KR101432090B1 - Coated nanoparticles and quantitative method of radical using the same - Google Patents

Abstract

The present invention relates to nanoparticles for coating and a method for quantifying radicals using the same. The nanoparticles for coating, etched by a solution containing radicals, are measured by a spectrophotometer. An absorbance obtained by the measurement, as the concentration of the metal nanoparticles, is used to derive a reduction rate and a metering formula, and, by using the absorbance of a mixture containing the combined nanoparticles and an object to be measured, to obtain the reduction rate, the reduction rate is substituted into the metering formula to quantify the contents of radicals inside the object.

Description

Coated nanoparticles and methods for quantifying radicals using the same

The present invention relates to a method for quantitating the radical content contained in a sample to be measured by measuring the absorbance of the coated nanoparticles etched by the radical containing solution in the ultraviolet and visible regions and deriving the absorbance reduction rate and the calibration equation A nanoparticle coating technique used for quantifying radicals, and a method for quantifying radicals using the same.

The presence of reactive molecules, commonly referred to as free radicals or oxygen species, is known to be associated with aging, cancer, atherosclerosis, myocardial infarction, seizure, virus infection, It is well known that it becomes one of the causes of abnormal health including diseases and neurodegenerative diseases, and causes aging and deterioration of health.

These molecules are byproducts of physiological reactions and are produced by the metabolism of oxygen, for example by a very large number of enzymatic reactions indispensable for cellular respiration, immune function (killing of foreign objects) and metabolism.

In particular, mitochondria, which are intracellular organelles, transport electrons in the electron transport system but always generate electrons, and 2 to 0.2% of oxygen molecules used for respiration are reduced to active oxygen species. In addition, these reactive oxygen species usually occur in a normal environment. For example, sources of reactive oxygen species include polluted water, smoke, ionizing radiation, air pollutants, chemicals (carcinogens, many petrochemicals, biologic agents, pigments, solvents, cell division inhibitors, Heavy metals, and oxidized or rancid fat.

Among the most common reactive oxygen species are superoxide radicals, hydroxyl radicals, singlet oxygen and hydrogen peroxide, and in the broad sense, nitrogen monoxide, peroxynitrite ( peroxynitrite, alkoxyl radicals, and lipid peroxyl radicals. Lipid radicals such as superoxide, hydroxyl radical, nitrogen monoxide, lipid peroxyl radicals, alkoxyl radicals and the like are free radical molecular species.

Free radical molecules have oxidative toxicity to living organisms that cause structural damage to all biological molecules such as nucleic acids, proteins, and lipids. Damage of a molecule causes cell abnormalities, such as alteration of genetic code, abnormality of enzyme reaction, denaturation of the lipid membrane, and cell injury.

Thus, the free radical molecule has strong oxidizing power and the oxidative stress is generally referred to as oxidative stress. Accumulation of these oxidative stresses can cause neurological disorders, endocrine instability, increased allergy, vascular endothelial destruction, and joint destruction and inflammation at individual levels.

Oxidative stress is caused by the strong oxidizing ability of excess free radicals in cells. Most of the superoxide anion radicals (O ₂ ^- ) are generated by the leakage of electrons in the mitochondria from the Krebs cycle to the electron transport system. In addition, the superoxide anion radical is also generated by an oxidase such as NADPH oxidase or xanthine oxidase. The excess anion radicals reduce the transition metal, iron or copper, and react with hydrogen peroxide or Fenton to generate a hydroxyl radical (.OH).

Hydroxyl radicals are the most potent reactive oxygen species and react indiscriminately with nucleic acids, lipids and proteins.

On the other hand, the radical is a covalent bond. Since the electrons do not form a pair, the reactivity is very fast when used in a chemical reaction. Therefore, side reactions may occur due to the amount of radicals contained in the chemical, so that a desired yield of the material may not be obtained.

Researches using metal nanoparticles and oxides have been conducted to detect such radicals. However, in the case of using metal nanoparticles, since only a small amount of radicals exist, the rate at which metal nanoparticles are etched is too fast, so qualitative analysis is possible However, quantitative analysis has problems that are difficult to perform.

