Polypyridine-modified phenoxazine derivative fluorescent probe and synthesis method and application thereof
By modifying phenazine derivatives with polypyridine groups, a polypyridine-modified phenazine derivative fluorescent probe was developed, which solved the compatibility problem of detection in multiple polar environments in the prior art and realized rapid response and highly visualized detection in multiple polar environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHAANXI NORMAL UNIV
- Filing Date
- 2024-02-02
- Publication Date
- 2026-07-24
AI Technical Summary
Most existing fluorescent molecular probes can only detect one polarity change, making it difficult to be compatible with the response behavior of multiple polarity environments. They lack universality and cannot achieve accurate detection of fluctuations in multiple polarity environments.
A fluorescent probe based on a phenazine derivative modified with multiple pyridines was designed. By modifying the two ends of the phenazine derivative with multiple pyridine groups, its water solubility and environmental sensitivity were enhanced. Tunable multiple fluorescent groups were introduced to achieve the detection of various polar environments.
This fluorescent probe can rapidly respond to changes in various polar environments, has good chemical stability and visualization effects, is suitable for detection in various polar environments, is simple to operate, and is suitable for large-scale production.
Smart Images
Figure CN118027002B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polar environment detection technology, specifically relating to a fluorescent probe based on polypyridine-modified phenazine derivatives, its synthesis method, and its application. Background Technology
[0002] From both the perspective of everyday chemical reactions and actual production, environmental polarity is one of the most important environmental parameters. For example, organic solvents are indispensable in the materials, pharmaceutical, and chemical industries, participating in the synthesis, purification, and analysis of compounds and materials; even trace amounts of water in organic solvents can lead to the quenching of reaction intermediates; water contamination of fuel can affect machine performance, causing damage and malfunctions; different types of gasoline have different compositions, resulting in varying anti-knock properties. Therefore, accurately detecting environmental polarity plays a crucial role in chemical reactions, everyday applications, and industrial production.
[0003] Currently, although various detection methods such as electrochemical analysis, chromatographic analysis, and spectroscopic analysis have been developed for the detection of polar environments, ideal methods that can accurately detect polar fluctuations are still rare. Among the many methods for detecting polar environments, fluorescence sensors based on organic fluorescent small molecules are widely used due to their advantages such as good selectivity, high sensitivity, real-time online detection, and visualization capabilities.
[0004] However, most existing fluorescent molecules can only detect one type of change, and ensuring compatibility and diversity of various response behaviors remains a significant challenge. Therefore, it is particularly important to develop a fluorescent probe with strong universality to detect fluctuations in multiple polar environments. Summary of the Invention
[0005] The purpose of this invention is to provide a fluorescent probe based on a polypyridine-modified phenazine derivative. This fluorescent probe has a fast response speed, high visualization, and wide testing range, and can be widely used in the detection of fluctuations in various polar environments.
[0006] The structural formula of the phenazine derivative fluorescent probe based on polypyridine modification provided by this invention is as follows:
[0007]
[0008] The method for synthesizing the polypyridine-modified phenazine derivative fluorescent probe of the present invention includes the following steps:
[0009] Step 1: Under a nitrogen atmosphere, N,N-disubstituted-dihydrodibenzo[a,c]phenazine and N-bromosuccinimide were added to tetrahydrofuran and reacted with stirring at 35–45 °C for 24–48 h. After separation and purification, the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative shown in Formula II was obtained. The reaction equation is shown below:
[0010]
[0011] Step 2: Under a nitrogen atmosphere, the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative, 4-([2,2':6',2”-terpyridin-4'-yl)phenylboronic acid, potassium carbonate, and tetrakis(triphenylphosphine)palladium were added to a mixed solvent of tetrahydrofuran and water. The mixture was stirred at 75–85 °C for 24–48 h, and then purified to obtain the fluorescent probe based on polypyridine-modified phenazine derivatives as shown in Formula I. The reaction equation is shown below:
[0012]
[0013] In step 1 above, the preferred molar ratio of N,N-disubstituted-dihydrodibenzo[a,c]phenazine to N-bromosuccinimide is 1:2 to 3.
