CN111320585A - Double-colorimetric double-fluorescent phenanthroimidazole probe as well as preparation method and application thereof - Google Patents
Double-colorimetric double-fluorescent phenanthroimidazole probe as well as preparation method and application thereof Download PDFInfo
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- GZPPANJXLZUWHT-UHFFFAOYSA-N 1h-naphtho[2,1-e]benzimidazole Chemical compound C1=CC2=CC=CC=C2C2=C1C(N=CN1)=C1C=C2 GZPPANJXLZUWHT-UHFFFAOYSA-N 0.000 title claims abstract description 84
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Abstract
The invention discloses a double-colorimetric double-fluorescent phenanthroimidazole probe, a preparation method and application thereof, and relates to a phenanthroimidazole probe, a preparation method and application thereof. The colorimetric probe is used for solving the technical problems that the existing colorimetric probe is single in response object, low in response speed and incapable of realizing quantitative detection. The structural formula of the double-colorimetric double-fluorescent phenanthroimidazole probe is as follows:
the preparation method comprises the following steps: adding 2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde into an organic solvent I for reaction, filtering, washing, drying and recrystallizing precipitated solid to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe. The probe is used for Cu in solution2+And Ag+Detection of (3). Can be obtained by colorimetry or fluorescenceQualitative detection, and quantitative detection can be realized by a fluorescence standard curve method. The detection response time is 2-3 min, the detection concentration reaches the nM level, and the method can be used in the field of industrial wastewater and drinking water detection.
Description
Technical Field
The invention relates to a phenanthroimidazole probe, a preparation method and application thereof.
Background
Cu2+And Ag+Are all common heavy metal elements. The existence of trace amount is harmless to human body, but the excessive ion can directly cause harm to human body. Cu2+Can inhibit nitrite reductase, influence the absorption and utilization of nitrogen, finally cause physiological obstruction, inhibit development and even die. Ag+Can generate toxicity in biological aggregation, and can directly interact with active groups such as amine, imidazole, carboxylic acid and the like in a human body and non-active mercaptoenzyme, thereby harming the physiological environment of the human body. Meanwhile, Ag + is one of the common heavy metals in the living environment. Cu2+And Ag+The two heavy metal ions are the main metals of the antibacterial, antiviral and antitumor drugs. Cu in drinking water according to the World Health Organization (WHO) report2+The standard content should be less than 1.00mg/L, Ag+The content of the extract in drinking water should be less than 0.05 mg/L. Therefore, the Cu can be accurately, qualitatively and quantitatively detected in physiological environment and natural environment2+And Ag+The content of (A) has very important significance, and the Cu is detected at present2+And Ag+Among the methods, the fluorescence analysis method can avoid the limitation of environment and cost due to the characteristics of high selectivity and high sensitivity. The fluorescence analysis method mainly realizes the detection of the metal ions by utilizing the change of fluorescence caused by the chemical action between the fluorescent probe and the metal ions. Therefore, Cu in the ecological environment and in the living body is detected2+And Ag+Has important significance.
