A triphenylamine fluorescent derivative, fluorescent probe and supramolecular organometallic gel and preparation method and application thereof

Abstract

The present invention relates to the field of fluorescent probe technology, and specifically discloses a triphenylamine fluorescent derivative, a fluorescent probe and a supramolecular organometallic gel, as well as a preparation method and application. The structure of the triphenylamine fluorescent derivative is shown below. The triphenylamine fluorescent derivative provided by the present invention is insensitive to water and oxygen in the air, exhibits excellent thermodynamic stability and outstanding photochemical stability, and has good solubility. The fluorescent probe based on the triphenylamine fluorescent derivative can realize highly sensitive and highly selective detection and identification of gas / liquid phase CO and CO fluorescence imaging in cells. The supramolecular organometallic gel prepared based on the triphenylamine fluorescent derivative can realize rapid visual sensing detection and efficient removal of CO in the air, solving the problems of single detection mode, difficult visual detection and inability to simultaneously realize detection and removal in previous methods, and provides new ideas for the design of CO fluorescent probes with excellent performance.

Description

Technical Field

[0001] The invention relates to the technical field of fluorescent probes, and in particular to a triphenylamine fluorescent derivative, a fluorescent probe and a supramolecular organic metal gel, and a preparation method and application thereof. Background Art

[0002] Carbon monoxide (CO) is a product of incomplete combustion of carbon-containing fossil fuels such as coal and oil, as well as emissions from internal combustion engines. It is a colorless, odorless, non-irritating toxic gas. Poor water solubility and chemical inertness allow it to stay in the air for a long time, so it is called a silent killer. Because its binding ability is much stronger than that of oxygen molecules, CO will quickly bind to hemoglobin after entering the human body, causing tissue hypoxia and even suffocation and death. The World Health Organization has proven that CO content in the air above 100ppm will pose a threat to human health. At the same time, studies in recent years have shown that as an important neurotransmitter in living organisms, CO can participate in many life processes such as respiratory regulation, body temperature regulation, and cardiovascular regulation in organisms, and plays a very important role in many physiological and pathological processes. It can be seen that the development and development of quantitative analysis and detection technology that can achieve high-performance CO detection and identification has very important practical significance for environmental quality monitoring, safety supervision, and clinical medicine.

[0003] So far, people have developed a variety of detection technologies or methods. Gas chromatography, high performance liquid chromatography, X-ray diffraction, electrochemistry, infrared spectroscopy, Raman spectroscopy, chemiluminescence, capillary electrophoresis, etc. have been reported, but the above methods often need to be carried out on large instruments and equipment, and the operation process is cumbersome, which increases energy consumption and brings certain difficulties to in-situ online real-time detection. Fluorescent probes are increasingly valued because of their unique advantages such as high sensitivity, strong selectivity, simple synthesis, low dependence on equipment, easy operation, and the ability to achieve in-situ online detection at room temperature.

[0004] Currently, the fluorescent probes reported for detecting CO can be divided into three categories: Pd(0)-mediated Tsuji-Trost reaction, nitro reduction, and metal coordination reaction. However, these reported CO probes are mainly based on one detection mode of fluorescence intensity change or wavelength change, and probes that can perform multi-mode detection simultaneously are rarely reported. In addition, the reported fluorescent probes for detecting CO still have certain shortcomings, such as poor selectivity, slow response speed, quenching detection, and inability to achieve visual detection, which greatly limits their practical application. Summary of the invention

[0005] Aiming at the problems of poor selectivity, slow response speed, inability to realize visual detection and single detection mode of existing fluorescent probes for CO detection, the present invention provides a triphenylamine fluorescent derivative, a fluorescent probe and a supramolecular organometallic gel as well as a preparation method and application thereof.

[0006] In order to solve the above technical problems, the technical solution provided by the present invention is:

[0007] In a first aspect, the present invention provides a triphenylamine fluorescent derivative, the structure of which is shown in formula (I):

[0008]

[0009] Among them, n=2~10.

[0010] Compared with the prior art, the present invention combines the triphenylamine luminescent group with excellent luminescent properties with the N-benzyl tertiary amine group to obtain a series of N-benzyl tertiary amine-modified triphenylamine luminescent derivatives, which have excellent solubility, excellent photophysical properties and photochemical stability, and can quickly and sensitively identify and quantitatively detect carbon monoxide in a variety of media, and have the advantages of high sensitivity, strong specificity, and rapid response. The triphenylamine luminescent derivative modified with N-benzyl tertiary amine described in the present invention belongs to a photoluminescent material, which can realize dual-mode, visualized high-performance detection and identification of carbon monoxide without the aid of other instruments, providing a material basis for in-situ online real-time detection of carbon monoxide, and has broad application prospects in the field of carbon monoxide detection and identification.