[0014] In step 2 above, the preferred molar ratio of the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative, 4-([2,2':6',2”-terpyridin-4'-yl)phenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium is 1:2~3:3~5:0.2~0.3.
[0015] Furthermore, in step 2 above, the volume ratio of tetrahydrofuran to water in the mixed solvent is 1 to 3:1.
[0016] The present invention provides a fluorescent probe based on polypyridine-modified phenazine derivatives that can be used to distinguish and detect different organic solvents, wherein the organic solvents are any one or more of n-hexane, toluene, 1,4-dioxane, tetrahydrofuran, methanol, ethylene glycol, and dimethyl sulfoxide.
[0017] The present invention, based on a polypyridine-modified phenazine derivative fluorescent probe, can also be used to detect trace amounts of water in 1,4-dioxane.
[0018] The present invention utilizes a phenazine derivative fluorescent probe modified with polypyridine to further distinguish and detect different types of gasoline.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0020] 1. The fluorescent probe of this invention uses N,N′-disubstituted-dihydrodibenzo[a,c]phenazine with tunable multiple fluorescence as one of its fluorescent groups and backbones, and modifies both ends of it with 4-([2,2':6',2”-terpyridine]-4'-yl)phenyl containing multiple pyridine groups to increase its water solubility and environmental sensitivity, thus preparing a polypyridine-modified phenazine derivative with polar sensitivity. The fluorescent group and structure introduced by this derivative endow the probe molecule with the possibility of detecting multiple polar environments. It has both polar sensitivity and good fluorescence visual effect, and can respond to and distinguish changes in the polarity of multiple environments. It has the advantages of good chemical stability, fast response speed, high visualization degree, and the ability to detect fluctuations in multiple polar environments.
[0021] 2. The synthesis method of the fluorescent probe of this invention is simple to operate, requires minimal equipment, and is suitable for large-scale production. The fluorescent probe of this invention can be used to detect different organic solvents, trace or ultra-trace amounts of water within organic solvents, and different types of gasoline, providing excellent visualization. Attached Figure Description
[0022] Figure 1 This is a graph showing the fluorescence intensity changes of seven different organic solvents detected by the phenazine derivative fluorescent probe based on polypyridine modified by Example 1.
[0023] Figure 2 This is a fluorescence image of the phenazine derivative fluorescent probe based on polypyridine modified with 365nm handheld UV lamp excitation when detecting seven different organic solvents. (Example 1)
[0024] Figure 3 This is a differentiation diagram drawn from the fluorescence photographs of the red, yellow and blue primary colors extracted when the phenazine derivative fluorescent probe based on polypyridine modified with fluorescent probe synthesized in Example 1 detected seven different organic solvents.
[0025] Figure 4 This is a graph showing the fluorescence intensity changes of 1,4-dioxane with different water contents detected by a phenazine derivative fluorescent probe based on polypyridine modified with polypyridine synthesized in Example 1.
[0026] Figure 5 This is an example of a fluorescent probe based on a polypyridine-modified phenazine derivative synthesized in Example 1 used to detect water content in 1,4-dioxane at different water contents. 595 / I0 value relationship curve.
[0027] Figure 6 This is a fluorescence image of the phenazine derivative fluorescent probe based on polypyridine modified by Example 1, used to detect different water contents in 1,4-dioxane under a 365nm handheld UV lamp excitation.
[0028] Figure 7 The images show the intrinsic fluorescence of gasoline under visible light (a), under excitation by a 365nm handheld UV lamp (b), and under excitation by a 365nm handheld UV lamp when different types of gasoline are detected by the phenazine derivative fluorescent probe based on polypyridine modified by Example 1. The images also show the fluorescence of gasoline with the fluorescent probe added under excitation by a 365nm handheld UV lamp (c).
[0029] Figure 8 This is a graph showing the fluorescence intensity changes of different types of gasoline detected by a phenazine derivative fluorescent probe based on polypyridine modified with polypyridine, synthesized in Example 1. Detailed Implementation
[0030] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments. These descriptions are intended to explain the invention and not to limit it.
