POSS (polyhedral oligomeric silsesquioxane) derivative based on pyrene as well as synthesis

Abstract

The invention discloses a pyrene-based POSS (polyhedral oligomeric silsesquioxane) derivative as well as a synthesis method and application thereof, and belongs to the The structure of the derivative is shown as a formula (I), and the derivative is formed by connecting octavinyl polyhedral oligomeric silsesquioxane (POSS) and a pyrene group through a carbon-carbon double bond. The synthesis method comprises the following steps: under the protection of argon, dissolving octavinyl POSS, palladium acetate and triphenylphosphine in a tetrahydrofuran / triethylamine mixed solvent, carrying out Heck coupling reaction on the solution and 1-bromopyrene for 48 hours, and carrying out precipitation, column chromatography and Soxhlet extraction purification to obtain bright yellow powder. The derivative shows a solvent polarity dependent fluorescence characteristic in tetrahydrofuran, dimethyl sulfoxide, dichloromethane and N, N-dimethylformamide, and is especially suitable for the recognition of F, Cl, ClO and SO. The problems that a traditional probe is poor in solvent compatibility and not obvious in signal change are solved, and a novel detection tool is provided for environment monitoring and biological analysis.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent probes, specifically relating to pyrene-based POSS derivatives, their synthesis methods, and applications. Background Technology

[0002] Fluorescent probes have wide applications in fields such as bioimaging, environmental monitoring, and metal ion detection. Pyrene is a common aromatic fluorescent molecule with a strong π-π electron conjugation system, resulting in high fluorescence quantum yield and high sensitivity to environmental changes, making it suitable for constructing fluorescent probes. Covalently introducing the pyrene group into the POSS structure not only endows the material with excellent fluorescence properties but also utilizes the structural rigidity of POSS to improve fluorescence stability and reduce aggregation quenching effects.

[0003] Cage-like silsesquioxanes (POSS) possess advantages such as high order, rigidity, and ease of functionalization. As fluorescent probe carriers, they can effectively improve molecular stability, dispersibility, and fluorescence performance. Therefore, integrating POSS with a Py structure holds promise for obtaining a novel fluorescent probe with excellent fluorescence response.

[0004] As is well known, ion recognition is an indispensable part of modern sensor design and research, its role extending beyond detection and analysis to drive innovation in smart materials, precision medicine, and green industry. Fluorescent probe technology, with its advantages of high sensitivity, real-time detection, and ease of operation, has become an important method for anion detection. However, some probes are sensitive to metal ions but show little signal change, and many probes exhibit insolubility in various solvents. This invention synthesizes materials by polymerizing cage-type silsesquioxanes with pyrene groups, selects some typical anions for fluorescence intensity detection in various organic solvents, and performs adsorption recognition. Summary of the Invention

[0005] Technical problem solved: In view of the shortcomings of the prior art, the present invention provides pyrene-based POSS derivatives, their synthesis methods and applications.

[0006] Technical solution: A POSS derivative based on pyrene, the structural formula of which is shown below:

[0007]

[0008] The above-mentioned method for synthesizing pyrene-based POSS derivatives includes the following steps: (a) adding octavinyl POSS, palladium catalyst, and phosphine ligand to a mixed solvent of tetrahydrofuran and triethylamine, and bubbling to remove oxygen under an argon atmosphere; (b) adding 1-bromopyrene, and reacting at 80±5℃ under argon protection for 48±2 hours; (c) filtering the reaction solution to remove the palladium catalyst, collecting the filtrate, and adding a methanol solution containing 5% HCl to precipitate the product; (d) dissolving the precipitate in dichloromethane, and then purifying it by column chromatography using petroleum ether:dichloromethane = 3:1 (v / v) as the eluent; (e) sequentially extracting the purified product with methanol and n-hexane for 24 hours each to obtain a bright yellow powder.

[0009] Preferably, the palladium catalyst is palladium acetate, the phosphine ligand is triphenylphosphine, and the molar ratio of octavinylPOSS, palladium acetate, and triphenylphosphine is 1:0.4:0.8.

[0010] Preferably, the volume ratio of tetrahydrofuran to triethylamine in the above mixed solvent is 3:1.

[0011] The above-mentioned application of pyrene-based POSS derivatives as fluorescent probes in anion detection, wherein the anions include F - Cl - ClO4 - SO4 2- At least one of them.

