KR101847893B1 - Sensor electrode for measuring 1-OHP, preparation method of the same and electrochemical sensor for measuring 1-OHP comprising the same - Google Patents

Abstract

The present invention relates to a sensor electrode for measuring urinary 1-hydroxypyrene (1-OHP), a preparation method thereof, and an electrochemical sensor for measuring 1-OHP including the same, and more specifically, to a sensor electrode for measuring 1-OHP capable of measuring 1-OHP molecules which are biomarkers for evaluating biological exposure of carcinogenic polycyclic aromatic hydrocarbons at low costs in a short period of time in a simple and convenient manner with high sensitivity and high selectivity, a preparation method thereof, and an electrochemical sensor for measuring 1-OHP including the same.

Description

[0001] The present invention relates to a sensor electrode for measuring 1-OHP, a method of manufacturing the same, and an electrochemical sensor for measuring 1-OHP,

The present invention relates to a sensor electrode for 1-OHP measurement, a method for producing the same, and an electrochemical sensor for measuring 1-OHP comprising the same. More particularly, the present invention relates to a biomarker for evaluating biological exposure of carcinogenic polycyclic aromatic hydrocarbons, To a sensor electrode for 1-OHP measurement capable of measuring a molecule with high sensitivity and high selectivity, simply and conveniently at a low cost in a short time, a method for producing the same, and an electrochemical sensor for measuring 1-OHP comprising the same.

In recent years, with the development of industry, health damage caused by environmentally harmful substances has reached serious level. In particular, the major components of air pollutants including fine dust are known as heavy metals and polycyclic aromatic hydrocarbons (PAH).

PAH, which is caused by incomplete combustion of organic matter, is a carcinogen that is present in various environmental hosts and can induce cancer in a trace amount. It is a representative environmental pollutant having mutagenicity. It is a typical pollutant substance of hydrocarbon, , Tobacco smoke, and the like.

Many PAHs in the air are known to be adsorbed to particulate matter in the air, and are known to produce reactive radicals, intermediate oxides with potential toxicity, and oxidation products by photochemical reactions. PAH is exposed to the human body through various pathways, and it is important in that it is exposed to a large number of people and is continuous. It is widely distributed in various organs of the human body regardless of the route of introduction into the body, Is detected in abundant organs.

The PAH introduced into the body is hydrophilic by metabolism and is generally converted to phenols, diols, and tethols via the intermediate epoxy, cytochrome P-450, which is an oxidase, Glucuronic acid and glutathione. Most metabolisms are detoxified, but it is known that PAH activates with DNA coupled with dihydrodiol epoxide to induce tumors.

Since it is practically difficult to evaluate human exposure to various kinds of PAHs, the biomarker that reflects the human body exposure of PAH is used to measure the pyrene metabolite, 1-hydroxypyrone (1-OHP) And to assess the degree of exposure and degree of exposure. It is known that more than 80% of the 1-OHP released into the urine is bound to a specific functional group and less than 20% is freestyle, and 1-OHP in the urine is measured by liquid chromatography and fluorescence detector Mass spectrometry, mass spectrometry, enzyme-linked immunosorbent assay (ELISA), etc., have been developed by Jongeneelene et al. (FJ Jongeneelen et al., J. Chromatogr. 413. 227. (1987) .

These are accurate, reliable, and accurate analytical methods. However, they require expensive equipment and professional manpower, and are costly, costly, time-consuming, and complex in the preprocessing process. OHP measurement method is required.

Meanwhile, a molecular imprinting (MI) technique is a technique in which a polymer matrix is formed by polymerization of a functional monomer around a target molecule using a functional monomer capable of interacting with a target molecule as a target, By removing the molecules, it is possible to specifically bind target molecules by forming three-dimensional microvoids capable of recognizing molecules whose shape and size match with the target molecules.

Molecular imprinting technology is an artificial receptor technology that imitates biochemical actions such as mass transfer in the living body, signal transmission of the nervous system, catalysis of the enzyme, immune function of the antibody to the antigen, and genetic information transmission of the DNA. The material thus produced is physically and chemically stable and can be manufactured at a lower cost than the biomaterial, and can be used in a wide range.

