A kind of bisphenol a thio phosphine hydrazine class silver, zinc and cadmium ion fluorescence probe

Abstract

The application discloses a kind of bisphenol A thio phosphine hydrazine class silver, zinc and cadmium ion fluorescent probe, specifically utilize bisphenol A and hexamethylenetetramine under acidic conditions Duff aldehyde group reaction obtains bisphenol A dialdehyde compound, simultaneously utilize diphenyl phosphine chloride and sublimation sulfur carry out sulfuration reaction and obtain intermediate 1, again 1 and hydrazine hydrate carry out substitution reaction and obtain intermediate 2, intermediate 2 and bisphenol A dialdehyde compound carry out amine aldehyde condensation reaction and prepare probe DPSN.The fluorescent probe of the application responds quickly and has high specificity recognition chemical fluorescence sensor, can be used for the detection of trace Ag + 、Zn 2+ And Cd 2+ In environment, with good practical application and popularization value, and preparation raw material is easy to obtain, synthesis is simple, and yield is high.

Description

TECHNICAL FIELD

[0001] The application relates to a bisphenol A thio phosphine hydrazine silver, zinc and cadmium ion fluorescent probe, and belongs to the technical field of organic fluorescent functional materials. BACKGROUND

[0002] Silver, zinc and cadmium have very wide applications in human production and life. At present, silver is widely used in electronic, food and pharmaceutical industries, and the industrial wastewater generated thereby releases a large amount of pollutants into the environment. As one of heavy metal ions, silver ions can form strong binding with some microorganisms, thereby affecting the respiration of the microorganisms and causing apoptosis. Long-term contact of human body with silver can make the skin surface appear bluish gray, and high levels of Ag + in the body can cause toxicological disorders such as silver protein / silver protein disease, hypotension and skin diseases.

[0003] Zinc is an essential trace element for the human body, and plays an important role in various biological systems such as gene expression and nerve transmission. When the human body lacks a certain amount of zinc, it can also cause growth retardation, immune deficiency and nervous system dysfunction, etc. On the contrary, excessive intake of zinc can also damage various metabolic processes and induce cell apoptosis, and also increase the incidence of cardiovascular diseases. Zinc in the environment mainly comes from zinc mining, mechanical manufacturing, etc. Excessive existence of Zn 2+ in the environment can make the soil lose activity, thereby causing heavy metal ion pollution.

[0004] Unlike silver and zinc, cadmium is one of the most toxic and harmful heavy metals, and cadmium and related compounds are currently classified as class 1 carcinogens. Metallic cadmium is widely used in industrial and agricultural processes, including electroplating, metallurgy and military industry. Cadmium is not an essential element for the human body. Cadmium in the human body is generally enriched from the external environment. Long-term intake of cadmium ions can cause great harm to human health, leading to itai-itai disease, kidney damage and prostate cancer, etc.

[0005] Therefore, it is of great significance to detect the above three metal ions in water bodies, natural environments and organisms with high sensitivity for ecological environment protection and human health. However, the current methods for detecting metal ions mainly include spectrophotometry, inductively coupled plasma analysis and atomic absorption spectrometry. These testing methods generally have the disadvantages of inconvenient operation, high cost and slow signal response. Fluorescence analysis method has attracted widespread attention due to its high sensitivity, simple operation and low testing cost. Most of the currently reported fluorescent sensors for monitoring Ag + are fluorescence quenching, and few are fluorescence enhancement and have color change effect. For example, in 2023, Hongqi Li et al. developed a coumarin-based fluorescent probe with large stokes shift for monitoring Hg 2+ and Ag + . The probe has a high selectivity for Ag+ It exhibits fluorescence quenching. (Li, HQ; Yan, JB; Jiang, L.; Zhao, Y.; Song, YX; Yu, JR; Cheng, L., Selective and Sensitive Detection of Hg) 2+ and Ag + by a Fluorescent and Colorimetric Probe with LargeStokes Shift. [J]. Journal of Fluorescence. 2023); For the reported simultaneous monitoring of Zn 2+ and Cd 2+ Fluorescent probes often exhibit fluorescence quenching phenomena associated with multiple other ions. For example, in 2018, Jia Li et al. developed a probe based on isophthalaldehyde and benzothiazole for the detection of Zn. 2+ and Cd 2+ A fluorescent probe that, when added to Zn 2+ and Cd 2+ Subsequently, the fluorescence color of the solution changed from orange-yellow to green. A total of 18 ions were detected, with 8 ions showing slight quenching and 4 showing complete quenching. (J. Li, YH Chen, TT Chen, J. Qiang, ZJ Zhang, TW Wei, W. Zhang, F. Wang, XQ Chen, A benzothiazole-based fluorescent probe for efficient detection and discrimination of Zn) 2+ and Cd 2+ , using cysteine ​​as an auxiliary reagent. [J]. Sensors and Actuators B:Chemical. 2018, 268, 446-455). Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention aims to provide a novel bisphenol A thiophosphonyl hydrazine-based fluorescent probe for silver, zinc, and cadmium ions and its preparation method. This probe can be used for the detection of Ag... + Zn 2+ and Cd 2+ Rapid identification and detection of different metal ions.