[0011] In a second aspect, the present invention further provides a method for preparing the above triphenylamine fluorescent derivative, comprising the following steps:

[0012] Step a, in an organic solvent under an inert atmosphere, subjecting the TPA-OH compound represented by formula (II) and the compound 1 represented by formula (III) to an Ullmann coupling reaction under the action of a first acid binding agent to obtain a TPA-A compound represented by formula (IV);

[0013]

[0014] Step b, in an alcohol-water mixed solvent, the TPA-A compound and a strong base undergo a hydrolysis reaction, followed by acidification to obtain a TPA-B compound represented by formula (V);

[0015]

[0016] Step c, in a polar solvent, subjecting the TPA-B compound, 1-hydroxybenzotriazole (HOBT), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) and the compound 2 represented by formula (VI) to an amide condensation reaction under the action of an acid binding agent to obtain a triphenylamine derivative represented by formula (I);

[0017]

[0018]

[0019] Among them, n=2~10.

[0020] The synthesis method of the triphenylamine fluorescent derivative provided by the invention has a simple route, mild reaction conditions, strong adaptability to substrates, high product purity, and can be produced on a large scale, thus providing a material basis for subsequent carbon monoxide detection applications.

[0021] Specifically, the preparation method of the triphenylamine fluorescent derivative comprises the following steps:

[0022] Step a, in an organic solvent under an inert atmosphere, reacting the TPA-OH compound represented by formula (II), the compound 1 represented by formula (III) and the first acid-binding agent at 81° C. to 85° C. for 24 h to 28 h, naturally cooling the reaction solution to room temperature, filtering with suction, concentrating the filtrate, and separating by column chromatography to obtain the TPA-A compound represented by formula (IV);

[0023]

[0024] Step b, in an alcohol-water mixed solvent, the TPA-A compound and a strong base are mixed evenly, reacted at 80° C. to 85° C. for 4 h to 6 h, the reaction solution is naturally cooled to room temperature, a dilute acid is added to adjust the pH to 1 to 1.5, filtered, and the filter cake is vacuum dried to obtain a TPA-B compound represented by formula (V);

[0025]

[0026] Step c, in a polar solvent, react TPA-B compound, 1-hydroxybenzotriazole, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and a second acid binding agent at 20°C to 25°C for 2h to 3h, then add compound 2, continue to react at 20°C to 25°C for 16h to 20h, pour the reaction solution into water, let stand overnight, filter with suction, and separate the filter cake by column chromatography to obtain a triphenylamine derivative represented by formula (I);

[0027]

[0028] Among them, n=2~10.

[0029] Furthermore, in step a, the molar ratio of the TPA-OH compound, compound 1, the first acid binding agent and the organic solvent is 1:3-3.2:14-15:740-750.

[0030] Furthermore, in step a, the first acid binding agent is potassium carbonate, and the organic solvent is dry acetonitrile.

[0031] Furthermore, in step a, the eluent for column chromatography separation is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4 to 6:1.

[0032] Furthermore, in step b, the molar ratio of the TPA-A compound, the strong base, the alcohol and the water is 1:10-11:1700-1710:550-560.

[0033] Furthermore, in step b, the strong base is sodium hydroxide and the alcohol is anhydrous ethanol.

[0034] Exemplarily, in step b, the dilute acid is dilute hydrochloric acid, dilute nitric acid or dilute sulfuric acid, and the concentration of the dilute acid is 1 mmol / L to 3 mmol / L.

[0035] Furthermore, in step c, the polar solvent is N,N-dimethylformamide, and the second acid binding agent is triethylamine.

[0036] Furthermore, in step c, the molar ratio of the compound TPA-B, 1-hydroxybenzotriazole, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, the second acid binding agent, the polar solvent and the compound 2 is 1:1.2-1.5:1.2-1.5:3.5-4:130-150:3-3.2.

[0037] Furthermore, in step c, the eluent for column chromatography separation is a mixed solution of dichloromethane and methanol in a volume ratio of 25 to 30:1.

[0038] It should be noted that the above-mentioned inert atmosphere can be provided by conventional inert gases in the art, such as nitrogen and argon.

[0039] In a third aspect, the present invention provides a fluorescent probe, which is prepared using the above-mentioned triphenylamine fluorescent derivative as a raw material.

