Platinum complex fluorescent probe, preparation method thereof and application of platinum complex fluorescent probe in detection of water
By preparing and testing the platinum complex fluorescent probe Pt-Ph, the problems of complex synthesis and poor selectivity in water detection of existing fluorescent sensors were solved, and a water detection effect with high sensitivity and a wide detection concentration range was achieved.
Patent Information
- Application Number
- CN202511801245.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-02
- Publication Date
- 2026-02-13
AI Technical Summary
Existing fluorescence sensors for water detection suffer from problems such as complex synthesis, poor selectivity, slow detection speed, susceptibility to interference from coexisting substances, and high skill requirements, thus failing to meet current detection needs.
A platinum complex fluorescent probe was prepared by synthesizing the platinum complex fluorescent probe Pt-Ph through a specific chemical reaction, and then performing UV-Vis absorption and fluorescence spectroscopy tests in a specific solvent to establish a linear relationship and achieve high-sensitivity detection of water.
It achieves specific selectivity and high sensitivity detection of water, with a wide detection concentration range, meeting current detection needs.
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Figure CN121517469A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of chemical analysis and detection, and particularly relates to a platinum complex fluorescent probe, a preparation method thereof and application thereof in water detection. BACKGROUND
[0002] Water, as a key element for maintaining life, plays an indispensable role in biological systems and natural environments. However, in the process of chemical production and chemical reaction, the presence of water can significantly affect the reaction rate and bring safety hazards. Therefore, it is of great value to establish a precise and reliable water detection technology in the fields of chemical production, industrial manufacturing and environmental monitoring. Among them, the detection method based on fluorescence principle is gradually becoming an important analysis tool in the fields of environmental monitoring, biomedical research and clinical diagnosis due to its excellent sensitivity and specificity.
[0003] Although a variety of fluorescent sensors have been developed for water detection, due to the complex synthesis of fluorescent materials, poor selectivity for water, and limitations such as slow detection speed, high skill requirement for operators and susceptibility to coexisting substances, the detection cannot meet the current demand. SUMMARY
[0004] To solve the problems in the background art, the application provides a platinum complex fluorescent probe, a preparation method thereof and application thereof in water detection, which has the advantages of specific selectivity, high sensitivity, wide detection concentration range and the like, so that the detection can better meet the current demand.
[0005] To achieve the above-mentioned purpose, in a first aspect, the application provides a platinum complex fluorescent probe, which has a chemical formula of C 23 H 16 ClN3Pt;
[0006] The structural formula is: .
[0007] In a second aspect, the application provides a preparation method of the above-mentioned platinum complex fluorescent probe, which comprises the following steps:
[0008] Step 1, under the protection of argon, tripyridine, potassium tetrachloroplatinate, deionized water and dimethyl sulfoxide are mixed in a round-bottom flask, heated and stirred to reflux, then cooled to room temperature, concentrated hydrochloric acid is added, and a yellow precipitate is obtained by suction filtration, which is dried to obtain Pt-Cl;
[0009] Step 2, Pt-Cl, phenylacetylene, cuprous iodide, N,N-dimethylformamide and triethylamine are mixed in a round-bottom flask, then argon is replaced several times, and after reaction, the precipitate is obtained by suction filtration, then washed with a mixture of methanol and dichloromethane, and dried to obtain the platinum complex fluorescent probe Pt-Ph.
[0010] Further, in step 1, the molar ratio of terpyridine and potassium tetrachloroplatinate is 1:1, and the volume ratio of deionized water and dimethyl sulfoxide is 10:1.
[0011] Further, in step 1, the reaction temperature is 100℃, and the reaction time is 2 hours.
[0012] Further, in step 2, the molar ratio of Pt-Cl, phenylacetylene and cuprous iodide is 1:3.3:0.5, and the volume ratio of N,N-dimethylformamide and triethylamine is 10:1.
[0013] Further, in step 2, the reaction temperature is 25℃, and the reaction time is 24 hours.
[0014] In a third aspect, the present application provides a use of the above-mentioned platinum complex fluorescent probe in detecting water, wherein the platinum complex fluorescent probe is dissolved in a dimethyl sulfoxide solution of 1,4-dioxane to prepare a standard solution; then different volume ratios of water are added respectively, and ultraviolet-visible absorption and fluorescence spectrum tests are carried out, and a linear relationship is established.
[0015] Further, the volume fraction of the dimethyl sulfoxide solution of 1,4-dioxane is 95%, and the concentration of the standard solution is 10μM.
[0016] Further, the volume ratio of the added water and the standard solution is 0-5%.
