KR20160142669A

KR20160142669A - Colorimetric detection sensor and method for iodine anion using gold nanoparticles functionalized with glycol chitosan

Info

Publication number: KR20160142669A
Application number: KR1020150078705A
Authority: KR
Inventors: 이강봉; 남윤식; 김경민; 오인환
Original assignee: 한국과학기술연구원
Priority date: 2015-06-03
Filing date: 2015-06-03
Publication date: 2016-12-13
Also published as: KR101731496B1

Abstract

The present invention relates to a colorimetric detection sensor and a colorimetric detection method for detecting iodine anion using gold nanoparticles functionalized with glycol chitosan, and more particularly to a colorimetric detection sensor and colorimetric detection method using gold nanoparticles functionalized with glycol chitosan, It is possible to easily detect iodine components contained or dissolved in a biological sample, beverage, medicines, food or the like through color change of the colorimetric detection sensor solution, and to detect the iodine anion selectivity, sensitivity and quantitative And a colorimetric detection method using the same.

Description

Technical Field [0001] The present invention relates to a colorimetric detection sensor and a colorimetric detection method for detecting anion of an iodine using gold nanoparticles functionalized with glycol chitosan and a colorimetric detection method for colorimetric detection using the gold nanoparticle functionalized with glycol chitosan.

Iodine is a kind of halogen element that does not exist in the free state in nature and exists mainly as an organic compound in seaweeds and seafood. In the human body, it is an element that directly affects thyroid secretion that regulates cardiac activity, nerve response to stimulation, body growth rate, and metabolism. Simplicity Thyroglobulin is the most common form of iodine deficiency, especially in off-shore areas and mountainous areas and very low in coastal areas. If the deficiency of iodine is severe or persistent, the thyroid hormone is depleted and symptoms such as skin dryness, hair loss, facial edema, muscle weakness and weight gain appear. Insufficient iodine in infancy can lead to cretinism, which leads to severe developmental disabilities. Therefore, pregnant mothers should eat foods rich in iodine, and to prevent the deficiency of iodine, seafood and iodine-containing sodium should be taken periodically. In addition, residents near the nuclear power plant are required to consume iodine (KI), which is non-radioactive iodine, in order to prevent accumulation of iodine ( ¹³¹ I), which is a radioactive substance caused by a nuclear accident or nuclear test, Let it escape out.

Adults in Australia and New Zealand are recommended to consume an average of 100 μg of iodine per day, especially 160 μg and 190 μg for pregnant and breastfeeding women.

Iodine vapor causes strong inflammation of the mucous membranes and adversely affects upper and lower airways. Inhalation of iodine vapors can cause excessive tears, chest pressure, neck soreness and headaches. Usually, the concentration of 0.1 ppm does not interfere with life, but it suffers from the concentration of 0.15 to 0.2 ppm and does not work at the concentration of 0.3 ppm. The exposure limit is 0.1 ppm in Australia and Germany and 2 ppm in life.

Glycol chitosan can form nanoscale self-assemblies, and has biodegradability and temperature sensitivity properties, making it useful for drug delivery, therapeutic nanoparticles, and tissue engineering applications in a variety of fields, such as biological samples, .

The nanoparticle colorimetric sensor method using surface plasmon resonance phenomena such as gold nanoparticles can theoretically induce free electron oscillation of the surface of nanoparticles by absorbed light waves of nano-sized particles . At this time, a resonance phenomenon appears to emit a specific wavelength, and various colors are obtained depending on the size, shape and kind of the particles. However, when the metal nanoparticles bind to an external compound, the size of the nanoparticles may change due to agglomeration of the nanoparticles, and the color may be changed accordingly. Therefore, the nanoparticles may be applied to sensors for measuring and monitoring environmental pollutants (Environmental Technology Technology Trend Report 2011).

Existing iodine measurement methods include liquid chromatography (LC-MS) including mass spectrometry, liquid chromatography-atomic emission spectrometry, capillary electrophoresis and electrochemical detection for absorption and fluorescence detection, inductively coupled plasma mass Analyzer (ICP-MS) and ion chromatography. However, these techniques are time-consuming and costly, rely on expert skills in the analysis process, and the sample preparation process is complicated by various procedures.

