Two-dimensional Ag-CP fluorescent probe material as well as preparation method and application thereof
By developing two-dimensional Ag-CP fluorescent probe materials, the problem of detecting Trp molecules in water bodies is solved by using their high selectivity and sensitivity, achieving efficient and fast detection effects, and having good anti-interference and recycling.
Patent Information
- Application Number
- CN202510312235.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-17
- Publication Date
- 2025-06-13
AI Technical Summary
The prior art is difficult to detect the presence of tryptophan (Trp) molecules in water bodies efficiently and quickly, and there are environmental pollution problems.
A two-dimensional Ag-CP fluorescent probe material is developed, which forms a two-dimensional layered structure through a specific ligand coordination with silver ions, with high selectivity, sensitivity and anti-interference ability, and is used to detect the presence of Trp molecules in water bodies.
It realizes high selectivity and high sensitivity detection of Trp molecules in water, has good anti-interference and recycling, simplifies the preparation process and reduces costs.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of fluorescence sensors, and relates to a two-dimensional Ag-CP fluorescence probe material, a preparation method thereof and an application thereof. Background Art
[0002] Amino acids have extremely wide uses in aspects such as chemical industry, medicine and food. Amino acids are artificially produced and synthesized in large quantities through biological fermentation, chemical methods, etc. During the production process of amino acids, a large amount of production wastewater is often discharged, bringing many serious environmental pollution problems. The treatment of wastewater in the amino acid production industry has increasingly attracted people's attention.
[0003] Tryptophan is an essential amino acid for the human body and an indispensable part of synthesizing proteins. It has the functions of calming the nerves and improving sleep. Excessive absorption of tryptophan will promote a large number of nerve cells to secrete serotonin, leading to serotonin syndrome, which may cause side effects such as mental and behavioral abnormalities, motor system abnormalities and autonomic nervous system abnormalities. Therefore, there is an urgent need for an efficient and rapid detection method.
[0004] Metal coordination polymers are network structure crystals formed by the coordination of metal ions or metal clusters with organic ligands. They have a relatively high porosity, a large surface area and good fluorescence properties. They have the ability to fluorescence-recognize many harmful ions or molecules, and at the same time have high selectivity and sensitivity, low detection limits, and the advantages of being recyclable, etc. Therefore, they are often used as fluorescence probe materials to detect harmful pollutants. Summary of the Invention
[0005] The present invention aims to provide a two-dimensional Ag-CP fluorescence probe material, a preparation method thereof and an application thereof. The Ag-CP fluorescence probe material shows excellent sensitivity, selectivity, anti-interference ability and recyclability in the detection of Trp molecules in water, and the preparation method of the Ag-CP fluorescence probe material is simple and low in cost.
[0006] The Ag-CP fluorescence probe material described in the present invention has a two-dimensional layered structure, and its structural formula is: [Ag(HL)(L)] n , where in the structural formula: HL = 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid.
[0007] Further, the excitation wavelength of the Ag-CP fluorescence probe material is 284 nm, and the emission wavelength is 344 nm.
[0008] The preparation method of the above two-dimensional Ag-CP fluorescence probe material includes the following steps:
[0009] (1) Weigh a certain amount of the ligand 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid and a soluble silver salt respectively, add them to deionized water, and obtain a light brown suspension after ultrasonic treatment;
[0010] (2) At room temperature, transfer the light brown turbid liquid obtained in step (1) to a heat-resistant glass autoclave with a polytetrafluoroethylene lid, place it in a programmable temperature-controlled oven for reaction, and after the reaction is completed, cool it to room temperature to obtain colorless blocky crystals.
[0011] (3) Filter, wash, and dry the colorless rectangular flaky crystals obtained in step (2) to obtain a two-dimensional Ag-CP fluorescent probe material.
[0012] Preferably, the soluble silver salt in step (1) is silver acetate or silver nitrate.
[0013] Preferably, the molar ratio of the soluble silver salt to the ligand 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid is 1:2 to 4.