[0017] The present application has the following beneficial effects: the platinum complex fluorescent probe prepared by the present application has the advantages of specific selectivity, high sensitivity, wide detection concentration range, etc., and can be applied to detect water, so that the detection can better meet the current demand. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the platinum complex fluorescent probe Pt-Ph in DMSO-d6 in the embodiment 1 of the present application;
[0019] Figure 2 It is the ultraviolet-visible absorption spectrum and fluorescence spectrum of the platinum complex fluorescent probe Pt-Ph in the embodiment 1 of the present application; wherein, the left side is the ultraviolet-visible absorption spectrum of Pt-Ph; and the right side is the fluorescence spectrum under the excitation of 430nm;
[0020] Figure 3 It is the ultraviolet-visible absorption spectrum and fluorescence spectrum of the platinum complex fluorescent probe Pt-Ph in the embodiment 1 of the present application; wherein, the left side is the ultraviolet-visible absorption spectrum of Pt-Ph; and the right side is the fluorescence spectrum under the excitation of 430nm;
[0021] Figure 4The linear relationship diagram of different concentrations of water content and fluorescence intensity obtained in Example 2 of the present application; wherein, the change of the fluorescence intensity of Pt-Ph solution at 600 nm in the detection solution with the addition of water. DETAILED DESCRIPTION
[0022] The specific embodiments of the present application are further described in detail in the following examples. Unless otherwise specified, the instruments and equipment involved in the examples are all conventional instruments and equipment; the raw materials involved are all conventional commercially available raw materials; and the test methods involved are all conventional methods.
[0023] Example 1 Preparation and characterization of platinum complex fluorescent probe Pt-Ph
[0024] The chemical formula of Pt-Ph is: 23 H 16 ClN3Pt;
[0025] The structural formula of Pt-Ph is: .
[0026] The specific preparation method of Pt-Ph is as follows:
[0027] (1) Synthesis of Pt-Cl;
[0028] Under argon protection, terpyridine (0.50 g, 2.23 mmol), potassium tetrachloroplatinate (0.93 g, 2.23 mmol), deionized water (6 mL) and dimethyl sulfoxide (0.6 mL) were mixed in a 50 mL round-bottom flask. Stirring under reflux at 100°C for 2 h. After cooling to room temperature, 5 mL of concentrated hydrochloric acid was added, and the yellow precipitate was obtained by suction filtration. 60°C drying for 2 h to obtain the target product Pt-Cl (1.13 g, yield 97%).
[0029] The synthesis reaction equation of Pt-Cl is as follows:
[0030]
[0031] The characterization data of Pt-Cl are as follows: 1 H NMR (400 MHz, D2O) δ 7.94-7.86 (m, 3H), 7.68-7.63 (m, 5H), 7.48-7.43 (m, 1H), 7.19-7.09 (m, 2H). HRMS (ESI) m / z calcd for C 15 H 11 ClN3Pt(M) + 463.02838, found 463.02872.
[0032] (2) Synthesis of Pt-Ph;
[0033] Pt-Cl (0.20 g, 0.4 mmol), phenylacetylene (0.13 g, 1.32 mmol), cuprous iodide (40 mg, 0.2 mmol), N,N-dimethylformamide (10 mL) and triethylamine (1 mL) were mixed into a 50 mL round bottom flask. Then the flask was purged with argon three times and the reaction was carried out at room temperature for 24 h. After the reaction, yellow precipitate was formed and was filtered off. The precipitate was washed with a mixture of methanol and dichloromethane (1:1) and dried at 60 °C for 2 h to obtain yellow solid Pt-Ph (0.13 g, yield 58%).
[0034] The synthesis reaction equation of Pt-Ph is as follows:
[0035]
[0036] The nuclear magnetic resonance hydrogen spectrum of Pt-Ph in CDC13 is shown in Figure 1
[0037] The characterization data of Pt-Ph are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 8.50 (d, J = 4.5 Hz, 2H), 8.35 (d, J = 7.9 Hz, 2H), 8.31 (d, J = 7.8 Hz, 2H), 8.22 (t, J = 7.5 Hz, 3H), 7.62 (t, J = 6.3 Hz, 2H), 7.37-7.29 (m, 3H), 7.26 (d, J = 7.2 Hz, 2H). 13 C NMR (101 MHz, DMSO-d6) δ 158.51, 153.82, 153.76, 142.28, 142.19, 132.16, 129.92, 128.67, 126.98, 126.88, 126.28, 124.57, 103.25, 98.75. HRMS (ESI) m / z calcd for C 23 H 16 N3Pt (M) + 529.09865, found 529.09918.
[0038] (3) UV-visible absorption spectrum and fluorescence spectrum test of platinum complex fluorescent probe Pt-Ph;
[0039] Sample preparation: Accurately weigh Pt-Ph and prepare a 1 mmol / L tetrahydrofuran stock solution. Dilute the obtained stock solution to a 10 µmol / L tetrahydrofuran solution for testing. Tetrahydrofuran is used as the solvent to test the UV-Vis absorption and fluorescence spectra of the platinum complex, to study the optical properties of the platinum complex, and to determine the excitation and emission wavelengths. For subsequent water analysis, dimethyl sulfoxide / 1,4-dioxane solvent is used.
[0040] UV-Vis absorption spectroscopy test: First, a blank tetrahydrofuran was tested to remove background interference, and then a 10µmol / L Pt-Ph tetrahydrofuran solution was placed in the card slot for testing.
