Calcium pyrene tetrasulfonate complex fluorescent probe and preparation and application thereof

Abstract

The present application relates to pyrene tetrasulfonic acid calcium complex fluorescent probe and its preparation method and application, belong to the technical field of crystal material synthesis;The preparation method of the pyrene tetrasulfonic acid calcium complex fluorescent probe includes the following steps S1: weighing 2 equivalent metal calcium salt is dissolved in appropriate DMF, ultrasonic dissolution is uniform, S2: weighing 1 equivalent H-PTS is dissolved in appropriate DMF, ultrasonic dissolution is uniform;The DMF solution containing calcium salt is poured into the solution containing H-PTS, stirs 5min, shakes uniformly, moves to the oven, 130 DEG C heating 48h, after finishing, stationary cooling to room temperature, obtain white block crystal, wash three times with ether, confirm structure on X ray single crystal diffractometer, obtain pyrene tetrasulfonic acid calcium complex probe;The complex has higher sensitivity and better selectivity as fluorescent probe for detecting iron ion.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of crystal material synthesis, and particularly relates to a pyrene tetrasulfonic acid calcium complex fluorescent probe and a preparation and application thereof. BACKGROUND

[0002] Iron is the fourth most abundant element in the earth's crust, next to oxygen, silicon and aluminum, and is the second most abundant metal after aluminum. Iron is ubiquitous in daily life, and common iron-containing minerals mainly include magnetite (Fe3O4), hematite (Fe2O3), siderite (FeCO3), pyrite (FeS2), and limonite (2Fe2O3·3H2O). From the perspective of pollution or harm, the role of iron is less studied, but because it is a high-abundance element in the earth's crust and is ubiquitous, it is often considered as a pollution or harmful element. Therefore, it is of important practical significance to study the properties and characteristics of iron. With the acceleration of industrialization and urbanization, the development of non-ferrous metal smelting industry such as steel, a large amount of iron-containing wastewater is discharged, and the iron-containing wastewater enters the biosphere through the atmospheric circulation system, becoming a major hazard affecting biological life activities. Metal pollution has become a hot issue in current environmental science, and iron ions are essential for maintaining normal physiological functions or tissue structures, are important components of hemoglobin, myoglobin and cytochrome, and are one of the essential trace elements for the human body. However, excessive intake of iron ions can cause symptoms such as bacterial infection, pigmentation, and iron poisoning. Therefore, it is of great significance to detect the selectivity and sensitivity of trivalent iron ions compared to other metal ions. At present, the traditional methods for detecting metal ions mainly include ion mobility spectrometry (IMS), high-performance liquid chromatography (HPLC), and liquid chromatography-mass spectrometry (LCMS) methods. Although these detection methods have a relatively complex operation process and are time-consuming, there is an urgent need for a rapid and efficient detection technology for this specific environmental pollutant.

[0003] In recent years, luminescent metal-organic frameworks (LMOFs) have attracted increasing interest in sensing applications due to their diverse structures and topologies, outstanding optical properties and emission wavelengths. At present, most of the LMOFs used for fluorescence detection are based on transition or lanthanide metal ions, while LMOFs constructed from alkaline earth metal ions are rarely used for fluorescence detection, which may be due to the difficulties and unpredictable coordination modes in their crystallization process. In fact, alkaline earth metal-organic framework materials have many unparalleled advantages, such as low density, biocompatibility, non-toxicity and low cost, etc. More importantly, when alkaline earth metal-organic framework materials are used as fluorescence probes in some biological systems, the secondary pollution caused by heavy metal ions can be effectively avoided. Therefore, alkaline earth metal-organic framework materials are a very potential fluorescence material that can be applied to metal ion detection.

[0004] A fluorescent probe is a kind of molecule that can effectively express a molecular recognition event through a fluorescence signal. Fluorescent probe molecules have been widely used in the fields of chemistry, biological science, environmental detection and medicine due to their good selectivity, high sensitivity, simple operation, fast response, low detection limit and real-time in-situ detection. In recent years, designing and synthesizing high-selectivity fluorescent probes for detecting metal ions is one of the important research directions in the field of chemical research. SUMMARY

[0005] To solve the above problems, the application discloses a calcium complex fluorescent probe, a preparation method and application thereof. Therefore, the application selects tetrasodium pyrene tetrasulfonate as an organic ligand and synthesizes the complex with calcium salt by a solvothermal method. The complex has high sensitivity and strong selectivity when used as a fluorescent probe for detecting iron ions.