Therefore, in order to prevent aging and health problems caused by these radicals and to predict side reactions in chemical reactions, there is a demand for a technique for determining the contents of radicals contained in the compounds as well as the blood and water quality.

Korean Patent No. 0490808 Korean Patent No. 0498203

It is an object of the present invention to provide coating nanoparticles which are used for quantifying the radical content contained in a sample to be measured.

It is another object of the present invention to provide a method for quantifying radicals contained in a sample to be measured using the coated nanoparticles.

In order to achieve the above object, the coating nanoparticles used for the quantification of radicals of the present invention include metal nanoparticles; And a polymer electrolyte layer coated on the surface of the metal nanoparticles, and the metal nanoparticles can be etched by the radical containing solution.

The metal nanoparticles may be selected from the group consisting of rectangular metal nanocubes, spherical metal nanoparticles, metal nanoparticles having a pentagonal shape or larger, metal nanorods, and metal nanowires.

The metal of the metal nanoparticles may be gold or silver.

The polymer electrolyte is at least one selected from the group consisting of poly (arylamine hydrochloride), polyacrylic acid, poly (vinyl alcohol), poly (vinylpyrrolidone), poly (ethylene glycol) .

The polymer electrolyte for coating may be used in an amount of 0.01 to 3.0% by weight.

The radicals contained in the radical containing solution may be one selected from the group consisting of a chlorine radical, an oxygen radical, a hydroxyl radical, a carbon radical, a CF ₃ radical and a hydrogen-peroxy radical.

According to another aspect of the present invention, there is provided a method of quantifying a radical using coating nanoparticles, comprising: (A) measuring a mixture of a coating nanoparticle and a radical-containing solution and a coating nanoparticle using a spectrophotometer, Obtaining the absorbance of the coated nanoparticles by etching; (B) obtaining a reduction rate of nanoparticles according to concentration of a solution containing a radical in nanoparticles coated with a polymer electrolyte of a selected concentration using the obtained absorbance; (C) deriving a calibration equation according to the concentration of the polymer electrolyte coating the metal nanoparticles using the reduction rate; (D) measuring a mixture of the coated nanoparticles and the sample to be measured and the coated nanoparticles with a spectrophotometer to obtain respective absorbances; (E) obtaining a reduction rate of the mixture using the absorbance obtained in the step (D); And (F) substituting the reduction rate obtained in the step (E) into the calibration equation derived in the step (C) to quantify the content of the radicals contained in the sample to be measured.

The coating nanoparticles may be prepared by: synthesizing metal nanoparticles; And mixing the synthesized metal nanoparticles with a polymer electrolyte to prepare coated nanoparticles having a polymer electrolyte layer coated on the metal nanoparticles.

The radicals contained in the radical containing solution may be one selected from the group consisting of a chlorine radical, an oxygen radical, a hydroxyl radical, a carbon radical, a CF ₃ radical and a hydrogen-peroxy radical.

The metal nanoparticles may be prepared by (i) heating ethylene glycol in an oil bath at 120 to 180 ° C for 1 to 3 hours; (ii) adding sodium hydrogen sulfide after the heating and stirring for 3 to 10 minutes; (iii) stirring in step (ii), adding hydrochloric acid and stirring for 1 to 5 minutes; (Iv) adding polyvinylpyrrolidone after stirring in step (iii) and stirring for 1 to 5 minutes; And (v) adding the metal precursor after the step (iv), stirring the mixture for 20 to 60 minutes, and cooling the mixture in an ice bath.

The metal of the metal nanoparticles may be gold or silver.

The polymer electrolyte is at least one selected from the group consisting of poly (arylamine hydrochloride), polyacrylic acid, poly (vinyl alcohol), poly (vinylpyrrolidone), poly (ethylene glycol) .

The polymer electrolyte may be used in an amount of 0.01 to 3.0 wt%.

By using the method of quantifying radicals using the coating nanoparticles of the present invention, it is possible to detect radicals in a spectroscopic manner without using high performance liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR) Radicals can be quantified by simple analysis.

In addition, the radical quantification method using the coated nanoparticles of the present invention can quantify and detect radicals contained in the sample to be measured, for example, blood, water quality, etc., so that the aging or health abnormality caused by radicals can be prevented in advance . In particular, when water containing a large amount of free radicals is ingested, it may cause hypertension or diabetes, and thus, it is necessary to increase the amount of the radicals contained in the water.

