Fluorescent probe as well as preparation method and application thereof

Abstract

The invention provides a fluorescent probe as well as a preparation method and application thereof. The fluorescent probe has a structure as shown in a formula 1: # imgabs0. The fluorescent probe disclosed by the invention has the advantages of simplicity and convenience in operation, low cost, quick response, wide applicable concentration range and the like when being used for detecting DMP in mine water, and is expected to be applied to water quality detection of domestic sewage, mine water, coal chemical wastewater and the like in the future.

Description

Technical Field

[0001] The present invention relates to water quality organic matter detection, and in particular to a fluorescent probe, a preparation method and application thereof. Background Art

[0002] Dimethyl phthalate (DMP) is a common persistent organic pollutant (POPs) with teratogenicity, carcinogenicity, mutagenicity and reproductive toxicity. It mainly comes from emulsions, lubricants, gelling agents and adhesives, and is widely present in domestic sewage, mine water, industrial wastewater and coal chemical wastewater. It is a type of pollutant that needs to be controlled.

[0003] The annual production of coal mine water can reach 8 billion tons, and the comprehensive utilization rate is only 40%, which is a huge waste. Mine water contains a variety of pollutants, including suspended matter, salt, heavy metals, fluoride and organic matter. The general concentration range of the main pollutants is: suspended matter (500-3000 mg / L), alkalinity (CO3 2- and HCO3 - , 0-300mg / L), mineralization (NaCl, Na2SO4, CaCl2, CaSO4, MgCl2 and MgSO4, etc., 0-2000mg / L), fluoride (NaF, 2-7mg / L), heavy metals (Cu, Fe and Mn, etc., 0-1mg / L), organic matter (benzene, phenanthrene, anthracene, toluene, ethylbenzene, dichloromethane and dimethyl phthalate, etc., 0-2mg / L). Strictly controlling the concentration of DMP in coal mine water is a necessary link for the comprehensive utilization of coal mine water. Currently, the commonly used methods for detecting the concentration of DMP in mine water include: using large instruments such as gas chromatography (GC), high performance liquid chromatography (HPLC) and gas chromatography / mass spectrometry (GC-MS) for detection. Its advantage is that it can accurately qualitatively and quantitatively analyze it, and its disadvantages are complex operation, long experimental cycle, high price, lack of operability and economy.

[0004] In recent years, fluorescent probes / fluorescent sensors have begun to be explored in the field of organic pollutant detection, which can achieve simple, rapid and accurate detection of organic matter in water. "Study on the preparation of dual ratio fluorescence molecular imprinting and its visual selective detection of dimethyl phthalate" (Journal of Jilin Normal University (Natural Science Edition), 2020, 41(2):89-97) reported: "A new ratio fluorescence molecular imprinting sensor (FMIPs-r / g-FITC / SiO2) was synthesized by surface imprinting technology and used for visual selective detection of dimethyl phthalate (DMP); in the range of 0 to 1.94×10 -2In the mg / L concentration range, the fluorescent molecular sensor has a good linear relationship with the quenching degree of DMP. "This technology is mainly a fluorescent sensor developed for trace DMP in water. It cannot be used for the detection of higher concentrations of DMP and has a small scope of application. In addition, this technology is easily affected by suspended matter, salt, heavy metals, fluoride and organic matter in mine water, and cannot accurately detect the concentration of DMP in mine water. Therefore, it is very important to develop a fluorescent probe with a wide range of applications, simple operation and low cost for detecting the concentration of DMP in mine water. Summary of the invention

[0005] The main purpose of the present invention is to provide a fluorescent probe, a preparation method and application thereof, so as to solve the problem of high cost of the method for detecting DMP in mine water in the prior art.

[0006] In order to achieve the above object, according to a first aspect of the present invention, a fluorescent probe is provided, wherein the fluorescent probe has a structure as shown in Formula 1 below:

[0007]

[0008] To achieve the above object, according to a second aspect of the present invention, a method for preparing the above fluorescent probe is provided, the method comprising: subjecting carboxymethyl-β-cyclodextrin to an amidation reaction with a carbazole compound in an alkaline environment to obtain the fluorescent probe.