[0007] The application discloses a bisphenol A thio phosphinic hydrazine silver, zinc and cadmium ion fluorescent probe + , Zn 2+ and Cd 2+ The fluorescent probe has the characteristics of multiple response, rapid response time, wide pH application range, convenient and fast detection and remarkable identification effect.

[0008] The chemical structural formula of the bisphenol A thio phosphinic hydrazine silver, zinc and cadmium ion fluorescent probe is as follows:

[0009] ;

[0010] The preparation method of the fluorescent probe is as follows:

[0011] In step 1, bisphenol A and hexamethylenetetramine are dissolved in trifluoroacetic acid, heated to reflux for 3-4 hours, cooled to room temperature, acidified by adding hydrochloric acid while stirring, the product is extracted with ethyl acetate, and the obtained organic phase is separated by washing with water, dried by anhydrous sodium sulfate, evaporated and separated by column chromatography to obtain bisphenol A dialdehyde.

[0012] In step 2, sublimed sulfur is added to diphenyl phosphine chloride under an argon atmosphere, heated to reflux for 0.5 hours to obtain intermediate 1.

[0013] In step 3, anhydrous ethanol is added to intermediate 1, and then hydrazine hydrate is slowly added, heated to reflux for 2-3 hours, cooled to room temperature, and then filtered and washed with deionized water to obtain intermediate 2.

[0014] In step 4, intermediate 2 and bisphenol A dialdehyde are heated to reflux in anhydrous ethanol for 4-6 hours, cooled to room temperature, filtered, and recrystallized with ethanol to obtain the bisphenol A thio phosphinic hydrazine silver, zinc and cadmium ion fluorescent probe (DPSN).

[0015] In step 1, the equivalent ratio of bisphenol A and hexamethylenetetramine is 1:7, and the eluent for column chromatography separation is petroleum ether / ethyl acetate with a volume ratio of 10:1.

[0016] In step 2, the equivalent ratio of sublimed sulfur and diphenyl phosphine chloride is 1:1, and the reaction temperature is 150 DEG C.

[0017] In step 3, the equivalent ratio of intermediate 1 and hydrazine hydrate is 1:10, and the mass concentration of hydrazine hydrate is 80%.

[0018] In step 4, the equivalent ratio of intermediate 2 and bisphenol A dialdehyde is 2:1.

[0019] The reaction equation of the bisphenol A thio phosphinic hydrazine silver, zinc and cadmium ion fluorescent probe is as follows:

[0020] ;

[0021] DPSN is a target fluorescent probe molecule.

[0022] The beneficial effects of the present application are:

[0023] 1. The fluorescent probe of the present application becomes yellow-green fluorescence after adding Ag + , or becomes bright blue after adding Zn 2+ , or becomes blue after adding Cd 2+ , which can be obviously distinguished from other metal ions, and has a high specificity recognition chemical fluorescence sensor with rapid response.