As a method for detecting iodine and iodine compounds using known metal nanoparticles, Professor Mario of Laval University of Canada synthesizes a polythiophene derivative to specifically bind iodine and distinguishes between color and fluorescence And developed a chemosensor that could The synthesized polypyrrole selectively binds to iodine to change the yellow of the silver nanoparticles to pink, and binds the synthesized polymer with poly (3-alkoxy-4-methyl-thiophene) Iodine content was quantified using the decrease in fluorescence intensity due to the quenching effect (J. Am. Chem. Soc. 2003, 125, 4412-4413).

Professor Ahih-Ching Huang of Taiwan said that gold nanoparticles are modified with bovine serum albumin (BSA) to bind iodine anions (I ^- ) and disulfide anions (S ² ^- ) Anion was detected by the phenomenon of decrease in fluorescence intensity, disappearance of fluorescence upon binding with cyanide ion (CN ^- ), and recovery of fluorescence upon addition of cyanide ion. In this case, when hydrogen peroxide (H ₂ O ₂ ) is added as a masking agent, iodine anions can be detected with high selectivity by inhibiting cyanide ion and disulfide ion (ACS Appl. -2658).

Professor Han, Woo - Sang of Gyeongsang National University reacted the anion directly with polyvinyl chloride - bound gold nanoparticles. Among them, a colorimetric sensor which can selectively detect and react with iodine anions among various anions has been developed. The change in color of the membrane is due to aggregation due to the adsorption of iodide anion on the surface of the nanoparticles (Bull. Korean Chem. Soc. 2006, 27, 2081-2083).

Professor Lingin Chen of China has developed an iodine anion detection colorimetric sensor based on the anti-aggregation phenomenon of gold nanoparticles. Gold nanoparticles modified with thymine functionalized with mercapto groups (-SH) cross-link with mercury ions (Hg ² ⁺ ), resulting in agglomeration and color change. However, when mercury ions and iodine anions are present at the same time, iodine and mercury ions are combined to form mercury iodide (HgI ₂ ), and aggregation of gold nanoparticles is stopped. This phenomenon does not occur in the case of other halogen anions (F ^- , Cl ^- , Br ^- ), but only in the case of iodine anions (I ^- ). By this method, iodine anions can be detected within 5 minutes at a concentration of 10 nm (Sensors and Actuator B 2013, 182, 482-488).

Sensor technology for measuring harmful substances can quickly analyze and detect various components in the vicinity of contamination accident sites and hazardous substances, and can remove harmful substances by monitoring environmental pollution or harmful factors in advance. It is a key element technology that makes possible.

It is an object of the present invention to develop a colorimetric sensor comprising gold nanoparticles having high selectivity and sensitivity in the detection of iodine anions and to select a specific polymer compound to be bound to gold nanoparticles and to determine the molecular weight and amount of the polymer compound, PH, and temperature of the gold nanoparticles, it is possible to easily detect the iodine anions in real time and provide a basis for measuring the iodine anion concentration.

The present invention has been accomplished to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing iodine anion (I) comprising gold (Au) nanoparticles having a diameter of 100 nm or less and functionalized with glycol chitosan represented by the following formula ^- ) detection is provided.

[Chemical Formula 1]

In the above formula (1), x is from 25 to 320, y is from 25 to 320, and z is from 25 to 320.

The glycol chitosan preferably has a molecular weight (MW) of 20,000 to 250,000. When the molecular weight is less than 20,000, the number of functional groups is so small that it is not suitable for formation of nanoparticles and reaction with iodine ions. Therefore, when the molecular weight exceeds 250,000, the solubility is lowered due to viscosity and cross- .

The precursor of the gold nanoparticles is chloroauric acid hydrate (HAuCl ₄ .4H ₂ O), and the molar ratio of glycol chitosan to chloroauric acid hydrate is 0.03 × 10 ^-3 to 0.92 × 10 ^-3 .

The colorimetric detection sensor is capable of detecting iodine anions in the range of pH 2 to 7, preferably in the range of pH 5 to 6.

The colorimetric detection sensor can detect iodine anions in a temperature range of room temperature to 100 ° C, preferably 70-100 ° C.

