KR102544915B1 - Wireless Cancer Sensor based on ROS and GSH responsive polymer dots embedded hydrogel - Google Patents

Abstract

The present invention relates to a method for manufacturing a polymer dot-based hydrogel sensor for wireless diagnosis that recognizes active oxygen or glutathione, and more particularly, a first step of synthesizing a first compound by substituting functional group 1 based on component A in Formula 1; A second step of synthesizing a second compound, which is a polymer dot crosslinked with diselenide or disulfide, by carbonization synthesis of the component A; a third step of synthesizing a third compound by substitution synthesis of the conductive material functional group Z in the second compound; A fourth step of synthesizing a fourth compound having conductivity and hydrogen bonding strength by carbonizing dopamine or diselenide cross-linked dopamine in the third compound; a fifth step of synthesizing a fifth compound by supporting the fourth compound on the second compound or the third compound through a hydrophobic bond; And a sixth step of including the fifth compound in a matrix to prepare a sixth compound that is a hydrogel.

Description

Manufacturing method of polymer dot-based hydrogel sensor for wireless diagnostics recognizing reactive oxygen species or glutathione {Wireless Cancer Sensor based on ROS and GSH responsive polymer dots embedded hydrogel}

The present invention relates to a method for diagnosing cancer cells by pressure, tension, and electrochemical self-transformation of a hydrogel using a dot-hydrogel, a polymer that is sensitive to the concentration of active oxygen or glutathione.

Cancer remains one of the most devastating threats to human health. In the United States, cancer affects nearly 1.3 million new cases each year and is the second leading cause of death after heart disease, accounting for approximately a quarter of deaths. Cancer is also expected to surpass cardiovascular disease as the number one cause of death within five years. Solid tumors account for most deaths. While significant progress has been made in the medical treatment of certain cancers, overall 5-year survival rates for all cancers have only improved by about 10% over the past 20 years. Malignant solid tumors in particular metastasize and grow rapidly in an uncontrolled manner, making their timely detection and treatment extremely difficult.

Studies in humans with immune checkpoint inhibitors have demonstrated the bright prospects of harnessing the immune system to control and eradicate tumor growth. Programmed Death 1 (PD-1) Receptor and Its Ligand Programmed death-ligand 1 (PD-L1) is an immune checkpoint implicated in the suppression of immune system responses during chronic infections, pregnancy, tissue allografts, autoimmune diseases, and cancer. It is protein. PD-L1 modulates the immune response by binding to the inhibitory receptor PD-1 expressed on the surface of T-cells, B-cells, and monocytes. PD-L1 also negatively regulates T-cell function through interaction with another receptor, B7-1. Formation of the PDL1/PD-1 and PD-L1/B7-1 complex negatively regulates T-cell receptor signaling, resulting in subsequent downregulation of T-cell activation and suppression of anti-tumor immune activity.

Despite significant advances in cancer treatment, improved diagnostic methods are still being sought.

Republic of Korea Patent Publication 10-2019-0134631 Republic of Korea Patent Publication 10-2006-0076182 Republic of Korea Patent Publication 10-2005-0109498 Republic of Korea Patent Publication 10-2019-0134631

Therefore, the present invention has been made to solve the above conventional problems, and according to an embodiment of the present invention, a polymer dot having sensitivity to the concentration of active oxygen or glutathione is synthesized, and a hydrogel containing the polymer dot is utilized The purpose of this study is to apply it to a technique for wirelessly measuring diseases by self-transformation of conductivity, pressure, and tension according to the concentration of active oxygen or glutathione.

On the other hand, the technical problems to be achieved in the present invention are not limited to the above-mentioned technical problems, and other technical problems that are not mentioned will become clear to those skilled in the art from the description below. You will be able to understand.