[0009] Further, the alkaline environment is Na2CO3, K2CO3, NaHCO3 or KHCO3;

[0010] Preferably, the carbazole compound is selected from carbazole, imidazole, carbazole line or carbazole oxide;

[0011] Preferably, carboxymethyl-β-cyclodextrin and carbazole are subjected to an amidation reaction in an organic solvent containing a Na2CO3 solution; more preferably, the organic solvent is selected from acetonitrile, chloroform, methanol or ethanol;

[0012] Preferably, before obtaining the fluorescent probe, the preparation method further comprises the step of vacuum drying the product of the amidation reaction; more preferably, the vacuum drying is performed in a vacuum drying oven.

[0013] Furthermore, the organic solvent is selected from acetonitrile, and the mass volume ratio of carboxymethyl-β-cyclodextrin, carbazole, Na2CO3 and acetonitrile is: (1-2.5): (1.5-4.0): (1.5-4.0): (100-200).

[0014] Furthermore, the amidation reaction temperature is 70-85° C., and the reaction time is 24-72 h.

[0015] Furthermore, the vacuum drying is performed at a temperature of 65 to 75° C. and a time of 72 to 90 hours.

[0016] In order to achieve the above object, according to a third aspect of the present invention, a method for detecting DMP concentration is provided, the method comprising:

[0017] The fluorescence values ​​of the fluorescent probe after mixing with water and DMP solution were detected, recorded as F1 and F2, respectively, and the fluorescence difference ΔF was calculated;

[0018] The standard curve was drawn with the concentration of DMP solution as the abscissa and the fluorescence difference ΔF as the ordinate to obtain the linear regression equation;

[0019] Detect the fluorescence value after the fluorescent probe is mixed with the test solution, which is recorded as F3;

[0020] Substitute F3 into the linear regression equation to obtain the concentration of the solution to be tested;

[0021] Wherein, the fluorescent probe is the above-mentioned fluorescent probe or a fluorescent probe prepared by the above-mentioned preparation method.

[0022] Furthermore, the fluorescent probe is mixed with a substrate to obtain a mixed solution, wherein the concentration of the fluorescent probe in the mixed solution is 0.01-0.05 g / mL; wherein the substrate is selected from water, DMP solution or a solution to be tested.

[0023] Furthermore, the mixing time is 10 to 20 seconds; preferably, the excitation wavelength for detecting the fluorescence value is 360 to 380 nm, and the emission wavelength is 600 to 612 nm.

[0024] In order to achieve the above objectives, according to the fourth aspect of the present invention, there is provided an application of the above fluorescent probe, or the fluorescent probe prepared by the above preparation method, or the above method for detecting the concentration of DMP in mine water.

[0025] By applying the technical scheme of the present invention, after mixing the fluorescent probe of the present invention with the DMP solution, fluorescence quenching phenomenon will occur, and the fluorescence quenching value is linearly related to the concentration of DMP within a certain range. In addition, the fluorescent probe of the present invention has strong specificity, and the binding with the substrate DMP is not affected by other substances, such as NaCl, Na2SO4, CaCl2, CaSO4, MgCl2, MgSO4, NaF, CuSO4, FeSO4, MnCl2, CoCl2, dichloromethane, benzene, naphthalene and anthracene, etc. The fluorescent probe of the present invention is used to detect DMP in mine water, which has the advantages of simple operation, low cost, fast response, and wide applicable concentration range, and is expected to be applied to water quality detection such as domestic sewage, mine water and coal chemical wastewater in the future. DETAILED DESCRIPTION

[0026] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present invention can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0027] As mentioned in the background technology, the detection of organic pollutants in mine water - dimethyl phthalate mainly adopts methods such as gas chromatography (GC), high performance liquid chromatography (HPLC) and gas chromatography / mass spectrometry (GC-MS). These methods have the disadvantages of high cost and cumbersome operation. Fluorescent probes / fluorescent sensors are easy to operate and can achieve simple, rapid and accurate detection of organic matter in water, thus becoming one of the potential methods for detecting DMP in mine water. Although the prior art has disclosed a fluorescent molecular sensor with a range of 0 to 1.94×10 -2 In the mg / L concentration range, the fluorescent molecular sensor has a good linear relationship with the quenching degree of DMP, but the fluorescent molecular sensor has a small applicable concentration range and is easily affected by other pollutants in mine water, and cannot detect DMP in mine water. The inventors of the present invention attempt to develop a fluorescent probe that can specifically detect DMP in mine water based on the above foundation, and thus propose a series of protection schemes of the present invention.

[0028] In a first typical embodiment of the present invention, a fluorescent probe is provided, and the fluorescent probe has a structure shown in Formula 1 below:

[0029]

[0030] The fluorescent probe can emit fluorescence at an excitation wavelength of 360 to 380 nm and an emission wavelength of 600 to 612 nm. Using the fluorescent probe to detect the concentration of DMP has the advantages of simple operation and low cost.

