it increases to 0.5 and 50 equivalents.

<Example 2> Preparation of electrode coated with gallic acid introduced copolymer-based osmium complex

Gallic acid-introduced copolymer-based osmium complex prepared by varying the gallic acid introduction ratio (0, 0.5, 50 equivalents of gallic acid compared to 1 equivalent of osmium complex);

Glucose dehydorgenase enzyme at a concentration of 10 mg/mL; and

PEGDGE crosslinking agent at a concentration of 10 mg/mL;

were mixed at a volume ratio of 4:4:1, respectively, and then 10 μL was cast on a carbon electrode, dried for one day, and then used for the experiment.

<Experimental Example 1> Evaluation of the sensitivity linearity of the electrode according to the concentration of glucose contained in the sample

7 to 9 show the linearity of the response according to the glucose concentration in the electrode coated with the gallic acid-introduced copolymer-based osmium complex of Example 1, wherein the ratio of gallic acid (GA) to 1 equivalent of the osmium complex is 0 to 0.5 and 50 equivalents. is the indicated result.

As shown in FIG. 7, in the case of the copolymer-based osmium complex without gallic acid (GA) introduced, it exhibited a linearity of 0.91818,

As shown in FIG. 8, in the case of an osmium complex based on a copolymer introduced with gallic acid in an equivalent ratio of 0.5, a linearity of 0.96701 was exhibited,

As shown in FIG. 9 , in the case of an osmium complex based on a copolymer introduced with gallic acid in a 50 equivalent ratio, a linearity of 0.90999 was shown.

7 to 9 , it can be confirmed that the glucose response linearity of the osmium complex based on the gallic acid introduced copolymer at a 0.5 equivalent ratio is the best.

<Experimental Example 2> Current signal increase and stability evaluation according to the gallic acid introduction rate

The carbon electrode coated with the gallic acid-introduced copolymer-based osmium complex of Example 1 prepared in 0, 0.5, and 50 equivalents of gallic acid relative to 1 equivalent of the osmium complex was rotated at a speed of 500 rpm to examine long-term stability at a glucose concentration of 25 mM.

Specifically, in order to evaluate the increase and stability of the current signal, current-time amperometry was measured comparing the change in the current value for 1 hour, and it was measured with PBS for the first 300 seconds, and then 25 mM glucose concentration was added at the 300 second time point. .

10 is a current-time amperometry result comparing the current value change for 1 hour to evaluate the current signal increase and stability according to the gallic acid introduction ratio, a copolymer-based osmium complex (conventional material) in which gallic acid (GA) is not introduced. Corresponding to), it can be confirmed that the electrode coated with the osmium complex based on the gallic acid-introduced copolymer of 0.5 equivalent ratio exhibits about twice the current signal intensity and at the same time the intensity of the current is constantly stable for 1 hour, and also the 50 equivalent ratio of gallic acid The electrode coated with the introduced copolymer-based osmium complex showed a high signal, but the current signal continuously decreased for 1 hour and showed an unstable result, suggesting that an appropriate gallic acid (GA) concentration is important.

<Experimental Example 3> Electrode adhesion stability evaluation according to gallic acid introduction rate

The carbon electrode coated with the gallic acid-introduced copolymer-based osmium complex of Example 1 prepared at 0 and 0.5 equivalents of gallic acid compared to 1 equivalent of the osmium complex was washed with water 1 to 4 times, and then the current signal was measured.

11 is a result of washing the electrode with water and then measuring the current signal in order to evaluate the electrode adhesion stability according to the gallic acid introduction ratio. A copolymer-based osmium complex (corresponding to a conventional material) in which gallic acid (GA) is not introduced is applied. The current strength of the electrode coated with the gallic acid-introduced copolymer-based osmium complex of 0.5 equivalent ratio compared to that of the used electrode was about 10% higher or more, confirming that the electrode attachment stability was improved.

So far, with respect to the present invention, the preferred embodiments have been looked at. Those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (22)

a first monomer having a functional group capable of forming a bond by condensation reaction with a carboxyl group;
a second monomer having a functional group capable of forming a coordination bond with the metal complex;
a gallic acid moiety represented by the following Chemical Formula 1, which is bound to a functional group of the first monomer; and
and a metal complex moiety represented by the following formula 2A, which is bonded to the functional group of the second monomer;
wherein the gallic acid moiety is introduced into some of the repeating units of the first monomer,
The metal complex moiety is characterized in that it is introduced into some of the repeating units of the second monomer,
The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.05-50,
A metal complex based on a gallic acid introduced copolymer or a chloride thereof.
[Formula 1]

[Formula 2A]

