A fluorescent crystalline porous organic salt and a preparation method and application thereof

Abstract

The present application relates to a kind of fluorescent crystalline porous organic salt and its preparation method and application, belong to crystalline porous organic salt technical field.The preparation method of the fluorescent crystalline porous organic salt of the present application, first tetra (4- amidinophenyl) ethylene hydrochloride is dissolved in 1, 4-dioxane aqueous solution, obtain solution A;Then 4, 4'-diphenyl disulfonic acid is dissolved in 1, 4-dioxane aqueous solution, obtain solution B;Finally solution A and solution B are mixed, and the room temperature is above 8h, filter, obtain fluorescent crystalline porous organic salt, structure is as shown in formula I.The fluorescent crystalline porous organic salt structure is stable, has permanent porosity, to heavy metal ions (with Fe 3+ As representative) has very good fluorescence quenching effect, can be applied to the detection of heavy metal ions.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of crystalline porous organic salts, and particularly relates to a fluorescent crystalline porous organic salt, a preparation method and application thereof, in particular to application of the fluorescent crystalline porous organic salt in detection of heavy metal ions, especially Fe 3+ BACKGROUND

[0002] Crystalline porous organic salts (CPOSs) are a new type of porous organic material. It is a porous organic material with permanent porosity formed by self-assembly of organic acid and organic base through ionic bonds. The unique physical and chemical properties of CPOS, such as structural definiteness, permanent porosity and polar limited channels, make CPOS have a vigorous development in proton conduction, gas adsorption, negative linear compressibility, rapid transport of guest molecules and the like.

[0003] Heavy metal elements are widely used in medical treatment, alloy manufacturing, food additives, military industry and the like, and heavy metal ion pollution is getting more and more serious. Waste liquid containing heavy metal ions is discharged into the environment, polluting water sources and soil, and then affecting crops, animals and plants, and finally accumulating in the human body, causing serious diseases. So far, many methods for detecting heavy metal ions have been developed, including fluorescence spectroscopy, ion chromatography, inductively coupled plasma mass spectrometry and surface enhanced Raman spectroscopy, and these methods mostly need expensive equipment and tedious and time-consuming pretreatment. In contrast, fluorescence analysis is a simple, inexpensive and rapid non-contact detection method, which has the advantages of high selectivity, high sensitivity, low cost and simple operation. However, there are still problems such as poor stability, limitation of detection system temperature, pH value, water sample and the like, and it is urgent to develop new sensor structures to improve the existing detection system. SUMMARY

[0004] Therefore, the present application aims to provide a fluorescent crystalline porous organic salt, a preparation method and application thereof.

[0005] The technical scheme adopted by the present application to achieve the above-mentioned purpose is as follows.

[0006] The present application provides a fluorescent crystalline porous organic salt, the structure of which is shown in formula I:

[0007]

[0008] The present application also provides a preparation method of the above-mentioned fluorescent crystalline porous organic salt, comprising the following steps:

[0009] 1) Dissolve tetrakis(4-amidinophenyl) ethylene hydrochloride in 1,4-dioxane aqueous solution to obtain solution A;​

[0010] 2) Dissolve 4,4'-biphenyldisulfonic acid in 1,4-dioxane aqueous solution to obtain solution B;

[0011] 3) Mix solution A and solution B, stand at room temperature for more than 8 hours, filter to obtain fluorescent crystalline porous organic salt.

[0012] Preferably, in the step 3), the mass ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride in solution A to 4,4'-biphenyldisulfonic acid in solution B is (10-15):(10-15).

[0013] More preferably, in the step 1), the ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride to 1,4-dioxane aqueous solution is (10-15) mg:(6-10) mL.

[0014] Especially preferably, in the step 1), the volume concentration of 1,4-dioxane aqueous solution is 20-30%.

[0015] More preferably, in the step 2), the ratio of 4,4'-biphenyldisulfonic acid to 1,4-dioxane aqueous solution is (10-15) mg:(3-5) mL.

[0016] Especially preferably, in the step 2), the volume concentration of 1,4-dioxane aqueous solution is 40-60%.

[0017] Preferably, in the step 3), standing at room temperature for 8-12 hours.

[0018] The application also provides the application of the above-mentioned fluorescent crystalline porous organic salt in detecting heavy metal ions.

[0019] Preferably, the heavy metal ion is Fe 3+ .

