KR100973055B1 - Optical pH Sensing Polymeric Film Having Anti-fouling Property and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to a polymer film for an optical pH sensor having an antifouling property and a method for manufacturing the same, and more particularly, a crosslinking agent comprising an MPC having an antifouling property and a monomer having a fluorescein group as a fluorescent material. And a photopolymerization initiator and a basic monomer, followed by photopolymerization by irradiating the mixture with ultraviolet (UV) light, and a polymer membrane for an optical pH sensor manufactured by the method. .

The polymer membrane according to the present invention is physically and chemically stable and can be used for a long time, as well as selectively reacting with hydrogen ions, resulting in a linear fluorescence change at a wide range of pH and preventing the adhesion of microorganisms.

Optical pH sensor, antifouling, fluorescein, photopolymerization, UV

Description

Optical pH Sensing Polymeric Film Having Anti-fouling Property and Method for Preparing the Same}

The present invention relates to a polymer film for an optical pH sensor having an antifouling property and a method for manufacturing the same, and more particularly, a crosslinking agent comprising an MPC having an antifouling property and a monomer having a fluorescein group as a fluorescent material. And a photopolymerization initiator and a basic monomer, followed by photopolymerization by irradiating the mixture with ultraviolet (UV) light, and a polymer membrane for an optical pH sensor manufactured by the method. .

Fluorescent materials that are commonly used as phosphors for pH sensors currently exhibit linear fluorescence intensity in a narrow pH range, making them difficult to use in a wide pH range. In addition, the manufacturing of the sensor system by the conventional sol-gel method has the disadvantage of requiring precise work and difficult reproducibility, and in the case of a small molecule having a carrier molecular weight of 1000, a carrier leaching phenomenon occurs.

In general, fluorescein derivatives and rutenium complexes are well known as materials for fluorescent materials for pH sensors. Representatively, a technique for preparing a polymer material for pH sensor through photochemical polymerization using a fluorescein derivative has been disclosed to prepare a polymer material for pH sensor (M. Uttamlal et al. , Polym Int . 51: 1198, 2002). In addition, the pH sensitivity of the polymer material for pH sensor manufactured using the fluorescein derivative was measured to determine the efficacy as a pH sensor. As a result, it has been reported that the polymer material for pH sensor exhibits different fluorescence according to pH change only in the range of about pH 4-7 (HD Duong et. al ., Microchemical J. , 84:50, 2006).

In addition, phosphorylcholine (Phosphorylcholine, PC) derivative was used as a method to solve the problem that the lifespan of the sensor is reduced due to the adhesion of microorganisms and the sensitivity is reduced. However, in some applications of PC derivatives, the use of low molecular weight derivatives is weak and unstable. Therefore, it is used by copolymerizing with MPC, which is a PC derivative having a vinyl group, and other monomers. In this case, however, when the molecular weight of the polymer is 10 ⁴ or less, the physical property is weak, so that it is dissolved in an aqueous solution when used for a long time.

Conventionally, a method of independently, reversibly and optically measuring the pH value and ionic strength in an aqueous sample using two different sensors according to the fluorescence method (Korean Patent Publication No. 1997-7002991), ethyl acrylamide or methyl acrylamide and N Polymer system and production method sensitive to temperature and pH changes including N-dimethylaminoethyl methacrylate (Korea Patent No. 231,959) and anti-introduction membranes with nano-sized TiO ₂ particles with photocatalytic properties Although a method of manufacturing a reverse osmosis membrane having excellent fouling properties (Korean Patent No. 444,126) has been disclosed, the conventional method is difficult to use the sensor for a long time, it is expensive, and the manufacturing process is somewhat complicated, which takes time. There was this.

Accordingly, the present inventors have made efforts to improve the conventional problems, and as a result, a fluorescent dye having a group capable of polymerizing with 2-methacryloxyethylphosphorycholine (MPC), which is a PC derivative having the characteristics of antimicrobial adhesion, Photopolymerization of fluorescein methacrylate to produce a polymer membrane, and then showed a linear fluorescence change in a wide pH range, and confirmed that the antifouling effect is excellent, the present invention was completed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer film for an optical pH sensor and a method of manufacturing the same, which are physically and chemically stable and can be used for a long time and have antifouling properties.