[0040] In a fourth aspect, the present invention also provides a method for preparing the above fluorescent probe, comprising the following steps:

[0041] S1, dissolving the triphenylamine fluorescent derivative in an ultra-dry solvent to prepare a concentration of 5×10 -5 mol / L~1×10 -4 mol / L fluorescent compound solution;

[0042] S2, dissolve the palladium salt in an ultra-dry solvent to prepare a concentration of 5×10 -3 mol / L~1×10 -2 mol / L palladium salt solution;

[0043] S3, mixing the palladium salt solution and the fluorescent compound solution in a volume ratio of 3:29.5-30, reacting at 50° C.-60° C. for 20 h-24 h in an inert atmosphere and protected from light to obtain a fluorescent probe.

[0044] Furthermore, the ultra-dry solvent in S1 and S2 above is dimethyl sulfoxide or N,N-dimethylformamide.

[0045] Exemplarily, the palladium salt is palladium acetate.

[0046] The fluorescent probe prepared by the above method has the characteristics of good photochemical stability, high sensitivity and good selectivity, and is suitable for the detection of carbon monoxide and common interferences such as H2O2, NO, tBuOOH, NaOCl, Fe 3+ , H2S, etc. have no obvious fluorescence response, and the detection limit can reach 1.7ppb. It can realize rapid and sensitive real-time visual detection of carbon monoxide and has good application prospects.

[0047] In a fifth aspect, the present invention provides the use of the above-mentioned triphenylamine fluorescent derivatives in the detection and identification of CO in the air or cells.

[0048] Furthermore, the present invention provides the use of the fluorescent probe in detecting and identifying CO in the air or in fluorescent imaging of CO in cells.

[0049] The triphenylamine fluorescent derivative provided by the present invention is insensitive to water and oxygen in the air, exhibits excellent thermodynamic stability and outstanding photochemical stability, and has good solubility. It can not only realize rapid and sensitive detection of CO in the air, but also realize detection and identification of CO in biological cells. Therefore, it is prepared into a fluorescent probe, which can not only realize rapid visual real-time detection of CO in the environment, but also detect CO in cells through fluorescence imaging technology, evaluate and study the content and physiological function of CO in cells, and has potential application value for obtaining the physiological function of CO in biological tissue samples, and has broad application prospects.

[0050] In a sixth aspect, the present invention provides a supramolecular organometallic gel prepared using the above triphenylamine fluorescent derivative as a raw material.

[0051] In a seventh aspect, the present invention provides a method for preparing the supramolecular organometallic gel, comprising the following steps:

[0052] Step 1, dissolving the triphenylamine fluorescent derivative in an ultra-dry solvent to obtain a fluorescent compound solution with a concentration of 32 mmol / L to 35 mmol / L;

[0053] Dissolving the palladium salt in an ultra-dry solvent to obtain a palladium salt solution with a concentration of 145 mmol / L to 150 mmol / L;

[0054] Step 2: Evenly mix the fluorescent compound solution and the palladium salt solution according to the molar ratio of triphenylamine fluorescent derivative to palladium salt of 1:1-1.2, heat at 80° C.-90° C. for 1-2 min, and cool by standing to obtain supramolecular organometallic gel.

[0055] Furthermore, in step 1, the ultra-dry solvent is dimethyl sulfoxide or N,N-dimethylformamide.

[0056] Exemplarily, the palladium salt is palladium acetate.

[0057] The supramolecular organometallic gel formed by the reaction of the triphenylamine luminescent derivative modified with N-benzyl tertiary amine provided by the present invention and palladium ions can not only realize rapid, highly sensitive, highly selective, and visual detection and identification of CO, as well as intracellular fluorescence imaging, but also realize efficient removal of CO, thus solving the problems of single detection mode, difficult visual detection, and inability to realize detection and removal simultaneously in the existing methods, and has broad application prospects in the field of CO detection and identification.

[0058] In an eighth aspect, the present invention provides an application of the supramolecular organometallic gel in visual detection and identification of CO in the air or removal of CO in the air.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] The present invention uses a three-step reaction to simply and efficiently prepare a series of triphenylamine luminescent derivatives modified with N-benzyl tertiary amine. The preparation method of the triphenylamine luminescent derivative modified with N-benzyl tertiary amine has the outstanding advantages of simple operation, mild reaction conditions, large-scale production, strong adaptability to substrates, etc. Experimental verification shows that the prepared triphenylamine luminescent derivative modified with N-benzyl tertiary amine is insensitive to water and oxygen in the air, exhibits excellent thermodynamic stability and outstanding photochemical stability, and has good solubility, and can realize the detection and identification of CO in various media. Furthermore, by utilizing the coordination chelation properties of N-benzyl tertiary amine and the luminescence properties of triphenylamine fluorophore, the fluorescent probe and supramolecular organometallic gel formed by the triphenylamine luminescent derivative modified by N-benzyl tertiary amine prepared by the present invention after reacting with palladium ions can realize rapid, highly sensitive, highly selective, visualized detection and identification, intracellular fluorescence imaging and efficient removal of CO, which basically solves the problems of single detection mode, difficult visualized detection and inability to simultaneously realize detection and removal in previous methods. It is a new fluorescent probe for multi-mode response and removal of CO, which has very important practical significance for environmental quality monitoring, safety supervision and clinical medicine. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1This is a high-resolution mass spectrum of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention; wherein B is a partial enlarged view of A;