In 2018, Tianhuan et al, Proc. Oncology of higher school, volume 39, pp. 6, 1191-1196, article 4, 13-Dixobenzo-18Synthesis of crown-6 and p-Ag+Selective extraction of (2) A dithiabenz-crown ether derivative was synthesized and found to be extractable with different solvents for Ag+The recovery effect is achieved, but the compound has no obvious ultraviolet or fluorescence change and cannot react with Ag+Realizing quantitative detection. In 2019, an article "synthesis of N, N-bis (2-picolyl) amine-based truxene derivative and selective recognition of copper ions and copper ion pairs" of N, N-bis (2-picolyl) amine-based truxene derivative "by Zhu Yang Ming et al, organic chemistry, volume 39, pages 427 to 433 reports a fluorescent probe of the bis (2-picolyl) amine (DPA) -truxene derivative, and the probe is used for Cu2+And Ni2+Shows better recognition capability, and the probe is used for Cu2+The detection limit reaches 28nmol/L for Ni2+The detection limit reaches 41nmol/L, and the detection limit of the two ions is lower than the drinking water content standard specified by the World Health Organization (WHO), which indicates that the probe has potential application value. The literature also reports fluorescent probes that detect metal ions while capturing metal ions using fluorescence spectroscopy. In 2019, I Paul et al published in Journal of the American Chemical Society, Vol.141, No. 13, No. 5139, No. 5143, a Catch-Release System for quantitatively determining the Cyclic Catalytic Activity of Silver catalysts by Fluorescence method, a benzyne-crown ether derivative synthesized in methylene chloride-acetonitrile (CH-acetonitrile)2Cl2:CH3CN is 50:1) system for Ag+Has good selectivity, and is added with Ag+The emission wavelength at the later 554nm is gradually reduced, the fluorescence intensity at the 472nm is gradually enhanced, the fluorescence color is changed from yellow to blue, and the ratio fluorescence detection is realized. By crown ethers on Ag+Effective capture is realized by adding Zn2+Realize to Ag+Recovering the probe molecule pair Ag+The detection and capture of the (B) are very sensitive, but are easily interfered by water, so that the application performance of the (B) is limited.
According to the current literature report, Cu2+And Ag+The probe mainly has the following defects:
1. can realize simultaneous implementationExisting naked eye double-color comparison and fluorescence detection Cu2+Or Ag+The types of the probes are less;
2. cannot realize the simultaneous detection of Cu2+And Ag+Simultaneous precipitation of Cu adsorbed by probe2+And Ag+；
3. Most of fluorescent probes are fluorescent molecular probes, and Cu can be carried out only through organic solution2+And Ag+The detection of (2) has strict requirements on water content;
4、Ag+the detection limit of the probe is high, the nanomolar level is not easy to reach, and the probe is easy to be interfered by the external environment, so that the application range of the probe is limited.
Disclosure of Invention
The invention provides a double-colorimetric double-fluorescent phenanthroimidazole probe, a preparation method and application thereof, aiming at solving the technical problems that the existing colorimetric probe is single in response object, low in response speed and incapable of realizing quantitative detection.
The structural formula of the double-colorimetric double-fluorescent phenanthroimidazole probe is as follows:
the preparation method of the double-colorimetric double-fluorescent phenanthroimidazole probe comprises the following steps:
the preparation method comprises the following steps of (1-6) mixing 2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde in a mass ratio of: 1, adding the mixture into an organic solvent I, and reacting for 1-8 hours at the temperature of 20-80 ℃, wherein solids are separated out in the reaction process; after the reaction is finished, filtering, washing a filter cake by using an organic solvent II and distilled water in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using an organic solvent III to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe.
The reaction formula in the preparation process of the double-colorimetric double-fluorescent phenanthroimidazole probe is as follows:
the application of the double-colorimetric double-fluorescent phenanthroimidazole probe is to use the double-colorimetric double-fluorescent phenanthroimidazole probe in Cu in solution2+And Ag+Detection of (3).
Detection of Cu in solution by colorimetric method using double-colorimetric double-fluorescent phenanthroimidazole probe2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a HEPES solution with the concentration of 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, under natural light, the probe solution B is colorless;
if the color of the test solution C is green after standing for 2-3 min under natural light and green precipitate is generated, judging that the test solution C contains Cu2+；
If the color of the test solution C is light pink after standing for 2-3 min under natural light and light pink precipitation is generated, judging that the solution to be tested contains Ag+。
Qualitative detection of Cu in solution by fluorescence using dual-colorimetric dual-fluorescent phenanthroimidazole probe2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a mixed solution of DMF and HEPES solution with the volume ratio of 1:1, wherein the concentration of the HEPES solution is 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, standing the probe solution B for 2-3 min, and measuring the emission intensity of the fluorescence emission spectrum of the probe solution B when the emission wavelength is 461nm by taking 310nm as the excitation wavelength and recording the emission intensity as TB；
Fifthly, standing the test solution C for 2-3 min, measuring the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 461nm by taking 310nm as the excitation wavelength, and marking as TC；
Sixthly, comparing TBAnd TCIf 1/13TB＜TC≤1/6TBThen, the Cu content in the solution to be measured is determined2+(ii) a If TC≤1/13TBThen, it is determined that the solution to be measured contains Ag+。
Quantitative detection of Cu in wastewater by fluorescence method using double-colorimetric double-fluorescent phenanthroimidazole probe2+And Ag+The method of (1) is a standard curve method.