In addition, it is possible to quantify the amount of radicals contained in a particular chemical substance, so that a side reaction generated in the chemical reaction can be predicted, and the amount of the radicals contained in the microorganism existing in the soil can be quantified, thereby preventing environmental pollution .

FIG. 1A is a TEM photograph of a square metallic nanocube manufactured according to an embodiment of the present invention.
1B is a TEM photograph of spherical metal nanoparticles prepared according to an embodiment of the present invention.
2A is the absorbance of coated nanoparticles prepared according to one embodiment of the present invention.
Figures 2B-2L are absorbances of mixtures of coating nanoparticles and radical-containing solutions prepared according to one embodiment of the present invention by concentration.
FIG. 3 is a graph showing a reduction rate derived using the absorbance of FIG. 2. FIG.
Figure 4A is the absorbance of coated nanoparticles prepared according to another embodiment of the present invention.
4B to 4L are absorbances of a mixture of coating nanoparticles prepared according to another embodiment of the present invention and a solution containing radicals by concentration.
FIG. 5 is a graph showing a reduction rate derived using the absorbance of FIG.
6A is the absorbance of the uncoated metal nanoparticles and the absorbance of the coated nanoparticles prepared according to another embodiment of the present invention.
6B to 6E are absorbances of a mixture of the coating nanoparticles prepared according to still another embodiment of the present invention and the radical-containing solution by concentration.
FIG. 6F is a graph showing the reduction rate derived using the absorbances of FIGS. 6A to 6E.
7A is the absorbance of a mixture of uncoated metal nanoparticles and a radical containing solution at different concentrations.
FIG. 7B is an absorbance of a mixture of coating nanoparticles prepared according to an embodiment of the present invention and a radical-containing solution by concentration.
FIG. 7C is the absorbance of a mixture of coating nanoparticles prepared according to an embodiment of the present invention and a radical-containing solution by concentration.
FIG. 7D is a graph showing the reduction rate derived using the absorbance of FIGS. 7A-7C. FIG.

The present invention relates to coating nanoparticles for quantifying radicals capable of quantifying the radical content contained in a sample to be measured by deriving a reduction rate and a calibration equation using the absorbance of coated nanoparticles etched by the radical-containing solution, And a method for quantifying radicals.

Hereinafter, the present invention will be described in detail.

The method for quantifying radicals using the coating nanoparticles of the present invention comprises the steps of (A) obtaining a mixture of a coating nanoparticle and a radical-containing solution and coating nanoparticles with a spectrophotometer to obtain respective absorbances, (B) (C) deriving a calibration equation using the reduction rate, (D) determining a reduction rate of the metal nanoparticles by the concentration of the solution containing the metal nanoparticles, Obtaining the absorbance of each of the mixture of the nanoparticles and the sample to be measured and the absorbance of each of the coated nanoparticles, (E) obtaining a reduction rate of the mixture using the absorbance obtained in the step (D), and (F) And quantifying the content of the radicals contained in the sample to be measured by substituting the reduction rate obtained in the step (E) into the calibration equation derived in the step (C).

First, in step (A), each of the mixtures containing the radical-containing solutions and the coating nanoparticles having different concentrations was measured with a spectrophotometer to obtain respective absorbances, and only the coated nanoparticles were measured with a control to determine the absorbance .

The radicals contained in the radical containing solution are selected from the group consisting of a chlorine radical, an oxygen radical, a hydroxyl radical, a carbon radical, a CF ₃ radical and a hydrogen-peroxy radical, and the radical is not particularly limited as long as it is a solution containing the radical Do not.

The coated nanoparticles are coated with a polymer electrolyte. When the nanoparticles are mixed with a solution containing a radical, radicals pass through the polymer electrolyte layer and the metal nanoparticles are etched, thereby reducing the absorbance of the metal nanoparticles. For example, the absorbance measured by a spectrophotometer means the amount of metal nanoparticles. When the metal nanoparticles are etched much, the absorbance decreases greatly. When the amount of the metal nanoparticles is reduced, the absorbance decreases slightly (based on the absorbance of the unetched coating nanoparticles).

