Spiral 14-membered cucurbit urils-based supramolecular fluorescent probe as well as preparation and application thereof

Abstract

The invention discloses a spiral cucurbit [14] uril-based supramolecular fluorescent probe as well as preparation and application thereof. The supramolecular fluorescent probe disclosed by the invention is prepared from spiral cucurbit [14] uril and 1-(7-carboxyl heptyl)-4-(pyrene-1-yl) pyridine-1-onium as raw materials, and can be used for detecting Hg < 2 + > in an aqueous solution. The fluorescent probe is a novel fluorescent probe based on spiral cucurbit [14] uril, the preparation method is simple, and when the fluorescent probe is used for detecting Hg < 2 + > in an aqueous solution, the fluorescent probe is easy to operate, high in sensitivity, short in reaction time, visible in naked eyes and very worthy of wide popularization and application.

Description

Technical Field

[0001] The invention relates to a fluorescent probe and preparation and application thereof, in particular to a supramolecular fluorescent probe based on a spiral fourteen-membered cucurbitacin ring and preparation and application thereof. Background Art

[0002] Heavy metals enriched in nature and released by human production activities seriously threaten the natural ecological environment and human life and health. 2+ ) is a highly toxic heavy metal ion and is listed as a type of water pollutant. The World Health Organization (WHO) allows Hg 2+ The ion content must be less than 0.001 mg / L (5 μM).

[0003] The reason is Hg 2+ The highly toxic Hg is mainly produced by methylmercury through bacterial activity. It can be permanently accumulated in organisms through the food chain, causing central nervous system dysfunction, Hunter-Russell syndrome and Minamata disease, which seriously threatens human life and health. Therefore, Hg 2+ The detection and quantitative evaluation are crucial.

[0004] So far, methods such as inductively coupled plasma mass spectrometry (ICP-MS), atomic fluorescence spectrometry (AFS), atomic absorption spectrometry (AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES) have been used to specifically detect Hg in environmental and biological samples. 2+ Although these methods have the advantages of high accuracy and high sensitivity, their high cost and complexity limit the application of Hg 2+ Practicality of testing.

[0005] Therefore, it is necessary to develop a rapid and effective method to detect Hg 2+ The methods and reagents are very important for environmental detection and maintaining life and health. Among the many different analytical methods, supramolecular fluorescent probes have attracted much attention due to their unique advantages of simple technology, high sensitivity, non-invasiveness, fast response time and "naked eye" visualization. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a supramolecular fluorescent probe based on a helical 14-membered cucurbitacin ring and its preparation and application. The fluorescent probe of the present invention is a new type of fluorescent probe based on a helical 14-membered cucurbitacin ring, and its preparation method is simple and can be used to detect Hg in aqueous solution. 2+ It is easy to operate, has high sensitivity, fast response time, and can be seen by the naked eye, so it is very worthy of wide promotion and application.

[0007] One of the technical solutions of the present invention:

[0008] Provided is a supramolecular fluorescent probe based on a 14-membered cucurbit ring, the chemical structure of which is as follows:

[0009]

[0010] in, It is a spiral fourteen-membered cucurbit ring.

[0011] The second technical solution of the present invention:

[0012] Provided is a method for preparing the aforementioned supramolecular fluorescent probe based on a spiral fourteen-membered cucurbitacin ring, which is prepared using a spiral fourteen-membered cucurbitacin ring and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium as raw materials.

[0013] Preferably, the aforementioned method for preparing the supramolecular fluorescent probe based on the helical fourteen-membered cucurbit ring specifically comprises the following steps:

[0014] (1) Take a spiral 14-membered cucurbitacin ring and dissolve it in water to prepare solution A;

[0015] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium, add it to water and dissolve it to prepare solution B;

[0016] (3) Solution A and solution B are mixed and a supramolecular fluorescent probe is obtained through a self-assembly reaction.

[0017] Preferably, in the aforementioned method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbitacin ring, the concentration of the helical 14-membered cucurbitacin ring in the solution A is 0.5×10 -3 -1.5×10 -3 mol / L.