[0006] To achieve the above object, the technical scheme of the application is as follows:

[0007] The application provides a calcium pyrene tetrasulfonate complex (Ca-PTS) fluorescent probe, and a molecular formula of the calcium pyrene tetrasulfonate complex fluorescent probe is C 27.8 H 43.2 Ca2N4O 21 S4. Figure 1

[0008] The single crystal parameters and part of the bond length data are shown in the following table:

[0009]

[0010] Symmetry code: i 1-X,1 / 2+Y,3 / 2-Z ii 1-X,-1 / 2+Y,3 / 2-Z.

[0011] ​The coordination polymer for metal ion detection of the present invention has a long-range ordered crystal structure with regular pores and a one-dimensional chain structure. The main component is pyrenetetrasulfonic acid, and the four sulfonic acid groups on the ligand are coordinated with four calcium ions, which are surrounded by water and N,N-dimethylformamide (DMF).

[0012] The present invention also provides a method for preparing the aforementioned Ca-PTS for detecting metal ions, comprising the following steps:

[0013] S01: Pyrene tetrasulfonic acid tetrasodium salt is passed through an ion exchange column to prepare pyrene tetrasulfonic acid ligand (H-PTS) by an ion exchange method;

[0014] S02: Weigh a metal calcium salt and dissolve it in DMF, and dissolve it evenly by ultrasonication to obtain solution A;

[0015] S03: Weigh H-PTS and dissolve it in DMF, sonicate to dissolve it evenly, and obtain solution B;

[0016] S04: Pour the DMF solution A containing calcium salt into the solution B containing H-PTS, stir for 5-10 minutes, shake evenly, move to an oven, and heat at 120-130°C for 48-72 hours. After heating, let it stand and cool to room temperature to obtain white block crystals. Wash it three times with ether and confirm the structure on an X-ray single crystal diffractometer.

[0017] Furthermore, in step S02, the molar volume ratio of the metal calcium salt to DMF is 1:1-1:1.5; the metal calcium salt is one or more of CaCl2, Ca(AC)2, and CaCO3.

[0018] Furthermore, in step S03, the molar volume ratio of the pyrenetetrasulfonic acid ligand to DMF is 1:2-1:3.

[0019] Furthermore, in step S04, the molar ratio of the metal calcium salt in solution A to the pyrenetetrasulfonic acid ligand in solution B is 2:1-2:2.

[0020] The present invention also provides the use of the above-mentioned calcium pyrenetetrasulfonate complex fluorescent probe in measuring the optical properties of iron ions.

[0021] Furthermore, the application includes the following steps: adding the calcium pyrene tetrasulfonate complex fluorescent probe to water to prepare a fluorescent probe solution; then preparing a metal ion test solution; adding the fluorescent probe solution to a four-way cuvette, then adding the metal ion test solution and distilled water, and placing it in a fluorescence instrument for measurement.

[0022] Furthermore, the concentration ratio of the fluorescent probe solution to the metal ion test solution is 1:1.

[0023] Furthermore, in the four-way cuvette, the volume ratio of the fluorescent probe solution, the metal ion test solution, and distilled water is 1:1:30.

[0024] Furthermore, the step of preparing the metal ion test solution includes: adding one or more metal ions of ZnCl2, Pb(NO3)2, AgNO3, Cd(NO3)2, Fe2(NO3)3, FeCl3, Cr(NO3)2, Zn(NO3)2, Ba(oAC)2, Co(NO3)2, Ni(NO3)2, CuCl2, CaCl2, and MnCl2 to distilled water to obtain the metal ion test solution.