[0031] In a second typical embodiment of the present invention, a method for preparing a fluorescent probe is provided. The method comprises: subjecting carboxymethyl-β-cyclodextrin to an amidation reaction with a carbazole compound in an alkaline environment to obtain the fluorescent probe.

[0032] The alkaline environment is Na2CO3, K2CO3, NaHCO3 or KHCO3; preferably, the carbazole compound is selected from carbazole, imidazole, carbazole line or carbazole oxide; more preferably, carboxymethyl-β-cyclodextrin and carbazole are subjected to amidation reaction in an organic solvent containing Na2CO3 solution; more preferably, the organic solvent is selected from acetonitrile, chloroform, methanol or ethanol. The role of the organic solvent is to ensure that the reaction is fully carried out.

[0033] In a preferred embodiment of the present invention, the organic solvent is selected from acetonitrile, carboxymethyl-β-cyclodextrin and carbazole are subjected to amidation reaction in an acetonitrile solution containing a Na2CO3 solution (see reaction formula II), and the mass (g) volume (mL) ratio of the above carboxymethyl-β-cyclodextrin, carbazole, Na2CO3 and acetonitrile is: (1-2.5) g: (1.5-4.0) g: (1.5-4.0) g: (100-200) mL. The fluorescent probe prepared using the above ratio can better bind to DMP, causing fluorescence quenching of the fluorescent probe, and the fluorescence quenching change value is linearly related to the concentration of DMP.

[0034] The time and temperature of the chemical reaction may affect the properties of the fluorescent probe. In a preferred embodiment of the present invention, the temperature of the chemical reaction is 70-85°C and the time is 24-72 hours. The fluorescent probe generated under this condition can effectively bind to DMP, so that the fluorescence quenching value of the fluorescent probe and the DMP concentration show a linear relationship.

[0035] In order to further obtain a fluorescent probe with high purity, in a preferred embodiment of the present invention, after the amidation reaction is completed, the product of the amidation reaction needs to be vacuum dried. In a preferred embodiment of the present invention, a vacuum drying oven is used for vacuum drying. The vacuum drying method has the beneficial effects of no secondary pollution and good drying effect.

[0036] The temperature and time of vacuum drying may affect the properties of the fluorescent probe. In a preferred embodiment of the present invention, the vacuum drying temperature is 65-75°C and the time is 72-90 hours. The fluorescent probe obtained after the vacuum drying has the advantages of high purity and no secondary pollution.

[0037] In a third typical embodiment of the present invention, a method for detecting DMP concentration is provided, the detection method comprising: detecting the fluorescence values ​​of the fluorescent probe after mixing with water and DMP solution, respectively, recorded as F1 and F2, and calculating the fluorescence difference ΔF; plotting a standard curve with the concentration of the DMP solution as the abscissa and the fluorescence difference ΔF as the ordinate, and obtaining a linear regression equation;

[0038] The fluorescence value after the fluorescent probe and the test solution are mixed is detected and recorded as F3; F3 is substituted into the linear regression equation to obtain the concentration of the test solution; wherein the fluorescent probe is the above-mentioned fluorescent probe or the fluorescent probe prepared by the above-mentioned preparation method.

[0039] The principle of fluorescence quenching after the fluorescent probe of the present invention combines with DMP is that the ester group of dimethyl phthalate replaces groups, resulting in fluorescence quenching.

[0040] In the present invention, the experiment in which the fluorescent probe was mixed with water was the control group, and its fluorescence value was recorded as F1, while the experiment in which the DMP solution was mixed with the fluorescent probe was the experimental group, and its fluorescence value was recorded as F2. The calculation formula of the corresponding fluorescence change value ΔF was: ΔF = F2-F1. DMP solutions of different concentrations were prepared to obtain the corresponding fluorescence change values. The standard curve was drawn with the concentration of the DMP solution as the horizontal axis and the fluorescence difference ΔF as the vertical axis to obtain the linear regression equation (R 2 ≥0.99).

[0041] Similarly, the test solution and the fluorescent probe are mixed, and the fluorescence value is recorded as F3. The corresponding fluorescence change value is ΔF=F3-F1. ΔF is substituted into the linear regression equation to calculate the concentration of DMP in the test solution.