[0018] Preferably, in the aforementioned method for preparing a supramolecular fluorescent probe based on a spiral 14-membered cucurbit ring, the concentration of 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium in the solution B is 0.5×10 -3 -1.5×10 -3 mol / L.

[0019] Preferably, in the aforementioned method for preparing a supramolecular fluorescent probe based on a helical fourteen-membered cucurbitacin, when solution A and solution B are mixed, the molar ratio of the helical fourteen-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is 1:2.

[0020] Preferably, in the aforementioned method for preparing a supramolecular fluorescent probe based on a helical fourteen-membered cucurbitacin ring, the self-assembly reaction in step (3) is carried out at room temperature.

[0021] The third technical solution of the present invention:

[0022] Provide a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring for detecting Hg in aqueous solution 2+ application.

[0023] The fourth technical solution of the present invention:

[0024] Provided is a method for detecting Hg in aqueous solution using the supramolecular fluorescent probe 2+ The method comprises the following steps:

[0025] (1) Take the supramolecular fluorescent probe and add water to make a concentration of 1×10 -5 -3×10 -5 mol / L fluorescent probe standard solution;

[0026] (2) adding the aqueous solution to be tested to the fluorescent probe standard solution prepared in step (1), leaving it to stand for 5-10 minutes, and then measuring the fluorescence emission spectrum at a fixed excitation wavelength of 385 nm, and plotting a curve of the change in fluorescence intensity at the corresponding excitation wavelength of 521 nm;

[0027] (3) Compare the change curve drawn in step (2) with the change value ΔI of the fluorescence emission spectrum intensity at 521 nm to obtain the Hg 2+ Conduct testing.

[0028] Preferably, the supramolecular fluorescent probe described above detects Hg in aqueous solution. 2+ The method is that if the intensity of the fluorescence emission spectrum at 521 nm is significantly weakened before and after adding the aqueous solution to be tested, it indicates that the aqueous solution to be tested contains Hg 2+ On the contrary, it does not contain Hg 2+ .

[0029] Beneficial effects of the present invention:

[0030] 1. The supramolecular fluorescent probe of the present invention is a novel supramolecular fluorescent probe prepared using a spiral 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium as raw materials.

[0031] 2. The supramolecular fluorescent probe of the present invention is prepared by an aqueous solution of a spiral 14-membered cucurbitacin and an aqueous solution of 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium, and the preparation method is simple and the cost is low.

[0032] 3. The supramolecular fluorescent probe of the present invention is used to detect Hg in aqueous solution 2+ It can detect Hg in aqueous solution sensitively and quickly. 2+ The detection limit is as low as 0.177 μM, which is much lower than the Hg content in drinking water allowed by WHO. 2+content (5.0μM); and the results can be seen with the naked eye, and the operation is very easy.

[0033] In summary, the fluorescent probe of the present invention is a novel fluorescent probe based on a helical 14-membered cucurbit ring, the preparation method of which is simple, and the fluorescent probe can be used to detect Hg in aqueous solution. 2+ It is easy to operate, has high sensitivity, fast response time, and can be seen by the naked eye, so it is very worthy of wide promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Attached Figure 1 The structural formula and schematic diagram of a spiral fourteen-membered cucurbitacin (hereinafter referred to as tQ

[14] ) and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium (hereinafter referred to as Pyr-O);

[0035] Attached Figure 2 The fluorescence spectrum of Pyr-O was gradually added with tQ

[14] from 0.0, 0.1... to 2.0 equivalents;

[0036] Attached Figure 3 Job's diagram of the supramolecular fluorescent probe (hereafter referred to as Pyr-O@tQ

[14] );

[0037] Attached Figure 4 Fluorescence lifetime spectra of Pyr-O and Pyr-O@tQ

[14] ;

[0038] Attached Figure 5 SEM image of Pyr-O@tQ

[14] assembly;

[0039] Attached Figure 6 Fluorescence quantum yield spectra of Pyr-O and Pyr-O@tQ

[14] ;

[0040] Attached Figure 7 The diagram shows the NMR titration and inclusion pattern of tQ

[14] and Pyr-O; among them, (i) Pyr-O; (ii) Pyr-O: tQ

[14] = 10:1; (iii) Pyr-O: tQ

[14] = 10:2; (iv) Pyr-O: tQ

[14] = 10:4; (iv) Pyr-O: tQ

[14] = 2:1.

