KR101840410B1 - Sensor comprising silica chemically bound with spiropyran - Google Patents

Abstract

The present invention relates to a sensor comprising silica chemically bound with spiropyran, and a manufacturing method thereof. As stated above, according to the present invention, a problem of the prior art is solved, and the sensor can be manufactured with high purity without additional refinement. Moreover, solvent polarity or ultraviolet irradiation can be easily analyzed by using the sensor.

Description

[0001] The present invention relates to a sensor comprising silica chemically bonded with spiropyran and a process for producing the same,

The present invention relates to a sensor comprising silica chemically bonded to spiropyran and a method of making the same.

As shown in FIG. 1, the sipropyran (SP) molecule undergoes a structural change through a ring opening reaction with various stimuli such as light, heat, force, and solvent, And is observed visually. Recently, it has attracted much interest as a sensor material.

The spiropyran molecule is a molecule-based material that must be dissolved or dissolved in a liquid state to be used as a sensor material. However, the spiropyran has a disadvantage in that the stability of the pieran molecule decreases with time in the liquid state, and in the solid powder state, a large number of molecules are aggregated, which consumes more molecules than necessary.

Therefore, there is a need to develop a compound particle sensor that combines spiropyran molecules with monolayer of various shapes and sizes of carriers having a wide surface area, increases molecular stability and exhibits an efficient sensing effect with a minimal amount .

1. Korean Patent Publication No. 10-2012-0098512 2. Korean Patent Publication No. 10-2016-0091730

1. Douglas A. D., Andrew H., et al. (2009) "Force-induced activation of covalent bonds in mechanoresponsive polymeric materials Nature" 459: 68-72 2. Silvia S., Zarah W., et al. (2008). "Polystyrene bead-based system for optical sensing using spiropyran photoswitches." J. Mater. Chem 18: 5063-5071 3. Jae W. K., Yukyung J., et al. (2015). "Mechanoactivation of Spiropyran Covalently Linked PMMA: Effect of Temperature, Strain Rate, and Deformation Mode." Macromolecules 48 (5): 1335-1342

Accordingly, it is an object of the present invention to provide a sensor capable of overcoming the problems of the prior art and analyzing whether solvent polarity or ultraviolet ray is irradiated, a method for producing the same, and an analysis method using the same.

One aspect of the present invention is a sensor comprising silica chemically bonded with spiropyran, wherein the silica chemically bonded to the spiropyran has a structure represented by the following formula (1), wherein R is a substituent for controlling chemical solubility .

[Chemical Formula 1]

.

.

Another aspect of the present invention relates to a method for producing a spiropyran chemically coupled sensor comprising (B) mixing spiropyran having a carboxyl group introduced at one end thereof and silica particles having a hydroxy group introduced into its surface and performing an esterification reaction Wherein the spirofilane having a carboxyl group introduced at one end thereof has a structure represented by the following formula (2), and R in the following formula (2) is a substituent for controlling the chemical solubility of the spirofuran- And a manufacturing method thereof.

(2)

[Chemical Formula 1]

.

.

According to another aspect of the present invention, there is provided a process for preparing a compound represented by the following formula (3) by esterifying a compound represented by the following formula (3a) on the surface of silica particles having a hydroxy group introduced on its surface, A process for preparing silica chemically bonded with spiropyran according to claim 1, comprising the step of reacting a substance with a compound of the following formula (2b) to prepare silica chemically bonded with spiropyran of the following formula (1) will be.

[Chemical Formula 3]

(3)

(2b)

Another aspect of the present invention relates to (a) a solvent polarity measurement method comprising the step of injecting the sensor according to the above (1) or (2) into a solvent.

According to another aspect of the present invention, there is provided a method for measuring the absorbance of a sample, comprising the steps of: (a ') measuring an absorbance of light having a wavelength of 400 to 600 nm on a sample including the sensor according to the first or second aspect; and (b) And determining the ratio of the MC form and the SP form of the spiropyran to the ultraviolet irradiation.

