Compound with AIE characteristic and preparation method and application thereof
By preparing compounds with AIE characteristics and applying them to tryptophan detection, the problems of slow measurement speed and inconvenient operation in the prior art are solved, and a fast and accurate detection effect is achieved.
Patent Information
- Application Number
- CN202411235140.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-04
- Publication Date
- 2024-12-13
AI Technical Summary
In the prior art, tryptophan measurement speed is slow, inconvenient to operate, high detection cost, slow testing speed and high detection limit.
Using a preparation method of a compound with AIE characteristics, 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh3)4, K2CO3 at 1 ,4-dioxane and deionized water were reacted, and purified by heating and stirring, extraction, washing and silica gel column chromatography. Finally, the compound was obtained by dichloromethane and ethanol, and applied to tryptophan detection.
The compounds have transient response capabilities, which greatly shortens the tryptophan detection time, reduces the detection difficulty, and improves the detection efficiency and accuracy.
Smart Images
Figure CN119118774A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for preparing a compound with AIE characteristics, in particular to a compound with AIE characteristics and a preparation method and application thereof. Background Art
[0002] Tryptophan is an important amino acid required by the human body. It plays an important role in preventing pellagra, depression, improving sleep and regulating mood. Amino acids are widely used in the fields of food, medicine and feed additives. The analysis and determination of tryptophan is of great significance in the fields of biology, medicine and chemistry. At present, the methods for determining tryptophan mainly include spectrophotometry, fluorescence, high performance liquid chromatography, capillary electrophoresis, atomic absorption spectrometry and electrochemical method. However, the methods used in the prior art have technical problems, such as the need for specific instruments or trained personnel, inconvenient operation, high analysis cost, slow test speed and high detection limit. Summary of the invention
[0003] In order to overcome the technical problems of slow tryptophan measurement and inconvenient operation in the prior art, the present invention provides a compound with AIE properties and a preparation method and application thereof.
[0004] The technical solution adopted by the present invention to achieve the above-mentioned object is: a method for preparing a compound having AIE properties, comprising the following steps:
[0005] S1: Add 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh3)4, and K2CO3 into a reaction vessel containing 1,4-dioxane and deionized water;
[0006] S2: Under nitrogen protection, the mixed solution was heated and stirred until it reached 95°C, and the temperature was kept constant, and stirring was continued for 24 hours;
[0007] S3: After the stirring is completed, the mixed solution is cooled to room temperature;
[0008] S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine;
[0009] S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product;
[0010] S6: Dichloromethane is added dropwise to the crude product until the crude product is just dissolved, and then ethanol is added for recrystallization to obtain the compound.
[0011] Preferably, the molar ratio of 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh3)4, and K2CO3 in step S1 is: 250:50:17:1000.
[0012] A compound with AIE properties is prepared by the above method, and its structural formula is as follows:
[0013]
[0014] An application of a compound with AIE properties, wherein the compound with AIE properties is applied in tryptophan detection.
[0015] A method for preparing a compound having AIE properties comprises the following steps:
[0016] S1: Add 4-boronic acid biphenyl, 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh3)4, and K2CO3 into a reaction vessel containing 1,4-dioxane and deionized water;
[0017] S2: Under nitrogen protection, the mixed solution was heated and stirred until it reached 95°C, and the temperature was kept constant, and stirring was continued for 24 hours;
[0018] S3: After the stirring is completed, the mixed solution is cooled to room temperature;
[0019] S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine;
[0020] S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product;
[0021] S6: Dichloromethane is added dropwise to the crude product until the crude product is just dissolved, and then ethanol is added for recrystallization to obtain the compound.
[0022] Preferably, the molar ratio of 4-boronic acid biphenyl, 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh3)4, and K2CO3 in step S1 is: 250:50:17:1000.
[0023] A compound with AIE properties is prepared by the above method, and its structural formula is as follows:
[0024]
[0025] An application of a compound with AIE properties, wherein the compound with AIE properties is applied to tryptophan detection.
[0026] Compared with the prior art, the present invention has the following beneficial effects: the compound prepared by the present invention has an AIE effect, and the preparation process is relatively simple, the yield of the obtained compound is high, and the compound prepared by the present invention can respond instantaneously during the detection of tryptophan, which greatly shortens the time of tryptophan detection and reduces the difficulty of tryptophan detection. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 is the compound 1 of the embodiment of the present invention 1 HNMR spectrum.