[0024] 2. The detection limit of the fluorescent probe of the present application for Ag + , Zn 2+ and Cd 2+ is very low, which can reach 1.01*10 -7 M, 4.26*10 -6 M and 6.91*10 -6 M respectively, and the sensitivity is high, which can be used for qualitative and quantitative analysis and detection of trace Ag + , Zn 2+ and Cd 2+ ion concentration in the environment and water system, and has very good practical application value.

[0025] 3. The raw materials for preparing the fluorescent probe of the present application are easy to obtain, the synthesis is simple, and the yield is high. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 : the ultraviolet spectrum diagram of the fluorescent probe prepared by the present application after adding Ag + ;

[0027] Figure 2 : the fluorescence emission spectrum diagram of the fluorescent probe prepared by the present application after reacting with different metal ions;

[0028] Figure 3 : the fluorescence emission spectrum diagram of the fluorescent probe prepared by the present application after adding Ag + of different concentrations;

[0029] Figure 4 : the concentration fitting curve diagram of the fluorescent probe prepared by the present application after adding Ag + of different concentrations;

[0030] Figure 5 : the fluorescence emission spectrum diagram of the fluorescent probe prepared by the present application after adding Zn 2+ of different concentrations;

[0031] Figure 6 : Fluorescent probe prepared by the present application added with different concentrations of Zn 2+ concentration fitting curve diagram;

[0032] Figure 7 : Fluorescent probe prepared by the present application added with different concentrations of Cd 2+ after action fluorescence emission spectrum diagram;

[0033] Figure 8 : Fluorescent probe prepared by the present application added with different concentrations of Cd 2+ concentration fitting curve diagram;

[0034] Figure 9 : Job's Plot curve diagram of fluorescent probe DPSN-Ag prepared by the present application; +

[0035] Figure 10 : Job's Plot curve diagram of fluorescent probe DPSN-Zn prepared by the present application; 2+

[0036] Figure 11 : Job's Plot curve diagram of fluorescent probe DPSN-Cd prepared by the present application; 2+

[0037] Figure 12 : Ion competition columnar spectrum diagram of fluorescent probe DPSN-Ag prepared by the present application; +

[0038] Figure 13 : Ion competition columnar spectrum diagram of fluorescent probe DPSN-Zn prepared by the present application; 2+

[0039] Figure 14 : Ion competition columnar spectrum diagram of fluorescent probe DPSN-Cd prepared by the present application; 2+

[0040] Figure 15 : Fluorescence change diagram of fluorescent probe DPSN and DPSN-Ag prepared by the present application in different pH ranges; +

[0041] Figure 16 : Fluorescence change diagram of fluorescent probe DPSN and DPSN-Zn prepared by the present application in different pH ranges; 2+

[0042] Figure 17 : Fluorescence change diagram of fluorescent probe DPSN and DPSN-Cd prepared by the present application in different pH ranges; 2+ ​​​​​​​​​

[0043] Figure 18 H-NMR) spectrum of the fluorescent probe prepared by the present application; 1 H-NMR) spectrum of the fluorescent probe prepared by the present application;

[0044] Figure 19 H-NMR) spectrum of the fluorescent probe prepared by the present application; DETAILED DESCRIPTION

[0045] Example 1

[0046] Preparation of bisphenol A thio phosphine hydrazide fluorescent probe for silver, zinc and cadmium ions

[0047] Synthesis of bisphenol A dialdehyde:

[0048] A round bottom flask was charged with bisphenol A (2.2829 g, 10 mmol) and hexamethylenetetramine (9.8133 g, 70 mmol), and 30 mL of trifluoroacetic acid was gradually added, the reaction temperature was 75°C, and the reaction was heated to reflux for 3 h, the reaction progress was monitored by TLC thin layer chromatography, after the reaction was completed, it was cooled to room temperature, 50 mL of 1M aqueous HCl solution was added dropwise, and stirred at room temperature for 30 min, the obtained mixture was extracted with 50 mL of ethyl acetate three times, the organic phase was combined, washed with saturated brine three times, dried over anhydrous sodium sulfate, and concentrated by rotary evaporation to remove the ethyl acetate solvent, the obtained crude product was purified by column chromatography (eluent: ethyl acetate: petroleum ether = 1:10, v / v), to obtain bisphenol A dialdehyde white needle-like solid (1.5980 g, yield 70%).