According to the present invention, it is possible to overcome the above-mentioned problems of the prior art and to manufacture the sensor with high purity without further purification, and to easily analyze whether the solvent polarity or ultraviolet ray is irradiated.

Figure 1. Chemical structure of SP molecules; The SP molecule reacts to external stimuli (light, heat, force, solvent, etc.), and the ring opening reaction occurs in the form of SP in the form of SP, resulting in changes in color and fluorescence properties. When light in the visible light region is received, the SP molecule returns to a closed state, called the SP form, and the reaction is reversible.
2. Synthesis of SP molecules and Example of SP-silica composite particles in Example 1; (COOH-SP-R), (b) SP-silica complex through the chemical bonding of silica particles surface-treated with SP molecules and hydroxyl groups (OH) Preparation of particles.
Figure 3 is a schematic diagram of the preparation of SP-silica composite particles through Production Method 2; Preparation of SP-silica composite particles in which SP molecules are chemically bonded
Figure 4. Comparison of silica particles (left) surface-treated with hydroxyl groups (OH) before synthesis and SP-silica composite particles chemically bonded with SP
Figure 5. Sensor role of SP-silica composite particles according to solvent polarity
6. Comparison of absorption spectra at 400 to 600 nm wavelength; Silica solid (black solid line), SP-silica composite particle / UV group dictionary (red dotted line), SP-silica composite material / UV irradiated (red solid line)

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

One aspect of the present invention is a sensor comprising silica chemically bonded to spiropyran, wherein the silica chemically bonded to the spiropyran has a structure represented by the following formula (1), wherein R is a substituent for controlling chemical solubility .

[Chemical Formula 1]

.

.

In the present invention, examples of R, which is a substituent for controlling the chemical solubility, include one kind of substituent selected from the group consisting of a hydroxyl group (OH), a carboxyl group (COOH) and an amine group (NH ₂ ) . ≪ / RTI >

Chemical solubility is an essential condition to be considered when chemically bonding SP molecules to the silica surface. Since the SP molecule is completely dissolved in the solvent, the reaction with the hydroxyl group (OH) on the surface of the silica proceeds, so that the R-functional group having the optimal chemical solubility can be determined. For example, tetrahydrofuran (THF) and dimethylformamide (DMF) are well soluble in the case of spiropyran where R functional group is carboxyl group (COOH) in the following formula (2), but other solvents such as ethanol, methanol, dichloromethane, Because of the poor solubility, THF and DMF are advantageous for attaching SP molecules to silica.

(2)

In one embodiment, the sensor is a solvent polarity sensing or ultraviolet sensing sensor.

Another aspect of the present invention relates to a sensor for solvent polarity sensing or ultraviolet light sensing comprising a sensor according to various embodiments of the present invention.

Another aspect of the present invention relates to a method for producing a spiropyran chemically coupled sensor comprising (B) mixing spiropyran having a carboxyl group introduced at one end thereof and silica particles having a hydroxy group introduced into its surface and performing an esterification reaction Wherein the spirofilane having a carboxyl group introduced at one end thereof has a structure represented by the following formula (2), and R in the following formula (2) is a substituent for controlling the chemical solubility of the spirofuran- And a manufacturing method thereof.

(2)

[Chemical Formula 1]

.

.

In one embodiment, step (B) is preceded by (A) reacting a compound of formula (2a) and a compound of formula (2b) to obtain spirofilane having carboxyl groups at one end of formula , And X in the formula (2) is one selected from fluorine, chlorine and iodine.

(2a)

(2b)

.

.

In another embodiment, step (B) comprises reacting 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), N, N'- dicyclohexylcarbodiimide '- carbonyldiimidazole (DIC) is added to perform the reaction.