The double-colorimetric double-fluorescent phenanthroimidazole probe is a colorless transparent solution, Cu, in a test system2+1/6, the solution appears green in the naked eye state with generation of green precipitate and the fluorescence intensity is quenched to the probe intensity; ag+In the presence, the solution appeared to be light pink with light pink precipitation occurring with naked eye, and the fluorescence intensity was quenched to 1/13 of the probe intensity. Change in fluorescence intensity and Cu2+And Ag+The change of the concentration accords with a linear relation, and the Cu in the sample to be detected can be obtained through the corresponding fluorescence intensity2+And Ag+The content of (a). Realizing Cu in to-be-detected sample through fluorescence spectrum or visualization effect2+And Ag+Qualitative and quantitative detection.
The double-colorimetric double-fluorescent phenanthroimidazole probe provided by the invention has the advantages of stable structure, easiness in storage, low cost, convenience in use, obvious response effect, capability of realizing multiple responses and the like. Detecting Cu by using the probe2+And Ag+The method is simple to operate, can respond after 2-3 min, is quick in response, can detect ions with the concentration reaching nM level, is high in sensitivity, and can realize Cu2+And Ag+Qualitative and quantitative detection. The detection method is simple to operate, and the response is intuitive and quick. Can be used in the field of industrial wastewater and drinking water detection.
Drawings
FIG. 1 is a double colorimetric double fluorescent phenanthroimidazole probe solution (0.01mmol/L, V) prepared in example 1DMF:VHEPES＝1:9，pH＝7.40)、Cu2+In the presence of Ag+A colorimetric change profile in the presence;
FIG. 2 shows a double-colorimetric double-fluorescent phenanthroimidazole probe (0.01mmol/L, V) prepared in example 1DMF:VHEPES1:9, pH 7.40), wavelength on abscissa and fluorescence intensity on ordinate;
FIG. 3 is a double colorimetric double fluorescent phenanthroimidazole probe (0.01mmol/L, V) prepared in example 1DMF:VHEPES1:9, pH 7.40) detection of Cu2+Fluorescence emission spectrum at time (10.0. mu.M/L), wavelength on abscissa, and fluorescence intensity on ordinate;
FIG. 4 shows a double-colorimetric double-fluorescent phenanthroimidazole probe (0.01mmol/L, V) prepared in example 1DMF:VHEPES1:9, pH 7.40) Ag detection+Fluorescence emission spectrum at time (10.0. mu.M/L), wavelength on abscissa, and fluorescence intensity on ordinate;
FIG. 5 is a diagram of the detection of Cu by the double-colorimetric double-fluorescent phenanthroimidazole probe prepared in example 12+The standard curve of (2).
FIG. 6 is a diagram of Ag detection using the double-colorimetric double-fluorescent phenanthroimidazole probe prepared in example 1+The standard curve of (2).
Detailed Description
The first embodiment is as follows: the structural formula of the double-colorimetric double-fluorescent phenanthroimidazole probe of the embodiment is as follows:
the second embodiment is as follows: the method for preparing the double-colorimetric double-fluorescent phenanthroimidazole probe in the embodiment one comprises the following steps:
the preparation method comprises the following steps of (1-6) mixing 2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde in a mass ratio of: 1, adding the mixture into an organic solvent I, and reacting for 1-8 hours at the temperature of 20-80 ℃, wherein solids are separated out in the reaction process; after the reaction is finished, filtering, washing a filter cake by using an organic solvent II and distilled water in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using an organic solvent III to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe.