A first object of the present invention is a method for manufacturing a polymer dot-based hydrogel sensor, comprising: a first step of synthesizing a first compound by substituting functional group 1 based on component A in the following formula (1); A second step of synthesizing a second compound, which is a polymer dot crosslinked with diselenide or disulfide, by carbonization synthesis of the component A; a third step of synthesizing a third compound by substitution synthesis of the conductive material functional group Z in the second compound; A fourth step of synthesizing a fourth compound having conductivity and hydrogen bonding strength by carbonizing dopamine or diselenide cross-linked dopamine in the third compound; a fifth step of synthesizing a fifth compound by supporting the fourth compound on the second compound or the third compound through a hydrophobic bond; And a sixth step of preparing a sixth compound, which is a hydrogel, by including the fifth compound in a matrix; there is.

[Formula 1]

In Formula 1, Y is a copolymer containing any one of COOH, NH ₂ , SH, Br, and Cl functional groups.

And the component A compound is Hyaluronic acid (HA), Pluronic, Polyethylene Glycol (PEG), Poly(2-(dimethylamino) ethyl methacrylate) (PDMA), Polyvinylpyrrolidone (PVP), Alginate, Gelatin, Hydroxypropyl cellulose (HPC), Carboxyl At least one of methylcellulose (CMC), Hydroxypropyl methylcellulose (HPMC), and Polyacrylic acid (PAA), and a molecular weight of 1,000 to 10,000,000 g/mol.

In addition, the functional group 1 may be at least one of dopamine, caffeic acid, 2-bromo-3', 4'-dihydroxy acetophenone, 2-chloro-3', and 4'-dihydroxy acetophenone.

And in the second step and the fourth step, the carbonization reaction may be characterized by applying hydrothermal synthesis at a temperature of 10 to 500 ° C.

In addition, the second compound may be characterized by being represented by Chemical Formula 2 below.

[Formula 2]

In Chemical Formula 2, X is a compound including a functional group of either Se-Se (diselenide bond) or SS (disulfide bond).

In addition, the third compound may be characterized by being represented by Formula 3 below.

[Formula 3]

In Formula 3, the functional group Z includes any one compound of MnO ₂ , Cu ²⁺ , MXene, TiO ₂ , Graphene oxide, polyaniline, and PEDOT in Formula 2, and the content of Z is within 1 to 99%. do.

And the fourth compound may be characterized by being represented by Chemical Formula 4 below.

[Formula 4]

In addition, the composition content of the fourth compound in the fifth compound includes within 1 to 99%, and may be characterized in that it is represented by Chemical Formula 5.

[Formula 5]

And the composition content of the fifth compound in the sixth compound is within 1 to 99%, and the matrix includes at least one of PVA, Alginate, PVP, Collagen, Gelatin, PEG, Pluronic, Dopamine, Tannic acid, and Laponite. that can be characterized.

A second object of the present invention can be achieved as a polymer dot-based hydrogel sensor for wireless diagnosis that recognizes active oxygen or glutathione, characterized in that it is manufactured by the manufacturing method according to the above-mentioned first object.

According to the method for manufacturing a polymer dot-based hydrogel sensor for wireless diagnostics recognizing active oxygen or glutathione according to an embodiment of the present invention, a polymer dot sensitive to the concentration of active oxygen or glutathione is synthesized, and the hydrogel containing the polymer dot is utilized Therefore, it has an effect that can be applied to a technique for wirelessly measuring diseases by conductivity, pressure, and tensile autotransformation according to the concentration of active oxygen or glutathione.

On the other hand, the effects obtainable in the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below. You will be able to.

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and together with the detailed description of the invention serve to further understand the technical idea of the present invention, the present invention is limited only to those described in the drawings. and should not be interpreted.
1 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of polymer dots prepared according to Example 1 of the present invention.
Figure 2 is a graph showing the results of visible light spectroscopy (UV-vis) analysis prepared according to Example 1 of the present invention.
Figure 3 is a graph showing the results of fluorescence spectroscopy (Photoluminescence spectroscopy) analysis by active oxygen of the polymer dot prepared according to Example 3 of the present invention.
4 is a graph showing the results of electrochemical impedance spectroscopy (EIS) analysis according to the type and concentration of cells of the hydrogel prepared according to Example 4 of the present invention.
5 is a graph showing the results of analyzing the amount of change in electrochemical resistance (ΔR/R ₀ ) according to the type of cell and the tensile angle of the hydrogel prepared according to Example 4 of the present invention.
6 is a graph showing the results of analyzing the amount of change in electrochemical resistance (ΔR/R ₀ ) by cell type and pressure strength of the hydrogel prepared according to Example 4 of the present invention.
7 is a result of confirming the resistance change according to the cell type of the hydrogel prepared according to Example 4 of the present invention through a wireless measurement image.
8 is a graph showing the results of viscoelasticity analysis according to the number of images and cell types of self-healing ability of the hydrogel prepared according to Example 4 of the present invention.
Figure 9 is a graph showing the results of self-healing analysis and viscoelasticity analysis by the cell type ratio of the hydrogel prepared according to Example 4 of the present invention.