[0014] Preferably, the reaction temperature in step (2) is 90 - 110 °C, and the reaction time is 36 - 72 h.
[0015] Preferably, the cooling rate in step (2) is 5 °C / h.
[0016] Preferably, the pore size of the filter membrane used for filtration in step (3) is 22 μm.
[0017] Preferably, the solvent used for washing in step (3) is a deionized aqueous solution with a volume of 10 - 20 mL, and the number of washing times is 2 - 3 times.
[0018] Preferably, the drying temperature in step (3) is 50 - 80 °C, and the drying time is 9 - 15 h.
[0019] The above Ag-CP fluorescent probe material is used for detecting Trp molecules in water, including the following steps:
[0020] (1) Grind the two-dimensional Ag-CP fluorescent probe material, disperse it in deionized water and ultrasonicate to form an Ag-CP suspension, and measure its fluorescence excitation and emission spectra.
[0021] (2) Dissolve the Trp molecule analyte in deionized water to prepare an aqueous solution of the Trp molecule analyte.
[0022] (3) Use a pipette to transfer the aqueous solution of the Trp molecule analyte and drop it into the Ag-CP suspension in step (1) respectively. After ultrasonication for 30 s, immediately measure the fluorescence emission spectrum of the mixed suspension.
[0023] (4) Establish a linear relationship between the fluorescence relative intensity ratio (I / I 0 ) - 1 and the concentration (C Trp ) of the Trp molecule analyte, where I0 It represents the fluorescence intensity of the Ag-CP suspension at 344 nm. I represents the fluorescence intensity of the Ag-CP suspension at 344 nm after adding Trp solutions with different concentrations, and a linear regression equation is obtained.
[0024] (5) Detect Trp molecules in water: For the aqueous solution containing Trp, perform detection according to the method in step (3), and calculate the concentration of Trp molecules according to the linear regression equation in step (4).
[0025] Preferably, in step (1), the two-dimensional Ag-CP fluorescent probe material is ground into 60 - 80 mesh, the ultrasonic treatment time is 30 - 60 min, and the concentration of the Ag-CP suspension is 2 - 6 mg / mL.
[0026] Preferably, in step (2), the concentration of the prepared Trp molecule as the analyte is 5×10 -4 ~5×10 -3 M.
[0027] Preferably, in step (3), the volume ratio of the aqueous solution of the Trp molecule analyte to the Ag-CP suspension is 1:200 - 300.
[0028] Compared with the prior art, the beneficial effects of the present invention are as follows: The Ag-CP material prepared by the present invention can highly selectively and sensitively identify tryptophan (Trp) molecules in aqueous solution, and its fluorescence recognition ability has good stability, anti-interference ability, and recycling ability, and can be used as an excellent fluorescence sensor for identifying Trp molecules. Description of the Drawings
[0029] Figure 1 Two-dimensional layered structure diagram of Ag-CP;
[0030] Figure 2 Infrared spectrum diagram of the Ag-CP fluorescent probe material;
[0031] Figure 3 PXRD diagram of the Ag-CP fluorescent probe material;
[0032] Figure 4 TGA diagram of the Ag-CP fluorescent probe material;
[0033] Figure 5 Excitation and emission spectrum diagrams of the Ag-CP fluorescent probe material;
[0034] Figure 6 Fluorescence response spectrum diagrams of the Ag-CP fluorescent probe material to Trp molecules with different concentrations;
[0035] Figure 7Linear relationship diagram between fluorescence intensity ratio based on the S-V equation and Trp molecular concentration of the Ag-CP fluorescent probe material;
[0036] Figure 8 Comparison diagram of fluorescence intensity after adding various biomolecules and antibiotic molecules to the Ag-CP fluorescent probe material;
[0037] Figure 9 Comparison diagram of fluorescence intensity in 5 cycles of Trp molecule recognition by the Ag-CP fluorescent probe material. Specific implementation manners
[0038] The present invention is not limited to the following specific implementation manners. Those of ordinary skill in the art can implement the present invention in other various specific implementation manners according to the content disclosed in the present invention, or those that adopt the design structure and idea of the present invention and make simple changes or modifications all fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other.