The third concrete implementation mode: the difference between the second embodiment and the second embodiment is that the organic solvent i is glacial acetic acid, methanol, ethanol, N-dimethylformamide, benzene or toluene; the rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the second or third embodiment in that the organic solvent II for washing the filter cake is ethyl acetate, acetone, acetonitrile, diethyl ether, dichloromethane or chloroform; the other is the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that the organic solvent iii for recrystallization of the crude product is ethyl acetate, or ethyl acetate and petroleum ether are mixed according to a volume ratio of 1: (1-2), or the mixture of ethyl acetate and diethyl ether according to the volume ratio of 1: (1-3), or the volume ratio of ethyl acetate to dichloromethane is 1: (1-5) of the mixture; the other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the application of the double-colorimetric double-fluorescent phenanthroimidazole probe in the first embodiment is to apply the double-colorimetric double-fluorescent phenanthroimidazole probe to Cu in a solution2+And Ag+Qualitative and quantitative detection.
The seventh embodiment: in the embodiment, the double-colorimetric double-fluorescent phenanthroimidazole probe is used for detecting Cu in solution by a colorimetric method2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a HEPES solution with the concentration of 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, under natural light, the probe solution B is colorless;
if the color of the test solution C is green after standing for 2-3 min under natural light and green precipitate is generated, judging that the test solution C contains Cu2+；
If the color of the test solution C is light pink after standing for 2-3 min under natural light and light pink precipitation is generated, judging that the solution to be tested contains Ag+。
The specific implementation mode is eight: the difference between this embodiment and the seventh embodiment is that the organic solvent miscible with water in step one is methanol, ethanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran or acetonitrile. The rest is the same as the seventh embodiment.
The specific implementation method nine: the seventh or eighth embodiment is different from the seventh or eighth embodiment in that the solution to be measured in the third step is aquaculture wastewater, circuit board etching wastewater, battery industrial wastewater or electroplating wastewater. The others are the same as the seventh or eighth embodiments.
The detailed implementation mode is ten: the method utilizes the double-colorimetric double-fluorescent phenanthroimidazole probe to qualitatively detect Cu in the solution through fluorescence2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a mixed solution of DMF and HEPES solution with the volume ratio of 1:1, wherein the concentration of the HEPES solution is 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, standing the probe solution B for 2-3 min, and measuring the emission intensity of the fluorescence emission spectrum of the probe solution B when the emission wavelength is 461nm by taking 310nm as the excitation wavelength and recording the emission intensity as TB；
Fifthly, standing the test solution C for 2-3 min, measuring the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 461nm by taking 310nm as the excitation wavelength, and marking as TC；
Sixthly, comparing TBAnd TCIf 1/13TB＜TC≤1/6TBThen, the Cu content in the solution to be measured is determined2+(ii) a If TC≤1/13TBThen, it is determined that the solution to be measured contains Ag+。
The concrete implementation mode eleven: quantitative detection of Cu in solution by fluorescence method using double-colorimetric double-fluorescent phenanthroimidazole probe2+And Ag+The method of (3) is a standard curve method.
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the double-colorimetric double-fluorescent phenanthroimidazole probe provided by the embodiment is carried out according to the following steps:
2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde according to the mass ratio of 4: 1, adding the mixture into ethanol, reacting for 6 hours at the temperature of 25 ℃, and separating out solids in the reaction process; after the reaction is finished, filtering, washing a filter cake by using dichloromethane and distilled water in sequence, and drying the filter cake to obtain a crude product; recrystallizing the crude product with ethyl acetate to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe, wherein the yield is 95 percent, and the melting point is 320 ℃.