[0042] The fluorescent probe and substrate (water, DMP solution or test solution) are mixed to obtain a mixed solution. The concentration of the fluorescent probe in the mixed solution is 0.01-0.05 g / mL. When the concentration of the fluorescent probe is too high, the fluorescence response of the fluorescent probe itself will interfere with the accuracy of instrument detection. When the concentration of the fluorescent probe is too low, the fluorescence quenching reaction will not be complete.

[0043]

[0044] If the mixing time is too long, the fluorescence quenching value cannot be measured timely and accurately. If the mixing time is too short, the quenching reaction will be incomplete. In a preferred embodiment of the present invention, the fluorescent probe and the substrate are mixed for 10 to 20 seconds.

[0045] In a fourth typical embodiment of the present invention, a fluorescent probe or a fluorescent probe prepared by the above preparation method or the above method for detecting the concentration of DMP is provided for use in detecting the concentration of DMP in mine water.

[0046] The beneficial effects of the present invention will be further explained in detail below in conjunction with specific embodiments.

[0047] Example 1

[0048] In this embodiment, the excitation wavelength for detecting fluorescence value is 380 nm, and the emission wavelength is 612 nm.

[0049] ① Weigh carboxymethyl-β-cyclodextrin, carbazole and Na2CO3 in a mass ratio of 1:1.5:1.5, measure 150mL of acetonitrile solution, mix them and pour them into a beaker.

[0050] ② Place the beaker on the heating plate, control the temperature at 75℃, and continue heating and reacting for 24 hours.

[0051] ③ After the reaction is completed, the mixed liquid is placed in a vacuum drying oven for 72 hours at a temperature of 65°C until the liquid is completely evaporated to obtain a dry solid, and the solid is dissolved in pure water to obtain a fluorescent probe with a concentration of 0.027 g / mL.

[0052] ④ Prepare DMP solutions of different concentrations in pure water, which are 0.5, 1, 3, 5, 8, and 10 mg / L respectively.

[0053] ⑤ Add fluorescent probes to pure water (control group) and DMP solution (experimental group) at a volume ratio of 1:1, mix evenly for 20 seconds, and then detect the fluorescence values ​​of the control group and the experimental group.

[0054] ⑥ The fluorescence differences between the experimental groups and the control group, i.e., the fluorescence quenching values ​​ΔF, were 287.9, 289.5, 296.3, 302.4, 312.8, and 318.6, respectively. The fluorescence quenching values ​​ΔF were linearly related to the DMP concentration range (0.5-10 mg / L) (R 2 =0.9995≥0.99), the relationship is: ΔF=3.2561C+286.33; where: ΔF is the fluorescence quenching value, C is the DMP concentration in water (mg / L).

[0055] Example 2

[0056] In this embodiment, the excitation wavelength for detecting the fluorescence value is 360 nm, and the emission wavelength is 600 nm.

[0057] ① Weigh carboxymethyl-β-cyclodextrin, carbazole and Na2CO3 in a mass ratio of 2.5:4:4, measure 200 mL of acetonitrile solution, mix them and pour them into a beaker.

[0058] ② Place the beaker on the heating plate, control the temperature at 70℃, continue heating and react for 72 hours.

[0059] ③ After the reaction is completed, the mixed liquid is placed in a vacuum drying oven for 90 hours at a temperature of 75°C until the liquid is completely evaporated to obtain a dry solid, and the solid is dissolved in pure water to obtain a fluorescent probe with a concentration of 0.10 g / mL.

[0060] ④ Prepare DMP solutions of different concentrations in pure water, which are 0.5, 1, 3, 5, 8, and 10 mg / L respectively.

[0061] ⑤ Add fluorescent probes to pure water (control group) and DMP solution (experimental group) at a volume ratio of 1:1, mix evenly for 10 seconds, and then detect the fluorescence values ​​of the control group and the experimental group.

[0062] ⑥ The fluorescence differences between the experimental groups and the control group, i.e., the fluorescence quenching values ​​ΔF, were 289.65, 290.88, 297.55, 303.59, 313.89, and 320.11, respectively. The fluorescence quenching values ​​ΔF were linearly related to the DMP concentration range (0.5-10 mg / L) (R 2 =0.9996≥0.99), the relationship is: ΔF=3.2333C+287.79; where: ΔF is the fluorescence quenching value, C is the DMP concentration in water (mg / L).

[0063] Example 3

[0064] In this embodiment, the excitation wavelength for detecting fluorescence value is 370 nm, and the emission wavelength is 606 nm.