Selective adsorption of 1-OHP molecules and sensor technology using molecular imprinting technology have been developed and reported. Krisch N. (Krisch N. et al., Analyst. 126 (11), 1936 (2001)) discloses a method for the development of a potential sensor using styrene and divinylbenzene as functional monomers with 1-OHP We have developed a molecular recognition adsorbent for molecules and have reported selective adsorption characteristics using molecular recognition properties and electrochemical methods of adsorbents. However, it is difficult to produce adsorbents with high adsorption efficiency due to complicated production method, long adsorption time of 1-OHP, It has not been possible.

In the same group, molecular recognition sensor electrodes were fabricated by using functional vinyl monomers with (vinylbenzyl) trimethylammonium chloride and divinylbenzene or ethylene glycol dimethacrylate (Krisch N et al., Electroanalysis, 17 (7), 571 (2005)), the prepared sensor electrode was immersed in 1-OHP solution and adsorbed thereon, and then an electrochemical method was used. However, .

Although the WR Heineman research group at the University of Cicinnatei in the United States has published a paper on the development of high sensitivity sensors using spectroscopic electrochemical methods (RA Wilson et al., Anal. Chem. 83.3725 (2011) (X. Shen et al., J. Eelctroanl. Chem. 667.1. (2012)) by using an electrochemical method using a group of poly methylthiophene electrodes, Are not technologies in which molecular recognition technology is introduced, and in particular, do not contain any information on the molecular selectivity of similar molecules.

The present inventors have found that the molecular imprinting material of a metal oxide matrix using a precursor of Ti (O- ⁿ Bu) ₄ as a functional monomer has a faster binding capacity and thinning technology, excellent sensitivity sensing and selectivity than organic polymer matrix materials, It has been reported through the patent. In particular, a 1-OHP imprinting nano thin film prepared by a spin coating method and a surface coating method of a porous polymer bead with respect to 1-OHP molecules is excellent in molecular recognition and selectivity in a short period of time Yang et al., Microchim. Acta. 183. 1601 (2016)) and a paper (DH et al., Current Applied Physics 9. e136. I have reported.

Unlike the above-mentioned prior arts, the present inventors have repeatedly studied a new technique for easily and conveniently measuring 1-OHP molecules in the urine in a short period of time, and as a result, they have developed a molecular imprinting technology , It was found that the sensor electrode for 1-OHP measurement was fabricated and the detection and recognition ability of the prepared sensor electrode for 1-OHP molecules could be evaluated with high sensitivity and high selectivity by using an electrochemical method. I have come to completion.

Therefore, it is an object of the present invention to provide a method for detecting 1-OHP molecules, which is a biomarker for evaluating biological exposure of carcinogenic polycyclic aromatic hydrocarbons, at a high sensitivity and high selectivity, simple and convenient, A sensor electrode for 1-OHP measurement that can be measured at low cost, a method for producing the sensor electrode, and an electrochemical sensor for 1-OHP measurement including the same.

In order to achieve the above object,

A solid support on which an active group capable of physical or chemical interaction with the metal oxide is introduced on the surface, and a complex complex of a metal oxide precursor and 1-hydroxypyrrole (1-OHP) A 1-OHP imprinted thin film comprising a 1-OHP imprinted thin film having a pore capable of receiving 1-OHP molecules by removing 1-OHP molecules from the metal oxide / 1-OHP composite thin film formed from the solution to provide.

Herein, the solid support on which the activator is introduced is formed by forming a self-assembled thin film on the surface of the solid support using alkanethiol molecules modified at one end thereof, thereby providing a sensor electrode for 1-OHP measurement do.

Also, the present invention provides a sensor electrode for 1-OHP measurement, wherein the activator is a hydroxyl group (-OH).

The solid support may include at least one material selected from the group consisting of a metal-coated QCM, a carbon or a conductive polymer, a plastic coated with an electrically conductive material, silicon, and glass. , And a sensor electrode for 1-OHP measurement.

