JP2022042452A - Method for preparing water-soluble macroporous zirconium porphyrin structure compound and application thereof - Google Patents

Abstract

To provide the technical field of a spectrum probe, especially a method for preparing a water-soluble macroporous zirconium porphyrin structure compound, and the application thereof.SOLUTION: A method for preparing a water-soluble macroporous zirconium porphyrin structure compound includes a step of dissolving ZrCl4, H2-TCPP and benzoic acid into N, N diethyl formamide by ultrasonication to obtain a solution. Ultra-high sensitive detection of fluorine ions is achieved by using the concentration effect of a MOF porous structure to the fluorine ions and high selectivity of metal zirconium; the sensor has excellent chemical stability and extremely fast response speed; and the detection limit is lowered by one or more digits than values reported by articles of the prior art.SELECTED DRAWING: Figure 11

Description

The present invention relates to the field of spectroscopic probe technology, in particular to methods for preparing water-soluble macroporous zirconium porphyrin structural compounds and their uses.

Fluoride is a common pollutant in waters, and overdose of fluoride can cause fluorinosis, damage to human bones and teeth, kidney damage and thyroid hormone disorders.
Therefore, monitoring and management of fluorine ions in water bodies is an important factor in ensuring the safety of the water environment, and provides an accurate, fast and sensitive method for analyzing and detecting fluorine ions in water bodies. There is a need.

1. Invention Principles and Objectives Luminescent organic metal framework materials (LMOFs) are an important area of MOFs. The inherent porosity of LMOFs compared to other luminescent probe materials provides several important advantages. The porosity of LMOFs limits the distance between the analyte and the MOF, allowing for close interaction between the MOF and the analyte. Sensor interaction can be selectively controlled by changing the size of the pores and the hydrophobicity / polarity. LMOFs can also concentrate the analyte into pores and significantly improve sensitivity. Currently, there are some reports on the detection of fluorine ions by synthetic LMOF, but most of them cannot exist stably in an aqueous medium, and the sensitivity is high because the pore diameter is fine or the specific surface area is not large. It gets lower.

2. Solution In order to solve the above problems, the present invention provides a fluorescent probe having high selectivity for fluorine ions in waste water, and H2-TCPP (TCPP = tetra (4-carboxyphenyl)) is used as a ligand. ) Porphyrin), using a very stable Zr6 cluster as an assembly node, Zr Porphyrin MOF-PCN-222 (PCNFluor)
sCoordinationNetwork, porosity adjustment network) was synthesized normally.
PCN-222 has a large open channel, a very large specific surface area and excellent stability. PCN-222 selectively exhibits a remarkable fluorescence quenching response to F-with high sensitivity, and its utility is further verified by detecting spiked water samples.

Specifically, the technical solution is as follows.
S1, compound synthesis S11, ZrCl ₄ , H2-TCPP and benzoic acid are dissolved in N, N-diethylformamide by sonication to obtain a solution.
The solution prepared in S12 and step S11 is transferred to an autoclave of polytetrafluoroethylene, placed in a blast oven, heated to 120 ° C., and held for 48 hours.
After cooling the solution heated in S13, step S12 to room temperature, it was washed by suction filtration multiple times using N, N-dimethylformamide, and then acetone was used instead of N, N-dimethylformamide. Continue washing several times and finally harvest the product of the solid compound.
S2, compound activation S21, to optimize the activation process, first add a small amount of concentrated hydrochloric acid to the DMF suspension.
The product synthesized in step S213 is then immersed in DMF at 120 ° C. for 12 hours.
The product after soaking in S22 and step S21 is washed with DMF and acetone several times, and then the product is soaked in acetone and left for 24 hours.
The product left in S23 and step S22 is vacuum dried in a vacuum drying oven for 6 hours for activation treatment, and finally dried again at 120 ° C. for 12 hours using the degassing function.