[0062] Figure 2 This is the H NMR spectrum of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention;

[0063] Figure 3 The NMR carbon spectrum of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention;

[0064] Figure 4 The UV-visible absorption and fluorescence emission spectra of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention;

[0065] Figure 5 The photochemical stability spectrum of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention in a dimethyl sulfoxide solution, wherein the inset is a fluorescence intensity diagram at different wavelengths before and after continuous illumination;

[0066] Figure 6 The fluorescence spectrum of the triphenylamine fluorescent derivative prepared in Example 1 of the present invention after reacting with palladium ions in a dimethyl sulfoxide solution; wherein the illustration in the upper right corner is a linear graph of fluorescence intensity and palladium ion equivalent;

[0067] Figure 7 This is a fluorescence spectrum of the fluorescent probe prepared in Example 4 of the present invention in response to CO; wherein the illustration in the upper right corner is a linear graph of fluorescence intensity and CO concentration;

[0068] Figure 8 The selectivity spectrum of the fluorescent probe prepared in Example 4 of the present invention in response to CO;

[0069] Fig. 9 This is a fluorescence spectrum of the fluorescent probe prepared in Example 4 of the present invention in response to CORM-3 (CO releaser); wherein the illustration in the upper right corner is a linear graph of fluorescence intensity and CORM-3 concentration;

[0070] Fig.10 This is a process diagram of visual detection of CO by the supramolecular organometallic gel prepared in Example 4 of the present invention;

[0071] Fig.11 This is a diagram of the removal process of CO by the supramolecular organometallic gel prepared in Example 4 of the present invention;

[0072] Fig.12 This is a fluorescence imaging diagram of CO in Hela cells by the supramolecular organometallic gel prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0073] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0074] In order to better illustrate the present invention, further examples are given below.

[0075] The TPA-OH compound used in the following examples can be synthesized with reference to the literature (H Yu, C Shen, M Tian, ​​J Qu, and Z Wang. Macromolecules, 45 (2012), 5140-5150).

[0076] Compound 2 used in the following examples can be synthesized according to the literature (Malki, WH, Gouda, AM, Ali, HEA, Al-Rousan, R, Samaha, D, Abdalla, AN, Bustamante, J, Abd Elmageed, ZY, Ali HI. European Journal of Medicinal Chemistry, 152 (2018), 31-52).

[0077] Example 1

[0078] This embodiment provides a TPANN1 compound with the structure shown below:

[0079]

[0080] The preparation steps of TPANN1 compound are as follows:

[0081] 1) Preparation of compound TPA-A1

[0082] Under argon protection, 3 g of compound TPA-OH, 4.5 g of compound 1, and 10 g of potassium carbonate were weighed into a 500 mL two-necked flask equipped with a magnetic stirrer and a reflux condenser, and 200 mL of dry acetonitrile was added thereto. The mixture was heated to 85°C and reacted for 24 hours. The reaction solution was naturally cooled to room temperature, filtered, and then the solvent was removed by rotary evaporation. Column chromatography was performed using a petroleum ether: ethyl acetate = 4:1 (v, v) system as the eluent to obtain a white solid, namely compound TPA-A1, with a yield of 67%;

[0083]

[0084] 2) Preparation of compound TPA-B1

[0085] Compound TPA-A1 (1.18 g, 1 mmol) and NaOH (0.4 g, 10 mmol) were added to a mixed solution of 100 mL of anhydrous ethanol and 10 mL of water, and reacted at 80°C for 4 h. After the reaction was completed, the system was cooled to room temperature, 1 mmol / L of dilute hydrochloric acid was added to adjust the pH of the system to about 1, and the filter cake was vacuum dried to obtain a white solid, which was compound TPA-B1, with a yield of 90%;

[0086]

[0087] 3) Preparation of target product TPANN1 compound

[0088] Compound TPA-B1 (1.1 g, 1 mmol), HOBT (0.16 g, 1.2 mmol), EDCI (0.23 g, 1.2 mmol) and 0.5 mL of triethylamine were added to 10 mL of DMF, and the mixture was stirred at room temperature for 2 h, and compound 2 (0.5 g, 3 mmol) was added. After stirring and reacting for 16 h, the system was added to 250 mL of water, allowed to stand overnight, and filtered. The obtained solid was separated by column chromatography using a dichloromethane:methanol=25:1 (v, v) system as the eluent to obtain a white solid, namely, TPANN1 compound, with a yield of 55%;