[0025] The beneficial effects of the present invention are:

[0026] The synthesis method of metal complexes only requires the selection of simple calcium salts and ligands for hydrothermal reaction to obtain the metal complex. At the same time, the structure is characterized by X-ray single crystal diffractometer in terms of crystallography, which can clearly and clearly obtain the structural arrangement of the substance. At the same time, the selection of calcium salts for the complex reduces the interference of heavy metals in the test. In the presence of multiple ion interferences, the metal complex can be easily and quickly identified by fluorescence spectrometer as Fe 3+ By drawing the standard curve and performing simple calculations, the iron ion concentration in the sample to be tested can be obtained. This is an efficient, simple and fast identification operation, and is suitable for the detection and identification of iron ion pollution in water bodies. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a single crystal structure diagram of the fluorescent probe prepared in Example 1 of the present invention;

[0028] Figure 2 This is a cell diagram of the fluorescent probe prepared in Example 1 of the present invention;

[0029] Figure 3 This is the π-π stacking diagram of the fluorescent probe prepared in Example 1 of the present invention;

[0030] Figure 4 This is a diagram showing the stacking effect of the fluorescent probe prepared in Example 1 of the present invention;

[0031] Figure 5 The fluorescent probe (1×10 -5 )mol / L) of H2O solution with different metal ions added;

[0032] Figure 6 The fluorescence intensity of different metal analytes at 385 nm under 240 nm excitation light;

[0033] Figure 7 Figure 2 shows the effect of Ca-PTS on Fe3+ The fluorescence selection specificity;

[0034] Figure 8 0~110μLFe 3+ Linear change graph of fluorescence intensity;

[0035] Figure 9 0~110μLFe 3+ Fitting diagram of linear change of fluorescence intensity;

[0036] Figure 10 This is the X-ray single crystal diffraction pattern of the fluorescent probe prepared in Example 1. DETAILED DESCRIPTION

[0037] The present invention will be further explained below with reference to the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0038] Example 1

[0039] The preparation method of Ca-PTS for detecting metal ions of the present invention comprises the following steps:

[0040] S01: Commercially purchased tetrasodium pyrenetetrasulfonate (100 g of Aladdin) was passed through an ion exchange column to prepare the pyrenetetrasulfonic acid ligand (H-PTS) using an ion exchange method;

[0041] S02: Weigh 2M metal calcium salt and dissolve it in 2mL DMF, and dissolve it evenly by ultrasonication to obtain solution A;

[0042] S03: Weigh 1M H-PTS and dissolve it in 2mL DMF, and dissolve it evenly under ultrasonication to obtain solution B;

[0043] S04: Pour DMF solution A containing calcium salt into solution B containing H-PTS, stir for 5 minutes, shake evenly, move to an oven, and heat at 130°C for 48 hours. After the end, let it stand and cool to room temperature to obtain white block crystals, which were washed three times with ether with a yield of about 80%. The structure was confirmed on an X-ray single crystal diffractometer, as shown in FIG. Figure 10 shown.

[0044] The molecular formula of the calcium pyrene tetrasulfonate complex fluorescent probe prepared in this embodiment is C 27.8 H 43.2 Ca2N4O 21 S, single crystal structure of fluorescent probe Figure 1 As shown in the figure, the pyrene tetrasulfonic acid ligand coordinates with the calcium ion, and at the same time, DMF and water are coordinated around the calcium ion to form a complex structure. The overall structure is chain-like; the cell diagram is as follows Figure 2 As shown, the stacking of the complex structure in a crystal unit cell is shown in the figure; the π-π stacking diagram is shown in Figure 3 As shown, there is a π-π interaction between the pyrene tetrasulfonic acid ligands, and the distance between the two planes is The packing diagram of the fluorescent probe is shown in Figure 2. Figure 4 As shown, the complex presents a network structure, and there can be many cavities in the material, providing channels for ion recognition.

[0045] The single crystal parameters and part of the bond length data are shown in the following table:

[0046]

[0047] Symmetry code: i 1-X,1 / 2+Y,3 / 2-Z ii1-X,-1 / 2+Y,3 / 2-Z.