In the colorimetric detection sensor, when the iodine anion is detected, a color change to purple or dark blue appears.

The iodine anion detectable concentration is 0.1 ppm or more.

The detection concentration of the iodine anion can be quantified by measuring the color change of the colorimetric detection sensor with a spectrophotometer, a fluorescence photometer, or a colorimeter.

Further, the present invention is a colorimetric detection method for detecting an iodine anion,

An input step of inputting a sample to be detected into a colorimetric detection sensor; And

And a detection step of detecting an iodine anion of 0.1 ppm or more in the sample to be detected by the color change of the colorimetric detection sensor,

Wherein the colorimetric detection sensor comprises gold nanoparticles having a diameter of 100 nm or less, the surface of which is functionalized with glycol chitosan of formula (1).

The method may further include adjusting pH and temperature of the colorimetric detection sensor to enhance the stability and sensitivity of the nanoparticles before the step of injecting.

Wherein the color emission wavelength indicated by the colorimetric detection sensor in the applying step includes a range of 450 nm to 600 nm, and when the iodine anion is present in the sample to be detected, the color emission wavelength indicated by the colorimetric detection sensor in the sensing step is 500 nm to 800 nm , And the absorption ratio (A700 / A521) of the colorimetric detection sensor in the sensing step ranges from 0.07 to 0.96.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

FIG. 1A is a structural diagram showing, on a molecular scale, binding of gold nanoparticles (AuNPs) functionalized with glycol chitosan to an iodine anion (I ^- ) in a pH range of 5 to 8 according to an embodiment of the present invention. FIG. 1B is a schematic diagram showing the coagulation phenomenon and the color change due to the combination of the functionalized gold nanoparticles and the iodine anion.

1A, the reactant is red gold nanoparticles formed by reduction of chloroauric acid hydrate by an amine group (N-H) of glycol chitosan. This is a polymeric nanoparticle, which has a particle size of 100 nm or less and is uniform in size, so that the surface plasmon resonance phenomenon tends to occur.

When the iodine anion is added thereto, the iodine anion binds to the C = O of the amide group (RCONH) of the glycol chitosan attached to the gold nanoparticles, and the aggregation reaction occurs, thereby changing the color of the gold nanoparticles to purple 1A and 1B). Here, the assembling and aggregation of the gold nanoparticles are caused by surface plasmon resonance (hereinafter, referred to as " surface plasmon resonance "). As the distance between the particles approaches or the overall size of the nanoparticles increases, A change appears.

The iodine anion detection sensor of the present invention as described above is highly suitable for colorimetric detection due to its high selectivity and sensitivity to iodine anion. It is also suitable for detecting bio-samples including blood, mineral water, medicines and iodine There is an advantage that the negative ion detection can be quickly processed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing, in molecular units, (a) binding of gold nanoparticles (AuNPs) functionalized with glycol chitosan to an iodine anion (I ^- ) in accordance with an embodiment of the present invention, and (b) This is a schematic diagram showing the coagulation phenomenon and color change due to the combination of the nanoparticle and the iodine anion.
FIG. 2 is a graph showing the color change of (a) the colorimetric sensor solution according to the molar ratio of glycol chitosan and chloroauric acid (HAuCl ₄ ) according to Table 1 and (b) the change of UV-Vis absorbance.
FIG. 3A is a color change photograph and a UV-Vis absorbance graph before (left) and after (right) reaction of gold nanoparticles with iodine anions according to an embodiment of the present invention, and FIGS. FIG. 3 is a graph showing the size distribution of nanoparticles before and after the reaction. FIG.
Fig. 4 is a graph of (a) color change of gold nanoparticles according to pH in Example 1 and (b) UV-vis absorbance graph.
5 is a graph of (a) color change, (b) UV-vis absorbance graph, and (c) absorptivity ratio (A700 / A521) according to the reaction temperature in Example 2.
6 is a graph of (a) color change, (b) UV-vis absorbance graph, and (c) absorptivity ratio (A700 / A521) graph according to the NaCl concentration in Example 3. FIG.
7 is a graph showing the change of the extinction ratio (A700 / A521) according to the reaction time in Example 4. Fig.
8 is a graph showing a color change (a) and an absorption ratio (A700 / A521) according to the iodine anion concentration in Example 5. Fig.
9 is a graph showing a color change photograph (a), a UV-vis absorbance graph, and (c) an absorbance ratio (A700 / A521) of the colorimetric sensor solution with various anions added in Example 6.