Further, the metal oxide precursor is _{^{Ti (O- n Bu) 4,}} Zr (O- n Pr) 4, Al (O- n Bu) 3, (O- n Et) B 3, Ti (acac) 2, Si _{(OMe) 4, in (OC} 2 H 4 OMe) 3, Sn (O- i Pr) 4, InSn (OR) 4, BaTi (OR) 4 and VO 1 is selected from the group consisting of (O- ⁱ Pr) And a sensor electrode for measuring 1-OHP.

Here, the sensor electrode for 1-OHP measurement is characterized in that the metal oxide / 1-OHP composite thin film is a TiO ₂ /1-OHP composite thin film.

On the other hand, introducing an activator capable of physically or chemically interacting with the metal oxide on the surface of the solid support; Coating a complex complex solution containing a metal oxide precursor and 1-hydroxypyridine (1-OHP) on a surface to which the activator is introduced; Hydrolyzing the coating to form a metal oxide / 1-OHP composite thin film; And removing the 1-OHP molecule from the metal oxide / 1-OHP composite thin film. The present invention also provides a method of manufacturing a sensor electrode for 1-OHP measurement.

Herein, the step of introducing an activating group onto the surface of the solid support is performed by forming a self-assembled thin film on the surface using alkanethiol molecules modified at one end thereof. ≪ / RTI >

Also, the present invention provides a method for producing a sensor electrode for 1-OHP measurement, wherein the activator is a hydroxyl group (-OH).

The present invention further provides a method of manufacturing a sensor electrode for 1-OHP measurement, which further comprises polishing, cleaning, and then drying the surface before introducing an activator to the surface of the solid support.

Further, the complex complex solution contains ethanol and toluene in a volume ratio of 1: 1.

Also, the present invention provides a method of manufacturing a sensor electrode for 1-OHP measurement, wherein the step of removing 1-OHP molecules from the metal oxide / 1-OHP composite thin film is performed using ethanol.

On the other hand, an electrochemical sensor for 1-OHP measurement comprising the sensor electrode for 1-OHP measurement.

The present invention relates to a sensor electrode for 1-OHP measurement capable of detecting a 1-OHP molecule which is a biomarker for evaluating biological exposure of carcinogenic polycyclic aromatic hydrocarbons at a sub-ppb level, a method for producing the same, By providing an electrochemical sensor for OHP measurement, the 1-OHP molecule, which is a biomarker for bioinjection evaluation of carcinogenic polycyclic aromatic hydrocarbons in urine, can be accurately discriminated by the size and the functional group of the molecule, so that high sensitivity and high selectivity can be measured.

In addition, the electrochemical sensor for measuring 1-OHP according to the present invention is not limited to a conventional pretreatment process or an expensive skilled technician, but can be easily and conveniently installed at a low cost with a small equipment. Can be measured.

1 is a schematic diagram and a schematic diagram of a CV measurement method for producing a sensor electrode for 1-OHP measurement according to the present invention.
FIG. 2 is a graph showing the results of measurement of change in current value by oxidation-reduction reaction of 1.6 mm and 2.0 mm diameter gold electrodes into which hydroxyl groups are introduced in Test Example 1 according to the present invention.
FIG. 3 is a graph showing the results of a comparison between a Ti (O ⁿ Bu) ₄ precursor solution and a Ti (O ⁿ Bu) ₄ and 1-OHP complex complex solution prepared in Test Example 2 according to the present invention FIG. 2 is a graph showing the results of measurement of change in current value due to oxidation-reduction reaction of a sensor electrode after removing 1-OHP from a sensor electrode and a complex complex sensor electrode. FIG.
FIG. 4 is a graph showing the results of measurement of change in current value by oxidation-reduction reaction of a TiO ₂ thin film electrode fabricated on a gold electrode and a 1-OHP imprinted thin film electrode in Test Example 3 according to the present invention.
5 (a) is a graph showing a change in maximum current value due to an oxidation reaction with respect to a concentration change of 1-OHP molecules in a TiO ₂ thin film electrode and a 1-OHP imprinted thin film electrode, and FIG. Lt; / RTI > is a schematic representation of a template bound to a printed binding site.
FIG. 6 is a graph showing the 1-OHP measurement for the guest molecules in Test Example 4 according to the present invention and the CV peak change due to the oxidation-reduction reaction in the same range.
7 is a graph showing a change in maximum current value due to an oxidation reaction at a concentration of 1 x 10 < ^-9 > M of a guest molecule in each of a TiO ₂ thin film electrode and a 1-OHP imprinted thin film electrode.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments and drawings described in the present specification are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.