[0028] Figure 2 It is the fluorescence spectrum diagram of Example Compound 1 of the present invention when different amino acids are added.
[0029] Figure 3 It is the fluorescence spectrum diagram of Example Compound 1 of the present invention when different amino acids of different concentrations are added.
[0030] Figure 4 This is a test chart of the anti-interference performance of Example Compound 1 of the present invention.
[0031] Figure 5 It is the Job's curve diagram of Example Compound 1 of the present invention.
[0032] Figure 6 is the compound 2 of Example 2 of the present invention 1 HNMR spectrum.
[0033] Figure 7 It is the fluorescence spectrum diagram of Example Compound 2 of the present invention when different amino acids are added.
[0034] Figure 8 It is the fluorescence spectrum diagram of Example Compound 2 of the present invention when different amino acids of different concentrations are added.
[0035] Fig. 9 This is a test chart of the anti-interference performance of Example Compound 2 of the present invention.
[0036] Fig.10 It is the Job's curve diagram of Example Compound 2 of the present invention. DETAILED DESCRIPTION
[0037] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited by the embodiments. If technicians in this field make some non-essential improvements and adjustments to the present invention based on the above-mentioned contents of the present invention, they still fall within the protection scope of the present invention.
[0038] Example
[0039] A method for preparing a compound having AIE properties comprises the following steps:
[0040] S1: Add 5mmol of 4-boronic acid biphenyl, 1mmol of 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, 0.34mmol of Pd(PPh3)4, and 20mmol of K2CO3 into a double-necked bottle containing 150mL of 1,4-dioxane and 30mL of deionized water. 1,4-dioxane can completely dissolve 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, and Pd(PPh3)4, and deionized water can completely dissolve K2CO3;
[0041] S2: Under nitrogen protection, the mixed solution was heated in an oil bath and stirred with a magnetic stirrer. After heating to 95°C, the temperature was kept constant and stirring was continued for 24 hours.
[0042] S3: After the stirring is completed, the mixed solution is cooled to room temperature;
[0043] S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine;
[0044] S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product, wherein the volume ratio between petroleum ether and dichloromethane is 7:1;
[0045] S6: dichloromethane was added dropwise to the crude product until the crude product was just dissolved, and then ethanol was added for recrystallization to obtain compound 1. The mass of compound 1 obtained was 0.43 g, and the yield was 52.6%;
[0046] Among them, the preparation of 9,10-bis(dibromomethylene)-9,10-dihydroanthracene can be done by adding carbon tetrabromide and triphenylphosphine into a two-necked bottle containing toluene, turning on magnetic stirring under nitrogen protection, and fully reacting at room temperature for 1 hour, then adding anthraquinone into the two-necked bottle, heating to 80°C in an oil bath, and fully reacting for 24 hours. After the reaction mixture is cooled to room temperature, it is extracted with dichloromethane and water, washed with saturated brine, and then purified by silica gel column chromatography. Dichloromethane is added dropwise to the crude product until the crude product is just dissolved, and then ethanol is added for recrystallization.
[0047] The reaction principle of preparing compound 1 by the above method is as follows:
[0048]
[0049] Compound 1 prepared by the above method 1 H NMR spectrum Figure 1 As shown, its structural formula is:
[0050]
[0051] Compound 1 was dissolved in tetrahydrofuran (THF) to prepare a solution, THF was used as a good solvent and water was used as a poor solvent. The activity of compound 1 in its solution (10 -4 mol / L). The excitation wavelength of the fluorescence spectrum was set to 300nm, the slit width was set to 10:10, and the voltage was set to 500V. By changing the volume fraction of water (0%-90%), the results showed that the fluorescence intensity of compound 1 in pure THF solution was 49.25. When the water content increased to 70%, the fluorescence quantum yield was 14.64%, and the fluorescence intensity reached a maximum value of 7444, which was 151.15 times higher than that of pure THF solution. Correspondingly, the emission wavelength blue-shifted from 444.4nm to 402.8nm, indicating that it has AIE characteristics.