The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content will be thorough and complete and the spirit of the present invention will be sufficiently conveyed to those skilled in the art.

In this specification, when an element is referred to as being on another element, it means that it may be directly formed on the other element or a third element may be interposed therebetween. Also, in the drawings, the thickness of components is exaggerated for effective description of technical content.

Although terms such as first and second are used to describe various elements in various embodiments of the present specification, these elements should not be limited by these terms. These terms are only used to distinguish one component from another. Embodiments described and illustrated herein also include complementary embodiments thereof.

Terminology used herein is for describing the embodiments and is not intended to limit the present invention. In this specification, singular forms also include plural forms unless specifically stated otherwise in a phrase. The terms 'comprises' and/or 'comprising' used in the specification do not exclude the presence or addition of one or more other elements.

In describing the specific embodiments below, several specific contents are prepared to more specifically describe the invention and aid understanding. However, readers who have knowledge in this field to the extent that they can understand the present invention can recognize that it can be used without these various specific details. In some cases, it is mentioned in advance that parts that are commonly known in describing the invention and are not greatly related to the invention are not described in order to prevent confusion for no particular reason in explaining the present invention.

Hereinafter, a method for manufacturing a polymer dot-based hydrogel sensor for wireless diagnosis recognizing active oxygen or glutathione according to an embodiment of the present invention will be described.

The present invention synthesizes a polymer dot that is sensitive to the concentration of active oxygen or glutathione, and uses a hydrogel containing the polymer dot to wirelessly measure disease by conductivity, pressure, and tensile self-conversion according to the concentration of active oxygen or glutathione. It is characterized by application to.

The production of a polymer dot-based hydrogel sensor for wireless diagnostics recognizing active oxygen or glutathione according to an embodiment of the present invention is, as a whole, the first step of synthesizing a first compound by substituting functional group 1 based on component A in the following formula (1) ; A second step of synthesizing a second compound, which is a polymer dot crosslinked with diselenide or disulfide, by carbonization synthesis of the component A; a third step of synthesizing a third compound by substitution synthesis of the conductive material functional group Z in the second compound; A fourth step of synthesizing a fourth compound having conductivity and hydrogen bonding strength by carbonizing dopamine or diselenide cross-linked dopamine in the third compound; a fifth step of synthesizing a fifth compound by supporting the fourth compound on the second compound or the third compound through a hydrophobic bond; and a sixth step of preparing a sixth compound that is a hydrogel by including the fifth compound in a matrix.

[Formula 1]

In Formula 1,

Y is a copolymer containing any one of COOH, NH ₂ , SH, Br, and Cl functional groups.

In the first step, the component A compound is Hyaluronic acid (HA), Pluronic, Polyethylene Glycol (PEG), Poly(2-(dimethylamino) ethyl methacrylate) (PDMA), Polyvinylpyrrolidone (PVP), Alginate, Gelatin, Hydroxypropyl cellulose (HPC), Carboxyl methylcellulose (CMC), Hydroxypropyl methylcellulose (HPMC), and Polyacrylic acid (PAA), and has a molecular weight of 1,000 to 10,000,000 g/mol.

The first compound is synthesized by substituting functional group 1 based on the component A compound.

In addition, functional group 1 of Formula 1 of the present invention includes any one of dopamine, caffeic acid, 2-bromo-3',4'-dihydroxy acetophenone, and 2-chloro-3',4'-dihydroxy acetophenone.