The structure of the double-colorimetric double-fluorescent phenanthroimidazole probe obtained in the embodiment is characterized by using a fourier infrared spectrum and a nuclear magnetic resonance spectrum, and the obtained results are as follows:
IR(KBr):3432,1731,1579,1453,1426,1149,1110,1043,1013,964,923,743,722,615cm-1。
1H NMR(600MHz,DMSO-d6)δ:8.92(s,H,ArH),8.84(d,J＝8.92Hz,2H,ArH),8.64(d,J＝8.12Hz,2H,ArH),8.48(d,J＝9.8Hz,2H,ArH),8.17(d,J＝7.8Hz,H,ArH),7.72(m,3H,ArH),7.61(t,J＝8.63Hz,2H,ArH),7.55(d,J＝8.80Hz,2H,ArH)。
13C NMR(150MHz,DMSO-d6)δ:174.81,160.60,151.53,137.21,132.22,129.99,128.83,127.68,127.36,125.25,124.27,122.56,122.20。
from the above characterization results, the structural formula of the double-colorimetric double-fluorescent phenanthroimidazole probe prepared in this example is:
the double-colorimetric double-fluorescent phenanthroimidazole probe prepared in example 1 is used for detecting Cu in solution by a colorimetric method2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into N, N-dimethylformamide according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 1.00mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01mmol/L by using a HEPES solution with the concentration of 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C; wherein the solution to be detected is aquaculture wastewater, circuit board etching wastewater, battery industrial wastewater and electroplating industrial wastewater respectively;
fourthly, standing for 3min under the natural light condition, observing the color change of the solution to judge whether the solution to be detected contains Cu or not2+And Ag+The colors of the probe solution B and the test solution C under natural light are shown in Table 1 below.
TABLE 1 color of Probe solution B and test solution C
Under natural light, the probe solution B is colorless, the test solution C containing the aquaculture wastewater and the circuit board etching wastewater is green in color and accompanied by green precipitate generation, and then the aquaculture wastewater and the circuit board etching wastewater are judged to contain Cu2+。
Under natural light, the probe solution B is colorless, the color of the test solution C containing the battery industrial wastewater and the electroplating industrial wastewater is light pink, and the test solution C is accompanied by the generation of light pink precipitates, so that the battery industrial wastewater and the electroplating industrial wastewater are judged to contain Ag+。
Quantitative detection of Cu in solution by fluorescence using the Dual-colorimetric-Bifluorescent-phenanthroimidazole Probe of example 12+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into N, N-dimethylformamide according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 1mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B of 0.01mmol/L by using a mixed solution of DMF and HEPES solution in a volume ratio of 1:1, wherein the concentration of the HEPES solution is 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C; wherein the solution I to be detected is Cu with the concentration of 10.0 mu M/L2+The solution II to be tested is Ag with the concentration of 10.0 mu M/L+A solution;
fourthly, after the probe solution B is kept still for 3min, the fluorescence emission spectrum of the probe solution B is measured by taking 310nm as the excitation wavelength, and the emission intensity T is shown in figure 2 when the emission wavelength is 461nmB＝127；
Fifthly, after the test solution C is kept stand for 3min, the fluorescence emission spectrum of the test solution C is measured by taking 310nm as the excitation wavelength, wherein the fluorescence emission spectrum of the test solution C1 of the solution I to be tested is shown in figure 3, the fluorescence emission spectrum of the test solution C2 of the solution II to be tested is shown in figure 4,the emission intensity T at an emission wavelength of 461nm was recordedCWherein T isC1＝21，TC2＝6；
Sixthly, comparing TBAnd TC，TB＝127，TC121, 1/13T is satisfiedB＜TC1≤1/6TBThen, the Cu content in the solution I to be measured is judged2+；TB＝127，TC26, satisfies TC2≤1/13TBThen, the solution II to be measured is judged to contain Ag+。
Thereby verifying the accuracy of the method.