BRIEF DESCRIPTION OF THE DRAWINGS The invention may be varied in many ways and may have many embodiments, and particular embodiments are illustrated and described in detail in the drawings. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Manufacturing example 1 to 12: Preparation of functionalized gold nanoparticles

A glycol chitosan solution was prepared by dissolving glycol chitosan (GC) (Sigma-Aldrich Co., Glycol chitosan) having a molecular weight (MW) of 250,000 in a slightly acidic aqueous solution (pH 6, acetic acid aqueous solution) Twelve samples were made.

Twelve samples were prepared at concentrations as shown in Table 1 below, in which chloroauric acid hydrate (HAuCl ₄ .4H ₂ O) was dissolved in water to prepare a chloroauric acid solution.

The glycol chitosan solution and the aqueous chloroauric acid hydrate solution were mixed at a mixing ratio shown in Table 1 below so that the molar ratio of GC / Au became 0.03 × 10 ^-3 to 0.92 × 10 ^-3 , and the mixture was reacted at room temperature for 24 hours to form polymer- A colorimetric sensor solution containing a polymeric gold nanoparticle was prepared (Production Examples 1 to 12). Unreacted glycol chitosan and chloroauric acid hydrate were removed by centrifugation at 6,000 rpm for 10 minutes.

Manufacturing example GC HAuCl ₄ GC / Au mole ratio One 0.0450 g / 7.8 ml 23.08 [mu] M 8.5 mg / ml 25.01 mM 0.92 x 10 ^-3 2 0.0220 g / 7.8 ml 11.28 [mu] M 8.5 mg / ml 25.01 mM 0.45 x 10 ^-3 3 0.0110 g / 7.8 ml 5.64 μM 8.5 mg / ml 25.01 mM 0.23 x 10 ^-3 4 0.0050 g / 7.8 ml 2.56 [mu] M 8.5 mg / ml 25.01 mM 0.10 x 10 ^-3 5 0.0025 g / 7.8 ml 1.28 [mu] M 8.5 mg / ml 25.01 mM 0.05 x 10 ^-3 6 0.0012 g / 7.8 ml 0.62 [mu] M 8.5 mg / ml 25.01 mM 0.03 × 10 ^-3 7 0.0050 g / 7.8 ml 2.56 [mu] M 4.25 mg / ml 12.51 mM 0.21 x 10 ^-3 8 0.0025 g / 7.8 ml 1.28 [mu] M 4.25 mg / ml 12.51 mM 0.10 x 10 ^-3 9 0.0012 g / 7.8 ml 0.62 [mu] M 4.25 mg / ml 12.51 mM 0.05 x 10 ^-3 10 0.0450 g / 7.8 ml 23.08 [mu] M 17 mg / ml 50.13 mM 0.46 x 10 ^-3 11 0.0220 g / 7.8 ml 11.28 [mu] M 17 mg / ml 50.13 mM 0.23 x 10 ^-3 12 0.0110 g / 7.8 ml 5.62 [mu] M 17 mg / ml 50.13 mM 0.11 x 10 ^-3

Each photograph of the colorimetric sensor solution of Production Examples 1 to 12 is shown in Fig. Referring to FIG. 2A, in Production Examples 1 to 3, there was a red color. Among them, Production Example 3 showed the most clear red color. In the case of Production Examples 5 to 12, the glycol chitosan and the chloroauric acid hydrate coagulate to change the color of the gold nanoparticles, which is not preferable. Production Examples 7 to 12 were the same as or similar to those in Production Examples 1 to 6 (concentration of chloroauric acid aqueous solution was 25.01 mM) in the GC / Au molar ratio when the concentration of chloroauric acid aqueous solution was 12.51 mM or 50.13 mM, When mixed with glycol chitosan, the nanoparticles become unstable and the color of the particles changes, which is undesirable. In Examples 10 to 12, the concentration of chloroauric acid aqueous solution was increased to 50.13 mM to observe the formation of nanoparticles. The nanoparticles turned into hydrogels by cross-linking, which was not preferable.