In another embodiment, the silica: the coupling agent: the spirofilane having a carboxyl group introduced at one end thereof is introduced at a ratio of 4.5-5.5: 1: 2.5-3.5 to perform the reaction. If the value is out of the above range, synthesis efficiency and absorbance may be significantly lowered based on the surface area of 60 μm silica, which is not preferable.

In another embodiment, step (A) comprises the steps of: (i) contacting a solvent selected from the group consisting of ethanol, methanol, tetrahydrofuran, dichloromethane (DCM), acetone and mixtures of two or more thereof, And (iii) a reaction time of 5 to 8 hours.

(Ii) at a temperature of 0 to 40 DEG C and (iii) at a temperature of 16 [deg.] C, To 18 hours of reaction time.

In another embodiment, step (B) is carried out at a reaction temperature of from 0 to 5 < 0 > C and a pH of from 4 to 4.5. When the temperature is out of the above-mentioned range or out of the above-mentioned pH range, the physical adsorption between silica and the SP molecule of the above-mentioned formula (2) may be greatly increased, and the chemical bond may be significantly lowered.

In another embodiment, the step (B) is carried out in the following order. It was confirmed that excellent effects can be exhibited in the reaction efficiency and the suppression of the side reaction by following the detailed reaction process and the reaction conditions as described above.

(B1) introducing spirofion having a carboxyl group introduced into the solvent into the solvent,

(B2) raising the temperature of the solution to 65 to 75 DEG C,

(B3) lowering the temperature of the solution to 0 to 5 DEG C and introducing the coupling agent,

(B4) adjusting the pH of the solution to 4 to 4.5,

(B5) introducing the silica into the solution.

In still another embodiment, the method further includes the step of performing the following pre-processing step (A2) before the step (B). Through such pretreatment, the reactivity can be greatly improved by maximizing the activation of OH functional groups present on the silica surface.

(A2-1) heating at 550 to 650 DEG C for 4 to 6 hours to remove impurities,

(A2-2) Step of removing additional impurities from the solution mixed with sulfuric acid and hydrogen peroxide 2.5-3.5: 1 by volume.

The synthesis conditions of an optimized SP-silica sensor material exhibiting high efficiency / high absorption characteristics through the present invention will be described in more detail with reference to the following examples.

According to another aspect of the present invention, there is provided a process for preparing a compound represented by the following formula (3) by esterifying a compound represented by the following formula (3a) on the surface of silica particles having a hydroxy group introduced on its surface, A process for preparing silica chemically bonded with spiropyran according to claim 1, comprising the step of reacting a substance with a compound of the following formula (2b) to prepare silica chemically bonded with spiropyran of the following formula (1) will be.

[Chemical Formula 3]

(3)

(2b)

[Chemical Formula 1]

In the above formula, X is one kind selected from fluorine, chlorine and iodine, and R is a substituent for controlling the chemical solubility.

In yet another embodiment, step (A ') comprises: (i) reacting a compound of formula (I) with a compound selected from the group consisting of 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide (EDC), N, N'- dicyclohexylcarbodiimide ), 1,1'-carbonyldiimidazole (DIC), and (ii) a polar solvent. Examples of polar solvents include, but are not limited to, alcohols and water. The reaction is carried out for a reaction time of from 16 to 18 hours at a temperature of from 0 to 40 占 폚. The synthesis conditions of an optimized SP-silica sensor material exhibiting high efficiency / high absorption characteristics through the present invention will be described in more detail with reference to the following examples.

In another embodiment, step (B ') is performed in a solvent capable of dissolving the compound of formula (2b) at a temperature of 100 to 120 ° C for a reaction time of 5 to 8 hours.

Among the two manufacturing methods according to the present invention, the first method for independently synthesizing spiropyran molecules is to purify the spiropyran molecules synthesized through a more complicated process (such as column chromatography, extraction, recrystallization, etc.) Is essential. This is time consuming and can lead to price increases when introduced into actual processes. On the other hand, the second manufacturing method for supporting the synthesis of spiropyran molecules by using a carrier is advantageous in that it can be easily recovered without a complicated purification process, thereby supporting the piran molecules with an economical spy.