[0089]

[0090] Example 2

[0091] This embodiment provides a TPANN2 compound with the structure shown below:

[0092]

[0093] The preparation steps of TPANN2 compound are as follows:

[0094] 1) Preparation of compound TPA-A2

[0095] Under argon protection, 3 g of compound TPA-OH, 5.7 g of compound 1, and 10 g of potassium carbonate were weighed into a 500 mL two-necked flask equipped with a magnetic stirrer and a reflux condenser, and 200 mL of dry acetonitrile was added thereto. The mixture was heated to 85°C and reacted for 24 h. The reaction solution was naturally cooled to room temperature, filtered, and then the solvent was removed by rotary evaporation. Column chromatography was performed using a petroleum ether: ethyl acetate = 4:1 (v, v) system as the eluent to obtain a white solid, namely compound TPA-A2, with a yield of 68%;

[0096]

[0097] 2) Preparation of compound TPA-B2

[0098] Compound TPA-A2 (1.23 g, 1 mmol) and NaOH (0.4 g, 10 mmol) were added to a mixed solution of 100 mL of anhydrous ethanol and 10 mL of water, and reacted at 80°C for 4 h. After the reaction was completed, the system was cooled to room temperature, 1 mmol / L of dilute hydrochloric acid was added to adjust the pH of the system to about 1, and the filter cake was vacuum dried to obtain a white solid, namely compound TPA-B2, with a yield of 91%;

[0099]

[0100] 3) Preparation of target product TPANN2

[0101] Compound TPA-B2 (1.18 g, 1 mmol), HOBT (0.16 g, 1.2 mmol), EDCI (0.23 g, 1.2 mmol) and 0.5 mL of triethylamine were added to 10 mL of DMF. After stirring at room temperature for 2 hours, compound 2 (0.5 g, 3 mmol) was added. After stirring and reacting for 16 hours, the system was added to 250 mL of water and allowed to stand overnight. The solid was filtered and separated by column chromatography using dichloromethane:methanol=25:1 (v, v) as eluent to obtain a white solid, i.e., TPANN2 compound, with a yield of 55%.

[0102]

[0103] Example 3

[0104] This embodiment provides a TPANN3 compound with the structure shown below:

[0105]

[0106] The preparation steps of TPANN3 compound are as follows:

[0107] 1) Preparation of compound TPA-A3

[0108] Under argon protection, 3 g of compound TPA-OH, 6.2 g of compound 1, and 10 g of potassium carbonate were weighed into a 500 mL two-necked flask equipped with a magnetic stirrer and a reflux condenser, and 200 mL of dry acetonitrile was added thereto. The mixture was heated to 85°C and reacted for 24 h. The reaction solution was naturally cooled to room temperature, filtered, and then the solvent was removed by rotary evaporation. Column chromatography was performed using a petroleum ether: ethyl acetate = 4:1 (v, v) system as the eluent to obtain a white solid, namely compound TPA-A3, with a yield of 69%;

[0109]

[0110] 2) Preparation of compound TPA-B3

[0111] Compound TPA-A3 (1.31 g, 1 mmol) and NaOH (0.4 g, 10 mmol) were added to a mixed solution of 100 mL of anhydrous ethanol and 10 mL of water, and reacted at 80°C for 4 h. After the reaction was completed, the system was cooled to room temperature, 1 mmol / L of dilute hydrochloric acid was added to adjust the pH of the system to about 1, and the filter cake was vacuum dried to obtain a white solid, namely compound TPA-B3, with a yield of 92%;

[0112]

[0113] 3) Preparation of target product TPANN3

[0114] Compound TPA-B3 (1.26 g, 1 mmol), HOBT (0.16 g, 1.2 mmol), EDCI (0.23 g, 1.2 mmol) and 0.5 mL of triethylamine were added to 10 mL of DMF. After stirring at room temperature for 2 hours, compound 2 (0.5 g, 3 mmol) was added. After stirring and reacting for 16 hours, the system was added to 250 mL of water and allowed to stand overnight. The solid was filtered and separated by column chromatography using dichloromethane:methanol=25:1 (v, v) as eluent to obtain a white solid, namely TPANN3, with a yield of 56%.