[0039] The present invention will be further described below in conjunction with specific embodiments and the accompanying drawings.
[0040] Method for the Ag-CP fluorescent probe material, comprising the following steps:
[0041] Example 1
[0042] Add AgNO 3 (0.1 mmol, 0.017 g) and HL (4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid) (0.2 mmol, 0.0432 g) to 8 mL of deionized water, stir for 30 min to obtain a light brown turbid solution; then transfer the obtained light brown turbid solution to a 25 mL heat-resistant glass autoclave with a polytetrafluoroethylene lid, react in an oven at 90 °C for 36 h, cool to room temperature at a rate of 5 °C / h to obtain colorless block crystals, filter the product through a filter membrane with a pore size of 22 μm, wash with 10 mL of deionized water solution twice, dry at 80 °C for 9 hours, cool to room temperature, and grind with an agate mortar for 1 h to obtain the Ag-CP fluorescent probe material, with a yield of 71%.
[0043] Example 2
[0044] Add CH 3COOAg (0.1 mmol, 0.0167 g) and HL (4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid) (0.2 mmol, 0.0432 g) were added to 8 mL of deionized water. After stirring for 40 min, a light brown suspension was obtained. Then, the obtained light brown turbid solution was transferred to a 25 mL heat-resistant glass autoclave with a PTFE lid and reacted in an oven at 100 °C for 48 h. It was cooled to room temperature at a rate of 5 °C / h to obtain colorless block crystals. The product was filtered through a filter membrane with a pore size of 22 μm, washed twice with 15 mL of deionized water solution, dried at 80 °C for 10 hours, cooled to room temperature, and then ground in an agate mortar for 1 h to obtain the Ag-CP fluorescent probe material with a yield of 69%.
[0045] Example 3
[0046] Add CH 3 COOAg (0.1 mmol, 0.0167 g) and HL (4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid) (0.3 mmol, 0.0648 g) were added to 8 mL of deionized water. After stirring for 50 min, a light brown turbid solution was obtained. Then, the obtained light brown turbid solution was transferred to a 25 mL heat-resistant glass autoclave with a PTFE lid and reacted in an oven at 100 °C for 60 h. It was cooled to room temperature at a rate of 5 °C / h to obtain colorless block crystals. The product was filtered through a filter membrane with a pore size of 22 μm, washed three times with 18 mL of deionized water solution, dried at 80 °C for 12 hours, cooled to room temperature, and then ground in an agate mortar for 1 h to obtain the Ag-CP fluorescent probe material with a yield of 75%.
[0047] Example 4
[0048] Add AgNO 3 (0.1 mmol, 0.068 g) and HL (4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid) (0.4 mmol, 0.0864 g) were added to 8 mL of deionized water. After stirring for 30 min, a light brown turbid solution was obtained. Then, the obtained light brown turbid solution was transferred to a 25 mL heat-resistant glass autoclave with a PTFE lid and reacted in an oven at 110 °C for 72 h. It was cooled to room temperature at a rate of 5 °C / h to obtain colorless block crystals. The product was filtered through a filter membrane with a pore size of 22 μm, washed three times with 20 mL of deionized water solution, dried at 80 °C for 15 hours, cooled to room temperature, and then ground in an agate mortar for 1 h to obtain the Ag-CP fluorescent probe material with a yield of 79%.
[0049] Performance test experiment
[0050] 1. The Ag-CP fluorescent probe material prepared in Example 1 of the present invention was analyzed by X-ray single crystal diffraction. Ag-CP crystallizes in the monoclinic system C with Z = 2 2 space group. Both the HL ligand and the L - ligand ions adopt the μ 2 -κN:κO bridging coordination mode. Under the action of the μ 2 -bridging HL / L - ligand, adjacent Ag + ions are connected to form a two-dimensional layered structure, as Figure 1 shown.