Another object of the present invention to provide an optical pH sensor containing the polymer film.

In order to achieve the above object, the present invention provides a mixture of (a) a monomer having an antifouling property, a monomer having a fluorescein group, a base monomer, a crosslinking agent and a photopolymerization initiator to a solvent. Manufacturing; And (b) applying the mixture to the surface of the substrate, and then performing a photopolymerization reaction to irradiate ultraviolet rays to produce a polymer membrane, wherein the polymer membrane for an optical pH sensor has an antifouling property. It provides a polymer film for an optical pH sensor having an antifouling properties prepared by the above method.

The present invention also provides an optical pH sensor manufactured using the polymer membrane.

The polymer membrane according to the present invention is physically and chemically stable and can be used for a long time as well as selectively reacts with hydrogen ions, resulting in a linear fluorescence change at a wide range of pH and preventing the adhesion of microorganisms.

In accordance with the present invention, (a) adding a monomer having antifouling properties, a monomer having a fluorescein group, a base monomer, a crosslinking agent and a photopolymerization initiator to a solvent to prepare a mixture. And (b) applying the mixture to the surface of the substrate, and then performing a photopolymerization reaction to irradiate ultraviolet rays to produce a polymer membrane. The method of manufacturing a polymer membrane for an optical pH sensor having an antifouling property comprising the steps of: It is about.

In the present invention, with respect to 100 parts by weight of the basic monomer in the step (a), 0.1 to 10 parts by weight of the monomer having antifouling properties, 0.01 to 30 parts by weight of monomer having a fluorescein group, 1 to 100 parts by weight of crosslinking agent It is characterized by adding 0.001-20 parts by weight of the photopolymerization initiator and 1-100 parts by weight of the solvent.

If the amount of the monomer having an antifouling property is less than 0.1 with respect to 100 parts by weight of the basic monomer in step (a), there is a problem that the microbial adhesion increases, and if it exceeds 10, there is a problem that the physical properties of the prepared polymer membrane is inferior. .

If the monomer addition amount of the fluorescent material which is a fluorescein derivative with respect to 100 parts by weight of the basic monomer in step (a) is less than 0.01, the intensity of fluorescence is weak, and if it exceeds 30, the mechanical properties and self-quenching of the prepared polymer membrane There is a problem with (self-quenching).

If the amount of the crosslinking agent is less than 1 based on 100 parts by weight of the basic monomer in step (a), there is a problem in that no crosslinking reaction occurs.

If the amount of the photopolymerization initiator added to less than 0.001 with respect to 100 parts by weight of the basic monomer in the step (a) there is a problem that the photopolymerization reaction does not occur, and if it exceeds 20 there is a problem that the physical properties of the polymer film produced.

If the amount of the solvent is less than 1 with respect to 100 parts by weight of the basic monomer in step (a), there is a problem that the crosslinking agent and the basic monomer are not dissolved, and if it exceeds 100, there is a problem that the physical properties of the polymer membrane during photocrosslinking are inferior.

In the present invention, a fluorescein derivative having a wide pH range which can be measured as a fluorescent dye and having photostability is preferably used, and fluorescein methacrylate is preferably used.

In the present invention, the solvent is tetrahydrofuran (acetra), acetone (acetone), methanol (methanol), ethanol (ethanol), propanol (propanol), acetonitrile (acetonitrile), chloroform (chloroform), ethyl acetate (ethyl acetate) and methylethyl ketone (methylethyl ketone) may be any one or more selected from the group consisting of, but is not limited thereto.

In the present invention, the antifouling derivative having antimicrobial adhesion characteristics is characterized by using 2-methacryoloxyethylphosphorycholine (MPC) which is a PC derivative. The term 'antifouling derivative' used in the present invention refers to a compound having antimicrobial adhesion properties among PC derivatives. The MPC according to the present invention is prepared by treating trimethylamine in ethylene 2- (methacryloyl) ethyl phosphate, has antifouling characteristics, and has antimicrobial adhesion effects in sensor applications.