[0052] Compound 1 was applied to the detection of tryptophan, such as Figure 2 As shown, when 100 μM of 12 kinds of amino acids were added to compound 1, only when 100 μM Trp was added, the fluorescence intensity of compound 1 underwent a blue shift and a drastic change. When other equal amounts of amino acids were added under the same conditions, the fluorescence intensity only changed slightly and remained basically unchanged compared to when no amino acids were added, which indicates that the compound specifically recognizes tryptophan.
[0053] like Figure 3 As shown, 0-100 μM of 12 kinds of amino acids were added to compound 1. It can be seen that with the increase of Trp concentration, the fluorescence intensity of compound 1 increased dramatically. In the process of gradually increasing the concentration of other amino acids, the fluorescence intensity of compound 1 hardly changed.
[0054] like Figure 4 As shown, an interference experiment was conducted on compound 1. After tryptophan was added to compound 1, other amino acids and tryptophan were added alternately, and the corresponding fluorescence intensity was measured. The results are shown in FIG. Figure 4 As shown, after adding tryptophan, the fluorescence intensity increased significantly, but other amino acids had little effect on the fluorescence intensity, indicating that compound 1 was not interfered by other amino acids when detecting tryptophan and could specifically recognize tryptophan.
[0055] like Figure 5 As shown, Job's curve analysis was performed on compound 1 by controlling the total concentration of compound 1 and Trp to 100 μM and then changing the ratio of compound 1 to Trp. Figure 7 Through linear fitting, it can be observed that the fluorescence intensity of the combination of the two is the highest at about 0.5, indicating that the best effect is achieved when compound 1 and Trp combine in a 1:1 ratio.
[0056] Example
[0057] A method for preparing a compound having AIE properties comprises the following steps:
[0058] S1: Add 5 mmol of 4-boronic acid biphenyl, 1 mmol of 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene, 0.34 mmol of Pd(PPh3)4, and 20 mmol of K2CO3 into a two-necked bottle containing 150 mL of 1,4-dioxane and 30 mL of deionized water;
[0059] S2: Under nitrogen protection, the mixed solution was heated in an oil bath and stirred with a magnetic stirrer. After heating to 95°C, the temperature was kept constant and stirring was continued for 24 hours.
[0060] S3: After the stirring is completed, the mixed solution is cooled to room temperature;
[0061] S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine;
[0062] S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product, wherein the volume ratio between petroleum ether and dichloromethane is 7:1;
[0063] S6: Dichloromethane was added dropwise to the crude product until the crude product was just dissolved, and then ethanol was added for recrystallization to obtain compound 2. The mass of compound 2 obtained was 0.37 g, and the yield was 45.1%;
[0064] Among them, 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene can be added to a two-necked bottle containing toluene using carbon tetrabromide and triphenylphosphine, and magnetic stirring is turned on under nitrogen protection, and the reaction is fully reacted at room temperature for 1 hour. Then 2-methylanthraquinone is added to the two-necked bottle, and the oil bath is heated to 80°C, and the reaction is fully reacted for 24 hours. After the reaction mixture is cooled to room temperature, it is extracted with dichloromethane and water, and washed with saturated brine, and then the crude product is purified by silica gel column chromatography, and dichloromethane is added dropwise to the crude product until the crude product is just dissolved, and then ethanol is added for recrystallization.
[0065] The reaction principle of preparing compound 2 by the above method is as follows:
[0066]
[0067] Compound 2 prepared by the above method 1 H NMR spectrum Figure 6 As shown, its structural formula is:
[0068]
[0069] Compound 2 was dissolved in tetrahydrofuran (THF) to prepare a solution, THF was used as a good solvent and water was used as a poor solvent. The concentration of compound 2 in its solution (10 -4 mol / L). The excitation wavelength of the fluorescence spectrum was set to 300nm, the slit width was set to 10:10, and the voltage was set to 500V. The change in the fluorescence intensity of the solution was observed under ultraviolet light by changing the volume fraction of water (0%-90%). The results showed that the fluorescence intensity in pure THF solution was 81.88. When the water content increased to 80%, the fluorescence quantum yield was 6.8%, and the fluorescence intensity reached a maximum value of 5970, which was 72.91 times higher than that of pure THF solution. Correspondingly, the emission wavelength blue-shifted from 412.8nm to 403.2nm, indicating that it has AIE characteristics.