[0012] The above detection is carried out in an organic solvent selected from tetrahydrofuran, dimethyl sulfoxide, dichloromethane, and N,N-dimethylformamide.

[0013] In dichloromethane solvent, F - This causes an increase in fluorescence intensity, ClO4 - and SO4 2- This causes fluorescence quenching.

[0014] In dimethyl sulfoxide solvent, Cl - ClO4 - and SO4 2- This causes a decrease in fluorescence intensity.

[0015] An anion detection method includes the following steps: (1) dissolving the POSS derivative in an organic solvent to obtain a probe solution; (2) adding the anion solution to be tested to the probe solution; (3) measuring the change in fluorescence emission spectrum and identifying the type of anion based on the change in characteristic peak intensity.

[0016] In step (3), the anion type is distinguished by monitoring the change in the ratio of fluorescence peak intensity at 375 nm and 395 nm.

[0017] Beneficial effects: This invention utilizes pyrene-based POSS derivatives to exhibit excellent fluorescence performance in solvents of different polarities. The different fluorescence response behaviors of POSS-py and an anion in solvents of different polarities can be distinguished by fluorescence emission spectroscopy (F...). - Cl - ClO4 - and SO4 2- The novel fluorescent probe of the present invention, consisting of a cage-like silsesquioxane coupled with a pyrene group, exhibits fluorescent recognition function for anions in DMSO, DCM, DMF, and THF solvents. Attached Figure Description

[0018] Figure 1 The infrared spectrum of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene group synthesized in Example 1 is shown.

[0019] Figure 2 The proton spectrum of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene group synthesized in Example 1.

[0020] Figure 3 The image shows the liquid UV-Vis spectra of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene groups synthesized in Example 1 in DMSO, THF, DCM, and DMF.

[0021] Figure 4 The fluorescence emission spectra of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene groups synthesized in Example 1 are shown in DCM with the addition of different ions.

[0022] Figure 5 The fluorescence emission spectra of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene groups synthesized in Example 1 are shown in DMF with the addition of different ions.

[0023] Figure 6 The fluorescence emission spectra of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene groups synthesized in Example 1 are shown in DMSO with the addition of different ions.

[0024] Figure 7 The fluorescence emission spectra of the novel fluorescent probe with cage-like silsesquioxane coupled to pyrene groups synthesized in Example 1 are shown in THF with the addition of different ions.

[0025] Figure 8 The fluorescence emission spectra of the physical mixture of octavinylPOSS and 1-bromopyrene synthesized in Example 1 as a fluorescent probe with different ions added to DCM. Detailed Implementation

[0026] Example 1

[0027] Preparation of POSS derivatives based on pyrene

[0028] The preparation steps are as follows: A porous polymer was prepared by reacting Py and POSS using a Heck coupling method. 632 mg of octavinyl POSS (1 mmol), 90 mg of palladium acetate (0.4 mmol), and 210 mg of triphenylphosphine (0.8 mmol) were added to a mixed solvent (45 mL / 15 mL) of tetrahydrofuran and triethylamine (THF / NEt3) and placed in a 100 mL round-bottom flask equipped with a reflux condenser. The solution was bubbled with argon at room temperature for 30 minutes. After bubbling, 2.474 g of 1-bromopyrene was added, and the mixture was heated to 80 °C and reacted under argon protection for 48 h. After the reaction was complete, the mixture was cooled to room temperature. The palladium catalyst was initially filtered through a Buchner funnel, and the supernatant was precipitated by adding a methanol solution containing 5% HCl. The supernatant was rotary evaporated to obtain a pale yellow powder. The precipitate was redissolved in a minimal amount of dichloromethane (DCM) and subjected to column chromatography. The eluent was petroleum ether: dichloromethane = 3:1. The obtained product was extracted with methanol and n-hexane by Soxhlet extraction for one day each, and finally a bright yellow powder was obtained.

[0029] Material characterization: Fourier transform infrared spectroscopy (FTIR) was used. Figure 1 ) and solid-state nuclear magnetic resonance spectroscopy 1H ( Figure 2 ), ultraviolet-visible spectrum ( Figure 3 The chemical structure of the cage-like silsesquioxane and pyrene group polymer was confirmed, and the product structures were found to be correct after analysis.

[0030] The cage-like silsesquioxane and the novel fluorescent probe with a pyrene group from Example 1 were dissolved in an equal volume of organic solvent for liquid ultraviolet-visible light detection. Figure 3 As shown.