In the present invention, the basic monomer refers to a starting material or a basic unit capable of making a polymer by polymerization, acrylonitrile, acrylamide, methacrylamide, hydroxyethyl meta It is preferable to use a hydrophilic monomer selected from the group consisting of acrylate (hydroxyethyl methacrylate, HEMA), acrylic acid (methrylic acid), methacrylic acid (methacrylic acid) and styrene (styrene).

In the present invention, the crosslinking agent is a compound represented by CH ₂ = CR ₁ -R ₂ -CR ₁ = CH ₂ , wherein R ₁ is hydrogen or a methyl group, and R ₂ is-(CH ₂ ) _n as a linking group. -, C _{6 -10 aryl, COO- (CH 2) n -OOC} , -O- (CH 2) n -O- and -CONH- (CH _{2) n} -NHCO- (wherein, n is 1 to 10 Natural water), preferably, UDMA [1,6-bis (carbonyloxyethyl-meththacryloyl) -2,2,4-trimethylhaxane], divinylbenzene, or bis ( bis) -GMA (diglycidylether methacrylate of bisphenol A), 2,2-bis [4- (2-hydroxy-3-methacryloxy-propoxy) -phenyl] propane (2,2-bis [4- (2 -hydroxy-3-methacryloxy-propoxy) -phenyl] propane) and triethyleneglycol dimethacrylate.

In the present invention, the crosslinking agent is a substance that plays a role of connecting the chain of the polymer, and imparts mechanical strength and chemical stability such as firmness or elasticity of the polymer membrane.

In the present invention, the photopolymerization initiator is benzoin alkyl ether, benzoin isobutyl ether, benzophenone, acetophenone and benzophenone / amine It is selected from a group consisting of, but not limited to.

In general, an initiator refers to a substance that generates a polymerization reaction while forming an active radical in a medium containing monomers. The initiator is mainly used in polymer synthesis, and the photopolymerization initiator used in the present invention absorbs energy of irradiated ultraviolet rays. To initiate the photopolymerization reaction.

In the present invention, by preparing a polymer film by covalent bonding using a photochemical method, it is possible to avoid the drawback of the sol-gel method used to fix the fluorescent material in the prior art and the difficulty of the manufacturing method.

 In the present invention, the substrate on which the polymer film is formed is preferably glass, wood, ceramic, plastic, and silicon wafers, but any substrate may be used as long as the substrate on which the polymer film is formed.

In the present invention, the photopolymerization reaction may be performed by irradiating ultraviolet rays in the range of 200 to 400 nm for 1 minute to 4 hours depending on the light intensity.

As the above-described ultraviolet region, 200 to 400 nm is a conventional ultraviolet region, and if the wavelength of the ultraviolet ray is less than 200 nm, there is a problem that decomposition reaction occurs, and if it exceeds 400 nm, there is a problem that the photopolymerization reaction does not occur.

In addition, in the photopolymerization reaction, if the ultraviolet irradiation time is less than 1 minute, there is a problem that the polymerization reaction does not occur, and if it exceeds 4 hours, the irradiation time is long and there is a problem that the photolysis reaction occurs.

In another aspect, the present invention provides a polymer film for an optical pH sensor prepared by the above method, containing an antifouling derivative, a monomer of a fluorescein derivative, a basic monomer, and having an antifouling property. As the pH increases from pH 3 to 11, the fluorescence intensity decreases linearly.

On the other hand, under a constant pH, the fluorescence intensity of the polymer film for optical pH sensors is stable against changes in other external factors such as temperature, interference ions, and long term storage.

Therefore, the polymer membrane for optical pH sensor having anti-fouling properties according to the present invention reacts linearly in a wide pH range compared to the prior art, but has stability exhibiting a constant fluorescence intensity against changes in external factors except pH. .