And in the second step, the component A is carbonized and synthesized to synthesize a second compound, which is a polymer dot crosslinked with diselenide or disulfide.

This second compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2 above

X is a compound containing any one functional group of Se—Se (diselenide bond) or SS (disulfide bond).

That is, the second compound represented by Chemical Formula 2 is a polymer dot crosslinked with diselenide or disulfide, and is synthesized by carbonizing component A. Formula 2 is hydrothermal (temperature 10 to 500 ℃), solvothermal synthesis (temperature 10 to 500 ℃), acid catalyst (concentration 0.1N to 1N), electron beam accelerator (radiation 100,000 to 200,000 Gy ) method, and Formula 2 is prepared through hydrothermal synthesis.

The third step according to the present invention is a step of substituting and synthesizing the functional group Z of the conductive material in the second compound.

The third compound may be represented by Formula 3 below.

[Formula 3]

In Formula 3 above

The functional group Z includes any one compound of MnO ₂ , Cu ²⁺ , MXene, TiO ₂ , Graphene oxide, polyaniline, and PEDOT in Formula 2, and the content of Z is within 1 to 99%.

The fourth step according to the present invention is a step of synthesizing a fourth compound having conductivity and hydrogen bonding ability by carbonizing dopamine or diselenide cross-linked dopamine in the third compound.

This fourth compound may be represented by Chemical Formula 4 below.

[Formula 4]

That is, in the present invention, Chemical Formula 4 synthesizes a compound having excellent conductivity and hydrogen bonding through a carbonization reaction of dopamine or diselenide crosslinked dopamine. In this reaction, the carbonization reaction is hydrothermal (temperature 10 to 500 ° C), solvothermal (temperature 10 to 500 ° C), acid catalyst (concentration 0.1N to 1N), electron beam accelerator (radiation 100,000 to 500 ° C) 200,000 Gy), and Formula 4 is prepared through hydrothermal synthesis.

The fifth step of the present invention is a step of synthesizing a fifth compound by supporting the fourth compound on the second compound or the third compound through a hydrophobic bond.

In this fifth compound, the composition content of the fourth compound includes within 1 to 99%, and may be represented by Chemical Formula 5.

[Formula 5]

And the sixth step of the present invention is a step of preparing a sixth compound that is a hydrogel by including the fifth compound in a matrix. This sixth compound may be represented by Chemical Formula 6 below.

[Formula 6]

That is, in the present invention, Formula 6 prepares a matrix including Formula 5. The composition content of Formula 5 includes within 1 to 99%. The matrix includes one or more of PVA, Alginate, PVP, Collagen, Gelatin, PEG, Pluronic, Dopamine, Tannic acid, and Laponite.

[Example]

[Example 1: Production of active oxygen sensitive polymer dots]

In Formula 1, Y is charged with 1 g of a polymer having Br or Cl into a vial, and then 8 mL of a selenium solution is added and reacted at 60° C. for 4 hours. After the reaction, dialysis was performed for 24 hours, and then 0.8 g of cross-linked nanoparticles in powder form was obtained through lyophilization.

After dissolving 1 g of the obtained nanoparticles in 50 mL of distilled water, hydrothermal synthesis was performed at 60° C. for 24 hours. After the hydrothermal synthesis was completed, 0.56 g of crosslinked polymer dots were obtained through lyophilization.

[Example 2: Preparation of dopamine-based polymer dots with electrochemical properties]

After filling 1 g of dopamine single molecule into a 250 mL round-bottom flask, it was completely dissolved in 90 mL of distilled water. After adjusting the pH to 9.0 by adding 1mL of 1M sodium hydroxide solution and 10mL of ethanol, the mixture was reacted at 30℃ for 24 hours. After the reaction, the upper layer and lower layer are separated using a centrifuge. The separated lower layer was lyophilized to obtain 0.5 g of powdered nanoparticles.