[0070] Compound 2 was applied to the detection of tryptophan, such as Figure 7 As shown, when 100 μM of 12 kinds of amino acids were added to compound 2, only when 100 μM Trp was added, the fluorescence intensity of compound 2 underwent a blue shift and a drastic change. When other equal amounts of amino acids were added under the same conditions, the fluorescence intensity only changed slightly and remained basically unchanged compared to when no amino acids were added, which indicates that compound 2 specifically recognizes tryptophan.
[0071] like Figure 8 As shown, 0-100 μM of 12 kinds of amino acids were added to compound 2. It can be seen that with the increase of Trp concentration, the fluorescence intensity of compound 2 increased dramatically. In the process of gradually increasing the concentration of other amino acids, the fluorescence intensity of compound 2 hardly changed.
[0072] like Fig. 9 As shown, an interference experiment was conducted on compound 2. After tryptophan was added to compound 2, other amino acids and tryptophan were added alternately, and the corresponding fluorescence intensity was measured. The results are shown in FIG. Figure 4 As shown, after adding tryptophan, the fluorescence intensity increased significantly, but other amino acids had little effect on the fluorescence intensity, indicating that compound 2 was not interfered by other amino acids when detecting tryptophan and could specifically recognize tryptophan.
[0073] like Fig.10 As shown, Job's curve analysis was performed on compound 2. By controlling the total concentration of compound 2 and Trp to 100 μM, and then changing the ratio of compound 2 to Trp, Figure 7 Through linear fitting, it can be observed that the fluorescence intensity of the combination of the two is the highest at about 0.5, indicating that the best effect is achieved when compound 2 and Trp are combined in a 1:1 ratio.
[0074] The present invention is described by way of embodiments, and those skilled in the art will appreciate that various changes or equivalent substitutions may be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application belong to the protection scope of the present invention.
Claims
1. A method for preparing a compound having AIE properties, It is characterized in that The following steps are involved: S1: 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh 3 ) 4 , K 2 CO 3 Add to a reaction vessel containing 1,4-dioxane and deionized water; S2: Under nitrogen protection, the mixed solution was heated and stirred until it reached 95°C, and the temperature was kept constant, and stirring was continued for 24 hours; S3: After the stirring is completed, the mixed solution is cooled to room temperature; S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine; S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product; S6: Add dichloromethane dropwise to the crude product until the crude product is just dissolved, and then add ethanol for recrystallization to obtain the compound.
2. A method for preparing a compound having AIE properties according to claim 1, It is characterized in that The 4-boronic acid biphenyl, 9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh 3 ) 4 , K 2 CO 3 The molar ratio is: 250:50:17:1000.
3. A compound having AIE properties, It is characterized in that Prepared by the method described in any one of claims 1-2, its structural formula is as follows:
4. Application of a compound having AIE properties, It is characterized in that The compound with AIE properties as claimed in claim 3 is applied to tryptophan detection.
5. A method for preparing a compound having AIE properties, It is characterized in that The following steps are involved: S1: 4-boronic acid biphenyl, 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh 3 ) 4 , K 2 CO 3 Add to a reaction vessel containing 1,4-dioxane and deionized water; S2: Under nitrogen protection, the mixed solution was heated and stirred until it reached 95°C, and the temperature was kept constant, and stirring was continued for 24 hours; S3: After the stirring is completed, the mixed solution is cooled to room temperature; S4: extracting the mixed solution with dichloromethane and water, and washing with saturated brine; S5: using a petroleum ether / dichloromethane mixed solvent as an eluent, purifying the washed organic phase by silica gel column chromatography to obtain a crude product; S6: Dichloromethane is added dropwise to the crude product until the crude product is just dissolved, and then ethanol is added for recrystallization to obtain the compound.
6. A method for preparing a compound having AIE properties according to claim 1, It is characterized in that The 4-boronic acid biphenyl, 2-methyl-9,10-bis(dibromomethylene)-9,10-dihydroanthracene, Pd(PPh 3 ) 4 , K 2 CO 3 The molar ratio is: 250:50:17:1000.
7. A compound having AIE properties, It is characterized in that Prepared by the method described in any one of claims 5-6, its structural formula is as follows:
8. Application of a compound having AIE properties, It is characterized in that The compound having AIE properties according to claim 7 is applied to tryptophan detection.