[0051] 2. The Ag-CP fluorescent probe material prepared in Example 1 of the present invention was analyzed by infrared spectroscopy. The broad peak appearing between 3450 cm -1 is the O-H peak on the v as (COO) of the ligand. The peak at 1650 cm -1 is the C=O stretching vibration peak on the v as (COO) of the ligand. The peak at 1604 cm -1 is the C=N stretching vibration on the pyrazole ring of the ligand. The peak at 1383 cm -1 is the C-O peak on the v as (COO) of the ligand. The peak at 1039 cm -1 is the N-N stretching vibration peak on the pyrazole ring of the ligand, as Figure 2 shown.
[0052] 3. The Ag-CP fluorescent probe material prepared in Example 1 of the present invention was analyzed by X-ray powder diffraction. It can be seen through Figure 3 that the powder diffraction peaks basically correspond to the simulated peaks of the X-ray single crystal diffraction data, indicating that a large number of Ag-CP products exhibit good phase purity, and only the yields of Examples 1-4 are different.
[0053] 4. The Ag-CP fluorescent probe material prepared in Example 1 of the present invention was analyzed by thermogravimetric analysis. It can be seen from Figure 4 that Ag-CP basically does not change in the range of 40-290 °C, indicating that it has good thermal stability within 290 °C; then the Ag-CP skeleton begins to decompose and has not been completely decomposed until 850 °C.
[0054] 5. The fluorescence emission spectrum of the Ag-CP fluorescent probe material prepared in Example 1 of the present invention was detected. As Figure 5 shown, the excitation wavelength of the Ag-CP fluorescent probe material is 284 nm, and the emission wavelength is 344 nm.
[0055] 6. Perform fluorescence recognition experiments on tryptophan molecules using the Ag-CP fluorescent probe material prepared in Example 1 of the present invention:
[0056] (1) Grind the two-dimensional Ag-CP fluorescent probe material, disperse it in deionized water, and ultrasonicate for 30 min to form a 2 mg / mL Ag-CP suspension. Then measure its fluorescence excitation and emission spectra.
[0057] (2) Dissolve the tryptophan analyte in deionized water to prepare a tryptophan aqueous solution.
[0058] (3) Use a pipette to transfer 10 μL of the tryptophan aqueous solution and drop it into 2 mL of the Ag-CP suspension in step (1). After ultrasonication for 30 s, immediately measure the fluorescence emission spectrum of the suspension.
[0059] As Figure 6 shown, as the concentration of the Trp molecular solution increases, the emission intensity of the Ag-CP fluorescent probe material continuously increases, and the emission intensity can increase by up to 9.86 times.
[0060] 7. As Figure 7 shown, according to the fitting calculation of the S-V equation, the relative fluorescence intensity ratio (I / I 0 ) - 1 and C Trp show a linear relationship in the range of 0.02 - 0.035 mM. I 0 represents the fluorescence intensity of the Ag-CP suspension at 344 nm, and I represents the fluorescence intensity of the Ag-CP suspension at 344 nm after adding different concentrations of Trp solution. By linear fitting, K sv (Trp) = 1.658×10 5 M -1 , R 2 = 0.99414. The detection limit LOD = 5.06×10 -8 M is calculated by the formula LOD = 3σ / k.
[0061] 8. Conduct anti-interference experiment analysis on the Ag-CP fluorescent probe material prepared in Example 1 of the present invention. In the Ag-CP suspension, first successively add various anti-interference biomolecules and drug molecules (5×10 -4 M), and measure their fluorescence emission spectra respectively. Finally, add the Trp molecular aqueous solution and measure its fluorescence emission spectrum, and record the change in fluorescence emission intensity. As Figure 8 shown, in the presence of Trp molecules, it hardly affects the Ag-CP fluorescence response intensity, indicating that Ag-CP has good anti-interference performance for the detection of Trp molecules in water.