[0031] The cage-like silsesquioxane and the novel fluorescent probe with a pyrene group from Example 1 were dissolved in the same volume of organic solvent for fluorescence emission intensity detection. Figures 4-7 It is evident that the fluorescence properties of POSS-py are significantly affected by solvent polarity. The fluorescence intensity is highest in DCM, decreases in THF and DMF, and is lowest in DMSO.

[0032] The cage-like silsesquioxane and the novel fluorescent probe with a pyrene group from Example 1 were dissolved in the same volume of organic solvent for fluorescence emission intensity detection, and the same volume of anions were added. Figures 4-7 As shown. After comparison, F - Fluorescence is enhanced in DCM and THF, two solvents with lower polarity, while it is not obvious in DMSO and DMF. - ClO4 - and SO4 2-Fluorescence intensity decreased in both DMSO and DMF solvents, ClO4 - and SO4 2- It exhibits fluorescence quenching effect in DCM and THF.

[0033] The physical mixture of octavinylPOSS and 1-bromopyrene reactants from Example 1 was dissolved in an equal volume of DCM for fluorescence detection, and an equal volume of anion was added. Figure 8 As shown, through Figure 4 The comparison reveals that the highest peak of the fluorescence curve in the spectrum has been blue-shifted by approximately 40 nm, indicating that a new substance, POSS-py, was obtained through the HECK coupling reaction. The fluorescence intensity shows that the fluorescence intensity for the analyte ion, POSS-py, is relatively strong. Figure 4 and Figure 8 The comparison fully demonstrates that Pyrene POSS possesses crucial stability.

[0034] This invention is not limited to the above embodiments. Based on the technical solutions disclosed in this invention, those skilled in the art can make some substitutions and modifications to some of the technical features without creative effort, and all such substitutions and modifications are within the protection scope of this invention.

Claims

1. A POSS derivative based on pyrene, characterized in that, The structural formula is as follows:

2. The method for synthesizing POSS derivatives based on pyrene according to claim 1, characterized in that, Includes the following steps: (a) Octadecyl POSS, palladium catalyst, and phosphine ligand were added to a mixed solvent of tetrahydrofuran and triethylamine, and deoxygenated by bubbling under an argon atmosphere; (b) 1-bromopyrene was added, and the reaction was carried out at 80±5℃ under argon protection for 48±2 hours; (c) The reaction solution was filtered to remove the palladium catalyst, and the filtrate was collected and precipitated by adding a methanol solution containing 5% HCl; (d) The precipitate was dissolved in dichloromethane and purified by column chromatography using petroleum ether:dichloromethane = 3:1 (v / v) as the eluent; (e) The purified product was extracted sequentially with methanol and n-hexane for 24 hours each to obtain a bright yellow powder.

3. The synthesis method according to claim 2, characterized in that: The palladium catalyst is palladium acetate, the phosphine ligand is triphenylphosphine, and the molar ratio of octavinylPOSS, palladium acetate, and triphenylphosphine is 1:0.4:0.

8.

4. The synthesis method according to claim 2, characterized in that: The volume ratio of tetrahydrofuran to triethylamine in the mixed solvent is 3:

1.

5. The application of the pyrene-based POSS derivative as a fluorescent probe in anion detection according to claim 1, characterized in that: The anions include F. - Cl - ClO4 - SO4 2- At least one of them.

6. The application according to claim 5, characterized in that: The detection is carried out in an organic solvent selected from tetrahydrofuran, dimethyl sulfoxide, dichloromethane, and N,N-dimethylformamide.

7. The application according to claim 6, characterized in that: In dichloromethane solvent, F - This causes an increase in fluorescence intensity, ClO4 - and SO4 2- It causes fluorescence quenching.

8. The application according to claim 6, characterized in that: In dimethyl sulfoxide solvent, Cl - ClO4 - and SO4 2- This causes a decrease in fluorescence intensity.

9. A method for detecting anions, characterized in that, Includes the following steps: (1) Dissolve the POSS derivative of claim 1 in an organic solvent to obtain a probe solution; (2) Add the anion solution to be tested to the probe solution; (3) Measure the changes in fluorescence emission spectrum and identify the types of anions based on the changes in characteristic peak intensity.

10. The detection method according to claim 9, characterized in that: In step (3), the anion type is distinguished by monitoring the change in the ratio of fluorescence peak intensity at 375 nm and 395 nm.

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