(In Formula 2A,
R ¹ to R ⁴ are independently hydrogen, C _1-10 straight or branched chain alkyl, C _1-10 straight or branched alkoxy, halogen, carboxyl or amine;
M is osmium (Os), ruthenium (Ru) or iron (Fe);
X is halogen.)
According to claim 1,
The equivalence ratio of the metal complex moiety and the gallic acid moiety is 1:0.1-30.
3. The method of claim 2,
The equivalence ratio of the metal complex moiety and the gallic acid moiety is 1:0.1-20.
4. The method of claim 3,
The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.2-10, characterized in that the gallic acid introduced copolymer-based metal complex or a chloride thereof.
5. The method of claim 4,
The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.25-5, characterized in that the gallic acid introduced copolymer-based metal complex or a chloride thereof.
According to claim 1,
The first monomer is characterized in that acrylamide, acrylic acid, methacrylic acid, or vinyl acetate, a gallic acid-introduced copolymer-based metal complex or a chloride thereof.
According to claim 1,
The second monomer is vinylimidazole, vinylpyrrolidone, vinylpyridine, Acrylic acid-aminomethylpyridine (acrylic acid-aminomethylpyridine), or allylamine-bromomethylpyridine (allylamine)-bromomethylpyridine), a gallic acid-introduced copolymer-based metal complex or a chloride thereof.
According to claim 1,
The gallic acid-introduced copolymer-based metal complex is characterized in that represented by the following formula (3), a gallic acid-introduced copolymer-based metal complex or a chloride thereof.
[Formula 3]

(In Formula 3,
n and m are each an integer from 1-100,000;
Each Fn ¹ is

and

are each independently selected from the group consisting of, and at least one Fn ¹ of Fn ¹ is

will be;
Each Fn ² is

and

are each independently selected from the group consisting of, and at least one Fn ² of Fn ² is

will be;
R ¹ to R ⁴ are each hydrogen, C _1-10 straight-chain or branched alkyl, C _1-10 straight-chain or branched alkoxy, halogen, carboxyl or amine;
M is osmium (Os), ruthenium (Ru) or iron (Fe);
X is halogen).
obtaining a copolymer by polymerizing a first monomer having a functional group capable of forming a bond by condensation reaction with a carboxyl group and a second monomer having a functional group capable of forming a coordination bond with a metal complex (step 1);
reacting the copolymer obtained in step 1 with the metal complex represented by the following formula 2B (step 2); and
Including; reacting the reactant obtained in step 2 with gallic acid (step 3);
The equivalent ratio of the metal complex moiety and the gallic acid moiety is 1:0.05-50,
A method for preparing a metal complex based on a gallic acid-introduced copolymer.
[Formula 2B]

(In Formula 2B,
R ¹ to R ⁴ are independently hydrogen, C _1-10 straight or branched chain alkyl, C _1-10 straight or branched alkoxy, halogen, carboxyl or amine;
M is osmium (Os), ruthenium (Ru) or iron (Fe);
X is halogen.)
10. The method of claim 9,
In step 1, water, C _1-3 alcohol, ethylene glycol, or a mixture thereof is used as a solvent.
10. The method of claim 9,
In step 2, water, C _1-3 alcohol, ethylene glycol, or a mixture thereof is used as a solvent.
10. The method of claim 9,
In step 3, MES (2-(N-morpholino)ethanesulfonic acid) buffer, PBS (Phosphate buffered saline), Tris ((hydroxymethyl)aminomethane) buffer or a mixture thereof is used as a solvent as a solvent, Gallic acid introduced copolymer A method for preparing a base metal complex.
As an electron transport medium, the gallic acid-introduced copolymer-based metal complex of claim 1 or a chloride thereof; and
Including; oxidoreductase;
Reagent composition for redox reaction.
14. The method of claim 13,
The oxidoreductase is
glucose oxidase (GOX or GOD), glucose dehydrogenase (GDH), lactate oxidase (uricase; UOX), lactate dehydrogenase (LDH), galactose oxidase; GAOX), cellobiose dehydrogenase (CDH), fructose dehydrogenase, alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH), formic acid dehydrogenase One or more enzymes for an oxidation electrode selected from formate dehydrogenase, oxalate oxidase, pyruvate dehydrogenase (PDH) and membrane-bound hydrogenase (MBH) ; and
Bilirubin oxidase (BOD), Laccase, horseradish peroxidase (HRP), catalase (CAT), cytochrome c (CYCS), cytochrome oxidase; COX), and at least one enzyme for a reduction electrode selected from microperoxidase (MP-11);
A reagent composition for redox reaction, characterized in that at least one selected from among.
14. The method of claim 13,
The composition is
Polyethylene glycol diglycidyl ether, poly(dopamine), poly(vinylpyridine), poly(vinylimidazole), poly(acrylamide), poly(ethylene glycol), poly(ethyleneimine), polyvinylpyrrolidone and at least one crosslinking agent selected from Nafion.
The electrode, characterized in that the reagent composition for the redox reaction of claim 13 is applied.
17. The method of claim 16,
The electrode is characterized in that the anode or cathode, the electrode.
17. The method of claim 16,
The electrode material is carbon black, carbon nanotubes, graphene, graphite, gold, silver, copper, platinum, iron, and the electrode, characterized in that it comprises at least one of a composite thereof.
A biosensor comprising the electrode of claim 16 .
20. The method of claim 19,
The biosensor is a biosensor, characterized in that it senses one or more of glucose, cholesterol, dopamine, DNA, RNA and amino acids in the sample.
A biofuel cell comprising the electrode of claim 16 .
A cell culture device comprising the biofuel cell of claim 21 .

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