[0115]

[0116] Example 4

[0117] The triphenylamine fluorescent derivative TPANN1 compound prepared in Example 1 above was prepared into a fluorescent probe, and the steps were as follows:

[0118] Step 1: Dissolve TPANN1 compound in dimethyl sulfoxide to prepare 5×10 -4 mol / L mother solution; then dilute the mother solution to make 5×10 -5 mol / L fluorescent compound solution;

[0119] Step 2: Dissolve palladium acetate in dimethyl sulfoxide to prepare 5×10 -2 mol / L palladium acetate mother solution; then dilute the mother solution to make 5×10 -3 mol / L palladium acetate solution;

[0120] Step 3: Add stock solution 1 to stock solution 2 in the amount of 3000 μL of fluorescent compound solution to every 300 μL of palladium acetate solution, and react at 60°C under nitrogen protection and in the dark for 24 hours to obtain a fluorescent probe.

[0121] The triphenylamine fluorescent derivative TPANN1 compound prepared in the above Example 1 is prepared into a supramolecular organometallic gel, and the steps are as follows:

[0122] Step 1: dissolving the TPANN1 compound in dimethyl sulfoxide to prepare a 32 mmol / L fluorescent compound solution;

[0123] Step 2: dissolving palladium acetate in dimethyl sulfoxide to prepare a 145 mmol / L palladium acetate solution;

[0124] Step 3: Add the fluorescent compound solution and palladium acetate solution in a 5 mL gel tube according to the molar ratio of TPANN1 compound to palladium acetate of 1:1, heat at 90°C for 1 min, let stand, and naturally cool to room temperature to obtain a supramolecular organometallic gel.

[0125] Performance Testing

[0126] In order to verify the technical effect of the present invention, a large number of research experiments were conducted on the detection and identification of CO by the triphenylamine fluorescent derivative TPANN1 compound synthesized in Example 1, as follows:

[0127] 1. Chemical structure characterization

[0128] The basic chemical structure of the triphenylamine fluorescent derivative TPANN1 compound prepared in Example 1 was characterized by high-resolution mass spectrometry, nuclear magnetic resonance hydrogen spectrum, and carbon spectrum. Figure 1-3 The data in the figure can clearly and accurately characterize the structure of the prepared compound, and show that the prepared TPANN1 compound has a high purity, laying a material structure foundation for subsequent tests.

[0129] 2. Characterization of fluorescence behavior

[0130] The triphenylamine fluorescent derivative TPANN1 compound prepared in Example 1 was prepared to a concentration of 1×10 -5 mol / L dimethyl sulfoxide solution, and UV-visible absorption and fluorescence emission spectra were characterized by Shimadzu UV-2600 and Edinburgh Instruments FLS 980 single photon counting fluorescence spectrometer. The results are shown in Figure 4 As shown. Figure 4 It can be seen that the maximum absorption wavelength of this fluorescent derivative is 343nm, which is the characteristic absorption of the triphenylamine unit; its maximum emission wavelength is 415nm, and it is a broad peak without fine structure, showing blue fluorescence emission, which provides light source and detection wavelength information for the construction of fluorescent probes.

[0131] 3. Photochemical stability test of luminescent derivatives

[0132] Photobleaching is a very important phenomenon that limits the practical application of fluorescent probes. Therefore, it is very necessary to investigate the photochemical stability of fluorescent probes before using them for fluorescence detection. Figure 5 The triphenylamine luminescent derivative TPANN1 prepared in Example 1 was dissolved in a dimethyl sulfoxide solution (concentration 1×10 -5 The test results show that the triphenylamine fluorescent derivative TPANN1 compound prepared in this example exhibits excellent photochemical stability and successfully avoids the "photobleaching" phenomenon, laying a solid foundation for its subsequent practical application.

[0133] 4. Spectral properties of fluorescent probes constructed from TPANN1 compounds and palladium ions

[0134] Figure 6 The triphenylamine fluorescent derivative TPANN1 compound prepared in Example 1 was dissolved in a dimethyl sulfoxide solution (concentration 5×10 -5 mol / L) and palladium ions. It can be seen from the results in the figure that after adding 3 equivalents of palladium ions, the fluorescence of the fluorescent compound TPANN1 compound is basically quenched. Therefore, the present invention uses this system as a fluorescent probe to realize the light-up sensing detection of CO.

[0135] 5. Fluorescent probe detection experiment of CO gas and CORM-3

[0136] The fluorescent probe prepared in Example 4 was used to measure the actual samples, wherein the samples to be analyzed were CO gas and carbon monoxide release agent (CORM-3) in the air, and the interference substances were H2O2, NO, t-BuOOH, NaOCl, Fe 3+ , H2S. The test results are as follows Figure 7-9 shown.

[0137] Figure 7 The fluorescence sensing diagram of the above fluorescent probe to carbon monoxide gas in the air. The detected CO gas concentration is 0-5.5%, and the concentration interval is 0.5%. Figure 7 The test results show that the fluorescent probe responds to carbon monoxide in a fluorescent lighting type. With the increase of CO gas concentration, the emission peak intensity at 415nm increases significantly, and increases linearly in the CO concentration range of 0 to 4.5%. The detection limit is calculated to be 1.7ppb.