Preferably, the above preparation method specifically comprises
S1, compound synthesis S11, 75-100 mg ZrCl4, 50-70 mg H2-TCPP and 2.7
Dissolve ~ 3.6 g of benzoic acid in 8-12 ml of N, N-diethylformamide by sonication to give a solution.
Transfer the solution prepared in S12 and step S11 to an autoclave of polytetrafluoroethylene, place it in a blast oven, heat it to 120 ° C., and hold it for 48 hours.
After cooling the solution heated in S13 and step S12 to room temperature, the solution is washed by suction filtration 2 to 4 times using N, N-dimethylformamide, and then acetone is used instead of N, N-dimethylformamide. Then wash 2-5 times and finally harvest the product of the solid compound,
S2, activation of compound S21, first, 0.5 to 1 mL of concentrated hydrochloric acid is added to 20 to 40 ml of DMF suspension, and the product synthesized in step S13 is immersed in DMF at 120 ° C. for 12 hours.
The product soaked in S22 and step S21 is washed with DMF and acetone 2 to 5 times, and the product is washed with acetone and left for 24 hours.
The product left in S23 and step S22 is vacuum dried in a vacuum drying oven for 6 hours for activation treatment, and finally dried again at 120 ° C. for 12 hours using the degassing function.

According to one aspect of the invention, the water-soluble macroporous zirconium porphyrin structural compound prepared in the present invention is used as a fluorescent probe for detecting F- in waste water under ionic conditions.

According to one aspect of the present invention, the F-detection method using the fluorescent probe detects the fluorescence spectrum of an aqueous solution and obtains the F- concentration by detecting the fluorescence intensity at 421 nm.

According to one aspect of the present invention, the fluorescence quenching of the fluorescent probe by F-is relatively strong in the range of 1 to 100 μM (micromol), and the fluorescence quenching rate and F-concentration are within 1 to 20 μM (micromol). It has a remarkable linear relationship and can be used as a tool for quantitative detection of F-.

According to one aspect of the invention, the fluorescent probe has excellent selectivity for F-, a very low detection limit (56 nM), and a very fast response rate (<5s), while at the same time PCN-22.
Has excellent chemical stability in water resistance, acid resistance, and light resistance.

Compared with conventional fluorine ion fluorescent probes, PCN-222 prepared in the present invention has the following beneficial effects.
(1) MOF-PCN-222 having a fluorescent function was successfully prepared by a hydrothermal method, and 390.
It has a wide absorption band of about 450 nm, the maximum absorption wavelength is 421 nm, and it is 650 to 750 n.
There is a fluorescence emission band in m, and the maximum emission wavelength is 680 nm.
(2) PCN-222 shows a fluorescence quenching response to F- without modification, and PC by F-
The fluorescence quenching of N-222 is stronger in the range of 0 to 100 μM, and the fluorescence quenching rate and F-concentration are 0 to 0.
There is a remarkable linear relationship within 20 μM and it is used as a tool for quantitative detection of F-.
(3) PCN-222 has excellent selectivity for F-, very low detection limit (56nM),
And with a very fast response rate (<5s), PCN-22 has excellent chemical stability in water resistance, acid resistance and light resistance.
(4) Since F-detection by PCN-222 against tap water and Taihu water did not receive much interference and showed good results, this fluorescent probe detection method is suitable for normal detection of F- in water.

It is a scanning microscope SEM image of PCN-222 prepared by this invention. FT-IR spectrum and XRD spectrum of PCN-222 prepared in the present invention. FIG. 3 is a nitrogen adsorption-desorption isotherm and a corresponding pore size distribution map of PCN-222 prepared in the present invention at 77K. It is an ultraviolet visible light absorption spectrum and a three-dimensional fluorescence spectrum of the aqueous solution of PCN-222 prepared in this invention. It is the influence of F-concentration on the fluorescence emission intensity of PCN-222 of the present invention. It is a change tendency and a linear relationship according to the F-concentration of PCN-222 prepared in this invention. FIG. 5 is an X-ray diffraction (XRD) diagram of the original PCN-222 prepared in the present invention and the PCN-222 immersed in water for 24 hours. The fluorescence emission intensity of the PCN-222 solution prepared in the present invention under continuous excitation light irradiation. It is a graph which shows the fluorescence response time of the anion of PCN-222 prepared in this invention. It is a graph which shows the time-dependent change of the fluorescence intensity after the addition of 200 μM F- of PCN-222 prepared in this invention. It is a structural schematic diagram of PCN-222 prepared by this invention.