Next, in step (B), the reduction rate of the metal nanoparticles according to the concentration of the radical-containing solution is determined for the metal nanoparticles coated with the polymer electrolyte of the selected concentration using the absorbance obtained in the step (A). The reduction rate is obtained using the following equation (1) based on the absorbance of the non-etched coating nanoparticles.

[Equation 1]

Next, in the step (C), the calibration equation is derived by applying the appropriate statistical function of the reduction rate obtained in the step (B). The calibration equation may be derived from different calibration formulas depending on the type and content of the coating layer material (polymer electrolyte) and the kind of the radical-containing solution when the metal nanoparticles are coated.

Next, in order to quantify the radicals contained in the sample to be measured, in step (D), a mixture of the sample to be measured containing the radical and the coated nanoparticles was measured with a spectrophotometer to obtain the absorbance, Absorbance.

The sample to be measured is not particularly limited as long as it is a solution containing a radical, but it may preferably be water quality such as wastewater, drinking water, sewage, or blood.

Next, in step (E), the rate of reduction of the mixture prepared in step (D) is obtained in the same manner as in step (B).

Next, in step (F), the reduction rate obtained in step (E) is substituted into the calibration equation derived in step (C) to quantify the content of the radicals contained in the sample to be measured.

The present invention also provides a coated nanoparticle for use in quantifying radicals contained in a sample to be measured.

The coating nanoparticles of the present invention can be prepared by: synthesizing metal nanoparticles; And mixing the synthesized metal nanoparticles with a polymer electrolyte to prepare coated nanoparticles having a polymer electrolyte layer formed on the surface of the metal nanoparticles.

The method for producing the metal nanoparticles is not particularly limited as long as it can be produced by a conventional method.

Metal of the metal nanoparticles may be gold or eunil, to the metal precursor is _{CF 3 COOAg, CH 3 CH 2} C (CH 3) 2COOAg, (CH 3) 3SiCH 2 COOAg, C 2 H 5 COOAg, C 6 F _{13 COOAg, (CF 2) 3} (COOAg) 2, KAuO 2, HAuCl 4, KAu (NO 2) 4, AuCl 3, NaAuCl 4, KAu (OAc) 3 (OH), HAu (NO 3) 4 , and Au ( OAc) there may be mentioned one selected from the group consisting of _3.

In order to quantify radicals with high accuracy, metal nanoparticles are used in the form of rectangular metal nanocubes; Spherical metal nanoparticles; Metal nanoparticles having a pentagonal shape or larger, preferably 5 to 8 angstroms; Metal nanorods; Or metal nanowires.

Also, the polymer electrolyte may be selected from the group consisting of poly (arylamine hydrochloride), polyacrylic acid, poly (vinyl alcohol), poly (vinylpyrrolidone), poly (ethylene glycol) More than species.

The polymer electrolyte is added to the prepared metal nanoparticle solution in an amount of 0.01 to 3.0% by weight, preferably 0.02 to 1.5% by weight. When the content of the polymer electrolyte is less than the lower limit, the polymer electrolyte may not be uniformly coated on the metal nanoparticles. If the content of the polymer electrolyte is less than the lower limit, the polymer electrolyte may not be uniformly coated on the metal nanoparticles. Can be the same.

When the coating nanoparticles of the present invention are used, a large amount of metal nanoparticles are etched even with a low-concentration radical-containing solution, and the shape of the coated nanoparticles is uniform (FIG. 1), so that a more accurate calibration equation can be derived. On the other hand, when metal nanoparticles not coated with a polymer electrolyte are used, the metal nanoparticles are etched by 80 to 90% even at a low concentration, so that a calibration equation can not be derived. When a polymer electrolyte is added in the synthesis of metal nanoparticles, Accuracy is degraded.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  1 to 11. Coating Of silver nanoparticles  Produce

50 ml of ethylene glycol was heated in a 150 ° C oil bath for 2 hours, then 0.6 ml of 3 mM sodium hydrogen sulfide was added to the round bottom flask, and the mixture was stirred for 4 minutes. Then, 5 ml of 3 mM hydrochloric acid was added thereto, Respectively. Next, 12.5 ml of 2% by weight polyvinyl pyrrolidone (PVP) was added and stirred for 2 minutes, followed by addition of 4 ml of 282 mM CF ₃ COOAg, followed by stirring for 30 minutes, followed by cooling in an ice bath The temperature was lowered to produce a square silver cube.