[0065] ① Weigh carboxymethyl-β-cyclodextrin, carbazole and Na2CO3 in a mass ratio of 1.5:2:2, measure 100 mL of acetonitrile solution, mix them and pour them into a beaker.

[0066] ② Place the beaker on the heating plate, control the temperature at 85℃, continue heating and react for 48 hours.

[0067] ③ After the reaction is completed, the mixed liquid is placed in a vacuum drying oven for 80 hours at a temperature of 70°C until the liquid is completely evaporated to obtain a dry solid, and the solid is dissolved in pure water to obtain a fluorescent probe with a concentration of 0.020 g / mL.

[0068] ④ Prepare DMP solutions of different concentrations in pure water, which are 0.5, 1, 3, 5, 8, and 10 mg / L respectively.

[0069] ⑤ Add fluorescent probes to pure water (control group) and DMP solution (experimental group) at a volume ratio of 1:1, mix evenly for 16 seconds, and then detect the fluorescence values ​​of the control group and the experimental group.

[0070] ⑥ The fluorescence differences between the experimental groups and the control group, i.e., the fluorescence quenching values ​​ΔF, were 288.55, 290.12, 296.32, 302.55, 312.74, and 319.98, respectively. The fluorescence quenching values ​​ΔF were linearly related to the DMP concentration range (0.5-10 mg / L) (R 2 =0.9991≥0.99), the relationship is: ΔF=3.2892C+286.63; where: ΔF is the fluorescence quenching value, C is the DMP concentration in water (mg / L).

[0071] Example 4

[0072] The excitation wavelength and emission wavelength for detecting fluorescence values ​​in this embodiment are the same as those in Embodiment 1, that is, the excitation wavelength is 380 nm, and the emission wavelength is 612 nm.

[0073] (1) Preparation of fluorescent probes

[0074] Same as Example 1.

[0075] (2) Effect of mineralization in simulated mine water on specific binding of fluorescent probes

[0076] ① Self-prepared simulated mine water, which contains 100mg / L NaCl, 100mg / L Na2SO4, 100mg / LCaCl2, 100mg / L CaSO4, 100mg / L MgCl2, 100mg / L MgSO4 and 2.5mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response was found.

[0077] ② Add 0.027 g / mL of fluorescent probe to pure water (control group) and self-prepared water (experimental group) at a volume ratio of 1:1, mix well, and then detect the fluorescence values ​​of the control group and the experimental group.

[0078] ③ The fluorescence difference between the control group and the experimental group, i.e., the fluorescence quenching value ΔF, is 294.5, which is substituted into the formula described in Example 1: ΔF=3.2561C+286.33; where ΔF is the fluorescence quenching value, and C is the DMP concentration in the water (mg / L). The DMP concentration in the self-mixed water is calculated to be 2.51 mg / L, and the measurement result is accurate.

[0079] ④ Repeat the above steps 3 times, and the concentration of DMP in the self-prepared water is 2.509±0.070 mg / L, which proves that the above salts in the mine water have no obvious interference with the quenching of the fluorescent probe.

[0080] Example 5

[0081] Self-prepared simulated mine water, the simulated mine water contains 500mg / L NaCl, 300mg / L Na2SO4, 200mg / LCaCl2, 100mg / L CaSO4, 700mg / L MgCl2, 600mg / L MgSO4 and 3.0mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response was found.

[0082] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.008±0.021 mg / L, which proves that the above salts in the mine water have no significant interference with the quenching of the fluorescent probe.

[0083] Example 6

[0084] Self-prepared simulated mine water, the simulated mine water contains 300mg / L NaCl, 100mg / L Na2SO4, 60mg / LCaCl2, 50mg / L CaSO4, 30mg / L MgCl2, 40mg / L MgSO4 and 8.0mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response was found.

[0085] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 8.010±0.008 mg / L, which proves that the above salts in the mine water have no obvious interference with the quenching of the fluorescent probe.

[0086] Example 7

[0087] Self-prepared simulated mine water containing 3 mg / L NaF and 5.5 mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0088] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 5.49±0.09 mg / L, which proves that the sodium fluoride in the mine water has no significant interference with the quenching of the fluorescent probe.

[0089] Example 8

[0090] Self-prepared simulated mine water containing 7 mg / L NaF and 5.0 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0091] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 5.02±0.04 mg / L, which proves that the sodium fluoride in the mine water has no significant interference with the quenching of the fluorescent probe.