However,
In FIG. 2, (a) is an FT-IR spectrum and (b) is an XRD spectrum.
FIG. 3 shows a pore size distribution map of PCN-222.
In FIG. 4, (a) is an ultraviolet visible light absorption spectrum, (b) is a three-dimensional fluorescence spectrum, and the darker the color in the figure, the stronger the fluorescence intensity.
In FIG. 5, (λEx = 421 nm)
In FIG. 6, (a) is a trend diagram of the change of fluorescence quenching efficiency according to F-concentration, and (b) is a linear relationship diagram of fluorescence quenching efficiency and F-concentration (0 to 20 μM), λEx = 421 nm. λEm = 6
80nm
In FIG. 8, the F-concentration is 200 μM.
In FIG. 9, (a) is a fluorescence response graph of a low concentration (20 μM) anion of PCN-222, and (b) is a fluorescence response graph of a high concentration (200 μM) anion of PCN-222.

To further illustrate the methods and effects achieved by the present invention, the technical solutions of the present invention, together with the accompanying drawings, will be described clearly and completely below.

Example 1
In this example, the method for preparing the fluorescent probe-PCN-222 of the water-soluble macroporous zirconium porphyrin structural compound designed by the present invention will be mainly described.

表２ 実験試薬

1. Experimental equipment and reagents The equipment and reagents used in the present invention are shown in Tables 1 and 2.
Table 1 Experimental equipment

Table 2 Experimental reagents

2. Preparation of PCN-222 S11, ZrCl4 (80 mg), H2-TCPP (50 mg) and benzoic acid (2.7)
g) is dissolved in N, N-diethylformamide (8 ml) by sonication to obtain a solution.
The solution prepared in S12 and step S11 is transferred to an autoclave of polytetrafluoroethylene, placed in a blast oven, heated to 120 ° C., and held for 48 hours.
After cooling the solution heated in S13, step S12 to room temperature, it was washed twice by suction filtration using N, N-dimethylformamide, and then using acetone instead of N, N-dimethylformamide 3 Continue washing and finally harvest the product of the solid compound.
S2, compound activation S21, 20 mL DMF first with 0.5 mL concentrated hydrochloric acid to optimize the activation process
In addition to the suspension, the product synthesized in step S213 is then immersed in DMF at 120 ° C. for 12 hours.
The product soaked in S22 and step S21 was washed twice with DMF and then with acetone for 3
Wash once and finally soak the product in acetone and leave for 24 hours.
The product left in S23 and step S22 is vacuum dried in a vacuum drying oven for 6 hours for activation treatment, and finally dried again at 120 ° C. for 12 hours using the degassing function.

Example 2
In Example 2, a method for preparing a composition different from that in Example 1 will be mainly described, but the same as in Example 1 except for the following contents.
S1, compound synthesis S11, ZrCl4 (100 mg), H2-TCPP (60 mg) and benzoic acid (3 g)
) Is dissolved in N, N-diethylformamide (12 ml) by sonication to obtain a solution.
The solution prepared in S12 and step S11 is transferred to an autoclave of polytetrafluoroethylene, placed in a blast oven, heated to 120 ° C., and held for 48 hours.
After cooling the solution heated in S13, step S12 to room temperature, it was washed four times by suction filtration using N, N-dimethylformamide, and then acetone was used instead of N, N-dimethylformamide 3 Continue washing and finally harvest the product of the solid compound.
S2, compound activation S21, to optimize the activation process, first add 1 mL of concentrated hydrochloric acid to 40 mL of DMF suspension, then place the product synthesized in step S213 in 120 ° C. DMF for 12 hours. Soak.
The product soaked in S22 and step S21 was washed 3 times with DMF and then 3 with acetone.
Wash once and finally soak the product in acetone and leave for 24 hours.
The product left in S23 and step S22 is vacuum dried in a vacuum drying oven for 6 hours for activation treatment, and finally dried again at 120 ° C. for 12 hours using the degassing function.