[0020] The principle of the application is that the crystalline porous organic salt has rich binding sites, special ionic bonds and polar channels, and has rapid adsorption and transmission capacity for the ions to be detected; tetrakisphenyl ethylene (TPE) exhibits bright luminescence in the aggregation state, has high fluorescence quantum yield, and can selectively identify the ions to be detected; the application introduces TPE into the CPOS framework to construct TPE-CPOS material, and then realizes efficient and rapid ion detection.

[0021] Compared with the prior art, the application has the following beneficial effects:

[0022] The fluorescent crystalline porous organic salt of the application has stable structure and permanent porosity.

[0023] The preparation method of the fluorescent crystalline porous organic salt is simple and easy to operate, is pollution-free to the environment, and is suitable for continuous production.

[0024] The fluorescent crystalline porous organic salt has a good fluorescence quenching effect on heavy metal ions (represented by Fe 3+ , and can be applied to detection of heavy metal ions. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort on the basis of these drawings.

[0026] Figure 1 is a powder X-ray diffraction pattern of the TPE-CPOS prepared in Example 1 of the present application;

[0027] Figure 2 is a scanning electron microscope image of the TPE-CPOS prepared in Example 1 of the present application;

[0028] Figure 3 is a TGA curve of the TPE-CPOS prepared in Example 1 of the present application under air atmosphere;

[0029] Figure 4 is an infrared spectrum of the TPE-CPOS prepared in Example 1 of the present application;

[0030] Figure 5 is an ultraviolet absorption spectrum of the TPE-CPOS prepared in Example 1 of the present application;

[0031] Figure 6 is a CO2 adsorption graph of the TPE-CPOS prepared in Example 1 of the present application;

[0032] Figure 7 is a photoluminescence spectrum of the TPE-CPOS prepared in Example 1 of the present application;

[0033] Figure 8 is a fluorescence emission spectrum of the TPE-CPOS prepared in Example 1 of the present application on different metal salts. DETAILED DESCRIPTION

[0034] In order to further understand the present application, the preferred embodiments of the present application are described as follows, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present application, and are not limitations on the claims of the present application.

[0035] The fluorescent crystalline porous organic salt of the present application has a structure as shown in Formula I:

[0036]

[0037] The preparation method of the fluorescent crystalline porous organic salt of the present application comprises the following steps:

[0038] 1) Dissolve tetrakis(4-amidinophenyl)ethylene hydrochloride in 1,4-dioxane aqueous solution to obtain solution A;

[0039] 2) Dissolve 4,4'-diphenyldisulfonic acid in 1,4-dioxane aqueous solution to obtain solution B;

[0040] 3) Mix solution A and solution B, and stand at room temperature for more than 8 hours to generate colorless transparent crystals, and filter to obtain the fluorescent crystalline porous organic salt.

[0041] In the above technical solution, preferably in step 3), the mass ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride in solution A to 4,4'-diphenyldisulfonic acid in solution B is (10-15):(10-15); preferably in step 1), the ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride to 1,4-dioxane aqueous solution is (10-15) mg:(6-10) mL, and the volume concentration of the 1,4-dioxane aqueous solution is 20-30%; preferably in step 2), the ratio of 4,4'-diphenyldisulfonic acid to 1,4-dioxane aqueous solution is (10-15) mg:(3-5) mL, and the volume concentration of the 1,4-dioxane aqueous solution is 40-60%; and preferably in step 3), standing at room temperature for 8-12 hours.

[0042] The fluorescent crystalline porous organic salt of the present application can be applied in detecting heavy metal ions, preferably Fe 3+ .

[0043] In the present application, the terms used generally have the meanings commonly understood by those of ordinary skill in the art, unless otherwise defined.

[0044] In order for those skilled in the art to better understand the technical solutions of the present application, the present application will be further described in detail below in conjunction with the embodiments.

[0045] In the following examples, various processes and methods that are not described in detail are conventional methods known in the art. The materials, reagents, devices, instruments, equipment, etc. used in the following examples can be obtained from commercial channels unless otherwise specified.

[0046] Example 1

[0047] The preparation method of the fluorescent crystalline porous organic salt comprises the following steps:

[0048] 1) 12.93 mg (0.02 mmol) of tetrakis(4- amidinophenyl) ethylene hydrochloride was dissolved in 8 mL of 25% volume concentration aqueous 1,4-dioxane solution to obtain solution A;

[0049] 2) 12.57 mg (0.04 mmol) of 4,4'-biphenyldisulfonic acid was dissolved in 4 mL of 50% volume concentration aqueous 1,4-dioxane solution to obtain solution B;

[0050] 3) Solution A obtained in step 1) and solution B obtained in step 2) were mixed and left at room temperature overnight, during which colorless transparent crystals were generated, which were filtered to obtain fluorescent crystalline porous organic salt, noted as TPE-CPOS, with a yield of 50%.