[0092] Example 9

[0093] Self-prepared simulated mine water containing 2 mg / L NaF and 7.0 mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0094] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 7.01±0.04 mg / L, which proves that the sodium fluoride in the mine water has no significant interference with the quenching of the fluorescent probe.

[0095] Example 10

[0096] Self-prepared simulated mine water, which contains 1.5 mg / L CuSO4, 1.5 mg / L FeSO4, 1.5 mg / L MnCl2, 1.5 mg / L CoCl2 and 3 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0097] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.02±0.05 mg / L, which proves that the heavy metals in the mine water have no significant interference with the quenching of the fluorescent probe.

[0098] Embodiment 11

[0099] Self-prepared simulated mine water containing 1.0 mg / L CuSO4, 0.5 mg / L FeSO4, 0.9 mg / L MnCl2, 0.8 mg / L CoCl2 and 3 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0100] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.01±0.05 mg / L, which proves that the heavy metals in the mine water have no significant interference with the quenching of the fluorescent probe.

[0101] Example 12

[0102] Self-prepared simulated mine water containing 0.5 mg / L CuSO4, 1 mg / L FeSO4, 0.4 mg / L MnCl2, 1.0 mg / L CoCl2 and 3 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0103] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.06±0.02 mg / L, which proves that the heavy metals in the mine water have no significant interference with the quenching of the fluorescent probe.

[0104] Embodiment 13

[0105] Self-prepared simulated mine water containing 2 mg / L dichloromethane, 2 mg / L benzene, 2 mg / L naphthalene, 2 mg / L anthracene and 4 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0106] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 4.08±0.08 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0107] Embodiment 14

[0108] Self-prepared simulated mine water containing 1 mg / L dichloromethane, 0.5 mg / L benzene, 1.5 mg / L naphthalene, 1 mg / L anthracene and 4 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0109] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 4.02±0.05 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0110] Embodiment 15

[0111] Self-prepared simulated mine water containing 0.5 mg / L dichloromethane, 1 mg / L benzene, 2 mg / L naphthalene, 0.5 mg / L anthracene and 4 mg / L DMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0112] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 4.01±0.02 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0113] Example 16

[0114] Self-prepared simulated mine water containing 300 mg / L NaHCO3, 300 mg / L Na2CO3 and 3 mg / LDMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0115] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.05±0.02 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0116] Embodiment 17

[0117] Self-prepared simulated mine water containing 100 mg / L NaHCO3, 200 mg / L Na2CO3 and 3 mg / LDMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0118] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.01±0.03 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0119] Embodiment 18

[0120] Self-prepared simulated mine water containing 200 mg / L NaHCO3, 50 mg / L Na2CO3 and 3 mg / LDMP. The fluorescence intensity of the self-prepared water was tested in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0121] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.06±0.03 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0122] Embodiment 19

[0123] Self-prepared simulated mine water contains 100mg / L NaCl, 100mg / L Na2SO4, 100mg / LCaCl2, 100mg / L CaSO4, 100mg / L MgCl2, 100mg / L MgSO4, 3mg / L NaF, 1.5mg / L CuSO4, 1.5mg / LFeSO4, 1.5mg / L MnCl2, 1.5mg / L CoCl2, 200mg / L NaHCO3, 250mg / L Na2CO3, 1mg / L dichloromethane, 1mg / L benzene, 1mg / L naphthalene, 1mg / L anthracene and 3mg / L DMP. The fluorescence intensity of the self-prepared water is detected in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response is found.

[0124] The remaining steps are the same as in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 3.07±0.02 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0125] Embodiment 20

[0126] Self-prepared simulated mine water, the simulated mine water contains 200mg / L NaCl, 80mg / L Na2SO4, 120mg / LCaCl2, 050mg / L CaSO4, 100mg / L MgCl2, 100mg / L MgSO4, 2mg / L NaF, 1mg / L CuSO4, 0.8mg / LFeSO4, 1mg / L MnCl2, 1mg / L CoCl2, 200mg / L NaHCO3, 150mg / L Na2CO3, 0.5mg / L dichloromethane, 1mg / L benzene, 1mg / L naphthalene, 1mg / L anthracene and 3mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response was found.