[0049] Synthesis of intermediate 1:

[0050] Under an argon atmosphere, a 50 mL round bottom flask was sequentially charged with diphenylphosphine chloride (0.4518 g, 2.05 mmol) and sulfur sublimation (0.0657 g, 2.05 mmol), without adding other solvents, the reaction was carried out at 150°C for 0.5 h, the reaction progress was monitored by TLC thin layer chromatography, after the reaction was completed, a yellow oily liquid was obtained, which was intermediate 1.

[0051] Synthesis of intermediate 2:

[0052] 15 mL of anhydrous ethanol was directly added to the above-mentioned round bottom flask containing intermediate 1, and then 2 mL of hydrazine hydrate compound (mass fraction 80%) was slowly added. The mixture was refluxed at 85°C for 2 h, a light yellow precipitate appeared, and the precipitate was cooled to room temperature, filtered under reduced pressure, washed with deionized water several times and dried, to obtain a light yellow solid, which was intermediate 2 (0.3992 g, yield 78.5%).

[0053] Synthesis of probe DPSN:

[0054] Intermediate 2 (0.2483 g, 1 mmol) and bisphenol A bis-aldehyde (0.1422 g, 0.5 mmol) were dissolved in 10 mL of anhydrous ethanol and heated to reflux at 80 °C for 6 h. After the reaction was completed by TLC monitoring, the solution was cooled to room temperature and filtered to obtain bisphenol A thio-phosphonohydrazide fluorescent probe DPSN (0.3382 g, yield 86.6%).

[0055] 1 H NMR (500 MHz, Chloroform- d ) delta 9.72 (s, 2H), 7.89 (dd, J = 13.9,7.6 Hz, 8H), 7.77 (s, 2H), 7.53 (d, J = 7.5 Hz, 4H), 7.47 (q, J = 6.8, 5.9Hz, 8H), 7.02 (d, J = 8.6 Hz, 2H), 6.86 (s, 2H), 6.72 (d, J = 8.6 Hz, 2H),6.59 (d, J = 16.9 Hz, 2H), 1.56 (s, 6H).ESI-MS calculated for C 41 H 38 N4O2P2S2,744.85, found(m / z), 744.8[M] + .

[0056] Example 2

[0057] UV detection of bisphenol A thio-phosphonohydrazide fluorescent probe DPSN

[0058] 0.0372 g of fluorescent probe DPSN was weighed, dissolved in methanol solvent (MeOH) and diluted to a 50 mL volumetric flask to prepare a solution with a concentration of 1 mmol / L, which was the fluorescent probe DPSN stock solution.

[0059] The test was carried out in a MeOH:H2O = 3:1 (v / v) solution system. 21 5 mL centrifuge tubes were taken, 150 μL of fluorescent probe DPSN stock solution was added to each tube, and 2100 μL of MeOH solution was added. One of the centrifuge tubes did not add metal ion solution to form a blank control, and the remaining 20 centrifuge tubes added 750 μL of 1 mmol / L metal ion solution including Li+ Na + Mg 2+ Al 3+ K + Ca 2+ Cr 3+ Mn 2+ Fe 2+ Fe 3+ Co 2+ Ni 2+ Cu 2+ Zn 2+ Ag + Cd 2+ Ba 2+ Hg 2+ Ce 3 + Zr 4+ After mixing thoroughly, the mixture was transferred to a 1 cm × 1 cm standard quartz cuvette, and the changes in its ultraviolet spectrum were measured.

[0060] The probe dilution solution without added metal ions is colorless and visible to the naked eye. With the addition of Ag... + The detection solution turned light brown, and the full spectrum was scanned using a UV-Vis spectrophotometer. Figure 1 As shown. DPSN+Ag + A new absorption peak appeared at 346 nm in the detection solution.