The colorimetric sensor solutions of Production Examples 1 to 9 were measured for absorbance in the range of 350 to 800 nm using a UV-vis spectrophotometer, and they are shown in FIG. 2B. Production Example 3 exhibited a maximum absorbance at 521 nm. In summary, when comparing the size and color of the gold nanoparticles and the results of UV-vis absorbance in the above-mentioned production examples, it was confirmed that the optimum condition for maintaining the stability of the nanoparticles was Production Example 3.

Example One: pH Stability of functionalized gold nanoparticles according to changes

The color change and stability of the gold nanoparticles according to the pH of the colorimetric sensor solution obtained in Production Example 3 were examined. The pH was adjusted using 1 M HCl and 1 M NaOH and samples were made to pH 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, respectively. A photograph of the sample having each pH is shown in FIG. 4A, and the absorbance spectrum of each sample was measured by UV-Vis, and it is shown in FIG. 4B.

Referring to FIG. 4A, red color was similar to the typical color of gold nanoparticles at pH 5, 6, 8 to 11. In FIG. 4B, when the wavelength is 520 nm, the nanoparticles formed under the condition of pH 6 exhibit the strongest absorbance. Generally, chitosan dissolves easily in aqueous solution because it releases electrons from acid (protonization), but does not dissolve in neutral and basic aqueous solution. Glycol Chitosan has a good melting property in weak acid, and it can be seen that when gold nanoparticles are reduced by glycol chitosan, they maintain the strongest red color and high solubility at pH 6. Thus, it was confirmed that the gold nanoparticles formed at pH 6 maintained a constant state of nanoparticles without changing color.

3A shows the absorbance spectrum (black) and the photograph (left) for functionalized gold nanoparticles (GC-AuNPs) after adjusting the pH of the colorimetric sensor solution obtained in Production Example 3 to 6, and 5 ppm of iodine anion (Red color) and photograph (right) for gold nanoparticles (I-GC-AuNPs) after the reaction. As can be seen from the photograph, it was red before the reaction, but the color changed to purple after the reaction. FIG. 3B is a graph showing the size distribution of the nanoparticles before reaction with the iodine anion and FIG. 3C is a graph showing the size distribution of the nanoparticles after the reaction with the iodine anion. 3B and 3C, the average size of the nanoparticles was 181 nm before the reaction with the iodine anion, but it was found that the size of the nanoparticles was increased to 569 nm after the reaction.

Example 2: Reactivity and stability of functionalized gold nanoparticles according to reaction temperature

The pH of the colorimetric sensor solution obtained in Preparation Example 3 was adjusted to 6, and 5 ppm of iodine anion was added. The reaction temperature was changed to 25, 30, 40, 50, 60, 70, 80, Min, and the color change of each sample was observed. A photograph of each sample is shown in Fig. 5A, and a UV-vis spectrum is shown in Fig. 5B.

Referring to FIG. 5A, although the color change was not large until 70 ° C., the color changed to purple at 80 ° C. to 100 ° C., indicating that the reactivity of the particles was increased. This tendency can be confirmed also in the UV-vis spectrum of FIG. 5B. Fig. 5C is a graph showing the extinction ratio (A700 / A521) at 700 nm and 521 nm at wavelengths in Fig. 5B, showing the highest absorptivity at 100 캜.

Example 3: Sodium chloride ( NaCl ) Reactivity and Stability of Functionalized Gold Nanoparticles by Concentration

The pH of the colorimetric sensor solution obtained in Preparative Example 3 was adjusted to 6 and 12 samples were collected and analyzed for NaCl concentrations of 1, 5, 10, 20, 30, 40, 50, 100, 150, 200, 300 and 500 NaCl < / RTI > After adding 10 ppm of iodine anion (I-) to each sample, the reaction was allowed to proceed at a reaction temperature of 100 ° C for 25 minutes, and color change was observed. A photograph of each sample is shown in Fig. 6A, and a UV-vis spectrum is shown in Fig. 6B.