[0031] Example 1
[0032] Step 1:
[0033] Under a nitrogen atmosphere, 100 mg (0.23 mmol) of N,N-disubstituted-dihydrodibenzo[a,c]phenazine and 113 mg (0.46 mmol) of N-bromosuccinimide were weighed and added to a 50 mL single-necked flask. 10 mL of tetrahydrofuran was added to dissolve the mixture completely. The mixture was then stirred at 40 °C for 36 h to obtain a dark brown reaction solution. After cooling the reaction solution to room temperature, tetrahydrofuran was removed by vacuum distillation to obtain a dark brown oily compound. The oily compound was extracted with water and dichloromethane. The resulting brownish-black organic phase was dried over anhydrous Na₂SO₄ for 2 h, and dichloromethane was removed by vacuum distillation. Finally, the compound was purified by column chromatography on a silica column using a 5:1 volume ratio of dichloromethane to n-hexane as the eluent to obtain the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative of formula II. The reaction equation is as follows:
[0034]
[0035] Step 2: Under a nitrogen atmosphere, 50 mg (0.085 mmol) of dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative, 75 mg (0.211 mmol) of 4-([2,2':6',2”-terpyridin-4'-yl)phenylboronic acid, 27 mg (0.338 mmol) of potassium carbonate, and 23 mg (0.021 mmol) of tetrakis(triphenylphosphine)palladium were added to 12 mL of a mixed solvent of tetrahydrofuran and water in a volume ratio of 2:1. The mixture was stirred at 80 °C. The reaction was stirred for 48 h. After the reaction was complete, tetrahydrofuran was removed under reduced pressure. Then, the organic phase was extracted with saturated sodium bicarbonate aqueous solution and dichloromethane. The extracted organic phase was dried with anhydrous Na2SO4 for 2 h, and dichloromethane was removed by distillation under reduced pressure. Then, column chromatography was performed on an alumina column using a mixed solvent of n-hexane and ethyl acetate in a volume ratio of 1:5 as the eluent. The crude product was recrystallized from methanol and dichloromethane to obtain the phenazine derivative fluorescent probe based on polypyridine modified with formula I. The reaction equation is as follows:
[0036]
[0037] The above-mentioned NMR and mass spectrometry data of the polypyridine-modified azine derivative fluorescent probes are as follows: 1 H NMR(600MHz,CD2Cl2)δ8.75 2H),8.66(4H),8.61-8.58(4H),8.57(4H),8.09(2H),7.80(10H),7.68-7.62(2H),7.59-7.53(6H),7.37(6H),7.26(4H),7.14-7.01(4H); 13 C NMR (151MHz, CD2Cl2) δ156.04,155.88,149.54,149.05,147.17,144.51,141.06,137.89,136.82,136.49,132.74,130.04,129.83,129. 15,127.46,127.44,127.36,127.08,126.82,126.76,125.69,124.48,123.81,123.19,121.06,118.35,116.76,99.99; APCI-MS(m / z)(C 74 H 48 N8)[M+H] + Theoretical value: 1049.4075, measured value: 1049.4066.
[0038] Example 2
[0039] The phenazine derivative fluorescent probe based on polypyridine modified with polypyridine synthesized in Example 1 is used for the differentiation of organic solvents and visual sensing. Its usage method is as follows:
[0040] (1) Prepare the solution
[0041] A polypyridine-modified azine derivative fluorescent probe was weighed into a sample vial, and 1,4-dioxane was added. The sample was then sonicated for 10 min to obtain a sample size of 2.5 × 10⁻⁶. -3 M's fluorescent probe stock solution.
[0042] (2) Draw standard atlases
[0043] Measure 2.5 mL each of n-hexane, toluene, 1,4-dioxane, tetrahydrofuran, methanol, ethylene glycol, and dimethyl sulfoxide into a cuvette, and add 10 μL of 2.5 × 10⁻⁶ mL of each. -3 The stock solution of fluorescent probe M was mixed thoroughly using capillary stirring. Fluorescence spectroscopy measurements were performed on a single-photon fluorescence spectrometer (FS5, Edinburgh) with a 150W xenon lamp as the light source. The excitation wavelength for all samples was 350 nm, and the excitation and emission slits were 2.0 nm and 1.0 nm, respectively. After the mixed solution reached equilibrium, fluorescence spectra showing the changes in fluorescence intensity of the fluorescent probe in different organic solvents were obtained, as shown in [the figure]. Figure 1 As shown in the figure, the fluorescence intensity of the fluorescent probe with a concentration of 10 μmol / L changes significantly with different organic solvents in the system, indicating that the fluorescent probe is highly sensitive to changes in different organic solvents and has the ability to distinguish between them.