The present invention relates to a solid support in which an active group capable of physically or chemically interacting with a metal oxide is introduced on a surface thereof and a solid support formed on the surface to which the activator is introduced and comprising a metal oxide precursor and a 1- 1-OHP complex thin film formed from a complex complex solution of 1-OHP, wherein the 1-OHP complex thin film has a 1-OHP imprinted thin film having pores capable of accommodating 1-OHP molecules, Thereby providing a sensor electrode.

The sensor electrode for 1-OHP measurement may include: introducing an activator capable of physically or chemically interacting with the metal oxide by pretreating the surface of the solid support;

Forming a metal oxide / 1-OHP composite thin-film electrode by coating a composite complex solution prepared by stirring a metal oxide precursor and 1-hydroxypyrrole in a mixed solution of ethanol and toluene on the surface of the solid support; And

 And removing the 1-OHP molecules from the metal oxide / 1-OHP composite thin-film electrode by a method of manufacturing a sensor electrode for 1-OHP measurement.

As the solid support used in the present invention, a solid support capable of being electrically conductive may be used. For example, a metal support such as aluminum, silver, platinum, an ITO based, various metal coated QCM, An electrode using a conductive polymer, and an electrode coated with an electrically conductive material on a solid support such as a plastic substrate, a silicon substrate, and a glass, but the present invention is not limited thereto.

In one embodiment of the present invention, the step of pretreating and activating the solid support comprises washing the gold electrode polished with an alumina abrasive with distilled water and ethanol, and then adding a pyrahas solution (96% sulfuric acid / 30-35.5% hydrogen peroxide , 2/1, v / v) for 3 minutes, washed with distilled water and ethanol, dried with nitrogen gas, and reacted with a gold electrode using a molecule containing a hydroxyl group. As a result, Lt; / RTI > can be obtained.

In the present invention, the solid support is used after the surface treatment by forming the surface activity. For example, a self-assembled thin film can be formed by using an alkane thiol molecule having one end modified with a pretreated solid support.

In the present invention, the process of forming a metal oxide / 1-OHP composite thin film electrode on a solid support is performed by mixing a metal complex precursor and 1-hydroxypyrrole in a mixed solution of ethanol and toluene to form a complex complex solution on the surface of the solid support Coating.

As the metal oxide precursor, metal oxide precursors capable of forming complex complexes with 1-OHP may be used in the present invention. For example, a metal oxide is _{^{Ti (O- n Bu) 4,}} Zr (O- n Pr) 4, Al (O- n Bu) 3, B (O- n Et) 3, Ti (acac) 2, _{Si (OMe) 4, In (} OC 2 H 4 OMe) 3, (O- i Pr) Sn 4, InSn (OR) 4, BaTi (OR) 4, VO (O- i Pr) , and the like, Ti (O ⁿ Bu) ₄ is preferably used.

In one embodiment of the present invention, Ti (O ⁿ Bu) ₄ and 1-hydroxypyrrole are mixed with a metal oxide precursor in a mixed solution of ethanol and toluene (1: 1, v / v) To prepare a complex complex solution.

The complexed complex solution prepared as described above may be dropped on a solid support, coated, and dried and hydrolyzed to form a TiO ₂ /1-OHP composite thin film electrode.

In one embodiment of the invention, the complexing agent solution is coated on the solid support surface using, for example, spin coating, dip coating, spray coating, surface sol-gel method, electrospinning, TiO ₂ /1-OHP composite thin-film electrode can be formed.

In the present invention, the complex complex solution is coated on the surface of the solid support and then left in a nitrogen atmosphere for 10 minutes to evaporate ethanol and toluene used as a solvent from the complex complex. Thereafter, an electrode for an electrochemical sensor coated with the complex complex Followed by hydrolysis to form a TiO ₂ /1-OHP composite thin film electrode (see FIG. 1).