Quantitative detection of Cu-containing by fluorescence method Using the Dual-colorimetric Dual-fluorescent phenanthroimidazole Probe prepared in example 12+Cu in wastewater2+The concentration method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into N, N-Dimethylformamide (DMF) according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 1mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the step one into a probe solution B with the concentration of 0.01mmol/L by using a mixed solution of DMF and HEPES solution in a volume ratio of 1: 1; wherein the concentration of the HEPES solution is 0.01mol/L, pH-7.40;
thirdly, preparing Cu according to the concentration of 0.1 MuM/L, 0.2 MuM/L, 0.3 MuM/L, 0.4 MuM/L, 0.5 MuM/L, 0.6 MuM/L, 0.7 MuM/L, 0.8 MuM/L, 0.9 MuM/L and 1.0 MuM/L2+A standard solution; fully mixing the probe solution B obtained in the second step with 1 mu L of each standard solution to obtain a test solution C1；
Fourthly, preparing Ag according to the concentration of 0.1 MuM/L, 0.2 MuM/L, 0.3 MuM/L, 0.4 MuM/L, 0.5 MuM/L, 0.6 MuM/L, 0.7 MuM/L, 0.8 MuM/L, 0.9 MuM/L and 1.0 MuM/L+A standard solution; fully mixing the probe solution B obtained in the second step with 1 mu L of each standard solution to obtain a test solution C2；
Fifthly, after the determination solution is kept stand for 3min, the probe solution B and each test solution C are determined by taking 310nm as the excitation wavelength1Reading out the emission intensity at an emission wavelength of 461nm with Cu2+The concentration is used as a horizontal standard, the emission intensity is used as a vertical standard, the graph is drawn, and the obtained standard curve is fitted: y is-0.5741 x +1.0513, and the calculation shows that the Cu is opposite to the Cu2+The lowest detection concentration of (a) was 523.4nM, as shown in FIG. 5;
sixthly, after the determination solution is kept stand for 3min, the probe solution B and each test solution C are determined by taking 310nm as an excitation wavelength2Reading out the emission intensity at an emission wavelength of 461nm as Ag+The concentration is used as a horizontal standard, the emission intensity is used as a vertical standard, the graph is drawn, and the obtained standard curve is fitted: y is-4.9043 x +1.0478, and the calculation results show that the Ag is opposite to the Ag+The lowest detection concentration of (a) was 6.1nM, as shown in FIG. 6;
seventhly, fully mixing the probe solution B obtained in the step two with aquaculture wastewater, circuit board etching wastewater, battery industrial wastewater and electroplating industrial wastewater respectively to obtain an aquaculture wastewater test solution, a circuit board etching wastewater test solution, a battery industrial wastewater test solution and an electroplating industrial wastewater test solution;
eighthly, after the measuring solution is kept stand for 3min, the fluorescence emission spectrum of each measuring solution is measured by taking 310nm as the excitation wavelength, the emission intensity at the emission wavelength of 460nm is read out and is recorded as TCReuse of TCFinding Cu in aquaculture wastewater, circuit board etching wastewater, battery industrial wastewater and electroplating industrial wastewater from the standard curve respectively2+And Ag+The concentration of (c); the results are shown in Table 2 below,
TABLE 2 Cu in wastewater2+And Ag+Concentration of (2)
As can be seen from the data in Table 2, the application of the double-colorimetric double-fluorescent phenanthroimidazole probe in example 1 to Cu in wastewater2+And Ag+And (4) quantitatively detecting the content.
Test of the Dual colorimetric Dual fluorescent Phenanthroimidazole Probe for Cu-containing detection in example 1 Using sample application recovery2+The recovery rate of the waste water. The sample to be tested is a sample containing Cu2+Waste waterIn a sample solution containing Cu2+Adding Cu with different concentrations into aquaculture wastewater with the concentration of 60-80 ng/mL2+The concentrations were 100ng/mL, 200ng/mL and 500ng/mL, respectively, and the results of the analysis by the standard curve method are shown in Table 3.