[0041] Fluorescence spectroscopy test: The maximum absorption wavelength in the ultraviolet absorption spectrum is used as the excitation wavelength, the fluorescence spectral parameters are set, and the test is performed.
[0042] The UV-Vis absorption and fluorescence spectra of Pt-Ph are shown below. Figure 2 As shown. Figure 2 In the image, the left side shows the UV-Vis absorption spectrum of Pt-Ph; the right side shows the fluorescence spectrum under 430 nm excitation. (Testing) Figure 2 The purpose is to study the optical properties of platinum complexes, laying the groundwork for subsequent detection of the excitation wavelength and spectrum of the solution.
[0043] Example 2: Application of platinum complex fluorescent probe Pt-Ph in water detection
[0044] Absorption and fluorescence titration experiments of water detection using the platinum complex fluorescent probe Pt-Ph;
[0045] A Pt-Ph standard solution was prepared using dimethyl sulfoxide (5% v / v) / 1,4-dioxane (95% v / v) to achieve a concentration of 1×10⁻⁶. -5 A standard solution of mol / L was prepared, and its fluorescence intensity was measured. Then, 10 μL of the water to be tested was added to the standard solution each time. After stirring thoroughly, the fluorescence intensity was measured again. This process was repeated until the absorbance and fluorescence intensity no longer changed.
[0046] Specifically, quantitative detection of water content in the solution;
[0047] The concentration of the platinum complex fluorescent probe of this invention is 1.0 × 10⁻⁶. -5Different volumes of water were added to a mol / L standard solution, namely 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100 μL, which represent 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, and 5% of the standard solution volume, respectively. The mixture was stirred thoroughly, and the UV-Vis absorption spectra of the standard solutions at different water contents and the fluorescence emission spectra were measured at a fixed excitation wavelength of 430 nm.
[0048] Test results as follows Figure 3 As shown.
[0049] It can be seen that different amounts of water can cause varying degrees of decrease in absorbance and fluorescence in the platinum complex fluorescent probe solution. Figure 3 From top to bottom, the corresponding water content increases, absorbance decreases, and fluorescence intensity increases.
[0050] Based on the linear relationship between the gradual decrease in fluorescence intensity and different water contents, the detection limit is 0.05%, as shown in the results. Figure 4 As shown, the fluorescence change has a good linear relationship with the water content, enabling accurate detection of water.
[0051] In summary, the method for detecting water content using platinum complex fluorescent probes is as follows:
[0052] (1) To a concentration of 1.0×10 -5 Add the test solution / water of different concentrations to a mol / L platinum complex fluorescent probe standard solution, stir, and set aside.
[0053] (2) Measure the fluorescence intensity of the test solution / water with different contents at 600 nm.
[0054] (3) Plot the linear relationship between water content and fluorescence intensity, and calculate the water content in the solution to be tested.
Claims
1. A platinum complex fluorescent probe, characterized in that, Its chemical formula is: C 23 H 16 ClN3Pt; Its structural formula is: .
2. A method for preparing a platinum complex fluorescent probe as described in claim 1, characterized in that, Includes the following steps: Step 1: Under argon protection, terpyridine, potassium tetrachloroplatinate, deionized water and dimethyl sulfoxide are mixed in a round-bottom flask, heated and stirred under reflux, cooled to room temperature, concentrated hydrochloric acid is added, the precipitate is obtained by suction filtration, dried and Pt-Cl is obtained. Step 2: Mix Pt-Cl, phenylacetylene, cuprous iodide, N,N-dimethylformamide and triethylamine into a round-bottom flask, then purge with argon gas several times. After the reaction, filter to obtain the precipitate, wash and dry it to obtain the final product.
3. The method for preparing the platinum complex fluorescent probe according to claim 2, characterized in that, In step 1, the molar ratio of terpyridine to potassium tetrachloroplatinate is 1:1, and the volume ratio of deionized water to dimethyl sulfoxide is 10:
1.
4. The method for preparing the platinum complex fluorescent probe according to claim 2 or 3, characterized in that, In step 1, the reaction temperature is 100℃ and the reaction time is 2 hours.
5. The method for preparing the platinum complex fluorescent probe according to claim 2, characterized in that, In step 2, the molar ratio of Pt-Cl, phenylacetylene, and cuprous iodide is 1:3.3:0.5, and the volume ratio of N,N-dimethylformamide and triethylamine is 10:
1.
6. The method for preparing the platinum complex fluorescent probe according to claim 2 or 5, characterized in that, In step 2, the reaction temperature is 25℃ and the reaction time is 24 hours.
7. The application of the platinum complex fluorescent probe as described in claim 1 in the detection of water, characterized in that, The platinum complex fluorescent probe was dissolved in a 1,4-dioxane dimethyl sulfoxide solution to prepare a standard solution; then water of different volume ratios was added, and UV-Vis absorption and fluorescence spectra were measured to establish a linear relationship.
8. The application of the platinum complex fluorescent probe according to claim 7 in the detection of water, characterized in that, The volume fraction of the 1,4-dioxane dimethyl sulfoxide solution is 95%; the concentration of the standard solution is 10 μM.