Finally, the 1-OHP molecule is removed from the TiO ₂ /1-OHP composite thin film electrode using, for example, ethanol to form an artificial receptor having excellent selectivity for 1-OHP molecules.

The present invention also provides a sensor electrode for 1-OHP measurement manufactured according to the above-described method and an electrochemical sensor for measuring 1-OHP comprising the same.

Example 1 - Preparation of sensor electrode for 1-OHP measurement

(1) Reagent

Titanium (IV) n-butoxide (Ti (O- ⁿ Bu) ₄ ) is described in Acros Chem. 1-OHP, naphthalene, and anthracene were purchased from TCI (Japan). Pyrene, 1-pyrenecarboxylic acid (1 (1-aminopyrene, AMPY), 1-nitropyrene (NIPY) and potassium ferricyanide (III) were purchased from Aldrich (USA) . Mercaptoethanol and potassium chloride (KCl) were purchased from TCI (Japan), and other analytical reagents were used without further purification. The distilled water (18.3 MΩm) was ultrafine deionized distilled water manufactured by AquaMax ^TM -Ultra of Korea Research Institute of Technology.

(2) Pretreatment process of gold electrode

The gold electrode polished with alumina abrasive was washed with distilled water and ethanol and treated with pirahasolutin (96% sulfuric acid / 30-35.5% hydrogen peroxide, 2/1, v / v) for 3 minutes for 1 minute, Washed with distilled water and ethanol and dried with nitrogen gas. Subsequently, a self-assembled monolayer (SAM) was obtained using alkanethiol molecules modified at one end.

(3) TiO ₂ / 1-OHP composite thin film electrode manufacturing process

To the pretreated gold electrode, 200 mM Ti (O ⁿ Bu) ₄ and 10 mM 1-OHP were stirred in a mixed solution of ethanol: toluene (1: 1, v / v) at 25 ° C for 2 hours 10 μL of a complex complex was coated on a gold surface and allowed to stand in a nitrogen atmosphere for 10 minutes to evaporate ethanol and toluene as a solvent from the complex complex. The electrode for an electrochemical sensor coated with the complex complex thus prepared was maintained at 25 ° C., TiO ₂ /1-OHP composite thin film electrodes were prepared by hydrolysis at 90% humidity and 6 hours in a humidifier. 1-OHP-imprinted (MIP) electrodes were prepared by preparing molecular complexes in which 1-OHP molecules selectively interacted by removing 1-OHP molecules using ethanol.

Test Example 1 - Electrochemical Characterization Test of Working Electrode

Electrochemical properties were measured using Potentiostat (Compactstat, Ivium Technologies, Netherlands). A typical three-electrode system was used, using gold electrodes with diameters of 1.6 mm and 2.0 mm, reference electrodes for Ag / AgCl (saturated KCI) electrodes and counter electrodes for Pt wires. The electrolyte solution was ultrasonically treated with 1M KCl aqueous solution containing 2 mM potassium ferricyanide (Ⅲ) for 30 minutes using nitrogen gas to remove oxygen, and electrochemical characteristics were measured using a cyclic voltammetry (CV) Respectively.

The redox characteristics of the electrolyte solutions of 1.6 mm and 2.0 mm diameter gold electrodes to which hydroxyl groups had been introduced through pretreatment as in Example 1 were measured using CV. After each electrode was installed, the scan speed was increased to 0.01, 0.02, 0.05, and 0.1 V / s in the range of 0.2 to 0.6 V starting from 0.00 V, and oxidation and reduction of the ferricyanide present in the electrolyte solution The results of measuring the change in current value by the reaction are shown in Fig. The graph of each voltage-current curve shows the average value of the remaining 7-minute graphs except for the initial 3-time graphs obtained by repeating the measurement ten times. The oxidation peak near 0.3 V and the reduction peak near 0.23 V were reversibly observed regardless of the area of the two electrodes.