In FIG. 6A, the color change continued until the NaCl concentration of 30 mM, and the purple color remained at 40 mM. This tendency can be confirmed also in the UV-vis spectrum of FIG. 6B. FIG. 6C is a graph showing the extinction ratio (A700 / A521) at 700 nm and 521 nm of wavelength in FIG. 6B according to the NaCl concentration. It can be seen that the concentration of 40 mM NaCl is the optimum salt concentration for detecting iodine anion. The addition of NaCl utilizes the salting out effect, which can remove the interfering substances for iodine anion detection by segregating various components contained in the aqueous solution of the sample.

Example 4: Reaction time of functionalized gold nanoparticles with iodine anion concentration

The pH of the colorimetric sensor solution obtained in Preparation Example 3 was adjusted to 6, and the NaCl concentration was adjusted to 40 mM. (A700 / A521) was measured continuously over time with the addition of iodine anions at 0.5, 1, 3, 5 and 7 ppm to each sample and reaction at 100 ℃. Is shown in Fig.

7, the extinction ratio (A700 / A521) increased very rapidly up to 10 minutes, then gradually increased from 10 minutes to 25 minutes. It can be seen that the reaction hardly occurs from 25 minutes. Therefore, it is considered that the reaction between the nanoparticles and the iodine anion under the above conditions is completed within about 25 minutes.

Example 5: Sensitivity of colorimetric sensor solution according to iodine anion concentration Calibration curve

The pH of the colorimetric sensor solution obtained in Preparation Example 3 was adjusted to 6, and the NaCl concentration was adjusted to 40 mM. To confirm the quantitative measurement of iodine anions, iodine anions were added to give concentrations of iodine anions of 0.1, 0.3, 0.5, 1, 2, 3, 4, 5, 7 and 10 ppm, respectively. The reaction was carried out at a reaction temperature of 100 ° C for 25 minutes, and color change was observed. A photograph of each sample is shown in Fig. 8A, and an absorption ratio (A700 / A521) according to the iodine anion concentration is shown in Fig. 8B.

8A, it can be seen that the purple color increases with an increase in the amount of iodine added. 8B, the linearity (r ² = 0.9248) according to the extinction ratio is maintained, and the linear equation shows y = 0.0344x-0.0045. Thus, it can be seen that the colorimetric sensor solution according to the present invention can quantitatively analyze iodine anions. Table 2 below shows the details of the linear equation of FIG. 8B.

equation y = a + b * x weight instrumental Residual sum of squares (RSS) 43.17037 Pearson's r 0.96495 Adj. R-Square 0.9213 value Standard error B Intercept -0.00102 9.4201E-4 Slope 0.03194 0.00328

Example 6: Selectivity of colorimetric sensor solution for other anionic compounds

The pH of the colorimetric sensor solution obtained in Preparation Example 3 was adjusted to 6, and the NaCl concentration was adjusted to 40 mM. In order to determine the selectivity for different anions, prepare 16 samples and for each of the samples ^{1) I -, 2) NO} 3 -, 3) Cl -, 4) Br -, 5) SO 4 2 -, 6) PO _{^{4 2 -, 7) CN -}} , 8) SCN -, 9) IO 3 -, 10) NO 2 -, 11) F -, 12) S 2 -, 13) CH 3 COO -, 14) ClO 4 -, _{15) C 6 H 4 (COO} - _{a) 2, 16) C 3 H} 5 O (COO) followed by the addition of _^3-3 by 10 ppm, and reacted at a reaction temperature of 100 ℃ for 25 minutes a color change was observed. A photograph of each sample is shown in Fig. 9A, and a UV-vis spectrum is shown in Fig. 9B.

In Fig. 9A, the iodine anion shows purple or indigo color differently from other anions, so that the reactivity between the iodine anion and other ions can be clearly distinguished by the color change alone. In addition, it can be confirmed that the iodine anions show the absorbances A521 and A600, which are different from other ions, in Fig. 9B. FIG. 9C is a graph showing the absorption ratio of FIG. 9B. It can be seen that the iodine anion has a very high selectivity for the nanoparticles of the present invention, unlike the other anions. That is, the detection system of the present invention has a high selectivity to distinguish it from other anions through analysis of the extinction ratio, so that the sensitivity to the iodine anion is high enough to be visually discriminable as compared with other anions.