[0127] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 2.97±0.02 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0128] Embodiment 21

[0129] Self-prepared simulated mine water, the simulated mine water contains 100mg / L NaCl, 200mg / L Na2SO4, 300mg / LCaCl2, 200mg / L CaSO4, 80mg / L MgCl2, 100mg / L MgSO4, 2mg / L NaF, 0.5mg / L CuSO4, 0.5mg / LFeSO4, 1mg / L MnCl2, 1.2mg / L CoCl2, 300mg / L NaHCO3, 300mg / L Na2CO3, 0.6mg / L dichloromethane, 0.5mg / L benzene, 0.4mg / L naphthalene, 0.5mg / L anthracene and 2mg / L DMP. The fluorescence intensity of the self-prepared water was detected in a fluorescence spectrophotometer (excitation wavelength 380nm, emission wavelength 612nm), and no fluorescence response was found.

[0130] The remaining steps are the same as those in Example 4. The concentration of DMP in the self-dispensed water was calculated to be 2.07±0.05 mg / L, which proves that the above organic matter in the mine water has no obvious interference with the quenching of the fluorescent probe.

[0131] Embodiment 22

[0132] (1) Preparation of fluorescent probes

[0133] The fluorescent probe of the present invention was prepared according to the method described in Example 1. In addition, the fluorescent probe Cu, Fe-NC nanozyme and water-soluble fluorescent probe were prepared according to the methods described in patent applications CN113933272A and CN116903647A.

[0134] (2) Detection of DMP in mine water using different methods

[0135] ① Collect mine water from a mining area in Shenhua, and use liquid phase mass spectrometry to detect dimethyl phthalate in the mine water, and its concentration is 0.79 mg / L.

[0136] ② The same method as in Example 4 was used to detect the mine water in a certain mining area in Shendong. The concentration of DMP in the mine water was 0.75±0.09 mg / L, which confirmed that the fluorescent probe had a strong specific binding ability with the target pollutant in the actual mine water, and the detection result was accurate.

[0137] ③ The fluorescent probe Cu,Fe-NC nanozyme was used to detect the mine water in the Shendong mining area according to the method described in patent application CN113933272A. The concentration of DMP in the mine water was 0.59 mg / L, which deviated from the actual result.

[0138] ④ Using a water-soluble fluorescent probe to detect the mine water in the Shendong mining area according to the method described in patent application CN116903647A, the concentration of DMP in the mine water was 0.62 mg / L, which deviated from the actual result.

[0139] Embodiment 23

[0140] Self-prepared simulated mine water contains 100mg / L NaCl, 100mg / L Na2SO4, 100mg / LCaCl2, 100mg / L CaSO4, 100mg / L MgCl2, 100mg / L MgSO4, 3mg / L NaF, 1.5mg / L CuSO4, 1.5mg / LFeSO4, 1.5mg / L MnCl2, 1.5mg / L CoCl2, 1mg / L dichloromethane, 1mg / L benzene, 1mg / L naphthalene and 1mg / L anthracene.

[0141] DMP was then added to the simulated mine water to prepare simulated mine water containing 0.1 mg / L, 0.15 mg / L, 0.2 mg / L, 0.25 mg / L, 0.3 mg / L, 0.35 mg / L, 0.4 mg / L, 0.45 mg / L, 0.5 mg / L, 12 mg / L, 14 mg / L, 16 mg / L, 18 mg / L, 20 mg / L, 22 mg / L, 24 mg / L, 26 mg / L, 28 mg / L and 30 mg / L of DMP. The fluorescence intensity of the simulated mine water was detected in a fluorescence spectrophotometer (excitation wavelength 380 nm, emission wavelength 612 nm), and no fluorescence response was found.

[0142] The remaining steps are the same as in Example 4. The calculated concentrations of DMP in the simulated mine water are 0.102±0.005mg / L, 0.152±0.008mg / L, 0.205±0.002mg / L, 0.253±0.001mg / L, 0.305±0.010mg / L, 0.356±0.005mg / L, 0.405±0.003mg / L, 0.502±0.006mg / L, 12.012±0.010mg / L, 14.125±0.050mg / L, respectively. The experimental results show that the fluorescent probe of the present invention is suitable for detecting mine water with DMP of 0.1 mg / L to 30 mg / L.

[0143] Comparative Example 1

[0144] ① Weigh carboxymethyl-β-cyclodextrin, carbazole and Na2CO3 in a mass ratio of 1:5:5, measure 300 mL of acetonitrile solution, mix them and pour them into a beaker.

[0145] ② Place the beaker on the heating plate, control the temperature at 90℃, continue heating and react for 12 hours.