This reversible oxidation-reduction peak is believed to be attributed to a peak due to an electrochemical process due to the oxidation / reduction system of ferricyanide / ferrocyanide. In addition, as shown in the graph of the two electrodes, it was shown that the oxidation / reduction peak was increased by increasing the scan speed. The current value by oxidation of the gold electrode of 1.6 mm diameter (cross section: 2.01 mm ² ) at a scanning speed of 0.1 V / s and a voltage of 0.3 V was 9.5 μA and oxidation of the gold electrode of 2.0 mm diameter (cross section: 3.14 mm ² ) The current value was 13.5 μA and the current value was increased in proportion to the area of the electrode. It is considered that the increase of the oxidation current value due to the increase of the electrode surface area is caused by the increase of the number of pericyanide molecules contacting the electrode surface.

Test Example 2 - Electrochemical Characterization Test of Sensor Electrode

FIG. 3 shows the results of a pretreatment process. In the pretreatment, a pure 200 mM Ti (O ⁿ Bu) ₄ precursor solution, 10 μL of a 200 mM Ti (O ⁿ Bu) ₄ and a 10 mM 1-OHP complex complex solution After removing the 1-OHP from the sensor electrode and the complex electrode sensor electrode, the sensor electrode was used as a working electrode and the scan speed was set to 0.01, 0.02, 0.05, 0.1 V / s, and the change of the current value due to the oxidation / reduction reaction of the ferricyanide present in the electrolyte solution is measured. The graph of each voltage-current curve shows the average value of the remaining 7-minute graphs except for the initial 3-time graphs obtained by repeating the measurement ten times. FIG. 3 (a) is a graph showing the results of measurement of the concentration of 200 mM Ti (O ⁿ Bu) ₄ TiO ₂ with precursor solution In the case of the thin film electrode, an oxidation peak near 0.32 V and a reduction peak near 0.22 V were reversibly observed. This reversible phosphorylation / reduction peak coincided with the peak due to the ferricyanide / ferrocyanide redox system of the pure gold electrode into which the hydroxyl group was introduced. The oxidation / reduction peak was also increased by increasing the scanning speed, , The current value was about 2.7 μA at a voltage of 0.32 V, and the current value was reduced by about 80% as compared to the uncovered electrode. This decrease in current is due to the fact that the surface of the gold electrode is TiO ₂ It is judged that this is because the coating by the matrix hinders the movement of ferricyanide as an electroactivity probe. FIG. 3 (b) is a graph showing the relationship between two oxidation peaks near the voltages of 0.01 V and 0.35 V and 0.02 V near the voltage of 0.01 V and 0.35 V in the case of the TiO ₂ /1-OHP composite thin film using the complex complex of 200 mM Ti (O ⁿ Bu) ₄ and 10 mM 1-OHP And two reduction peaks near 0.23 V were observed. This phenomenon is believed to be due to the oxidation and reduction of 1-OHP molecules in complex complexes. The oxidation peak near 0.01 V and the reduction peak near 0.02 V are peaks derived from the 1-OHP molecule, respectively. The oxidation and reduction peaks near 0.35 V and 0.23 V are peaks derived from the ferricyanide in the electrolyte solution . From these results, it can be confirmed that 1-OHP molecules are present in the complex complex. In addition, the oxidation-reduction peak was also increased by increasing the scan speed of the complex complex thin film electrode, but the peak value of the oxidation peak was 4.69 μA at a scan rate of 0.1 V / s as compared with the pure gold electrode, Which is about 65% lower than the current value. However, TiO ₂ There was a 43% increase in current compared to the thin film electrode. This is because TiO ₂ This is because the internal voids are formed more because of the existence of the organic material 1-OHP than when only the matrix exists. FIG. 3 (c) is a CV graph of the sensor electrode imprinted with 1-OHP after removing 1-OHP molecules from the complex complex. Interestingly, the oxidation peak near 0.01 V and the reduction peak near 0.02 V of the 1-OHP molecule in the composite thin film disappeared, and around 0.33 V, 0.23 V due to the ferricyanide / ferrocyanide redox system And the maximum oxidation current value was also increased by about 65% at 7.26 μA.