Experimental Example 1
Experimental Example 1 is characterized for PCN-222 prepared by the method of Example 1 above, and an object thereof is to explain a scanning electron micrograph, Fourier transform infrared spectrum and XRD spectrum of PCN-222. do.
The scanning electron microscope (SEM) image of PCN-222 is shown in FIG. 1, and the photograph is PCN.
It is shown that the three-dimensional morphology of -222 is a rod-like structure having a thickness of 0.5 to 1 μm, which is consistent with the morphology of PCN-222 reported in the literature.
FIG. 2A shows the Fourier transform infrared (FT-IR) spectrum of PCN-222.
The absorption peak at 1697 cm ^- 1 is due to the expansion and contraction vibration of C = O, the absorption peak at 1602 cm ^- 1 corresponds to the expansion and contraction vibration of C = C, and the absorption peak at 1413 cm ^- 1 is CH and O-. Corresponding to the bending vibration of H, the absorption peak at 1178 cm ^- 1, 1020 cm ^- 1 is C-
Corresponding to the expansion and contraction vibration of O, the absorption peak between 700 cm ^- 1 to 1000 cm ^- 1 corresponds to the bending vibration of CH, and all of these characteristic bands are consistent with the characteristic bands of PCN-222 reported in the literature. ing.
FIG. 2B shows the XRD spectrum of PCN-222, and the diffraction peak in the figure is 2.4 °, 4
.. It appears at 8 °, 7.1 ° and 9.8 ° and is very consistent with the XRD spectra of PCN-222 reported in the literature. Based on the results of infrared feature evaluation and XRD feature evaluation, PCN-
Further proof that the synthesis of 222 was successful.

Experimental Example 2
In Experimental Example 2, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
For the purpose of showing the surface area and pore diameter information of CN-222, as shown in FIG. 3, PC
The results of the nitrogen adsorption / desorption isotherm and pore size distribution of N-222 are shown.
The results show that the Brunauer-Emmett-Teller (BET) specific surface area of PCN-222 is 2080 m2g-1, which indicates that PCN-222 has a very large specific surface area. Density functional theory (DFT) results based on the nitrogen adsorption curve are PCN-2
22 indicates that there are two types of pores, 1.3 nm and 3.2 nm (Figure 3), respectively, and PCN-222 indicates that there are very large open channels, which are reported in the literature. It is consistent with the hole structure of PCN-222. The above results indicate that the synthesis of PCN-222 was successful, and its structural characteristics also well support the detection performance.

Experimental Example 3
In Experimental Example 3, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
For the purpose of explaining the ultraviolet visible light absorption spectrum and the fluorescence emission spectrum of CN-222, the detection of the two spectra is performed in an aqueous solution.
As shown in FIG. 4A, 1 between 390 nm and 450 nm of the ultraviolet visible light absorption spectrum.
Two absorption peaks are observed, the maximum absorption wavelength is 421 nm (Soret band), which is a characteristic absorption peak in the ultraviolet visible light region of the porphyrin compound, and it is verified that PCN-222 has a porphyrin structure.
FIG. 4B is a three-dimensional fluorescence spectrum of PCN-222, which clearly shows the strong fluorescence emission of PCN-222 between 650 nm and 750 nm, the maximum emission wavelength is 680 nm, and at the same time between the strong fluorescence emission regions. The corresponding excitation wavelength is also 390 nm to 450 nm, which is similar to the result of the absorption spectrum.

Experimental Example 4
In Experimental Example 4, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
The fluorescence response of the interaction in an aqueous solution was investigated for the purpose of determining the sensitivity of CN-222 to F-, and is specifically shown in FIG.
The specific experimental method is as follows.
Add 5 mL of PCN-222 solution to each tube in an equal volume of 10 mL centrifuge tube, and add PCN-222 to each tube.
Fluorine ions of various concentrations (0 to 500 μM) were added to the centrifuge tube containing the solution, mixed for 30 s, and the fluorescence emission spectrum of the PCN-222 solution in each centrifuge tube was measured.
As shown in FIG. 5, when the F-concentration gradually increases from 0 to 500 μM, PCN-222
The fluorescence intensity of PCN-222 gradually decreased, indicating that F-quenched the fluorescence of PCN-222.