[0044] Measure 2.5 mL each of n-hexane, toluene, 1,4-dioxane, tetrahydrofuran, methanol, ethylene glycol, and dimethyl sulfoxide into cuvettes, and add 10 μL of 2.5 × 10⁻⁶ ppm of methyl sulfoxide. -3 The fluorescent probe stock solution of M was mixed thoroughly using capillary stirring. Visual fluorescence images were obtained by exciting the mixture at 365 nm. (See [link]). Figure 2 Furthermore, by using the RGB values of the fluorescence image as signal units, a three-signal fingerprint spectrum of the fluorescent probe for seven organic solvents can be obtained, see [link to relevant documentation]. Figure 3 It has the ability to distinguish and identify.
[0045] Example 3
[0046] The fluorescent probe based on a polypyridine-modified phenazine derivative synthesized in Example 1 was used for the detection of trace amounts of water in 1,4-dioxane. Its application method is as follows:
[0047] (1) Prepare the solution
[0048] A polypyridine-modified azine derivative fluorescent probe was weighed into a sample vial, and 1,4-dioxane was added. The sample was then sonicated for 10 min to obtain a sample size of 2.5 × 10⁻⁶.-3 M's fluorescent probe stock solution.
[0049] Add 5 μL, 10 μL, 25 μL, 50 μL, 75 μL, 100 μL, 125 μL, 150 μL, 200 μL, 250 μL, 300 μL, 400 μL, 500 μL, 600 μL, 800 μL, 1 mL, 1.25 mL, and 2.5 mL of deionized water to 25 mL volumetric flasks, respectively. Then, add 1,4-dioxane to the flasks and bring the volume to a final volume. After sonicating the solutions for 10 min, a series of 1,4-dioxane solutions with water content ranging from 0.1% to 10% were obtained.
[0050] (2) Draw the standard curve
[0051] Take 2.5 mL of a series of 1,4-dioxane solutions with water content ranging from 0.1% to 10%, and add 10 μL of 2.5 × 10⁻⁶ solution. -3 The fluorescent probe stock solution of M was mixed thoroughly with capillary stirring. Fluorescence spectroscopy measurements were performed on a single-photon fluorescence spectrometer (FS5, Edinburgh) using a 150W xenon lamp as the light source. The excitation wavelength for all samples was 350 nm, and the excitation and emission slits were 2.0 nm and 1.0 nm, respectively. After the mixed solution reached equilibrium, fluorescence spectra of a series of 1,4-dioxane solutions with water contents ranging from 0.1% to 10% were plotted as a function of water content. (See figure). Figure 4 The fluorescence intensity at 595 nm was collected, and I was plotted. 595 The standard curve of / I0 value versus water content is shown below. Figure 5 .
[0052] Depend on Figure 5 As can be seen, the fluorescence intensity at 595 nm varies significantly with the water content of 1,4-dioxane in the range of 0.1%–10%, which is helpful for the detection of trace amounts of water in 1,4-dioxane. Figure 5 As can be seen from the illustration, there is a good linear relationship in the water content range of 0.1% to 1%, and the linear equation is:
[0053] Y = 0.523X + 0.9660
[0054] In the formula, Y represents I when the water content is in the range of 0.1% to 1%. 595 / I0 value, X is the water content in the 1,4-dioxane solution, correlation coefficient R 2 It is 0.993.
[0055] 10 μL of 2.5 × 10⁻⁶ microliters of liquid was added to the product after excitation with a 365 nm UV lamp. -3 Solutions of 1,4-dioxane with different water contents in the fluorescent probe stock solution of M can be obtained Figure 6The photographs show obvious visual differences within a water content range of 1%, demonstrating that the fluorescent probe of this invention can be well applied to the detection of trace amounts of water in 1,4-dioxane.