Example 7: Evaluation of effectiveness of detection system containing functionalized gold nanoparticles

For the detection of iodine anions in mineral water, commercially available drinking water was purchased to confirm the presence of iodine anions in the product, and after confirming that iodine anions were not present, it was used as a blank.

The samples were added with iodine anions of 1 ppm and 5 ppm, respectively, in the blank, and the absorbance was measured with a UV-vis. The absorbance was measured using the calibration curve prepared in Example 5, the coefficient of variation (CV) Recovery (%) was measured and is shown in Table 3 below.

I ^- Addition concentration
(ppm) Detection concentration
(ppm) CV (Coefficient of Variation) Recovery rate
(%) Detection limit
(ppm) 1.00 0.96 ± 0.6 9.5 90.4 ± 5.3 0.1 5.00 4.68 ± 0.3 7.4 100.6 ± 10.6

As shown in Table 3, the detection limit (LOD) of iodine anion using the colorimetric sensor solution was 0.1 ppm. 1 ppm and 5 ppm, respectively, were 0.96 ± 0.6 and 4.68 ± 0.3, respectively, which were close to the actual additions. The coefficient of variation was also excellent at 9.5 and 7.4, and the recoveries were also 90.4 ± 5.3 and 100.6 ± 10.6. Generally, many obstacles may exist in detecting iodine anions for products made of various compositions such as drinking water and beverages. However, the colorimetric sensor solution containing the polymer-type gold nanoparticles according to the present invention has excellent performance The selectivity is high.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. And falls within the scope of the present invention.

Claims

As a colorimetric detection sensor for detecting iodine anion (I ^- ),
(Au) nanoparticles having a diameter of 100 nm or less, the surface of which is functionalized using glycol chitosan represented by the following formula (1) as a modifier.
[Chemical Formula 1]

The method according to claim 1,
Wherein the glycol chitosan has a molecular weight (MW) of 20,000 to 250,000.

The method according to claim 1,
Wherein the precursor of the gold nanoparticles is a chloroauric acid hydrate (HAuCl ₄ .4H ₂ O).

The method of claim 3,
Wherein the molar ratio of glycol chitosan to chloroauric acid hydrate is 0.03 x ^10-3 to 0.92 x ^10-3 .

The method according to claim 1,
Wherein the colorimetric detection sensor detects an iodine anion in a range of pH 2 to 7.

6. The method of claim 5,
Wherein the colorimetric detection sensor detects an iodine anion in a range of pH 5 to 6.

The method according to claim 1,
Wherein the colorimetric detection sensor detects an iodine anion in a temperature range of room temperature to 100 ° C.

8. The method of claim 7,
Wherein the colorimetric detection sensor detects iodine anions in a temperature range of 70 to 100 占 폚.

The method according to claim 1,
Wherein the colorimetric detection sensor has a color change to purple or dark blue when iodine anion is detected.

The method according to claim 1,
Wherein the iodine anion detectable concentration is 0.1 ppm or more.

The method according to claim 1,
Wherein the detection concentration of the iodine anion is quantified by measuring a color change of the colorimetric detection sensor with a spectrophotometer, a fluorescence photometer, or a colorimeter.

A colorimetric detection method for detecting iodine anions,
An input step of inputting a sample to be detected into a colorimetric detection sensor; And
A detection step of detecting an iodine anion of 0.1 ppm or more in the sample to be detected by the color change of the colorimetric detection sensor;
And a coloring step of coloring the coloring material,
Wherein the colorimetric detection sensor comprises gold nano-particles having a diameter of 100 nm or less and surface-functionalized with glycol chitosan of formula (1).

13. The method of claim 12,
Further comprising adjusting the pH and temperature of the colorimetric detection sensor to enhance the stability and sensitivity of the nanoparticle prior to the step of injecting.

13. The method of claim 12,
Wherein the color emission wavelength indicated by the colorimetric detection sensor in the applying step includes a range of 450 nm to 600 nm, and when the iodine anion is present in the sample to be detected, the color emission wavelength indicated by the colorimetric detection sensor in the sensing step is 500 nm to 800 nm Of the color gamut.

13. The method of claim 12,
Wherein an absorption ratio (A700 / A521) of the colorimetric detection sensor in the sensing step is 0.07 to 0.96.