[0061] Example 3

[0062] Fluorescence selectivity determination of bisphenol A thiophosphonic hydrazide-based fluorescent probe DPSN

[0063] The test was conducted in a MeOH : H2O = 3 : 1 (v / v) solution system. Twenty-one 5 mL centrifuge tubes were used, and 150 μL of the fluorescent probe DPSN stock solution and 2100 μL of MeOH solution were added to each tube, respectively. One centrifuge tube was used as a blank control without metal ion solution. The remaining 20 centrifuge tubes were each added with 750 μL of a 1 mmol / L metal ion solution containing Li. + Na + Mg 2+ Al 3+ K + Ca 2+ Cr 3+ Mn 2+ Fe 2+ Fe 3+ Co 2+ Ni 2+ Cu 2+ Zn 2+Ag + Cd 2+ Ba 2+ Hg 2+ Ce 3 + Zr 4+ After mixing thoroughly, the mixture was transferred to a 1 cm × 1 cm standard quartz cuvette, and the changes in its fluorescence spectrum were measured.

[0064] The fluorescence detection performance of the fluorescent probe DPSN for different metal ions is as follows: Figure 2 As shown. Experiments show that this fluorescent probe molecule interacts with Ag. + Zn 2+ and Cd 2+ After binding, both exhibited obvious fluorescence color change and enhancement, with Ag showing the most significant increase. + The fluorescence color changed from light purple to yellowish-green, Zn 2+ and Cd 2+ The fluorescence color changed from light purple to blue. The results indicate that the fluorescent probe DPSN of this invention is effective against Ag. + Zn 2+ and Cd 2+ They exhibit different fluorescence selectivity effects.

[0065] Example 4

[0066] Fluorescent titration of three ions using bisphenol A thiophosphonic hydrazine-based fluorescent probe DPSN.

[0067] The test was conducted in a MeOH : H2O = 3 : 1 (v / v) solution system. Three sets of 5 mL centrifuge tubes were taken, and 60 μL of the above-mentioned fluorescent probe DPSN stock solution was added to each 5 mL centrifuge tube. Different proportions of Ag were added to the first set of tubes. + Stock solution (0.2 eq ~ 5 eq). The second group was supplemented with different proportions of Zn. 2+ Stock solution (0.2 eq ~ 9 eq). The third group was supplemented with different proportions of Cd. 2+ Stock solution (0.9 eq ~ 10 eq).

[0068] The fluorescence increment was detected using a fluorescence spectrometer at an excitation wavelength of 349 nm (e.g., Figure 3 As shown), the probe fluorescence intensity increases with Ag. + The effect increases with increasing concentration, at 1.2 eq Ag + The maximum fluorescence intensity is reached at a certain concentration. Using the fluorescent probe [Ag] + ] / 10 -5 With M as the x-axis and the fluorescence intensity at 535 nm as the y-axis, plot a linear fitting curve (e.g., M = 535 nm).Figure 4 As shown in the figure, the lowest detection limit (LOD) was calculated to be 1.01 × 10⁻⁶ based on the slope of the linearly fitted line from the scatter plot. -7 M.

[0069] like Figure 5 As shown, the probe fluorescence intensity changes with Zn 2+ The effect increases with increasing concentration, at 8 eq Zn 2+ The maximum fluorescence intensity is reached at a certain concentration. The fluorescent probe [Zn] is used. 2+ ] / 10 -5 With M as the x-axis and the fluorescence intensity at 477 nm as the y-axis, plot a linear fitting curve (e.g., ...). Figure 6 As shown in the figure, the lowest detection limit (LOD) was calculated to be 4.26 × 10⁻⁶ based on the slope of the linearly fitted line from the scatter plot. -6 M.

[0070] like Figure 7 As shown, the probe fluorescence intensity changes with Cd 2+ The effect increases with increasing concentration, at 6 eq Cd 2+ The maximum fluorescence intensity is reached at a concentration of [Cd]. 2+ ] / 10 -5 With M as the x-axis and the fluorescence intensity at 473 nm as the y-axis, plot a linear fitting curve (e.g., M = M * fluorescence intensity at 473 nm). Figure 8 As shown in the figure, the lowest detection limit (LOD) was calculated to be 6.91 × 10⁻⁶ based on the slope of the linearly fitted line from the scatter plot. -6 M.