Table 3 shows the results of the sample recovery method
In Table 3, in which Cu is contained2+Original Cu in aquaculture wastewater with concentration of 60-80 ng/mL2+The results of three repeated tests using the standard curve method are shown. Recovery rate-detected Cu2+/(Cu2+Original Cu in wastewater2++ Cu after addition2 +) 100%. As can be seen from the data in Table 3, Cu detection was performed by applying the sample2+The recovery rate is more than 93 percent, which shows that the method has high precision and can accurately detect Cu-containing substances2+Cu in wastewater2+。
Testing of the double-colorimetric double-fluorescent phenanthroimidazole Probe of example 1 by sample application recovery method2+The recovery rate of the waste water. The sample to be tested is a sample containing Ag+Additional sample solution of wastewater, i.e. in Ag2+Adding Ag with different concentrations into electroplating industrial wastewater with the concentration of 60-80 ng/mL2+The concentrations were 100ng/mL, 200ng/mL and 500ng/mL, respectively, and the results obtained by analyzing the samples by the standard curve method are shown in Table 4.
Table 4 shows the results of the sample recovery method
In Table 3, in which Ag is contained+Original Ag in the electroplating industrial wastewater+Results were obtained by repeating the test three times using the standard curve method. Recovery rate is detectedAg of (A)+/(containing Ag)+Original Ag in wastewater++ Ag in the wastewater after addition+) 100%. As can be seen from the data in Table 3, Ag was detected by applying the sample+The recovery rate is more than 96 percent, which shows that the method has high precision and can accurately detect one Ag+Ag in wastewater+。
Example 2: the preparation method of the double-colorimetric double-fluorescent phenanthroimidazole probe of the embodiment is carried out by the following steps:
2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde according to the mass ratio of 2: 1, adding the mixture into methanol, reacting for 4 hours at the temperature of 20 ℃, and separating out solids in the reaction process; after the reaction is finished, filtering, washing a filter cake by using petroleum ether, dichloromethane and distilled water in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using ethyl acetate to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe with the yield of 93.8%.
Example 3: the preparation method of the phenanthroimidazole-based double-colorimetric double-fluorescent phenanthroimidazole probe of the embodiment is implemented by the following steps:
2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde according to the mass ratio of 4: 1, adding the mixture into glacial acetic acid, reacting for 3 hours at the temperature of 60 ℃, and separating out solids in the reaction process; after the reaction is finished, filtering, washing a filter cake by using distilled water and ether in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using ethyl acetate to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe with the yield of 95.3 percent.
Example 4: the preparation method of the double-colorimetric double-fluorescent phenanthroimidazole probe provided by the embodiment comprises the following steps:
2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde according to the mass ratio of 2: 1 is added into N, N-dimethylformamide and reacts for 2 hours at the temperature of 80 ℃, and solids are separated out in the reaction process; after the reaction is finished, filtering, washing a filter cake by using distilled water and ethanol in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using a mixed solution of ethyl acetate and petroleum ether in a ratio of 1:3 to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe with the yield of 89.9%.
Example 5: the preparation method of the double-colorimetric double-fluorescent phenanthroimidazole probe provided by the embodiment comprises the following steps:
2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde according to the mass ratio of 5: 1, adding the mixture into toluene, reacting for 6 hours at the temperature of 25 ℃, and separating out solids in the reaction process; after the reaction is finished, filtering, washing a filter cake with ethanol and distilled water in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using a mixed solution of ethyl acetate and dichloromethane in a ratio of 1:1 to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe with the yield of 71.9%.
Claims (10)
1. A double-colorimetric double-fluorescent phenanthroimidazole probe is characterized in that the structural formula of the probe is as follows:
2. the method for preparing the double-colorimetric double-fluorescent phenanthroimidazole probe according to claim 1, which is characterized by comprising the following steps:
the preparation method comprises the following steps of (1-6) mixing 2- (4-aminophenyl) phenanthroimidazole and m-phthalaldehyde in a mass ratio of: 1, adding the mixture into an organic solvent I, and reacting for 1-8 hours at the temperature of 20-80 ℃, wherein solids are separated out in the reaction process; after the reaction is finished, filtering, washing a filter cake by using an organic solvent II and distilled water in sequence, and drying the filter cake to obtain a crude product; and recrystallizing the crude product by using an organic solvent III to obtain the double-colorimetric double-fluorescent phenanthroimidazole probe.