In another embodiment, the silica: the coupling agent: the spirofilane having a carboxyl group introduced at one end thereof is introduced at a ratio of 4.5-5.5: 1: 2.5-3.5 to perform the reaction. If the value is out of the above range, synthesis efficiency and absorbance may be significantly lowered based on the surface area of 60 μm silica, which is not preferable.

In another embodiment, step (B ') is carried out at a reaction temperature of 0 to 5 ° C and a pH of 4 to 4.5. If the temperature is out of the above-mentioned range or out of the above range, the physical adsorption between the silica and the compound of the formula (2b) may be greatly increased, and the chemical bonding may be significantly lowered.

In yet another embodiment, (a) before step (A ') further comprises performing the following pre-treatment process. Through such pretreatment, the reactivity can be greatly improved by maximizing the activation of OH functional groups present on the silica surface.

(a1) heating at 550 to 650 DEG C for 4 to 6 hours to remove impurities,

(a2) removing additional impurities from the mixture of sulfuric acid and hydrogen peroxide in a volume ratio of 2.5-3.5: 1.

In another embodiment, the step (B ') is carried out by performing the reaction in the following order. It was confirmed that excellent effects can be exhibited in the reaction efficiency and the suppression of the side reaction by following the detailed reaction process and the reaction conditions as described above.

(B1 ') introducing the compound of formula (2b) into a solvent,

(B2 ') raising the temperature of the solution to 65 to 75 DEG C,

(B3 ') lowering the temperature of the solution to 0 to 5 DEG C and introducing the coupling agent,

(B4 ') adjusting the pH of the solution to 4 to 4.5,

(B5 ') introducing the silica into the solution.

Another aspect of the present invention relates to (a) a solvent polarity measurement method comprising the step of injecting the sensor according to the above (1) or (2) into a solvent.

The higher the polarity of the solvent, the darker the red color of the solution, and the polarity of the solvent can be grasped visually even without a separate spectroscopic analysis.

(A ') irradiating a sample containing the sensor according to the first or second aspect with light having a wavelength of 400 to 600 nm and observing the color with naked eyes, The present invention relates to a method of analyzing whether

If the sample including the sensor according to various embodiments of the present invention is not irradiated with ultraviolet rays, the sample hardly absorbs light and becomes pale yellow or fleshy. On the other hand, when the sample is irradiated with ultraviolet rays, it becomes brown or reddish brown due to light absorption, so that it can be visually confirmed.

However, if the sample is sufficiently irradiated with visible light after ultraviolet irradiation, it will again become pale yellow or fleshy.

According to another aspect of the present invention, there is provided a method of measuring the absorbance of a sample, comprising the steps of: (a ') measuring an absorbance of light having a wavelength of 400 to 600 nm on a sample including the sensor according to the first or second aspect; and (b) And determining the ratio of the MC form and the SP form of the spiropyran to the ultraviolet irradiation. Quantitative analysis of ultraviolet radiation dose may be possible through this ratio.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. 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 and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example

In order to bind the spiropyran molecule to the carrier, one end of the spiropyran molecule must contain a functional group capable of chemically bonding with the carrier. The composite particle sensor was fabricated by the following two methods by combining with spiropyran molecules using silica powder as a lag.

Example 1: Synthesis of Spiropyran Molecule Combined with silica powder to prepare composite particle sensor

The spiropyran molecules were independently synthesized and then bonded to silica powder to produce a composite particle sensor. For chemical bonding with silica powder whose surface is an OH group, a method of first synthesizing a pyran molecule with a spy where a carboxyl group (COOH) is located at one end and another functional group (R) is located at the other end, And Fig. 2B.

Specifically, as shown in FIG. 2, which is a reaction formula of the production method of synthesizing spiropyran molecules independently and bonding them to silica powder, a carboxyl group (COOH) is introduced at one end for bonding with the silica powder to the spiropyran molecule .