Experimental Example 5
In Experimental Example 5, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
The tendency of change and the linear relationship according to the F-concentration of CN-222 are shown, and specifically shown in FIG.
FIG. 6A shows the relationship between the PCN-222 fluorescence quenching rate and the F-concentration, and the fluorescence quenching rate means the ratio of the extinguished fluorescence intensity to the original fluorescence intensity (1-F / F0). Represented by, however, F
And F0 are fluorescence intensities in the presence and absence of F-, respectively (λEx = 421 nm,
λEm = 680 nm).
As can be seen from FIG. 6 (a), the quenching efficiency rapidly increases in the range of 0 to 100 μMF-, and then the increase rate decreases. More importantly, as can be seen from FIG. 6 (b), the quenching efficiency (
1-F / F0) and F-concentration have a good linear relationship in the range of 0-20 μM, which is the PC.
N-222 is shown to be used as a fluorescence sensor for quantitatively detecting F-concentration. The detection limit of PCN-222 for F- obtained by the detection limit calculation formula (LOD = 3σ / slope, σ is the standard deviation of the blank sample) is 56 nM, which is defined for the drinking water of WHO. Significantly below the limit of (~ 1.5 mg / L) and below the F-detection limit of most MOF sensors reported.
There are two possible reasons why the detection limit is low. First, due to the strong interaction between the Zr (IV) cation and F- in the metallic porphyrin structure, PCN-222 and F- are very susceptible to reaction, second, PCN-222 has a very large specific surface area and pore path. Because it has
F- is concentrated to produce an effect.

Experimental Example 6
In Experimental Example 6, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
A 24-hour soaked and non-soaked PCN for the purpose of explaining the stability of CN-222 in water.
An XRD image of -222 is shown, specifically shown in FIG.
The specific experimental method is as follows.
Equally add 5 mL of PCN-222 solution to each of the two 10 mL centrifuge tubes, and 2 to one.
00 μM of fluorine ion was added, and the same volume of pure water was added to the other.
As shown in FIG. 7, it was observed that the XRD images before and after the inundation were almost the same, and the main structure of PCN-222 was basically unchanged, and the result was that PCN-222 had excellent water stability. Shown to have.

Experimental Example 7
In order to achieve the detection purpose by changing the fluorescence intensity, the fluorescent probe will be described in Experimental Example 7 for PCN-222 prepared by the method of Example 1 above, and under the excitation light of PCN-222. For the purpose of explaining the fluorescence stability, the original PCN-222 solution and the F-added PCN-222 solution are continuously irradiated with excitation light for 1 hour, respectively, and the fluorescence intensity is measured every 1 minute. Measured and specific results are shown in FIG.
The specific experimental method is as follows.
Using a fluorescence spectrometer, the PCN-222 solution in the two centrifuge tubes is dynamically detected, detected for 1 hour so as to be detected once every minute, and irradiated with excitation light during the detection process. continue.
As shown in FIG. 8, the fluorescence intensity of the original PCN-222 solution without F-addition and the fluorescence intensity of the PCN-222 solution extinguished with F- did not change significantly within 1 hour. This is a PC
N-222 has good fluorescence stability, indicating that there are conditions for use as a fluorescent probe. Based on the above results, PCN-222 is a material with water stability, acid stability and photostability at the same time, and the reason for its excellent chemical stability is Zr6 in the PCN-222 structure.
Considered to be a cluster, it is considered that the Zr6 cluster is one of the most stable building units in the MOF structure.

Experimental Example 8
In Experimental Example 8, PCN-222 prepared by the method of Example 1 above will be described as a target, and P.
Some common ions (F-, K +, Mg2 +, Ca2 +, Al3 +, ^Cl- , Br- ^, I ^- , NO3-, B
The effect of rO3-, SO42-, CO32-) on the fluorescence intensity of PCN-222 was measured.
To make the conclusion more convincing, at the same time low concentration (20 μM) and high concentration (200)
Experiments with two concentrations of μM) were performed and specific results are shown in FIG.
The specific test method is as follows.
This experiment is divided into a low concentration group and a high concentration group, and aims to detect the selectivity of PCN-222 for low concentration and high concentration fluorine ions.
Low Concentration Group: Equally add 5 mL of each tube to a 10 mL centrifuge tube and add various anions (F-,) of the same volume and concentration (20 μM) to the centrifuge tube containing the PCN-222 solution, respectively. K +, Mg2 +, Ca2 +, Al3 +, ^Cl- , Br- ^, I-, ^NO3-
, BrO3-, SO42-, CO32-), only the same volume of pure water was added in the blank control group, and after mixing for 30 s, the fluorescence emission spectrum of the PCN-222 solution in each centrifuge tube was measured. Three groups of experiments were conducted in parallel.
High Concentration Group: Equally add 5 mL of PCN-222 aqueous solution to each tube in a 10 mL centrifuge tube and place various anions (F-) in the centrifuge tube containing the PCN-222 solution in the same volume and concentration (200 μM). , K +, Mg2 +, Ca2 +, ^Al3 +, ^Cl- , Br-, I-, NO
3- ^, SO42-, ^BrO3- , CO32-) were added, only the same volume of pure water was added in the blank control group, and after mixing for 30 s, the fluorescence emission spectrum of the PCN-222 solution in each centrifuge tube was measured. Three groups of experiments were conducted in parallel.
As a result, it was shown that the low-concentration (FIG. 9a) and high-concentration (FIG. 9b) F-s had a remarkable quenching effect on the fluorescence intensity of PCN-222, and the other ions had a very small effect on the fluorescence intensity.
This indicates that PCN-222 has a very strong selectivity for F- and is suitable for an F-detection probe. The reason for the high selectivity is that the affinity between Zr (IV) and F- is Zr.
This is because it is much higher than the affinity between (IV) and other anions.