In the present invention, the polymer is characterized in that it has a thickness of 0.1 ~ 200㎛, if the thickness of the polymer membrane is less than 0.1㎛ there is a problem that the stability of the polymer membrane is lowered, if it exceeds 200㎛ the profit from the increase of the thickness of the polymer membrane There is no

In another aspect, the present invention provides an optical pH sensor using the polymer membrane.

The optical pH sensor uses a conventional optical pH sensor manufacturing method, it can be prepared by coating the end of the optical fiber using the polymer film according to the present invention.

Since the polymer membrane according to the present invention has excellent pH sensitivity, stability, and reproducibility as described above, it is a sensing membrane that can measure pH sensitively, and a fluorescent indicator capable of measuring pH for a long time in various fields such as medical, environment, and food. It can be applied as an indicator. In addition, the anti-fouling effect by the MPC has the characteristics of anti-microbial adhesion, there is an advantage that the life of the sensor is extended compared to the conventional, the sensitivity does not decrease.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1 Preparation of MPC (JE Brown, MJ Driver, JC Russel, J. Chem. Soc., Perkin Trans, 653)

1.1 Synthesis of Ethylene diisopropylphosphoramidite

 Scheme 1

Lower the temperature of the circulator to -10 ^o C and install a 250 mL three-neck flask. Add 50 mL of dry dichloromethane under nitrogen atmosphere and lower the temperature of the solvent. 2.8mL (4-g, 0.03mol) of 2-chloro-1,3,2-dioxaphospholane was added to the solvent, and diisopropylamine 22.3mL (16g, 0.16mol) was added dropwise using a separatory funnel. give. The reaction mixture is stirred at room temperature for 24 hours until the reaction is in equilibrium. After completion of the reaction, the filtered solution was filtered to remove salt (diisopropylammonium chloride), and the filtered solution was condensed by using a rotary evaporator until half of the solvent remained. The solution is cooled again in an ice bath and filtered, then the filtered solution is again blown off with a rotary evaporator, cooled and refiltered (cooling and filtering three times to remove salt completely). The filtered solution was completely removed by solvent using a rotary evaporator, followed by vacuum drying at room temperature. The synthesized material is pure ethylene diisopropylphosphoramidite by vacuum distillation at 60.

1.2 Ethylenedioxy -2-( methacryloyloxy ) ethoxyphosphine  synthesis

 Scheme 2

In a 100 mL three-necked flask equipped with a drying tube under nitrogen atmosphere, add 0.716 g (5.2 mmol) of 4,5-dichloroimidazole to 20 mL of anhydrous acetonitrile and stir at room temperature. Add 0.716 g (5.2 mmol) of HEMA. After stirring for 2 hours at room temperature, a dropping funnel was installed, and 1 g of the No. 22 material was dissolved in 5 mL of anhydrous acetonitrile and then dropwise added little by little. The reaction is carried out at room temperature for 3 hours. The salt produced during the reaction (diisopropylammonium dichloroimidazolide) is filtered out. The filtered solution is removed by using a rotary evaporator and then vacuum dried at room temperature.

1.3 Synthesis of Ethylene 2- (methacryloyl) ethyl phosphate (24)

 Scheme 3

In a 100 mL three-necked flask, add 10 mL of anhydrous acetonitrile and 0.373 g (4.9 mmol) of trimethylamine- N -oxide, and then stir at room temperature. Install a dropping funnel in a three-necked flask, add 1.09 g (4.9 mmol) of substance No. 23 and 10 mL of acetonitrile, and then dropwise dropwise. After stirring at room temperature for 3 hours, the solvent was removed using a rotary evaporator, followed by vacuum drying at room temperature.

1.4 HEMA - PC  4. Synthesis

 Scheme 4

After reducing the temperature of the pressure bottle to -20 ^o C, add 20 mL of cold anhydrous acetonitrile to the synthesized substance No. 24 (2.7g, 11.4mmol) and add the dissolved solution. After adding 7.0mL of trimethylamine in excess, react for 50 hours in a 50 incubator. The solvent is removed using a rotary evaporator.