In step 1, the structure of Part (A), which is 5-carboxyl-1,2,3,3-tetramethyl-3H-indolium iodide, and Part (B), which is 2-hydroxy- (Ethanol, methanol, THF, DCM, acetone, etc.) in which the two reagents can be dissolved. In this embodiment, ethanol is used as a solvent. The reaction can be carried out at 100 to 120 ° C for 5 to 8 hours, and in this embodiment, the reaction is carried out at 100 ° C for 5 hours.

In this case, a small amount of a catalyst (nitrogen-based compound such as piperidine) may be added in a small amount in order to accelerate the reaction. In this embodiment, triethylamine is used as a catalyst. After completion of the reaction, a ③ molecule of the COOH-SP-R structure was obtained through a series of purification steps (extraction and reversed phase column). The R-functional group can be freely determined by considering the chemical solubility which can be well mixed with the solvent.

In step 2, a silica powder surface-treated with a hydroxyl group (OH), and COOH-SP-R, ③ are bonded to ④ to finally produce silica composite particles chemically bonded with spiropyran. At this time, a coupling agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) was added to facilitate the reaction. The solvent can be any solvent (ethanol, methanol, THF, DCM, acetone, etc.) that can dissolve the spiropyran. (Reaction temperature: 0 占 폚, reaction time: 16 hours).

When SP is synthesized on the silica powder, the following pretreatment process is performed to maximize the OH functional groups present on the silica surface. 1) It is heated at 600 ℃ to remove impurities, 2) Mixture of sulfuric acid and hydrogen peroxide in volume ratio of 3: 1 can remove the additional impurities and improve the reactivity by generating OH groups with high pollution on the surface.

Based on the surface area of 60 μm silica, the silica: EDC coupling agent: SP exhibits high synthesis efficiency and the highest absorbance when reacted at a mass ratio of 5: 1: 3.

A synthesis temperature below 0 ° C is desirable to minimize chemical adsorption between silica and SP while at the same time producing chemical bonds. The slow reactivity due to the low temperature is corrected to some extent by adjusting the pH of the solvent to 4 to 4.5. Thus, the experimental conditions for minimizing adsorption and maximizing chemical bonding are a reaction temperature of 0 ° C and a pH between 4 and 4.5.

The reaction sequence of silica, EDC coupling agent, and SP also greatly affects the synthesis efficiency of SP-silica. When EDC and SP are added to the solvent and the reaction is carried out in the order of bonding to silica, the dissolution rate of the SP in the solvent is extremely low (the dissolution kinetics of the SP is considerably low) and incomplete reaction proceeds. Therefore, it is desirable to go through the following process; 1) add SP to the solvent, 2) raise the solvent temperature to 70 ° C to increase the dissolution rate of the SP, 3) lower the temperature to 0 ° C as the reaction temperature, then add EDC, and 4) adjust the pH to 4 to 4.5, 5) add silica powder.

Example 2: Preparation of SP-silica composite particle sensor using carrier

As can be seen from FIG. 3, SP-silica composite particle sensor, ⑥, can be manufactured by chemically bonding Part (A) and Part (B) sequentially to the support. Part (A) -silica chemistry was synthesized by first chemically bonding Part (A), ① to the silica powder through esterification reaction and then reacting Part (B) in a chain reaction. Finally, SP-silica composite To produce particles.

In step 1 in FIG. 3, the silica particles, (4) and Part (A), (1) can be reacted in the same manner as in the present embodiment under 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide . At this time, any solvent in which Part (A) is well soluble can be used (alcohol, polar solvent, water, etc.), and in this embodiment, ethanol is used as a solvent. The reaction was carried out at 0 to 40 캜 for 16 to 18 hours, but in this embodiment, the reaction was carried out at 0 캜 for 16 hours.