After dissolving 1 g of the obtained nanoparticles in 50 mL of dimethyl sulfoxide, hydrothermal synthesis was performed at 180° C. for 6 hours. After the hydrothermal synthesis was completed, 0.491 g of cross-linked carbon quantum dots in powder form was obtained through freeze-drying.

[Example 3: Preparation of polydopamine-polymer dots having active oxygen sensitivity]

After filling a vial with 100 mg of the crosslinked polymer dot obtained in Example 1, it was completely dissolved in 20 mL of a phosphate buffer solution. Thereafter, 10 mg of carbonized polydopamine obtained in Example 2 was dissolved in 2 mL of dimethyl sulfoxide, added to a vial, and reacted by stirring at room temperature for 24 hours. After the reaction, the supernatant and the lower layer were separated using a centrifugal separator, and the supernatant was subjected to dialysis, and then 80 mg of polymer dots containing carbonized polydopamine in powder form were obtained through freeze-drying.

[Example 4: Preparation of hydrogel containing polydopamine-polymer dots having active oxygen sensitivity]

After filling a vial with 10 mg of the polymer dot obtained in Example 3, 1 mL of a phosphate buffer solution was added thereto and dispersed using a superimposer for 10 minutes. Thereafter, 100 mg of acrylamide, 2 mg of N,N'-methylene bisacrylamide crosslinking agent, and 10 mg of laponite were added to the vial, followed by stirring in an ice batch under nitrogen for 10 minutes. After stirring, 10 mg of ammonium sulfate as an initiator and 20 μL of N, N, N', N'-tetramethyl ethylenediamine as a catalyst were added, stirred, poured into a mold, and molded at room temperature for 6 hours to obtain a hydrogel.

[Experimental example]

[Experimental Example 1. Confirmation of Active Oxygen Sensitive Polymer Dot Structure]

In order to confirm the structure of the organic copolymer of the present invention, the following experiments were conducted.

The analysis of the structure of the polymer dot obtained in Example 1 was confirmed by X-ray photoelectron spectroscopy (XPS), ultraviolet visible light spectroscopy (UV-vis), and the like, and the results are shown in FIGS. 1 and 2.

1 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of polymer dots prepared according to Example 1 of the present invention. And Figure 2 is a graph showing the results of visible light spectroscopy (UV-vis) analysis prepared according to Example 1 of the present invention.

As shown in FIG. 1, according to the results of X-ray photoelectron spectroscopy (XPS) analysis, the Se 3d peak of the diselenide bond at 100 eV and the C double bond at 284.6 eV were confirmed.

As shown in FIG. 2, according to the results of ultraviolet-visible spectroscopy (UV-vis) analysis, the absorbance graphs of the catechol group at 280 nm and 360 nm were confirmed.

[Experimental Example 2. Confirmation of characteristics of active oxygen sensitive polymer dot containing carbonized polydopamine]

In order to measure the active oxygen sensitive characteristics of the polymer dots obtained in Examples 1 to 3 above, photoluminescence spectroscopy was measured. The results are shown in Figure 3.

Figure 3 is a graph showing the results of fluorescence spectroscopy (Photoluminescence spectroscopy) analysis by active oxygen of the polymer dot prepared according to Example 3 of the present invention. As shown in FIG. 3, it was confirmed that the diselenide bond, which is sensitive to active oxygen, is broken after addition of hydrogen peroxide (H ₂ O ₂ ), which is an active oxygen, and fluorescence increases.

[Experimental Example 3. Cancer cell wireless diagnosis by conductivity, pressure, and tensile autotransformation of hydrogel containing polydopamine-polymer dots having active oxygen sensitivity]

Electrochemical impedance spectroscopy (EIS) and LCR meter were measured to confirm the conductivity, pressure, and tensile self-conversion characteristics of the hydrogel obtained in Example 4 by active oxygen sensitivity. The results are shown in Figures 4 to 7.