[0056] Example 4
[0057] The fluorescent probe based on polypyridine-modified phenazine derivative synthesized in Example 1 was used to distinguish and detect different types of gasoline. Its usage is as follows:
[0058] (1) Prepare the solution
[0059] A polypyridine-modified azine derivative fluorescent probe was weighed into a sample vial, and 1,4-dioxane was added. The sample was then sonicated for 10 min to obtain a sample size of 2.5 × 10⁻⁶. -3 M's fluorescent probe stock solution.
[0060] (2) Plotting the standard curve and obtaining fluorescence images
[0061] Measure 2.5 mL of gasoline into a cuvette. Under visible light or a 365 nm ultraviolet lamp, 92#, 95#, and 98# gasoline show similar colors. Figure 7 (a) and 7(b). Then 10 μL of 2.5 × 10⁻⁶ solution was added. -3 The fluorescent probe stock solution of M (final concentration 10 μM) showed completely different fluorescence colors in gasoline samples under a 365 nm UV lamp, see [reference needed]. Figure 7 (c) 92#, 95#, and 98# gasoline emitted blue, purple, and pink fluorescence, respectively, effectively distinguishing the different types of gasoline. Fluorescence spectroscopy tests were performed on a single-photon fluorescence spectrometer (FS5, Edinburgh) using a 150W xenon lamp as the light source. The excitation wavelength for all samples was 350 nm, and the excitation and emission slits were 2.0 and 1.0 nm, respectively. After the tests were completed, fluorescence spectra of different gasoline grades were plotted, as shown in the figure. Figure 8 The fluorescence intensity of the fluorescent probe with a concentration of 10 μmol / L varies significantly with different gasoline types, indicating that the fluorescent probe of this invention has the ability to distinguish between different types of petroleum.
Claims
1. A fluorescent probe based on a polypyridine-modified phenazine derivative, characterized in that, The structural formula of the fluorescent probe is as follows: 。 2. A method for synthesizing a fluorescent probe based on a polypyridine-modified phenazine derivative as described in claim 1, characterized in that, Includes the following steps: Step 1: Under a nitrogen atmosphere, N,N-diphenyldihydrodibenzo[a,c]phenazine and N-bromosuccinimide were added to tetrahydrofuran and stirred at 35-45°C for 24-48 h. After separation and purification, the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative with the following structural formula was obtained. Step 2: Under a nitrogen atmosphere, the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative, 4-([2,2':6',2''-terpyridine]-4'-yl)phenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium were added to a mixed solvent of tetrahydrofuran and water. The mixture was stirred at 75–85 °C for 24–48 h, and then purified to obtain a fluorescent probe based on polypyridine-modified phenazine derivative.
3. The method for synthesizing a phenazine derivative fluorescent probe based on polypyridine modification according to claim 2, characterized in that, In step 1, the molar ratio of N,N-diphenyldihydrodibenzo[a,c]phenazine to N-bromosuccinimide is 1:2 to 3.
4. The method for synthesizing a phenazine derivative fluorescent probe based on polypyridine modification according to claim 2, characterized in that, In step 2, the molar ratio of the dibromo-modified N,N-disubstituted-dihydrodibenzo[a,c]phenazine derivative, 4-([2,2':6',2''-terpyridine]-4'-yl)phenylboronic acid, potassium carbonate, and tetra(triphenylphosphine)palladium is 1: 2-3: 3-5: 0.2-0.
3.
5. The method for synthesizing a phenazine derivative fluorescent probe based on polypyridine modification according to claim 2, characterized in that, In step 2, the volume ratio of tetrahydrofuran to water in the mixed solvent is 1 to 3:
1.
6. The use of the phenazine derivative fluorescent probe based on polypyridine modification according to claim 1 in distinguishing and detecting different organic solvents, wherein the organic solvent is any one or more of n-hexane, toluene, 1,4-dioxane, tetrahydrofuran, methanol, ethylene glycol, and dimethyl sulfoxide.
7. The use of the polypyridine-modified phenazine derivative fluorescent probe of claim 1 in the detection of trace amounts of water in 1,4-dioxane.
8. The use of the phenazine derivative fluorescent probe based on polypyridine modification as described in claim 1 in distinguishing and detecting different types of gasoline.