When Part (A) is synthesized on silica powder, the following pretreatment process is carried out to maximize OH functional groups present on the silica surface. 1) It is heated at 600 ℃ to remove impurities, 2) Mixture of sulfuric acid and hydrogen peroxide in volume ratio of 3: 1 can remove the additional impurities and improve the reactivity by generating OH groups with high pollution on the surface.

Based on the surface area of 60 μm silica, the silica: EDC coupling agent: Part (A) exhibits high synthesis efficiency and the highest absorbance when reacted at a mass ratio of 5: 1: 3.

A synthesis temperature below 0 ° C is desirable to minimize chemical adsorption between the silica and Part (A) while creating chemical bonds. The slow reactivity due to the low temperature is corrected to some extent by adjusting the pH of the solvent to 4 to 4.5. Thus, the experimental conditions for minimizing adsorption and maximizing chemical bonding are a reaction temperature of 0 ° C and a pH between 4 and 4.5.

The reaction sequence of silica, EDC coupling agent, Part (A) also has a great effect on the synthesis efficiency of Part (A) - silica. When EDC and Part (A) were added to the solvent and reacted, the reaction was carried out in the order of bonding to the silica. Part (A) had a very low dissolution rate in the solvent (dissolution kinetics of Part (A) An incomplete reaction proceeds. Therefore, it is desirable to go through the following process; 1) Add Part (A) to the solvent, 2) increase the dissolution rate of Part (A) by raising the solvent temperature to 70 ° C, 3) lower the temperature to 0 ° C as the reaction temperature, 4) Adjust pH to 4 to 4.5 with acetic acid, 5) Add silica powder.

In addition, the addition of a step of washing with Part (A) -silica immediately after synthesis with alcohols (ethanol, methanol ...) can maximize the sensor effect of the final SP-silica. In the case of Part (A) -silica, it is considered that the activity of the halogen ion (X-) of Part (A) rapidly decreases with time, and thus the process of stabilizing it through the solvent of alcohol is considerably helpful. Resulting in improved reactivity with Part (B).

In Step 2, the compound (5) obtained in Step 1 is reacted in a solvent capable of dissolving Part (B) without any purification process to finally obtain SP-silica composite particles (reaction temperature: 100 to 120 ° C, reaction time: 5 To 8 hours). In this embodiment, the reaction was carried out at 100 DEG C for 5 hours.

Test Example

A photograph of the SP-silica composite particle prepared in Example 2 is shown in FIG. The silica particles surface-treated with a hydroxyl group (OH) that can be easily purchased in the market have a fine white powder form, whereas when chemically bonded with the spiropyran molecule, they become fleshy (pale yellow) Can be confirmed. As a result, it was confirmed that the color of the SP-silica composite particles changed from pale yellow to yellow as the synthesis concentration of spiropyran increased compared to silica.

If the spiropyranecarboxylic group (COOH) is not contained, it simply adsorbs the hydroxyl group (OH) on the surface of the silica particle without any chemical bonding reaction. In this case, even if the SP-silica composite particle appears to be synthesized, it can be confirmed that when the solvent is added and stirred, the spiropyran molecules fall off into the solvent. That is, the chemical reaction of the spiropyran and silica particles is essential for the stability of the composite particles.

To confirm the sensor sensitivity of the SP-silica composite particles, SP-silica was added to three different solvents (hexane, tetrahydrofuran (THF), water) and recovered again after 5 minutes (FIG. As can be seen in the picture, hexane, THF, and water are gradually reddish in order, which is consistent with increasing solvent polarity (solvent polarity: hexane <THF <water).

The graph below the photograph shown in FIG. 5 shows that the red color becomes stronger depending on the degree of polarity, and the RGB analysis shows the value. As the polarity of the solvent increases, the color of SP-silica particles can be quantitatively analyzed. As a result, the SP-silica composite particles can be used as a sensor material for the degree of polarity of the solvent.