4 is a graph showing the results of electrochemical impedance spectroscopy (EIS) analysis according to the type and concentration of cells of the hydrogel prepared according to Example 4 of the present invention. As shown in Figure 4, in order to confirm the electrical conductivity of the hydrogel changed by (a) normal cells (MDCK) and (b) cancer cells (MDAMB), the resistance value was measured according to the cell concentration. (a) In normal cells, there was little change in the resistance value of the hydrogel according to the cell concentration, whereas in FIG. 4 (b) cancer cells, it was confirmed that the resistance value of the hydrogel decreased according to the cell concentration. Through this, it was confirmed that electrochemical diagnosis of cancer cells is possible.

5 is a graph showing the results of analyzing the amount of change in electrochemical resistance (ΔR/R ₀ ) according to the type of cell and the tensile angle of the hydrogel prepared according to Example 4 of the present invention. That is, FIG. 5 is the result of measuring the electrical characteristics by the tensile angle with an LCR meter. As shown in FIG. 5, in order to confirm the change in resistance (ΔR/R ₀ ) of the hydrogel changed by normal cells (MDCK) and cancer cells (MDAMB), the resistance value was measured according to the tensile angle of the hydrogel. Results It was confirmed that the change in resistance (ΔR/R ₀ ) of the hydrogel was larger in cancer cells (MDAMB) than in normal cells (MDCK), and it was confirmed that the change in resistance (ΔR/R ₀ ) increased as the tensile angle increased. .

6 is a graph showing the results of analyzing the amount of change in electrochemical resistance (ΔR/R ₀ ) by cell type and pressure strength of the hydrogel prepared according to Example 4 of the present invention. That is, FIG. 6 is a result of measuring electrical characteristics by pressure intensity with an LCR meter. As shown in FIG. 6, in order to confirm the change in resistance (ΔR/R ₀ ) of the hydrogel changed by normal cells (MDCK) and cancer cells (MDAMB), the resistance value was measured according to the pressure strength of the hydrogel. Results It was confirmed that the change in resistance (ΔR/R ₀ ) of the hydrogel was larger in cancer cells (MDAMB) than in normal cells (MDCK), and it was confirmed that the change in resistance (ΔR/R ₀₎ increased as the pressure intensity increased. .

7 is a result of wirelessly measuring electrical characteristics by electrical conductivity and pressure intensity. As shown in FIG. 6, it was confirmed that the change in resistance (ΔR/R ₀ ) due to the pressure intensity was higher in the cancer cells (MDAMB) than in the normal cells (MDCK), and the electrical conductivity was high.

[Experimental Example 4. Analysis of self-healing and viscoelasticity of hydrogel containing polydopamine-polymer dots having active oxygen sensitivity]

A rheometer was measured to confirm the self-healing and viscoelasticity of the hydrogel obtained in Example 4 by active oxygen sensitivity. The results are shown in Figures 8 to 9.

8 is a graph showing the results of viscoelasticity analysis according to the number of images and cell types of self-healing ability of the hydrogel prepared according to Example 4 of the present invention. That is, FIG. 8 is the result of measuring the number of times of self-healing and viscoelasticity using a rheometer. As shown in FIG. 8, as a result of measuring the number of self-healing after treatment with cancer cells (MDAMB), it was confirmed that self-healing occurred up to a total of three times through the image of FIG. 8 (a). In addition, as a result of measuring viscoelasticity according to the type of cell, it was confirmed through the graph of FIG. 8 (b) that viscoelasticity was recovered after treatment with cancer cells (MDAMB), unlike normal cells (MDCK).

Figure 9 is a graph showing the results of self-healing analysis and viscoelasticity analysis by the cell type ratio of the hydrogel prepared according to Example 4 of the present invention. That is, FIG. 9 shows the results of measuring self-healing and viscoelasticity according to the ratio of normal cells and cancer cells. As shown in FIG. 9, it was confirmed through the image of FIG. 9 (a) that self-healing occurs as the concentration of cancer cells (MDAMB) is higher than that of normal cells (MDCK). It was confirmed through the graph of FIG. 9 (b) that recovery should be higher than that of (MDCK).

In addition, the device and method described above are not limited to the configuration and method of the above-described embodiments, but all or part of each embodiment is selectively combined so that various modifications can be made. may be configured.