[0071] Example 5

[0072] Job's Plot curves of three ions from the bisphenol A thiophosphonic hydrazine-based fluorescent probe DPSN.

[0073] The test was conducted in a MeOH : H2O = 3 : 1 (v / v) solution system, with the sum of the concentrations of the probe DPSN and the ions controlled at 200 μM. The concentration ratios of the fluorescent probe DPSN and the ions were 1∶9, 2∶8, 3∶7, 4∶6, 5∶5, 6∶4, 7∶3, 8∶2, and 9∶1, respectively.

[0074] The fluorescence intensity at 535 nm was detected using a fluorescence spectrometer at an excitation wavelength of 349 nm. Figure 9 As shown, [DPSN] / {[DPSN]+[Ag + The fluorescence intensity reaches its maximum around 0.33, and increasing Ag... + The proportional fluorescence intensity decreases, such as Figure 10As shown, the fluorescence intensity at 477 nm was detected, [DPSN] / {[DPSN]+[Zn 2+ The fluorescence intensity reaches its maximum around 0.33, and increasing Zn... 2+ The proportional fluorescence intensity decreases, such as Figure 11 As shown, the fluorescence intensity detected at 473 nm indicates that [DPSN] / {[DPSN]+[Cd 2+] The fluorescence intensity reaches its maximum around 0.33, and increasing Cd... 2+ The proportional fluorescence intensity decreases, from which we can infer the presence of probes DPSN and Ag. + Zn 2+ and Cd 2+ The complexation ratios were all 1:2.

[0075] Example 6

[0076] Bisphenol A thiophosphonyl hydrazine-based fluorescent probe DPSN's interference-resistant detection of three ions

[0077] With Ag + For example, in a MeOH:H2O = 3:1 (v / v) solution system, 40 5 mL centrifuge tubes were divided into two groups, A and B, with 20 tubes in each group. In group A, each centrifuge tube contained 60 μL of 1 mmol / L DPSN stock solution, 2190 μL of MeOH solution, and 450 μL of aqueous solution. The solution in the first centrifuge tube served as a blank. The other 19 centrifuge tubes contained 300 μL of 1 mmol / L Li2O solution. + Na + Mg 2+ Al 3+ K + Ca 2+ Cr 3+ Mn 2+ Fe 2 + Fe 3+ Co 2+ Ni 2+ Cu 2+ Zn 2+ Cd 2+ Ba 2+ Hg 2+ Ce 3+ and Zr 4+ Aqueous solution. In Group B, each centrifuge tube was filled with 60 μL of 1 mmol / L DPSN stock solution, 2190 μL of MeOH solution, and 300 μL of 1 mmol / L Ag. +Aqueous solutions and 150 μL of aqueous solution were added to each of the other 19 centrifuge tubes. The solution in the first centrifuge tube served as the blank group, and 300 μL of 1 mmol / L Li was added to each of the other 19 centrifuge tubes. + Na + Mg 2+ Al 3+ K + Ca 2+ Cr 3+ Mn 2+ Fe 2+ Fe 3+ Co 2+ Ni 2+ Cu 2+ Zn 2+ Cd 2 + Ba 2+ Hg 2+ Ce 3+ and Zr 4+ Aqueous solution. After thorough mixing, the fluorescence intensity was measured at the maximum emission wavelength of 535 nm.

[0078] Zn 2+ and Cd 2+ The testing method is the same as that for silver ions, measuring the fluorescence values ​​of both at their maximum emission wavelengths. Figures 12-14 As shown, this indicates that DPSN, after binding with these three ions, exhibits good anti-interference ability in the presence of different metal ions. Furthermore, according to... Figure 12 It can be seen that when Ag is present in the solution... + and Zn 2+ or Ag + and Cd 2+ At that time, the solutions all showed Ag. + The fluorescence phenomenon observed by the fluorescent probe DPSN is therefore relevant to Ag. + Its anti-interference performance is higher than that of Zn 2+ and Cd 2+ Similarly, in Zn 2+ and Cd 2+ In the comparison of the anti-interference capabilities of the two, according to Figure 13 and Figure 14 It can be seen that DPSN is related to Zn 2+ Its anti-interference ability is higher than that of Cd. 2+ .