Example  2: pH  Polymer film for sensor

To the two test tubes, add 0.65 mL (5.4 mmol) of 2-hydroxyethyl methacrylate (HEMA), 0.72 g (6.6 mmol) of urethanedimethacrylate (UMDA), and add 2.35 mL of methanol. The total solution was made to 3 mL. To this, 4.8 mg (0.016 mmol) of 2-methacryloloxyethyl phosphorycholine (MPC) and 24 µl of benzoin isobuthyl ether were added, followed by fluorescein in each test tube. 21.6 mg (0.054 mmol) and 43.2 mg (0.108 mmol) of methacrylate (fluorescein methacrylate, FM) were added, and nitrogen gas was blown for 15 minutes to remove oxygen from the solution (see Table 1 below).

[Table 1] Manufacturing Conditions of Polymer Membranes I and II

Crosslinked polymer membrane FA
mg (mmol) HEMA
g (mmol) UDMA
g (mmol) MPC
mg (mmol) Enzoin
isobutyl ether
(mmol)
Adhesion I 21.6 (0.054) 0.7 (5.4) 0.72 (6.6) 4.8 (0.016) 24 (0.094) 4B II 43.2 (0.108) 0.7 (5.4) 0.72 (6.6) 4.8 (0.016) 24 (0.094) 4B

60 μl of the prepared solution was put into a 24-well plate, and then put into a glove box filled with nitrogen and irradiated with UV light of 310 nm for 15 minutes to prepare a polymer membrane, and then dipped in tertiary distilled water for about 1 day. After stabilization it was dried. The process is represented by the following scheme.

The thickness of the prepared polymerized polymer membrane was 4.99 μm, and the transmittance was measured using UV / Vis spectrum. As a result of measuring the hardness of the polymer membrane with a cross hatch cutter, it was found to be 4B. Here, the cross hatch cutter is a method of measuring the strength of the surface to the extent of the shape of the broken pattern and peeling after making a pattern of 25 squares by cutting the six-blade cutter horizontally and vertically twice on the surface of the coating material. . If the shape of the pattern is completely square and does not fall off, it falls under 5B of the American Society of Testing Materials (ASTM) method, and in 4B when the cross and vertical cross sections are affected within 5%. .

Experimental Example  One: pH In accordance Fluorescence intensity  Measure

1.0 mL of buffer solution was added sequentially in the order of pH 3 to pH 12 on the light-crosslinked polymer membrane on the 24-well plate, and λ _ex (excitation wavelength) / λ _em (emission wavelength) = 395 nm The intensity of fluorescence was measured at / 530 nm. After the measurement, the buffer solution was removed, and then the buffer solution was added in the order of pH 12 to pH 3 and measured in the same manner. After repeating the measurement 10 times in the same manner to obtain the average value, the error range was measured using the standard deviation.

As a result, as shown in FIG. 1 (a), the fluorescence change according to the pH of the polymer membrane II was more sensitive in the range of pH 3 to 12, and as shown in FIG. Of linearity R ² (correlation coefficient) The value was found to be 0.9928. Therefore, it was found that the measurement error of pH can be reduced by using the polymer membrane II having excellent linearity of fluorescence intensity with respect to pH.

Experimental Example  2. Measurement of Stability of Polymer Membrane According to Contact Time

Investigation of the stability of the polymer membrane with respect to pH according to the contact time with the buffer solution using the polymer membrane II of the polymer membrane I, II prepared in Example 1 was confirmed that the linearity of the fluorescence intensity with respect to the pH change in Experimental Example 1 It was. Put 1.0 mL of buffer solution of pH 6 on the photocrosslinked polymer membrane II on the 24-well plates and λ _ex using a fluorescence spectrum / λ _em After fluorescence intensity was measured 80 times at 7 second intervals at a wavelength of 395 nm / 530 nm, the buffer solution was discarded, and the pH 7 buffer solution was added again. Fluorescence intensity was also measured for buffers having a pH of 8 to 11, respectively, as described above.