[0048] Example 2

[0049] S01: Commercially purchased pyrene tetrasulfonic acid tetrasodium salt (Aldrich 100g) was subjected to ion exchange column to obtain pyrene tetrasulfonic acid ligand (H-PTS) by ion exchange method;

[0050] S02: 4M metal calcium salt was weighed and dissolved in 2 mL DMF, and ultrasonic dissolution was performed to obtain solution A;

[0051] S03: 1M H-PTS was weighed and dissolved in 2 mL DMF, and ultrasonic dissolution was performed to obtain solution B;

[0052] S04: The DMF solution A containing calcium salt was poured into the solution B containing H-PTS, stirred for 5 min, and shaken uniformly, then transferred into an oven, heated at 150°C for 72 h, after the end, cooled to room temperature, and white block crystals were obtained, washed with ether three times, and the structure was confirmed on the X-ray single crystal diffractometer, which was still the structure of Example 1, but the yield was decreased to about 50%. Preferably, the ratio of metal calcium salt to H-PTS is 2:1.

[0053] Example 3

[0054] Application of Ca-PTS prepared in Example 1 as a fluorescent probe in the optical properties of iron ion determination.

[0055] The specific steps are as follows: 15 mg of the Ca-PTS fluorescent probe was added to 20 mL of water to prepare a fluorescent probe solution with a molar concentration of 1×10 -5 mol / L; and then a fluorescent probe solution with a molar concentration of 1×10 -51 mol / L ZnCl2, Pb(NO3)2, AgNO3, Cd(NO3)2, Fe2(NO3)3, FeCl3, Cr(NO3)2, Zn(NO3)2, Ba(oAC)2, Co(NO3)2, Ni(NO3)2, CuCl2, CaCl2, and MnCl2 metal ion test solutions were tested on a fluorimeter. Weigh 100 μL of Ca-PTS aqueous solution into a four-way cuvette, then add 100 μL of the metal solution to be tested, followed by 3 mL of distilled water, and place in the fluorimeter for measurement.

[0056] The fluorescent probe prepared in this embodiment (1×10 -5 )mol / L) H2O solution was added with different metal ions ZnCl2, Pb(NO3)2, AgNO3, Cd(NO3)2, Fe2(NO3)3, FeCl3, Cr(NO3)2, Zn(NO3)2, Ba(oAC)2, Co(NO3)2, Ni(NO3)2, CuCl2, CaCl2, MnCl2. The fluorescence intensity of the metal ions to be tested is shown in the figure. Figure 5 As shown, through instrument measurement, it was found that Fe 3+ The ion-pair calcium pyrene tetrasulfonate complex has a strong fluorescence quenching effect.

[0057] Under 240nm excitation light, the fluorescence intensity of different metal analytes at 385nm is as follows Figure 6 As shown, under the excitation of 240nm, the peak of the emission spectrum is located at about 385nm. As the content of trivalent iron ions increases, the intensity of the emission spectrum decreases. The ratio of the emission spectrum intensity has a good linear relationship with the amount of trivalent iron ions added.

[0058] In order to investigate the selective response of Ca-PTS to iron ions, different interfering substances were added to the system to detect the fluorescence changes. After adding 100 μL of other interfering substances: silver ions, chromium ions, manganese ions, cadmium ions, copper ions, barium ions, lead ions, zinc ions, and calcium ions, 100 μL of iron ion solution was added in sequence. The change in the fluorescence intensity emitted at 385 nm was not affected by other interfering substances, thus achieving specific recognition of iron ions. 3+ The fluorescence selection specificity is as follows Figure 7 As shown in the figure, in the presence of common metal cation interference, calcium complexes still have the ability to resist Fe 3+ The specific identification can be applied to various interferences in actual environments to achieve the purpose of detection.

[0059] Example 4

[0060] 15 mg of the Ca-PTS fluorescent probe was added to 20 mL of water to prepare a molar concentration of 1×10-5 mol / L fluorescent probe solution was reconstituted to a molar concentration of 1×10 -5 mol / L FeCl3 solution. Weigh 100μL Ca-PTS aqueous solution and add it to a four-way cuvette, then add 0-110μL FeCl3 solution and 3mL distilled water, and place it in a fluorescence instrument for measurement. 3+ The linear change of fluorescence intensity is shown in Figure 8-Figure 9 As shown, Fe 3 The fluorescence quenching effect of Ca-PTS is linear. That is, the detection of Fe can be achieved by drawing a standard curve. 3 Purpose of content.