[0079] Example 7

[0080] Fluorescence changes of bisphenol A thiophosphonic hydrazide-based fluorescent probes DPSN and ions at different pH values

[0081] Test in MeOH: H2O = 3: 1 (v / v) solution system, prepare four groups of pH 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 test solvents, the first group respectively add 60 μL of the above fluorescent probe DPSN stock solution for determination; The second group respectively add 60 μL of the above fluorescent probe DPSN stock solution and 300 μL of the above Ag + stock solution; The third group respectively add 60 μL of the above fluorescent probe DPSN stock solution and 300 μL of the above Zn 2+ stock solution; The fourth group respectively add 60 μL of the above fluorescent probe DPSN stock solution and 300 μL of the above Cd 2+ stock solution. By fluorescence spectrometer at 349 nm excitation wavelength, respectively, measure the fluorescence value at 535 nm, 477 nm and 473 nm, draw point line graph (such as Figure 15 、 Figure 16 and Figure 17 ). The pH range of the fluorescent probe DPSN for detecting Ag + is 6 ~ 10, the pH range of the fluorescent probe DPSN for detecting Zn 2+ is 5 ~ 10, and the pH range of the fluorescent probe DPSN for detecting Cd 2+ is 5 ~ 10.

Claims

1. A bisphenol A thio-phosphonohydrazide based fluorescent probe for silver, zinc and cadmium ions characterized in that: The chemical structural formula of the fluorescent probe is: 。 2. The bisphenol A thio-phosphonohydrazide based silver, zinc and cadmium ion fluorescent probe according to claim 1, characterized by: The preparation method of the fluorescent probe is as follows: Step 1: Bisphenol A and hexamethylenetetramine are dissolved in trifluoroacetic acid, heated to reflux for 3-4 h, after the reaction is completed, cooled to room temperature, while stirring, add hydrochloric acid, the product is extracted with ethyl acetate, the obtained organic phase is washed with water, dried with anhydrous sodium sulfate, evaporated and separated by column chromatography to obtain bisphenol A dialdehyde; Step 2: Under argon atmosphere, sublimed sulfur is added to diphenyl phosphine chloride, heated to reflux for 0.5 h to obtain intermediate 1; Step 3: Intermediate 1 is added to anhydrous ethanol, then hydrazine hydrate is slowly added, heated to reflux for 2-3 h, then cooled to room temperature, filtered, washed with deionized water to obtain intermediate 2; Step 4: Intermediate 2 and bisphenol A dialdehyde are heated to reflux in anhydrous ethanol for 4-6 h, then cooled to room temperature, filtered, recrystallized with ethanol to obtain bisphenol A thio phosphine hydrazine silver, zinc and cadmium ion fluorescent probe.

3. The bisphenol A thio-phosphonohydrazide based silver, zinc and cadmium ion fluorescent probe according to claim 2, characterized by: In step 1: the equivalent ratio of bisphenol A and hexamethylenetetramine is 1:7, and the eluent for column chromatography separation is petroleum ether / ethyl acetate with a volume ratio of 10:

1.

4. The bisphenol A thiophosphonyl hydrazine-based fluorescent probe for silver, zinc, and cadmium ions according to claim 2, characterized in that: In step 2: the equivalent ratio of sublimed sulfur and diphenyl phosphine chloride is 1:1, and the reaction temperature is 150℃.

5. The bisphenol A thiophosphonyl hydrazine-based fluorescent probe for silver, zinc, and cadmium ions according to claim 2, characterized in that: In step 3: the equivalent ratio of intermediate 1 and hydrazine hydrate is 1:10, and the mass concentration of hydrazine hydrate is 80%.

6. The bisphenol A thiophosphonyl hydrazine-based fluorescent probe for silver, zinc, and cadmium ions according to claim 2, characterized in that: In step 4: the equivalent ratio of intermediate 2 and bisphenol A dialdehyde is 2:1.

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