As a result, as shown in FIG. 2, the measurement result showed that the fluorescence intensity increased as the pH was changed from acidic to basic, and when the pH was kept constant, the polymer membrane II was increased even if the contact time between the polymer membrane II and the buffer solution was increased. The fluorescence intensity of was also almost constant.

Experimental Example  3: Reproducibility Measurement

Immobilization of the fluorescent dye on the matrix is most important for the long-term use of the pH sensing film and to prevent the fluorescent dye from leaching. Put 1.0 mL of buffer solution of pH 6 on the photocrosslinked polymer membrane II on the 24-well plates and λ _ex using the fluorescence spectrum After measuring fluorescence intensity for 30 times at intervals of 7 seconds at a wavelength of λ _em = 395 nm / 530 nm, the buffer solution was discarded, and then the fluorescence intensity was measured for 210 seconds by adding 1.0 mL of pH 11 buffer solution. . In the same manner as described above, repeated measurements were repeated five times using alternating buffers of pH 6 and pH 11.

As a result, as shown in Figure 3, the response time of the polymer membrane II according to the pH change appeared to be relatively fast as about 7 seconds, the stable fluorescence intensity value at each pH appeared. As the protons penetrate into the polymer membrane II rapidly, the fluorescence change is stable and quick and reproducible according to the pH change. Therefore, the polymer membrane II may be usefully used as a fluorescence sensor for pH measurement.

Experimental Example  4: temperature Impact  Measure

Put 1.0 mL of the buffer solution of pH 6 to pH 11 at 25 ° C., 28 ° C., 31 ° C., 34 ° C., and 37 ° C. on a 24-well plate, and then use fluorescence spectra to measure λ _ex / λ. The change in fluorescence intensity was measured for 20 times at a wavelength of _em = 395nm / 530nm. During the measurement, the temperature of the polymer membrane II was maintained for about 30 minutes so as to be constant with the temperature inside the apparatus.

As a result, as shown in FIG. 4, it was found that the photocrosslinked polymer membrane II was stable even with temperature change because there was almost no change in fluorescence intensity value as the temperature was changed. Therefore, it was found that the photocrosslinked polymer membrane II was not significantly affected by the temperature in this range.

Experimental Example  5: Ion Selectivity Measurement

In order to determine whether the polymer membrane prepared in Example 1 is not affected by ions other than protons and reacts only to proton ions, an ion selectivity measurement experiment of the polymer membrane was performed. In order to measure the change in fluorescence intensity according to the type of ions of the photocrosslinked polymer membrane II, a buffer solution of neutral pH 7 and pH 10 was used to prepare a 50 mM concentration of an inorganic compound containing different types of ions. The ion solution was prepared by dissolving each inorganic compound in 1.0 mL of MeOH. At this time, inorganic compounds that can be used are KI, KCl, NaCl, NaBr, Na ₂ SO ₄ , cupric nitrate, CuSO ₄ , CaCl ₂ , MgSO ₄ , BaCl ₂ , NH ₄ Cl, nickel (II), sulfate hexahydrate, tetraethyl ammonium bromide, urea and cobalt nitrate, but are not limited to these.

Put 0.98 mL of pH 7 buffer solution on the photocrosslinked polymer membrane II in a 24-well plate and use fluorescence spectrum to λ _ex The fluorescence intensity (F ₀ ) at / λ _em = 395 nm / 530 nm was measured 20 times. 20 μl each of 50mM ionic solution was added thereto so as to have an ion concentration of 1.0 mM, and the fluorescence intensity (F) was repeated 20 times. pH 10 buffer was also measured in the same manner. Relative fluorescence change value (%) was calculated by averaging each measured value.

Relative fluorescence change value (%) = ΔF / F ₀ × 100

Where ΔF = FF _o ego, F ₀ is the fluorescence intensity measured in the buffer solution when no ions are added, and F is the fluorescence intensity when the ion is added to the buffer solution. When ions were present in the respective ionic solutions, the relative fluorescence intensity change (%) of the polymer membrane II was measured at pH 7 and pH 10 using fluorescence spectra. As a result, as shown in Table 2, some inorganic compounds did not dissolve at pH 7 and pH 10, and the relative fluorescence intensity change of the polymer membrane II was within 4%, almost unaffected by various ions and selective only to hydrogen ions. It was found to be affected.