Experimental Example 9
Experimental Example 9 is described for PCN-222 prepared by the method of Example 1 above, and F-
The change over time in the fluorescence intensity of PCN-222 after the addition will be described, and more specifically, it is shown in FIG.
As shown in FIG. 10, it is clearly shown that the fluorescence intensity tends to be almost completely quenched and stabilized within 5 s after the addition of F-. This indicates that this detection method has the advantage of high response speed.

ただし、
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文献４：２０１７「ＤｅｖｅｌｏｐｍｅｎｔｏｆａｎＩｎｎｅｒＦｉｌｔｅｒＥｆｆｅｃ
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文献５：２０１７「Ｂｏｒｉｃ－Ａｃｉｄ－ＦｕｎｃｔｉｏｎａｌＬａｎｔｈａｎｉｄｅ
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」、
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ａ」、
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ａｙ」、
文献８：２０１５「Ｆｌｕｏｒｅｓｃｅｎｔｃａｒｂｏｎｎａｎｏｄｏｔｓｆｏｒｏｐｔ
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」。 Experimental Example 10
In Experimental Example 10, PCN-222 prepared by the method of Example 1 above will be described as a target.
Table 3 compares the PCN-222 fluorescent probe detection method prepared in the present invention with the F- fluorescence detection method reported in recent years, and the specific results are shown in Table 3.
In Table 3, the fluorescent probe number described in Document 1 is 1, the fluorescent probe number described in Document 2 is 2, the fluorescent probe number described in Document 3 is 3, and the fluorescent probe number described in Document 4 is. 4. The fluorescent probe number described in Document 5 is 5, the fluorescent probe number described in Document 6 is 6, the fluorescent probe number described in Document 7 is 7, and the fluorescent probe number described in Document 8 is 8. do.
Table 3 Fluorine ion fluorescence detection methods reported in recent years

However,
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Document 8: 2015 "Fluorescentcarbonnodotsfort
icardectionoffluorideioninaqueousmediaa
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表４に示すように、水道水サンプルの回収率は８８．０％～１０３．５％であり、太湖水
サンプルの回収率は９３．０％～１０５．６％であり、これは、ＰＣＮ－２２２による実
際の水サンプル中のフッ素イオンの検出は顕著な干渉を受けなかった。これらの結果から
分かるように、この蛍光プローブ検出方法は高い正確性および信頼性を有し、水サンプル
中のＦ‐の測定に使用され得る。 Experimental Example 11
In Experimental Example 11, PCN-222 prepared by the method of Example 1 above will be described as a target.
In order to verify the applicability of the PCN-222 fluorescent probe prepared in the present invention to fluorine ion analysis in water, F- spike detection is further performed using an actual water sample.
In this example, two actual water samples, a tap water sample and a Taihu water sample, are used for analysis. The water sample was pretreated, and various concentrations of known standard fluoride were added to the treated water sample, followed by fluorescence detection using PCN-222, and the measurement results obtained are shown in Table 4. Shown.
The specific experimental method is as follows.
Several water samples of tap water and Taiko water were taken and filtered through a 0.22 μm filter membrane to remove impurities in the water. Various concentrations in water samples (20, 40, 60, 80, 10
Add 0 μM) of fluoride ions to prepare a series of water samples of fluoride ions of different concentrations, mix the water sample with the PCN-222 dispersion at a ratio of 1: 9 (ie, dilute 10-fold, at this time. Fluorine ion concentration is 2, 4, 6, 8, 10 μM, respectively), add 5 mL of the mixed solution to each tube in an equal volume of 10 mL centrifuge tube, and measure the fluorescence emission spectrum of the PCN-222 solution in each centrifuge tube. did.
Table 4 F-spike detection results for tap water samples and Taihu water samples