[0051] TPE-CPOS obtained in Example 1 was detected. Figure 1 is the powder X-ray diffraction pattern of TPE-CPOS, from Figure 1 It can be seen that TPE-CPOS has high phase purity. Figure 2 is the scanning electron microscope image of TPE-CPOS, from Figure 2 It can be seen that TPE-CPOS is in the form of thin rod-like single crystal with a size of 20 x 170 microns. Figure 3 is the TGA curve of TPE-CPOS in air atmosphere, from Figure 3 It can be seen that the structure starts to collapse at 350°C, indicating that TPE-CPOS has high thermal stability. Figure 4 is the infrared spectrum of TPE-CPOS, from Figure 4 It can be seen that the wave number in the range of 3580-3260 cm -1 may be attributed to water molecules, hydroxyl groups, amino groups, primary amine cations and hydrogen bonds formed in TPE-CPOS; 1290-1126 cm -1 correspond to asymmetric stretching vibration of sulfonate anions, indicating the synthesis of TPE-CPOS. Figure 5 is the ultraviolet-visible absorption spectrum of TPE-CPOS, from Figure 5 It can be seen that TPE-CPOS has a wide absorption at 220 nm and between 300-400 nm. Figure 6 is the CO2 gas adsorption experiment of TPE-CPOS at 273 K, from Figure 6 It can be seen that TPE-CPOS has permanent porosity, with micropore surface area of 298.86 m 2 g -1 . Figure 7 is the photoluminescence spectrum of TPE-CPOS, with emission spectrum obtained under excitation light at 380 nm, from Figure 7 It can be seen that the slit width is 0.4. Figure 8by mixing TPE-CPOS with different metal salts (Cl - as counter ions) in equimolar amount (0.01 mmol:0.01 mmol), testing fluorescence emission spectrum, from Figure 8 It can be seen that TPE-CPOS shows effective fluorescence quenching effect on Fe 3+ , reaching 93%, and the detection limit is 6 μmol / g, and still has good fluorescence quenching effect under the interference of other metal ions, indicating that the TPE-CPOS of the present application has good detection performance on Fe 3+ .

[0052] Obviously, the above examples are only examples for clearly illustrating, but not limitation to the examples. Other different forms of changes or variations can be made on the basis of the above description for those skilled in the art. Here, it is not necessary and also impossible to exhaust all the examples. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A fluorescent crystalline porous organic salt characterized in that, The structure is shown as formula I:

2. The method for preparing the fluorescent crystalline porous organic salt according to claim 1, characterized in that: The method comprises the following steps: 1) dissolving tetrakis(4-amidinophenyl)ethylene hydrochloride in 1,4-dioxane aqueous solution to obtain solution A; 2) dissolving 4,4'-diphenyl disulfonic acid in 1,4-dioxane aqueous solution to obtain solution B; 3) mixing solution A and solution B, standing at room temperature for more than 8 hours, filtering to obtain fluorescent crystalline porous organic salt.

3. The method for preparing the fluorescent crystalline porous organic salt according to claim 2, wherein: In step 3), the mass ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride in solution A to 4,4'-diphenyl disulfonic acid in solution B is (10-15):(10-15).

4. The method for preparing the fluorescent crystalline porous organic salt according to claim 3, characterized in that: In step 1), the ratio of tetrakis(4-amidinophenyl)ethylene hydrochloride to 1,4-dioxane aqueous solution is (10-15) mg:(6-10) mL.

5. The method for preparing the fluorescent crystalline porous organic salt according to claim 4, characterized in that: In step 1), the volume concentration of 1,4-dioxane aqueous solution is 20-30%.

6. The method for preparing the fluorescent crystalline porous organic salt according to claim 3, characterized in that: In step 2), the ratio of 4,4'-diphenyl disulfonic acid to 1,4-dioxane aqueous solution is (10-15) mg:(3-5) mL.

7. The method for preparing the fluorescent crystalline porous organic salt according to claim 6, characterized in that: In step 2), the volume concentration of 1,4-dioxane aqueous solution is 40-60%.

8. The method for preparing the fluorescent crystalline porous organic salt according to claim 2, characterized in that: In step 3), standing at room temperature for 8-12 hours.

9. The use of the fluorescent crystalline porous organic salt according to claim 1 or prepared by the method according to any one of claims 2-8 in detecting heavy metal ions, and the detection is not for the purpose of disease diagnosis or treatment.

10. Use according to claim 9, characterized in that, The heavy metal ion is Fe 3+ .

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