[0062] 9. The cyclic stability of the Ag-CP fluorescent probe material prepared in the above Example 1 of the present invention was detected. The Ag-CP fluorescent probe material after the above experiment was filtered and collected, washed thoroughly with water and dried, and then prepared into the above Ag-CP suspension again by the same method, and the aqueous solution of Trp molecules was fluorescence-identified. As Figure 9 shown, the Ag-CP fluorescent probe material still had the ability to identify Trp molecules in water after being recycled five times, indicating that the material had good cyclic stability and recyclability.
[0063] In summary, the present invention designed and synthesized a new type of Ag-CP fluorescent probe material, which can detect Trp molecules in water, and showed good sensitivity and anti-interference ability during the identification process. Moreover, the Ag-CP fluorescent probe material was simple to prepare and had low cost.
[0064] The above-described embodiments are only the preferred experimental schemes of the present invention. It should be noted that for those skilled in the art of operation techniques, there are different ways of expressing the experimental schemes, and appropriate polishing and modification can be made on the basis of the embodiments of the present invention, but all are within the protection scope of the present invention.
Claims
1. A two-dimensional Ag-CP fluorescent probe material, characterized in that: Its structural formula is: [Ag(HL)(L)] n , in the structural formula, HL = 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid.
2. The two-dimensional Ag-CP fluorescent probe material according to claim 1, characterized in that: [Ag(HL)(L)] n The coordination polymer crystallizes in the monoclinic system with a space group of C2y , Unit cell parameters: α=90°, β=124.7980(19)°, γ=90°.
3. A method for preparing the two-dimensional Ag-CP fluorescent probe material according to claim 1 or 2, characterized in that: The following steps are involved: (1) Weigh 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid and a soluble silver salt respectively, add them into deionized water, and obtain a light brown suspension after ultrasonic treatment; (2) at room temperature, the light brown suspension obtained in step (1) was transferred to a heat-resistant glass kettle with a polytetrafluoroethylene cover, and placed in a programmable temperature-controlled oven for reaction. After the reaction, the suspension was cooled to room temperature to obtain colorless block crystals; (3) Filter, wash and dry the colorless block crystals obtained in step (2) to obtain a two-dimensional Ag-CP fluorescent probe material.
4. The method for preparing the two-dimensional Ag-CP fluorescent probe material according to claim 3, characterized in that: The soluble silver salt in step (1) is silver acetate or silver nitrate, and the molar ratio of the soluble silver salt to the ligand 4-(3,5-dimethyl-1H-pyrazol-1-yl)benzoic acid is 1:2-4.
5. The method for preparing the two-dimensional Ag-CP fluorescent probe material according to claim 3, characterized in that: The reaction temperature in step (2) is 90-110°C, the reaction time is 36-72h, and the cooling rate is 5°C / h.
6. The use of the two-dimensional Ag-CP fluorescent probe material according to any one of claims 1 or 2, characterized in that: the Ag-CP fluorescent probe material is used as a fluorescent sensor to detect tryptophan molecules in water.
7. The use of the Ag-CP fluorescent probe material according to claim 6, characterized in that: The steps include: (1) grinding the Ag-CP fluorescent probe material, dispersing it in deionized water and ultrasonicating it for 30 minutes to form an Ag-CP suspension, and measuring its fluorescence excitation spectrum and emission spectrum; (2) dissolving Trp molecules in deionized water to prepare a Trp molecule aqueous solution; (3) Add the Trp molecular aqueous solution into the Ag-CP suspension, and after ultrasonication, immediately test the fluorescence emission spectrum of the suspension.
8. The use of the Ag-CP fluorescent probe material according to claim 7, characterized in that: The steps include: The Ag-CP fluorescent probe material in step (1) is ground into 60-80 mesh; the ultrasonic treatment time is 30-60 min; the concentration of the Ag-CP suspension is 2-6 mg / mL.
9. The use of the Ag-CP fluorescent probe material according to claim 7, characterized in that: The volume ratio of the Trp molecular detection aqueous solution to the Ag-CP suspension in step (3) is 1:200-300.