[0041] Attached Figure 8 The specific recognition fluorescence spectra of Pyr-O@tQ

[14] for 18 cations;

[0042] Attached Fig. 9 Add different concentrations of Hg to the Pyr-O@tQ

[14] solution 2+ Fluorescence titration spectrum curve of ion solution;

[0043] Attached Fig.10To detect Hg using smartphones 2+ Schematic diagram of

[0044] Attached Fig.11 Add Hg to Pyr-O@tQ

[14] 2+ The fluorescence titration detection limit of the solution is

[0045] Attached Fig.12 The fluorescence comparison diagram of the cuvette of Pyr-O@tQ for specific recognition of 18 cations (under 365nm UV light);

[0046] Attached Fig.13 Pyr-O@tQ

[14] contains 18 perchlorate cations Hg 2+ The anti-interference histogram (λ em =521nm).

[0047] Attached Fig.14 The specific recognition bar graph of Pyr-O@tQ

[14] for 18 perchlorate cations (λ em =521nm). DETAILED DESCRIPTION

[0048] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0049] Embodiments of the present invention

[0050] Example 1

[0051] The preparation steps of the supramolecular fluorescent probe based on the helical 14-membered cucurbit ring are as follows:

[0052] (1) Take the fourteen-membered spiral cucurbitacin ring and dissolve it in water to a concentration of 1×10 -3 mol / L solution A;

[0053] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium and dissolve it in water to a concentration of 1×10 -3 mol / L solution B;

[0054] (3) Solution A and solution B are mixed, and the molar ratio of the helical 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is controlled to be 1:2. The supramolecular fluorescent probe can be obtained by allowing the self-assembly reaction to stand for a while at room temperature.

[0055] Example 2

[0056] The preparation steps of the supramolecular fluorescent probe based on the helical 14-membered cucurbit ring are as follows:

[0057] (1) Take the fourteen-membered spiral cucurbitacin ring and dissolve it in water to a concentration of 0.5×10 -3 mol / L solution A;

[0058] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium and dissolve it in water to a concentration of 0.5×10 -3 mol / L solution B;

[0059] (3) Solution A and solution B are mixed, and the molar ratio of the helical 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is controlled to be 1:2. The supramolecular fluorescent probe can be obtained by allowing the self-assembly reaction to stand for a while at room temperature.

[0060] Example 3

[0061] The preparation steps of the supramolecular fluorescent probe based on the helical 14-membered cucurbit ring are as follows:

[0062] (1) Take the fourteen-membered spiral cucurbitacin ring and dissolve it in water to a concentration of 0.8×10 -3 mol / L solution A;

[0063] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium and dissolve it in water to a concentration of 0.8×10 -3 mol / L solution B;

[0064] (3) Solution A and solution B are mixed, and the molar ratio of the helical 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is controlled to be 1:2. The supramolecular fluorescent probe can be obtained by allowing the self-assembly reaction to stand for a while at room temperature.

[0065] Example 4

[0066] The preparation steps of the supramolecular fluorescent probe based on the helical 14-membered cucurbit ring are as follows:

[0067] (1) Take the fourteen-membered spiral cucurbitacin ring and dissolve it in water to a concentration of 1.2×10 -3 mol / L solution A;

[0068] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium and dissolve it in water to a concentration of 1.2×10 -3 mol / L solution B;

[0069] (3) Solution A and solution B are mixed, and the molar ratio of the helical 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is controlled to be 1:2. The supramolecular fluorescent probe can be obtained by allowing the self-assembly reaction to stand for a while at room temperature.