As shown in Table 4, the recovery rate of the tap water sample is 88.0% to 103.5%, and the recovery rate of the Taihu lake water sample is 93.0% to 105.6%, which is PCN-. The detection of fluorine ions in the actual water sample by 222 was not significantly interfered with. As can be seen from these results, this fluorescent probe detection method has high accuracy and reliability and can be used for the measurement of F- in water samples.

Claims (6)

S1, compound synthesis S11, ZrCl ₄ , H2 _- TCPP and benzoic acid are dissolved in N, N-diethylformamide by sonication to obtain a solution.
In steps S12, the solution prepared in step S11 is transferred to an autoclave of polytetrafluoroethylene, placed in a blast oven, heated to 120 ° C., and held for 48 hours.
After cooling the solution heated in S13, step S12 to room temperature, wash with multiple suction filtrations using N, N-dimethylformamide and use acetone instead of N, N-dimethylformamide. Steps to continue washing and harvesting the product of the solid compound,
S2, compound activation S21, concentrated hydrochloric acid was added to the DMF suspension, and then the product synthesized in step S13 was added to 120.
The step of immersing in DMF at ° C for 12 hours and
The product after soaking in S22 and step S21 was washed with DMF and acetone, and then the product was soaked in acetone and left for 24 hours.
The product left in S23 and step S22 is vacuum-dried in a vacuum-drying oven for 6 hours for activation treatment, and finally dried again at 120 ° C. for 12 hours using the degassing function.
A method for preparing a water-soluble macroporous zirconium porphyrin structural compound, which comprises. S1, compound synthesis S11, 75-100 mg ZrCl ₄ , 50-70 mg H2 _- TCPP and 2.7
A step of dissolving ~ 3.6 g of benzoic acid in 8-12 ml of N, N-diethylformamide by sonication to obtain a solution.
In steps S12, the solution prepared in step S11 is transferred to an autoclave of polytetrafluoroethylene, placed in a blast oven, heated to 120 ° C., and held for 48 hours.
After cooling the solution heated in S13 and step S12 to room temperature, the solution was washed with N, N-dimethylformamide by suction filtration 2 to 4 times, and acetone was used instead of N, N-dimethylformamide. The step of harvesting the product of the solid compound by continuing the washing 2 to 5 times,
S2, compound activation S21, first adding 0.5 to 1 mL of concentrated hydrochloric acid to 20 to 40 ml of DMF suspension, and immersing the product synthesized in step S13 in DMF at 120 ° C. for 12 hours.
The product after soaking in S22 and step S21 was washed with DMF and acetone 2 to 5 times, and the product was immersed in acetone and left for 24 hours.
S23, the product after being left in step S22 is vacuum dried in a vacuum drying oven for 6 hours to perform an activation treatment, and finally, a step of drying again at 120 ° C. for 12 hours using a degassing function is included. The preparation method according to claim 1. Use of a compound prepared by the method according to claim 1 or 2, characterized in that it is used as a fluorescent probe for detecting F ⁻ in wastewater under ionic conditions. The method of detecting F ⁻ using the fluorescent probe detects the fluorescence spectrum in an aqueous solution and
The application according to claim 3, wherein the F ^- concentration is obtained by detecting the fluorescence intensity at 421 nm. The third aspect of claim 3, wherein the F ^- concentration has quenching of the fluorescence of the fluorescent probe in the range of 1 to 100 μM, and the fluorescence quenching rate and the F-concentration have a linear relationship within 1 to 20 μM. Use. The application according to claim 3, wherein the detection limit of F-of the fluorescent probe is 56 nM, and the response speed of F- is less than 5 s.

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