These results indicate that 1-OHP molecules can be successfully removed from complex complexes, and since 1-OHP imprinted sensor electrodes have formed a molecular gap or artificial receptor capable of selectively recognizing 1-OHP molecules, It is considered that the movement of ferricyanide as an electroactivity probe is more smoothly carried out and the current value is increased. 3 (d) shows a non-coated gold electrode, TiO ₂ The CV graph shows the scanning speed of the thin film electrode, the TiO ₂ /1-OHP composite thin film electrode, and the 1-OHP imprinted sensor electrode at 0.05 V / s. Change of current value by ferricyanide / ferrocyanide oxidation / reduction system is uncovered electrode> 1-OHP Imprinted electrode> TiO ₂ /1-OHP composite thin film electrode> TiO ₂ Thin-film electrodes, and the non-coated gold electrode is most likely to have a ferricyanide / ferrocyanide redox system because there are no barriers that interfere with ferricyanide migration.

Test Example 3 - Molecular imprinting (MI) effect evaluation test

FIG. 4 shows the results of a pretreatment process in which a TiO ₂ Thin-film electrodes and thin-film electrodes imprinted with 1-OHP were used as working electrodes, and the scanning speed was set to 0.05 V / s in the range of 0.2 to 0.6 V and the concentration of 1-OHP was set to 1 × 10 ^-9 M (0.25 ppb ) To 5 × 10 ^-7 M (50.0 ppb), which is a graph showing the results of measurement of the change in current value due to the oxidation / reduction reaction of ferricyanide present in the electrolyte solution. TiO ₂ In the case of using the thin film electrode actively, even if the 1-OHP concentration was increased, the change of the current value of the ferricyanide by the oxidation-reduction reaction was almost constant, but the 1-OHP imprinted sensor thin film was used as the working electrode The maximum current value due to the oxidation and reduction reaction decreases as the concentration of 1-OHP increases.

This change in current value is due to the formation of molecular voids capable of selectively adsorbing 1-OHP molecules in the 1-OHP imprinted sensor thin film, and when the electrolyte solution is present, the ferricyanide molecules move freely in the pores, The peak due to the reduction system appears. It is judged that the peak is naturally decreased because the number of free-moving pericyanide molecules is decreased by adding 1-OHP molecule into the electrolyte solution (FIG. 5B). (A) of Figure 5, the TiO ₂ Figure 1 shows the maximum current change due to the oxidation reaction of the 1-OHP imprinted thin-film electrode at 0.33V.

Test Example 4 - Selectivity test of guest molecule

FIG. 6 is a graph showing the molecular selectivity of a 1-OHP imprinted thin film electrode. In order to confirm the molecular selectivity, naphthalene having two benzene rings as a guest molecule, pyrene having no functional group in four benzene rings identical to 1-OHP, 1-pyrenecarboxylic acid (PYCA) containing one carboxylic acid group that easily interacts with the TiO ₂ matrix to form a complex, and an amino group in one of the four benzene rings 1-OHP measurement of 1 × 10 ^-9 M to 5 × 10 ^-7 M concentration of the guest molecules at a scanning rate of 0.05 V / s in the range of 0.2 to 0.6 V starting from 0.00 V at 1-aminopyrene (AMPY) And the CV peak change due to the oxidation / reduction reaction in the same range. As the concentration of each guest molecule was increased, a reduction in the current value of the reversible redox peak due to the redox reaction was observed. This result is due to the fact that the migration of ferricyanide is disturbed by the adsorption of guest molecules on the molecular pores generated in the thin film electrode imprinted with 1-OHP, but the adsorption of 1-OHP molecules (Fig. 4 (b) When compared with the amount of change caused by

The small change in the current value due to the maximum oxidation / reduction reaction shows that the 1-OHP imprinted thin film electrode selectively adsorbs to the 1-OHP molecule. Selective adsorption of AMPY having an amino group at the same molecular size, such as naphthalene, anthracene, pyrene of the same molecular size, and PYCA having a carboxylic acid at the same molecular size, as compared with 1-OHP is shown by 1-OHP imprinted Thin-film electrodes show a selective response to 1-OHP molecules due to the molecular size and molecular voids capable of accurately recognizing the functional groups contained in the molecules, that is, the artificial receptors of the molecule recognition function represented by the biomolecules are formed in the sensor thin film.