[0070] Example 5

[0071] The preparation steps of the supramolecular fluorescent probe based on the helical 14-membered cucurbit ring are as follows:

[0072] (1) Take the fourteen-membered spiral cucurbitacin ring and dissolve it in water to a concentration of 1.5×10 -3 mol / L solution A;

[0073] (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium and dissolve it in water to a concentration of 1.5×10 -3 mol / L solution B;

[0074] (3) Solution A and solution B are mixed, and the molar ratio of the helical 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is controlled to be 1:2. The supramolecular fluorescent probe can be obtained by allowing the self-assembly reaction to stand for a while at room temperature.

[0075] Example 6

[0076] The present invention uses a supramolecular fluorescent probe to detect Hg in aqueous solution. 2+ The method is as follows:

[0077] (1) Take the supramolecular fluorescent probe prepared in Example 1 and add water to make it constant to a concentration of 2.00×10 -5 mol / L fluorescent probe standard solution;

[0078] (2) Weigh the analytically pure standard products of various perchlorate cations required and dissolve them in deionized water with a pH of 6.75 to obtain a concentration of 1.00×10 -1 mol / L standard solutions of other metal ions;

[0079] (3) adding the metal ion standard solution of step (2) to the fluorescent probe standard solution prepared in step (1), leaving it for 5 minutes, then measuring the fluorescence emission spectrum at a fixed excitation wavelength of 385 nm, and plotting a change curve of the fluorescence intensity at an emission wavelength of 521 nm;

[0080] (4) Calculate the change value ΔI of the fluorescence emission spectrum intensity at 521 nm before and after the addition of the metal ion standard solution to the fluorescent probe standard solution according to the curve in step (3). If the intensity of the fluorescence emission spectrum at 521 nm before and after the addition of the metal ion standard solution is significantly weakened, it indicates that the metal ion standard solution contains Hg 2+ , and the concentration is 0-2 times (excluding 0 and 2) of TPAPy@tQ

[14] . If the intensity of the fluorescence emission spectrum at 521 nm does not change significantly before and after the addition of the metal ion standard solution, it indicates that the metal ion standard solution does not contain Hg 2+ .

[0081] Example 7

[0082] The present invention uses a supramolecular fluorescent probe to detect Hg in aqueous solution. 2+ The method is as follows:

[0083] (1) Take the supramolecular fluorescent probe prepared in Example 1 and add water to make it constant to a concentration of 1.00×10 -5 mol / L fluorescent probe standard solution;

[0084] (2) Weigh the analytically pure standard products of various perchlorate cations required and dissolve them in deionized water with a pH of 6.75 to obtain a concentration of 1.00×10 -1 mol / L standard solutions of other metal ions;

[0085] (3) adding the metal ion standard solution of step (2) to the fluorescent probe standard solution prepared in step (1), leaving it for 5 minutes, then measuring the fluorescence emission spectrum at a fixed excitation wavelength of 385 nm, and plotting a change curve of the fluorescence intensity at an emission wavelength of 521 nm;

[0086] (4) Calculate the change value ΔI of the fluorescence emission spectrum intensity at 521 nm before and after the addition of the metal ion standard solution to the fluorescent probe standard solution according to the curve in step (3). If the intensity of the fluorescence emission spectrum at 521 nm before and after the addition of the metal ion standard solution is significantly weakened, it indicates that the metal ion standard solution contains Hg 2+ , and the concentration is 0-2 times (excluding 0 and 2) of TPAPy@tQ

[14] . If the intensity of the fluorescence emission spectrum at 521 nm does not change significantly before and after the addition of the metal ion standard solution, it indicates that the metal ion standard solution does not contain Hg 2+ .