TABLE 2

Interference ^a Relative fluorescence
change value (%) ^b
at pH 7.00 Relative fluorescence
change value (%) ^b
at pH 10.02 KI -3.22 -1.33 KCl 0.94 3.97 NaCl -2.22 -3.04 NaBr -3.90 1.36 Na ₂ SO ₄ 2.91 2.45 Cupiric nitrate - - CuSO ₄ - - CaCl ₂ - - MgSO ₄ -2.65 - BaCl ₂ - - NH ₄ Cl -3.85 -0.35 Nickel () sulfate hexahydrate - - Tetraethyl ammonium bromide 0.32 2.62 Urea -2.22 3.42 Cobalt nitrate -

^a concentration (1 × 10 ^-3 mol L ^-1 )

^b (ΔF / F) × 100, wherein F _o and F are the fluorescence intensities when the fluorescent film is in contact with a potassium phosphate buffer solution at pH 7 and pH 10, respectively.

As a result, the polymer membrane II prepared in Example 1 showed a large change in fluorescence only for protons, and a change in fluorescence intensity did not appear significantly in the presence of other interfering ions, so that the interfering ions did not affect pH measurement. Could. From this result, it was found that the polymer membrane prepared in Example 2 was not disturbed in measuring the pH even if various inorganic ions were present.

Experimental Example  6: stability measurement

Put 1.0 mL of buffer solution of pH 10 at room temperature on the photocrosslinked polymer membrane II on the 24-well plate and apply λ _ex The fluorescence intensity is measured using the fluorescence spectrum at a wavelength of λ _em = 395 nm / 530 nm. PH 10 buffer solution used was measured after a storage in room temperature air for a period of time to discard again using a buffer solution of pH 10 λ _ex Fluorescence intensity was measured at a wavelength of λ _em = 395 nm / 530 nm. The photopolymerized polymer membrane was measured for a long time using a buffer solution of pH 10 at room temperature and normalized to the initial measured fluorescence intensity value.

As a result, as shown in FIG. 5, it was confirmed that the initial fluorescence intensity value and the fluorescence intensity value over time were maintained substantially constant.

Experimental Example  7: Microbial Adhesion Measurement

Antimicrobial adhesion adhesion experiment of the polymer film prepared in Example 2 was performed. The polymer film on the silanized glass plate is sterilized with a UV lamp. The strain was inoculated with 3 mL of LB medium and activated at 37 ° C. and 180 rpm for 24 hours. 50 μl of activated strain, 5 mL of culture solution, and a polymer membrane on two glass plates were added to a glass tube, and the cells were incubated at 37 ° C. and 180 rpm for 15 hours. The cultured polymer membrane was washed once with distilled water and dried. Dyeing with crystal violet for 1 minute, washed thoroughly with distilled water and dried, and then treated with iodine, a mordant for 1 minute and dried. After destaining with 95% ethanol for 30 seconds and dried, and dyed again with safranin O for 30 seconds, and observed under a microscope. As a result, as shown in Figure 6, it was confirmed that the polymer membrane without MPC has a high degree of microbial adhesion (Fig. 6 (a)), the polymer membrane containing MPC was confirmed that the microbial adhesion is very low (Fig. 6). (b)). Therefore, it was confirmed that the polymer film containing MPC was significantly lower in microbial adhesion than the polymer film containing no MPC.

Having described the specific parts of the present invention in detail, it will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Figure 1 (a) is a graph showing the measurement results of the fluorescence intensity according to the pH of the polymer membranes I, II according to the present invention, Figure 1 (b) shows the change in fluorescence intensity according to the pH of the polymer membrane II at pH 6 ~ 11 A graph

2 is a graph showing the stability measurement results of the contact time of the polymer membrane II according to the present invention.

3 is a graph showing the measurement results of reproducibility of the polymer membrane II according to the present invention.