Next, the poly (allyamine hydrochloride) (PAA) was mixed with the silver nanoparticle solution and the polyelectrolyte and reacted at 4 ° C for 2 hours. Then, the polymer electrolyte remained in the solution was removed by a centrifuge, And then redispersed in distilled water to prepare coated silver nanoparticles. 0.03, 0.04, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0 and 1.5 wt% in the total solution.

Example  12 to 22. Coating Of silver nanoparticles  Produce

Coated silver nanoparticles were prepared using polyacrylic acid (PAAc) as a polymer electrolyte in the same manner as in Examples 1 to 11 above.

Example  23 to 26. Coating Of silver nanoparticles  Produce

Spherical silver nanoparticles having an average particle size of 20 nm instead of a quadrangle were prepared in the same manner as in Example 1 except that poly (arylamine hydrochloride) (PAA) and polyacrylic acid (PAAc) By weight to prepare coated silver nanoparticles.

Test Example  One. Example  Absorbance, reduction rate, and Calibration equation  deduction

1-1. Acquisition of absorbance

FIG. 2 shows the absorbance of the coated silver nanoparticles prepared in Examples 1 to 11 according to the concentration of THF peroxide and measured with a spectrophotometer (Cary 60 UV-vis, Agilent Technologies).

2A is the absorbance of the uncoated silver nanoparticles and the coated silver nanoparticles prepared in Examples 1 to 11, and FIGS. 2B to 2L are graphs showing the absorbance of the mixture of the coated silver nanoparticles prepared in Examples 1 to 11 and THF peroxide Absorbance. (D) 0.04 wt.%, (E) 0.05 wt.%, (F) 0.1 wt.%, (G) 0.2 wt.%, 0.3 wt% of (H), 0.4 wt% of (I), 0.5 wt% of (J), 1 wt% of (K) and 1.5 wt% of (L).

As shown in Figs. 2B to 2L, the decrease of the absorbance can detect that the silver nanoparticles are etched by the peroxide radicals.

As the concentration of THF peroxide increases, the shape of the peak changes, which means that the shape changes as the silver nanoparticles are etched.

1-2. Reduction rate

3 is a graph showing a reduction rate of silver nanoparticles etched by peroxide radicals according to the content of the polymer electrolyte.

The reduction rate of the silver nanoparticles was calculated from the absorbance of the uncoated coating nanoparticles (FIG. 2A) using the maximum value of the absorbance measured in Examples 1 to 11 (FIGS. 2B to 2L) Respectively.

1-3. Calibration equation  deduction

The calibration equation in the following Table 1 was derived using an exponential function using the graph of the reduction rate of FIG. 3 according to the content of the polymer electrolyte of the coated silver nanoparticles.

X of the above calibration equation is a concentration of THF peroxide, and Y is a reduction rate (%).

Test Example  2. Example  Absorbance, reduction rate, and Calibration equation  deduction

2-1. Acquisition of absorbance

FIG. 4 shows the absorbance of the coated silver nanoparticles prepared in Examples 2 to 22, as measured by a spectrophotometer (Cary 60 UV-Vis, Agilent Technologies) after mixing with the concentration of THF peroxide.

4A is the absorbance of the uncoated silver nanoparticles and the coated silver nanoparticles prepared in Examples 12 to 22, and FIGS. 4B to 4L are the absorbance of the mixture of the coated silver nanoparticles prepared in Examples 12 to 22 and THF peroxide Absorbance. (D) 0.04 wt.%, (E) 0.05 wt.%, (F) 0.1 wt.%, (G) 0.2 wt.%, 0.3 wt% of (H), 0.4 wt% of (I), 0.5 wt% of (J), 1 wt% of (K) and 1.5 wt% of (L).

As shown in Figs. 4B to 4L, the decrease of the absorbance indicates that the silver nanoparticles are etched by the peroxide radicals.