[0087] Example 8

[0088] The present invention uses a supramolecular fluorescent probe to detect Hg in aqueous solution. 2+ The method is as follows:

[0089] (1) Take the supramolecular fluorescent probe prepared in Example 1 and add water to make it constant to a concentration of 3.00×10 -5 mol / L fluorescent probe standard solution;

[0090] (2) Weigh the analytically pure standard products of various perchlorate cations required and dissolve them in deionized water with a pH of 6.75 to obtain a concentration of 1.00×10 -1 mol / L standard solutions of other metal ions;

[0091] (3) adding the metal ion standard solution of step (2) to the fluorescent probe standard solution prepared in step (1), leaving it for 5 minutes, then measuring the fluorescence emission spectrum at a fixed excitation wavelength of 385 nm, and plotting a change curve of the fluorescence intensity at an emission wavelength of 521 nm;

[0092] (4) Calculate the change value ΔI of the fluorescence emission spectrum intensity at 521 nm before and after the addition of the metal ion standard solution to the fluorescent probe standard solution according to the curve in step (3). If the intensity of the fluorescence emission spectrum at 521 nm before and after the addition of the metal ion standard solution is significantly weakened, it indicates that the metal ion standard solution contains Hg 2+ , and the concentration is 0-2 times (excluding 0 and 2) of TPAPy@tQ

[14] . If the intensity of the fluorescence emission spectrum at 521 nm does not change significantly before and after the addition of the metal ion standard solution, it indicates that the metal ion standard solution does not contain Hg 2+ .

[0093] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and inventive concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A supramolecular fluorescent probe based on a helical 14-membered cucurbit ring, characterized in that: Its chemical structure is as follows: in, It is a spiral fourteen-membered cucurbit ring.

2. A method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 1, characterized in that: The invention is prepared by taking spiral 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium as raw materials.

3. The method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 2, characterized in that: The specific steps include: (1) Take a spiral 14-membered cucurbitacin ring and dissolve it in water to prepare solution A; (2) Take 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium, add it to water and dissolve it to prepare solution B; (3) Solution A and solution B are mixed and a supramolecular fluorescent probe is obtained through a self-assembly reaction.

4. The method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 3, characterized in that: The concentration of the helical 14-membered cucurbitacin in solution A is 0.5×10 -3 -1.5×10 -3 mol / L.

5. The method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 3, characterized in that: The concentration of 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium in the solution B is 0.5×10 -3 -1.5×10 - 3 mol / L.

6. The method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 3, characterized in that: When the solution A and the solution B are mixed, the molar ratio of the spiral 14-membered cucurbitacin and 1-(7-carboxyheptyl)-4-(pyrene-1-yl)pyridin-1-ium is 1:

2.

7. The method for preparing a supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 3, characterized in that: The self-assembly reaction in step (3) is carried out at room temperature.

8. A supramolecular fluorescent probe based on a helical 14-membered cucurbit ring according to claim 1 for detecting Hg in aqueous solution 2+ application.

9. A method for detecting Hg in aqueous solution using the supramolecular fluorescent probe according to claim 1 2+ The method is characterized in that The steps include: (1) Take the supramolecular fluorescent probe and add water to make a concentration of 1×10 -5 -3×10 -5 mol / L fluorescent probe standard solution; (2) adding the aqueous solution to be tested to the fluorescent probe standard solution prepared in step (1), leaving it to stand for 5-10 minutes, and then measuring the fluorescence emission spectrum at a fixed excitation wavelength of 385 nm, and plotting a curve of the change in fluorescence intensity at the corresponding excitation wavelength of 521 nm; (3) Compare the change curve drawn in step (2) with the change value ΔI of the fluorescence emission spectrum intensity at 521 nm to obtain the Hg 2+ Conduct testing.

10. The supramolecular fluorescent probe according to claim 9 for detecting Hg in aqueous solution 2+ The method is characterized in that: If the fluorescence emission spectrum at 521 nm is significantly weakened before and after adding the aqueous solution to be tested, it indicates that the aqueous solution to be tested contains Hg. 2+ ; On the contrary, it does not contain Hg 2+ .

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