Claims (10)

As a method for manufacturing a polymer dot-based hydrogel sensor,
A first step of synthesizing a first compound by substituting functional group 1 based on component A in Formula 1 below;
A second step of synthesizing a second compound, which is a polymer dot crosslinked with diselenide or disulfide, by carbonization synthesis of the component A;
a third step of synthesizing a third compound by substitution synthesis of the conductive material functional group Z in the second compound;
A fourth step of synthesizing a fourth compound having conductivity and hydrogen bonding strength by carbonizing dopamine or diselenide cross-linked dopamine in the third compound;
a fifth step of synthesizing a fifth compound by supporting the fourth compound on the second compound or the third compound through a hydrophobic bond; and
A method for manufacturing a polymer dot-based hydrogel sensor for recognizing active oxygen or glutathione-type wireless diagnosis, comprising:
[Formula 1]

In Formula 1,
Y is a copolymer containing any one of COOH, NH ₂ , SH, Br, and Cl functional groups.
According to claim 1,
The component A compound is Hyaluronic acid (HA), Pluronic, Polyethylene Glycol (PEG), Poly(2-(dimethylamino) ethyl methacrylate) (PDMA), Polyvinylpyrrolidone (PVP), Alginate, Gelatin, Hydroxypropyl cellulose (HPC), Carboxyl methylcellulose At least one of (CMC), Hydroxypropyl methylcellulose (HPMC), and Polyacrylic acid (PAA), and a molecular weight of 1,000 to 10,000,000 g/mol Polymer dot-based hydrogel sensor manufacturing method for recognizing active oxygen or glutathione type wireless diagnosis, characterized in that .
According to claim 1,
The functional group 1 is at least one of dopamine, caffeic acid, 2-bromo-3′, 4′-dihydroxy acetophenone, 2-chloro-3′, 4′-dihydroxy acetophenone, characterized in that for active oxygen or glutathione recognition type radio diagnosis Polymer dot-based hydrogel sensor manufacturing method.
According to claim 3,
In the second step and the fourth step,
The carbonization reaction is a method of manufacturing a polymer dot-based hydrogel sensor for active oxygen or glutathione recognition type wireless diagnosis, characterized in that by applying hydrothermal at a temperature of 10 to 500 ° C.
According to claim 1,
The second compound is a polymer dot-based hydrogel sensor manufacturing method for wireless diagnosis of active oxygen or glutathione recognition, characterized in that represented by the following formula (2):
[Formula 2]

In Formula 2 above
X is a compound containing either a functional group of Se-Se (diselenide bond) or SS (disulfide bond).
According to claim 5,
The third compound is a polymer dot-based hydrogel sensor manufacturing method for wireless diagnosis of active oxygen or glutathione recognition, characterized in that represented by the following formula (3):
[Formula 3]

In Formula 3 above
The functional group Z includes any one compound of MnO ₂ , Cu ²⁺ , MXene, TiO ₂ , Graphene oxide, polyaniline, and PEDOT in Formula 2, and the content of Z is within 1 to 99%.
According to claim 6,
The fourth compound is a polymer dot-based hydrogel sensor manufacturing method for wireless diagnosis of active oxygen or glutathione recognition, characterized in that represented by the following formula (4):
[Formula 4]

According to claim 7,
The composition content of the fourth compound in the fifth compound is within 1 to 99%, and is represented by Chemical Formula 5, characterized in that active oxygen or glutathione recognition type wireless diagnostic polymer dot-based hydrogel sensor manufacturing method:
[Formula 5]

According to claim 1,
The content of the fifth compound in the sixth compound is within 1 to 99%, and the matrix contains at least one of PVA, Alginate, PVP, Collagen, Gelatin, PEG, Pluronic, Dopamine, Tannic acid, and Laponite. A method for manufacturing a polymer dot-based hydrogel sensor for wireless diagnostics recognizing active oxygen or glutathione.
A polymer dot-based hydrogel sensor for wireless diagnosis that recognizes active oxygen or glutathione, characterized in that it is manufactured by the manufacturing method according to any one of claims 1 to 9.

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