3. The method for preparing a double-colorimetric double-fluorescent phenanthroimidazole probe according to claim 2, characterized in that the organic solvent I is glacial acetic acid, methanol, ethanol, N-dimethylformamide, benzene or toluene.
4. The method for preparing a double-colorimetric double-fluorescent phenanthroimidazole probe according to claim 2 or 3, characterized in that the organic solvent II for washing the filter cake is ethyl acetate, acetone, acetonitrile, diethyl ether, dichloromethane or chloroform.
5. The method for preparing a double-colorimetric double-fluorescent phenanthroimidazole probe according to claim 2 or 3, characterized in that the organic solvent III for recrystallization of the crude product is ethyl acetate, or ethyl acetate and petroleum ether in a volume ratio of 1: (1-2), or the mixture of ethyl acetate and diethyl ether according to the volume ratio of 1: (1-3), or the volume ratio of ethyl acetate to dichloromethane is 1: (1-5).
6. The use of a dual-colorimetric dual-fluorescent phenanthroimidazole probe according to claim 1, characterized in that it uses the dual-colorimetric dual-fluorescent phenanthroimidazole probe in Cu solution2+And Ag+Qualitative or quantitative detection of (a).
7. The use of the dual-colorimetric dual-fluorescent phenanthroimidazole probe according to claim 6, characterized in that the dual-colorimetric dual-fluorescent phenanthroimidazole probe is used to detect Cu in solution by colorimetry2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a HEPES solution with the concentration of 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, under natural light, the probe solution B is colorless;
if the test solution C is kept stand for 2-3 min under natural light, the color is green, andjudging that the solution to be detected contains Cu when green precipitates are generated2+；
If the color of the test solution C is light pink after standing for 2-3 min under natural light and light pink precipitation is generated, judging that the solution to be tested contains Ag+。
8. The use of the bi-colorimetric bi-fluorescent phenanthroimidazole probe according to claim 7, characterized in that the organic solvent miscible with water in the first step is methanol, ethanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran or acetonitrile.
9. The use of the dual-colorimetric dual-fluorescent phenanthroimidazole probe according to claim 6, characterized in that the dual-colorimetric dual-fluorescent phenanthroimidazole probe is used to qualitatively detect Cu in solution by fluorescence2+And Ag+The method comprises the following steps:
firstly, dissolving a double-colorimetric double-fluorescent phenanthroimidazole probe into an organic solvent which can be mutually soluble with water according to the concentration of the double-colorimetric double-fluorescent phenanthroimidazole probe being 0.5-1 mmol/L to prepare a probe stock solution A;
secondly, diluting the probe stock solution A obtained in the first step into a probe solution B with the concentration of 0.01-0.05 mmol/L by using a mixed solution of DMF and HEPES solution with the volume ratio of 1:1, wherein the concentration of the HEPES solution is 0.01mol/L, pH-7.40;
thirdly, fully mixing the probe solution B obtained in the second step with the solution to be tested to obtain a test solution C;
fourthly, standing the probe solution B for 2-3 min, and measuring the emission intensity of the fluorescence emission spectrum of the probe solution B when the emission wavelength is 461nm by taking 310nm as the excitation wavelength and recording the emission intensity as TB；
Fifthly, standing the test solution C for 2-3 min, measuring the emission intensity of the fluorescence emission spectrum of the test solution C when the emission wavelength is 461nm by taking 310nm as the excitation wavelength, and marking as TC；
Sixthly, comparing TBAnd TCIf 1/13TB＜TC≤1/6TBThen judgeThe solution to be measured contains Cu2+(ii) a If TC≤1/13TBThen, it is determined that the solution to be measured contains Ag+。
10. The use of the dual-colorimetric dual-fluorescent phenanthroimidazole probe according to claim 6, characterized in that the dual-colorimetric dual-fluorescent phenanthroimidazole probe is used for quantitatively detecting Cu in solution by a fluorescence method2+And Ag+The method of (1) is a standard curve method.
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Application publication date: 20200623 |