[0138] Figure 8 This is the selectivity spectrum of the fluorescent probe for CO gas detection. As can be seen from the figure, the fluorescent probe has excellent selectivity for the detection of CO gas, and the presence of other common interferences will not interfere with the detection results, laying a foundation for its practical application.

[0139] Fig. 9 The fluorescence sensing diagram of the above fluorescent probe to CORM-3. The detected CORM-3 concentration is 0-150 μM, and the concentration interval is 10 μM. Fig. 9 The results show that as the CORM-3 concentration continues to increase, the fluorescence intensity of the fluorescent probe is significantly enhanced, and shows a linear increase within the test concentration range. The calculated detection limit reaches 160nM, indicating that its detection has high sensitivity.

[0140] 6. Visual detection and removal of CO gas by supramolecular organometallic gel

[0141] Fig.10 The present invention is an attempt to visualize the sensing of CO gas in the air based on the supramolecular organometallic gel prepared in Example 4. The supramolecular organometallic gel prepared in Example 4 was placed in a visualization detection device, the CO concentration in the device was 5000ppm, and the phase change of the gel in the CO atmosphere was observed over time. It can be seen from the figure that, on the one hand, the air will not interfere with the visualization sensing process; on the other hand, it can be observed that the color of the supramolecular organometallic gel obviously turns black within 1 minute, and a free-flowing liquid is obviously produced in about 3 minutes, indicating that the supramolecular organometallic gel partially collapses, and the collapse of the supramolecular organometallic gel becomes more obvious as time goes by. This shows that the supramolecular organometallic gel can realize the rapid visualization sensing of CO gas in the air, which provides the possibility for its practical application, and is of great significance for the development of CO rapid and sensitive detection technology and instruments.

[0142] Fig.11 The figure is a test chart of the efficient removal of CO gas in the air based on the supramolecular organometallic gel. The supramolecular organometallic gel prepared in Example 4 was placed in a CO removal device with good airtightness and equipped with a CO concentration detector. The initial concentration of CO in the device was 750ppm, and the change of CO gas concentration was observed over time. It can be seen from the figure that as time goes by, the concentration of CO in the device gradually decreases, proving that the supramolecular organometallic gel can achieve a high efficiency removal of CO gas in the air, and the adsorption efficiency can reach about 24%, laying a foundation for its practical application.

[0143] 7. Application of fluorescent probes in Hela cell fluorescence imaging

[0144] The HeLa cells were divided into three groups. First, a group of HeLa cells with only the fluorescent probe (5 μM) was imaged. The fluorescent probe was incubated in the cells for 60 min, and then the cells were imaged. The imaging results are shown in FIG. Fig.12As shown in A; then a group of HeLa cells with only CORM-3 (5 μM) were imaged, CORM-3 was incubated in the cells for 60 minutes, and then the cells were imaged. The imaging results are shown in Fig.12 As shown in B; the last group was incubated with 5 μM of the fluorescent probe and different concentrations (20 μM, 50 μM, 100 μM, 150 μM and 200 μM) of CORM-3 for 60 min, and then cell imaging was performed. The imaging results are shown in Fig.12 As shown in CG. As can be seen from the figure, the fluorescent probe has a good fluorescence imaging effect on carbon monoxide in cells. Fig.12 It can be seen that the fluorescence intensity of the probe itself is low, and as the concentration of carbon monoxide increases, the fluorescence intensity also increases, indicating that the probe can detect carbon monoxide in Hela cells.

[0145] The triphenylamine derivatives prepared in Example 2-3 and the compounds represented by formula (I) with n=2 and n=10 prepared in the same manner as above can achieve the effect of detecting and identifying CO substantially equivalent to that in Example 1.

[0146] By adopting other reaction conditions specified in the present invention, such as the ratio of reaction raw materials, reaction temperature and time, volume ratio of eluent, and type of acidified acid, as long as they are within the range specified in the specification of the present invention, a yield substantially equivalent to that of Example 1 and substantially equivalent effects on CO detection and identification and CO removal can be achieved.