[0061] It should be noted that the above content merely illustrates the technical idea of ​​the present invention and cannot be used to limit the scope of protection of the present invention. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications all fall within the scope of protection of the claims of the present invention.

Claims

1. A calcium pyrenetetrasulfonate complex fluorescent probe, characterized in that: The molecular formula, single crystal parameters and partial bond length data of the calcium pyrene tetrasulfonate complex fluorescent probe are shown in the following table: Symmetrical code:i 1-X,1 / 2+Y,3 / 2-Zii1-X,-1 / 2+Y,3 / 2-Z.

2. The method for preparing a calcium pyrenetetrasulfonate complex fluorescent probe according to claim 1, wherein The following steps are involved: S01: Pyrenetetrasulfonic acid tetrasodium salt is passed through an ion exchange column to obtain pyrenetetrasulfonic acid ligand; S02: Weigh a metal calcium salt and dissolve it in DMF, and dissolve it evenly by ultrasonication to obtain solution A; S03: Weigh the pyrenetetrasulfonic acid ligand prepared in step S01 and dissolve it in DMF, and dissolve it evenly by ultrasonication to obtain solution B; S04: Add solution A to solution B, stir for 5-10 minutes, shake evenly, move to an oven, and heat at 120℃-130℃ for 48-72 hours. After heating, let it stand and cool to obtain white block crystals, which are washed with ether to obtain a calcium pyrene tetrasulfonate complex fluorescent probe.

3. The method for preparing a calcium pyrene tetrasulfonate complex fluorescent probe according to claim 2, wherein In step S02, the molar volume ratio of the metal calcium salt to DMF is 1:1-1:1.5; the metal calcium salt is one or more of CaCl2, Ca(AC)2, and CaCO3.

4. The method for preparing a calcium pyrenetetrasulfonate complex fluorescent probe according to claim 2, wherein In step S03, the molar volume ratio of the pyrenetetrasulfonic acid ligand to DMF is 1:2-1:

3.

5. The method for preparing a calcium pyrenetetrasulfonate complex fluorescent probe according to claim 2, wherein: In step S04, the molar ratio of the metal calcium salt in solution A to the pyrenetetrasulfonic acid ligand in solution B is 2:1-2:

2.

6. Use of a calcium pyrenetetrasulfonate complex fluorescent probe as claimed in claim 1 in measuring the optical properties of iron ions.

7. The use of a calcium pyrene tetrasulfonate complex fluorescent probe according to claim 6 in measuring the optical properties of iron ions, characterized in that: The following steps are involved: The calcium pyrene tetrasulfonate complex fluorescent probe is added into water to prepare a fluorescent probe solution; and then a metal ion test solution is prepared; Add the fluorescent probe solution into a four-way cuvette, then add the metal ion test solution and distilled water, and place it into the fluorescence instrument for measurement.

8. The use of a calcium pyrene tetrasulfonate complex fluorescent probe according to claim 7 in measuring the optical properties of iron ions, characterized in that: The concentration ratio of the fluorescent probe solution to the metal ion test solution is 1:

1.

9. The use of a calcium pyrene tetrasulfonate complex fluorescent probe according to claim 7 in measuring the optical properties of iron ions, characterized in that: In a four-way cuvette, the volume ratio of the fluorescent probe solution, the metal ion test solution, and distilled water is 1:1:

30.

10. Use of a calcium pyrenetetrasulfonate complex fluorescent probe according to claim 7 in measuring the optical properties of iron ions, characterized in that: The steps of preparing the metal ion test solution include: adding one or more metal ions of ZnCl2, Pb(NO3)2, AgNO3, Cd(NO3)2, Fe2(NO3)3, FeCl3, Cr(NO3)2, Zn(NO3)2, Ba(oAC)2, Co(NO3)2, Ni(NO3)2, CuCl2, CaCl2, and MnCl2 into distilled water to obtain the metal ion test solution.

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