[0146] ③ After the reaction is completed, the mixed liquid is placed in a vacuum drying oven for 12 hours at a temperature of 60°C until the liquid is completely evaporated to obtain a dry solid, and the solid is dissolved in pure water to obtain a fluorescent probe with a concentration of 0.037 g / mL.

[0147] ④ Prepare DMP solutions of different concentrations in pure water, which are 0.5, 1, 3, 5, 8, and 10 mg / L respectively.

[0148] ⑤ Add fluorescent probes to pure water (control group) and DMP solution (experimental group) at a volume ratio of 1:1, mix well, and detect the fluorescence values ​​of the control group and the experimental group within 10 to 20 seconds.

[0149] ⑥ The fluorescence differences between the experimental groups and the control group, i.e., the fluorescence quenching values ​​ΔF, were 285.22, 286.23, 289.33, 290.12, 300.12, and 308.56, respectively. The fluorescence quenching values ​​ΔF were linearly related to the DMP concentration range (0.5-10 mg / L) (R 2=0.9305<0.99), the relationship is: ΔF=2.3119C+282.67; where: ΔF is the fluorescence quenching value, C is the concentration of dimethyl phthalate in water (mg / L).

[0150] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: (1) Based on the fluorescent probe technology, it realizes the rapid and instant detection of dimethyl phthalate in water, which is simple to operate and low in cost; (2) It broadens the detection scope of the existing related technologies, has a wider scope of application, and has broad application prospects.

[0151] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A fluorescent probe, characterized in that The fluorescent probe has a structure as shown in Formula 1:

2. The method for preparing the fluorescent probe according to claim 1, characterized in that: The preparation method comprises: Carboxymethyl-β-cyclodextrin and carbazole compounds are subjected to amidation reaction in an alkaline environment to obtain the fluorescent probe.

3. The preparation method according to claim 2, characterized in that: The alkaline environment is Na2CO3, K2CO3, NaHCO3 or KHCO3; Preferably, the carbazole compound is selected from carbazole, imidazole, carbazole line or carbazole oxide; More preferably, the carboxymethyl-β-cyclodextrin and the carbazole undergo the amidation reaction in an organic solvent containing the Na2CO3; More preferably, the organic solvent is selected from acetonitrile, chloroform, methanol or ethanol; Preferably, before obtaining the fluorescent probe, the preparation method further comprises the step of vacuum drying the product of the amidation reaction; More preferably, the vacuum drying is performed using a vacuum drying oven.

4. The preparation method according to claim 3, characterized in that: The organic solvent is selected from acetonitrile, and the mass volume ratio of the carboxymethyl-β-cyclodextrin, the carbazole, the Na2CO3 and the acetonitrile is: (1-2.5): (1.5-4.0): (1.5-4.0): (100～200)。 5. The preparation method according to claim 2 or 3, characterized in that: The temperature of the amidation reaction is 70-85° C. and the time is 24-72 hours.

6. The preparation method according to claim 3, characterized in that: The vacuum drying is performed at a temperature of 65 to 75° C. and a time of 72 to 90 hours.

7. A method for detecting DMP concentration, characterized in that: The method comprises: The fluorescence values ​​of the fluorescent probe after mixing with water and DMP solution were detected, recorded as F1 and F2, respectively, and the fluorescence difference ΔF was calculated; With the concentration of the DMP solution as the abscissa and the fluorescence difference ΔF as the ordinate, a standard curve is drawn to obtain a linear regression equation; Detect the fluorescence value after the fluorescent probe is mixed with the test solution, which is recorded as F3; Substituting F3 into the linear regression equation, the concentration of the solution to be tested is obtained; Wherein, the fluorescent probe is the fluorescent probe according to claim 1 or a fluorescent probe prepared by the preparation method according to any one of claims 2-6.

8. The method according to claim 7, characterized in that The fluorescent probe is mixed with a substrate to obtain a mixed solution, wherein the concentration of the fluorescent probe in the mixed solution is 0.01 to 0.05 g / mL; Wherein, the substrate is selected from the water, the DMP solution or the solution to be tested.

9. The method according to claim 7, characterized in that: The mixing time is 10 to 20 seconds; Preferably, the excitation wavelength for detecting the fluorescence value is 360-380 nm, and the emission wavelength is 600-612 nm.

10. Use of the fluorescent probe according to claim 1, or the fluorescent probe prepared by the preparation method according to any one of claims 2 to 6, or the method for detecting the concentration of DMP according to any one of claims 7 to 9 in detecting the concentration of DMP in mine water.

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