[0147] In summary, the present invention organically combines the triphenylamine luminescent group and the N-benzyl tertiary amine group with excellent photoelectric properties to obtain a series of triphenylamine fluorescent derivatives modified by N-benzyl tertiary amine. The triphenylamine fluorescent derivative modified by N-benzyl tertiary amine has excellent solubility, excellent photophysical properties and photochemical stability. The fluorescent probe and supramolecular metal organic gel prepared by using the triphenylamine fluorescent derivative modified by N-benzyl tertiary amine can achieve high sensitivity and high selectivity detection of CO. More importantly, it can also achieve visual detection and identification of CO and efficient removal, and realize the application of intracellular fluorescence imaging. In addition, the preparation method of the triphenylamine fluorescent derivative modified by N-benzyl tertiary amine provided by the present invention has the outstanding advantages of simple operation, mild reaction conditions, large-scale production and strong adaptability to substrates, and has a high value of promotion and application.

[0148] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A triphenylamine fluorescent derivative, characterized in that: Its structure is shown in formula (I): Among them, n=2~10.

2. A method for preparing the triphenylamine fluorescent derivative according to claim 1, characterized in that: The steps include: Step a, in an organic solvent under an inert atmosphere, subjecting the TPA-OH compound represented by formula (II) and the compound 1 represented by formula (III) to an Ullmann coupling reaction under the action of a first acid binding agent to obtain a TPA-A compound represented by formula (IV); Step b, in an alcohol-water mixed solvent, the TPA-A compound and a strong base undergo a hydrolysis reaction, followed by acidification to obtain a TPA-B compound represented by formula (V); Step c, in a polar solvent, subjecting the TPA-B compound, 1-hydroxybenzotriazole, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and the compound 2 represented by formula (VI) to an amide condensation reaction under the action of a second acid binding agent to obtain a triphenylamine derivative represented by formula (I); Among them, n=2~10.

3. The method for preparing the triphenylamine fluorescent derivative according to claim 2, characterized in that: In step a, the molar ratio of the TPA-OH compound, compound 1, the first acid binding agent and the organic solvent is 1:3-3.2:14-15:740-750; and / or In step a, the temperature of the Ullmann coupling reaction is 80° C. to 85° C., and the reaction time is 4 h to 6 h; and / or In step a, the first acid binding agent is potassium carbonate, and the organic solvent is dry acetonitrile; and / or In step b, the molar ratio of the TPA-A compound, the strong base, the alcohol and the water is 1:10-11:1700-1710:550-560; and / or In step b, the temperature of the hydrolysis reaction is 80°C to 85°C, and the reaction time is 4h to 6h; and / or In step c, the polar solvent is N,N-dimethylformamide, and the second acid binding agent is triethylamine; and / or In step c, the molar ratio of the compound TPA-B, 1-hydroxybenzotriazole, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, the second acid binding agent, the polar solvent and the compound 2 is 1:1.2-1.5:1.2-1.5:3.5-4:130-150:3-3.

2.

4. The method for preparing a triphenylamine fluorescent derivative according to claim 2 or 3, characterized in that: Step c is specifically as follows: reacting the TPA-B compound, 1-hydroxybenzotriazole, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and the second acid binding agent at 20° C. to 25° C. for 2 h to 3 h, then adding compound 2, and continuing the reaction at 20° C. to 25° C. for 16 h to 20 h to obtain the triphenylamine derivative represented by formula (I).

5. A fluorescent probe, characterized in that The preparation method of the fluorescent probe comprises the following steps: S1, dissolving the triphenylamine fluorescent derivative in an ultra-dry solvent to prepare a concentration of 5×10 -5 mol / L~1×10 -4 mol / L fluorescent compound solution; S2, dissolve the palladium salt in an ultra-dry solvent to prepare a concentration of 5×10 -3 mol / L~1×10 -2 mol / L palladium salt solution; S3, mixing the palladium salt solution and the fluorescent compound solution in a volume ratio of 3:29.5-30, reacting at 50° C.-60° C. for 20 h-24 h in an inert atmosphere and protected from light to obtain a fluorescent probe.

6. Use of the triphenylamine fluorescent derivative according to claim 1 or the fluorescent probe according to claim 5 in detecting and identifying CO in air or cells.

7. A supramolecular organometallic gel, characterized in that: The preparation method of the supramolecular organometallic gel comprises the following steps: Step 1, dissolving the triphenylamine fluorescent derivative in an ultra-dry solvent to obtain a fluorescent compound solution with a concentration of 32 mmol / L to 35 mmol / L; Dissolving the palladium salt in an ultra-dry solvent to obtain a palladium salt solution with a concentration of 145 mmol / L to 150 mmol / L; Step 2: Evenly mix the fluorescent compound solution and the palladium salt solution according to the molar ratio of triphenylamine fluorescent derivative to palladium salt of 1:1-1.2, heat at 80° C.-90° C. for 1-2 min, and cool by standing to obtain supramolecular organometallic gel.

8. Use of the supramolecular organometallic gel according to claim 7 in visual detection and identification of CO in the air or in removal of CO in the air.

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