4 is a graph showing the results of measuring the temperature influence of the polymer membrane II according to the present invention.

5 is a graph showing the stability measurement results of the polymer membrane II according to the present invention.

Figure 6 (a) shows the microbial adhesion measurement results of the polymer membrane without MPC, (b) shows the microbial adhesion measurement results of the polymer membrane according to the present invention containing MPC.

Claims (15)

A method for producing a polymer membrane for an optical pH sensor, which has the antifouling property, and exhibits a linear fluorescence change in a pH range of 3 to 11, comprising the following steps: (a) acrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate (HEMA), acrylic acid, methacrylic acid and 0.01 to 30 parts by weight of a monomer having a fluorescein group, 2-methacryoloxyethylphosphorycholine (MPC) monomers 0.1 to about 100 parts by weight of a basic monomer selected from the group consisting of styrene Preparing a mixture by mixing 10 parts by weight, 1 to 100 parts by weight of a crosslinking agent, 0.001 to 20 parts by weight of a photopolymerization initiator, and 1 to 100 parts by weight of a solvent; And (b) applying the mixture to the surface of the substrate, and then performing a photopolymerization reaction that irradiates ultraviolet rays to produce a polymer membrane. delete The method of claim 1, wherein the solvent of step (a) is tetrahydrofuran (acetra), acetone (acetone), methanol (methanol), ethanol (ethanol), propanol, acetonitrile (acetonitrile), chloroform (chloroform ), Ethyl acetate and methyl ethyl ketone, the production method characterized in that any one or more selected from the group consisting of. delete The method of claim 1, wherein the monomer having a fluorescein group in step (a) is fluorescein methacrylate (fluorescein methacrylate). delete The method of claim 1, wherein the crosslinking agent of step (a) is CH ₂ = CR ₁ -R ₂ -CR ₁ = CH ₂ compound, wherein R ₁ is hydrogen or methyl group, R ₂ is-(CH) _{2) n} -, C _{6 -10 aryl, COO- (CH 2) n -OOC} , -O- (CH 2) n -O- , and CONH- (CH _{2) n} -NHCO- (wherein, n is 1 to 10) natural water). The method of claim 7, wherein the crosslinking agent is UDMA [1,6-bis (carbonyloxyethyl-meththacryloyl) -2,2,4-trimethylhaxane], divinylbenzene, bis (bis) -diglycidylether methacrylate of bisphenol A ), 2,2-bis [4- (2-hydroxy-3-methacryloxy-propoxy) -phenyl] propane (2,2-bis [4- (2-hydroxy-3-methacryloxy-propoxy)- phenyl] propane) and triethyleneglycol dimethacrylate. The method of claim 1, wherein the photopolymerization initiator of step (a) is benzoin alkyl ether, benzoin isobutyl ether, benzophenone, acetophenone and benzophenone / Amine (benzophenone / amine) characterized in that the manufacturing method selected from the group consisting of. The method of claim 1, wherein the substrate of step (b) is selected from the group consisting of glass, wood, ceramic, plastic, and silicon wafers. The method of claim 1, wherein the photopolymerization reaction of step (b) is performed by irradiating ultraviolet rays in the range of 200 to 400 nm for 1 minute to 4 hours. A 2-methacryoloxyethylphosphorycholine (MPC) monomer prepared by the method of any one of claims 1, 3, 5, 7, and 8-11. , Monomers with fluorescein groups, acrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate (HEMA), acrylic acid Polymer membrane for optical pH sensor containing a basic monomer selected from the group consisting of, methacrylic acid (methacrylic acid) and styrene, has anti-fouling properties, and shows a linear fluorescence change in the pH range 3-11. The polymer membrane of claim 12, wherein the polymer membrane reacts linearly at pH 3-11. The polymer membrane of claim 12, wherein the polymer membrane has a thickness of 0.1 μm to 200 μm. Has antifouling properties containing the polymer membrane of claim 12, in the pH range 3-11 Optical pH sensor showing linear fluorescence change.

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