The SP-silica composite particles exhibit sensor characteristics that are sensitive to the polarity of the solvent as well as light (ultraviolet / visible). The untreated silica and SP-silica composite particles were irradiated with UV for 5 minutes and then the absorption spectra were measured in the wavelength range of 400 to 600 nm. (Spiropyran exhibits strong fluorescence properties when activated through the ring opening reaction, which can be analyzed via the absorption spectrum.) As shown in Figure 6, silica particles without UV treatment emit light between 400 and 600 nm Although not nearly absorbed (light yellow or flesh colored), the SP-silica composite particles show a distinct absorption of light after UV irradiation (red or reddish brown).

The absorption spectra of the SP-silica composite particles before and after UV irradiation show a large difference. Prior to UV irradiation, most of the spiropyran molecules bound to silica are in the SP form (ring closed form) and only a small amount exist in the MC form (ring open form). However, if UV is irradiated for 5 minutes, more SP form MC type, the intensity of the absorption spectrum is increasing. It is also possible to quantitatively calculate the ratio between the SP and MC shapes.

Claims (19)

delete delete (B) a process for producing a sensor comprising spiropyran chemically bonded silica comprising mixing spiropyran having a carboxyl group introduced at one end thereof and silica particles having a hydroxy group introduced on its surface and performing an esterification reaction ,
Wherein the spirofilane having a carboxyl group at one end thereof has a structure represented by the following formula (2), and R in the following formula (2) is a substituent for controlling chemical solubility. : &Lt;
(2)

[Chemical Formula 1]

. 4. The method of claim 3, further comprising the step of (A1) reacting a compound of the formula (2a) and a compound of the formula (2b) to obtain a spiropyran having a carboxyl group at one end thereof and,
A process for producing a sensor comprising silica chemically bonded with spiropyran, wherein X in the following formula (2) is one selected from the group consisting of fluorine, chlorine and iodine.
(2a)

(2b)

. 5. The method of claim 4, wherein step (B) comprises reacting 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), N, N'- dicyclohexylcarbodiimide (DCC) -Carbonyldiimidazole &lt; / RTI &gt; (DIC) is added to perform the reaction. &Lt; Desc / Clms Page number 20 &gt; 6. The method of claim 5, wherein the silica is the coupling agent. The spiropyran having the carboxyl group introduced therein at a ratio of 4.5-5.5: 1: 2.5-3.5 is subjected to the reaction. A method of manufacturing a sensor comprising chemically bonded silica. 7. The method according to claim 6, wherein said step (A1) comprises: (i) a solvent selected from the group consisting of ethanol, methanol, tetrahydrofuran, dichloromethane (DCM), acetone, (iii) a reaction time of 5 to 8 hours,
(Ii) at a temperature of 0 to 40 DEG C and (iii) at a temperature of from 16 to 18 DEG C, and (iii) at a temperature of from 0 to 40 DEG C in a solvent selected from the group consisting of ethanol, methanol, tetrahydrofuran, dichloromethane Wherein the spiropyran is carried out during the reaction time of the reaction. The method of claim 7, wherein the step (B) is performed at a reaction temperature of 0 to 5 ° C and a pH of 4 to 4.5. [8] The method according to claim 7, wherein the step (B) is performed by performing the reaction in the following order:
(B1) adding a spirofuran having a carboxyl group at one end thereof to a solvent to obtain a solution,
(B2) raising the temperature of the solution to 65 to 75 DEG C,
(B3) lowering the temperature of the solution to 0 to 5 DEG C and introducing the coupling agent,
(B4) adjusting the pH of the solution to 4 to 4.5,
(B5) introducing the silica into the solution. 10. The method of claim 9, further comprising the step of: (A) pre-treating (A2) before the step (B)
(A2-1) heating at 550 to 650 DEG C for 4 to 6 hours to remove impurities,
(A2-2) Step of removing additional impurities from the solution mixed with sulfuric acid and hydrogen peroxide 2.5-3.5: 1 by volume. delete delete delete delete delete delete delete delete delete

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