In FIG. 7, when the concentration of each guest molecule is 1 x 10 < ^-9 > M at 0.33 V in the 1-OHP imprinted thin film electrode, the current change amounts are 0.275 μA for 1-OHP, 0.097 μA for naphthalene, 0.077 μA for anthracene , 1-OHP imprinted at 0.109 μA for pyrene, 0.149 μA for 1-pyrenecarboxylic acid (PYCA), 0.082 μA for 1-aminopyrene (AMPY) and 0.0411 μA for 1-nitropyrene The molecular selectivity for 1-OHP molecules was 2.8-fold higher for naphthalene, 3.6-fold for anthracene, 2.6-fold for pyrene, 1.9-fold for PYCA, 3.4-fold for AMPY and 6.7-fold for NIPY .

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (13)

As a sensor electrode for 1-OHP measurement,
A solid support into which an active group capable of physical or chemical interaction with the metal oxide is introduced to the surface, and
The 1-OHP molecule is removed from the metal oxide / 1-OHP complex thin film formed from the complex complex solution of the metal oxide precursor and 1-hydroxypyridine (1-OHP) Lt; RTI ID = 0.0 > 1-OHP < / RTI > imprinted thin film,
Wherein a surface of the electrode is in contact with a ferricyanide. The method according to claim 1,
Wherein the solid support into which the activator is introduced is formed by forming a self-assembled thin film on the surface of the solid support by using an alkane thiol molecule having one end modified. 3. The method of claim 2,
Wherein the active group is a hydroxyl group (-OH). 4. The method according to any one of claims 1 to 3,
Characterized in that the solid support comprises at least one material selected from the group consisting of a metal coated QCM, carbon or conductive polymer, plastic coated with an electrically conductive material, silicon and glass. - Sensor electrode for OHP measurement. 4. The method according to any one of claims 1 to 3,
The metal oxide precursor is _{^{Ti (O- n Bu) 4,}} Zr (O- n Pr) 4, Al (O- n Bu) 3, B (O- n Et) 3, Ti (acac) 2, Si (OMe _{) 4, in (OC 2 H} 4 OMe) 3, Sn (O- i Pr) 4, InSn (OR) 4, BaTi (OR) 4 and VO (O- ⁱ Pr) at least one member selected from the group consisting of And a sensor electrode for measuring 1-OHP. 6. The method of claim 5,
Wherein the metal oxide / 1-OHP composite thin film is a TiO ₂ /1-OHP composite thin film. A method of manufacturing a sensor electrode for 1-OHP measurement,
Introducing into the surface of the solid support an activator capable of physical or chemical interaction with the metal oxide;
Coating a complex complex solution containing a metal oxide precursor and 1-hydroxypyridine (1-OHP) on a surface to which the activator is introduced;
Hydrolyzing the coating to form a metal oxide / 1-OHP composite thin film;
Removing 1-OHP molecules from the metal oxide / 1-OHP composite thin film; And
And contacting the surface of the electrode with a ferricyanide. 8. The method of claim 7,
Wherein the step of introducing an activator to the surface of the solid support is performed by forming a self-assembled thin film on the surface using alkanethiol molecules modified at one end thereof. 9. The method of claim 8,
Wherein the activator is a hydroxyl group (-OH). 10. The method according to any one of claims 7 to 9,
Further comprising the step of polishing, washing and drying the surface before introducing an activator to the surface of the solid support. 10. The method according to any one of claims 7 to 9,
Wherein the complex complex solution comprises ethanol and toluene at a volume ratio of 1: 1. 10. The method according to any one of claims 7 to 9,
Wherein the step of removing 1-OHP molecules from the metal oxide / 1-OHP composite thin film is performed using ethanol. An electrochemical sensor for 1-OHP measurement comprising a sensor electrode for 1-OHP measurement according to any one of claims 1 to 3.

Images