2-2. Reduction rate

5 is a graph showing the rate of reduction of silver nanoparticles etched by peroxide radicals according to the content of the polymer electrolyte.

The reduction rate of the silver nanoparticles was calculated from the maximum value of the absorbance (FIGS. 4B to 4L) measured in Examples 12 to 22 based on the absorbance of the unetched coating nanoparticles (FIG. 4A) Respectively.

2-3. Calibration equation  deduction

The calibration equation in the following Table 2 was derived by using the graph of the reduction rate of FIG. 5 according to the content of the polymer electrolyte of the coated silver nanoparticles.

Content of PAAc (% by weight) Calibration equation (Y = aX) 0.02 Y = 6.95X 0.03 Y = 4.24X 0.04 Y = 3.27X 0.05 Y = 3.08X 0.1 Y = 2.62X 0.2 Y = 2.09X 0.3 Y = 1.78X 0.4 Y = 1.48X 0.5 Y = 1.23X One Y = 0.87X 1.5 Y = 0.69X

In the calibration equation shown in Table 2, the sensitivities (reduction rates) of the radicals of the silver nanoparticles obtained by varying the concentration of the radical-containing solution for each concentration of PAAc were plotted, and then a calibration equation was obtained by a linear function. For the graph obtained for the slope and the concentration of the polymer electrolyte, a calibration equation was obtained using a linear function (Y = aX), and the slope in this calibration equation was expressed as a.

When Y is the reduction rate (%), a is the formula for the content of the polymer electrolyte, and X is the concentration of the radical, the following optimum calibration equation can be derived by substituting a for the calibration equation.

[Calibration formula]

Y = ^-0.53 X 0.74A

In the above calibration equation, Y is the reduction rate (%), A is the content (wt%) of the polymer electrolyte, and X is the concentration of the THF peroxide (uM).

Test Example  3. Example  Absorbance, reduction rate, and < RTI ID = 0.0 > Calibration equation  deduction

3-1. Acquisition of Absorbance and Derivation of Reduction Rate

Figure 6 shows the absorbance of the coated silver nanoparticles prepared in Examples 23 to 26 as measured by a spectrophotometer (Cary 60 UV-vis, Agilent Technologies) after mixing according to the concentration of THF peroxide.

6A is the absorbance of the uncoated silver nanoparticles and the coated silver nanoparticles prepared in Examples 23 to 26, and FIGS. 6B to 6E show the absorbance of the mixture of the coated silver nanoparticles prepared in Examples 23 to 26 and THF peroxide Absorbance. (B) 0.1 wt% PAA, (C) 1.5 wt% PAA, (D) 0.1 wt% PAAc, and (E) 1.5 wt% PAAc.

Even though the shape of the silver nanoparticles is spherical, it can be seen that the absorbance is reduced by etching with radicals. As a result, it can be seen that the metal nanoparticles can be etched by radicals regardless of the shape of the metal nanoparticles.

FIG. 6F is a graph showing the rate of reduction of silver nanoparticles etched by peroxide radicals according to the content of the polymer electrolyte. The reduction rate was determined in the same manner as in Test Example 1-2.

3-2. Calibration equation  deduction

The non-coated, 0.1 wt% PAAc and 1.5 wt% PAAc were calculated using the exponential function and the linear function using the graph of the reduction rate of FIG. 6F according to the polymer electrolyte content of the coated silver nanoparticles.

Test Example  4. Example  Absorbance, reduction rate, and Calibration equation  deduction

4-1. Acquisition of Absorbance and Derivation of Reduction Rate

FIG. 7 shows the absorbance of the coated silver nanoparticles prepared in Examples 11 and 22, as measured by a spectrophotometer (Cary 60 UV-vis, Agilent Technologies) after mixing according to the concentration of hydrogen peroxide.

7A is the absorbance of the mixture of uncoated silver nanoparticles and hydrogen peroxide concentration, FIG. 7B is the absorbance of the mixture of the coated silver nanoparticles prepared in Example 22 and hydrogen peroxide concentration, and FIG. The coated coating is the absorbance of the mixture mixed with the nanoparticles and the hydrogen peroxide concentration.

7A shows that even at low concentrations, 80 to 90% of the silver nanoparticles were etched and the calibration equation could not be derived.

Further, as shown in Figs. 7B and 7C, it can be seen that the decrease of absorbance shows that the silver nanoparticles are etched by hydrogen peroxide.

7D is a graph showing the rate of reduction of silver nanoparticles etched by hydrogen peroxide radicals according to the polymer electrolyte. The reduction rate was determined in the same manner as in Test Example 1-2.

4-2. Calibration equation  deduction

The calibration equation in Table 4 was derived using a linear function and an exponential function using the graph of the rate of decrease in FIG. 7D according to the polymer electrolyte of the coated silver nanoparticles.

In order to quantify the radicals of the sample to be measured using the calibration equation derived from Test Examples 1 to 4, the absorbance of the mixture of the coated nanoparticles and the sample to be measured is obtained to obtain the reduction rate (Y) The X value, for example, the content of the radical of the sample to be measured, can be obtained by substituting the Y value into the calibration equation detected according to the content of the polymer electrolyte and the kind of the radical-containing solution.

Claims (12)

Metal nanoparticles; And
And a polymer electrolyte layer coated on the surface of the metal nanoparticles,
Wherein the metal nanoparticles are etched by a radical-containing solution. The method of claim 1, wherein the metal nanoparticles are one selected from the group consisting of a quadrangular metal nanocube, a spherical metal nanoparticle, a pentagonal metal nanoparticle, a metal nanorod, and a metal nanowire. Coated nanoparticles. The coating nanoparticle as claimed in claim 1 or 2, wherein the metal of the metal nanoparticles is gold or silver. The polymer electrolyte of claim 1, wherein the polymer electrolyte comprises poly (arylamine hydrochloride), polyacrylic acid, poly (vinyl alcohol), poly (vinylpyrrolidone), poly (ethylene glycol) Wherein the coated nanoparticles are at least one member selected from the group consisting of the nanoparticles. The coating nanoparticle as claimed in claim 1 or 4, wherein the polymer electrolyte is used in an amount of 0.01 to 3.0 wt% to form a coating layer. The method of claim 1, wherein the radicals contained in the radical containing solution are one selected from the group consisting of a chlorine radical, an oxygen radical, a hydroxyl radical, a carbon radical, a CF ₃ radical and a hydrogen-peroxy radical. Coated nanoparticles. (A) measuring a mixture of the coated nanoparticles and the radical-containing solution and the coated nanoparticles with a spectrophotometer to obtain respective absorbances;
(B) obtaining the reduction rate of nanoparticles by concentration of the radical-containing solution in the metal nanoparticles coated with the polymer electrolyte at a concentration selected using the obtained absorbance;
(C) deriving a calibration equation using the reduction rate;
(D) measuring a mixture of the coated nanoparticles and the sample to be measured and the coated nanoparticles with a spectrophotometer to obtain respective absorbances;
(E) obtaining a reduction rate of the mixture using the absorbance obtained in the step (D); And
(F) quantifying the content of the radicals contained in the sample to be measured by substituting the reduction rate obtained in the step (E) into the calibration equation derived in the step (C). Method of quantifying radicals. 8. The method of claim 7, wherein the coated nanoparticles include: synthesizing metal nanoparticles; And
And mixing the synthesized metal nanoparticles with a polymer electrolyte to prepare coated nanoparticles having a polymer electrolyte layer coated on the metal nanoparticles. 8. The method of claim 7, wherein the radicals contained in the radical containing solution are one selected from the group consisting of a chlorine radical, an oxygen radical, a hydroxyl radical, a carbon radical, a CF ₃ radical and a hydrogen-peroxy radical. Method of quantifying radicals using particles. The method of claim 8, wherein the metal of the metal nanoparticles is gold or silver. 9. The polymer electrolyte of claim 8, wherein the polymer electrolyte comprises poly (arylamine hydrochloride), polyacrylic acid, poly (vinyl alcohol), poly (vinylpyrrolidone), poly (ethylene glycol) Wherein the at least one kind of coating nanoparticles is at least one selected from the group consisting of nanoparticles. [9] The method of claim 8, wherein the polymer electrolyte is used in an amount of 0.01 to 3.0% by weight.

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