Preparation of a nitrogen-containing phosphate resin monomer and its application in iron ion indication
By preparing nitrogen-containing phosphate resin monomers, the problem of low Fe³+ capture efficiency of resin-based sensing materials was solved, achieving high selectivity detection of iron ions and low background noise, reaching a detection limit of 9.5 μM, which is suitable for high-end manufacturing and biomedical fields.
Patent Information
- Application Number
- CN202610089775.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-22
- Publication Date
- 2026-05-26
AI Technical Summary
Existing resin-based sensing materials have low capture efficiency for Fe³⁺ and high background noise, making it difficult to break through the ppb/ppt threshold for detection limits and failing to meet the stringent purity standards for materials in high-end manufacturing and biomedical fields.
By constructing nitrogen-containing phosphate chelating sites through functionalization, nitrogen-containing phosphate resin monomers are prepared for ultrasensitive detection and signal amplification of iron ions, taking advantage of their high fluorescence quantum yield and photo/electric response characteristics.
It achieves highly selective detection of iron ions with a detection limit of 9.5 μM, and possesses high detection sensitivity and low environmental pollution characteristics.
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Figure CN122080073A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of new chemical materials technology, and more specifically, to the preparation of a novel nitrogen-containing phosphate resin monomer. This type of compound has a high fluorescence quantum yield and can be used for the indication of iron ions. Background Technology
[0002] Faced with stringent standards for material purity down to the ultra-trace level in high-end manufacturing and biopharmaceutical fields, constructing highly sensitive detection systems for specific metal ions has become a core challenge in quality control. While resin-based sensing materials are highly anticipated due to their ease of preparation and good reproducibility, existing systems are often limited by a sensitivity ceiling—specifically, for Fe³⁺ ions. + Plasma exhibits low capture efficiency and high background noise, making it difficult to break through the ppb / ppt detection limit. Given that the functional group structure of the adsorbent is the physicochemical basis determining the signal-to-noise ratio and sensitivity of the detection, this study aims to construct nitrogen-containing phosphate chelating sites with strong photo / electro-responsive properties through functionalization modification of the resin matrix. Based on this, the key scientific question focused in this study is: how can nitrogen-containing phosphate resin monomers achieve ultrasensitive detection and signal amplification of iron ions through coordination environment regulation? Summary of the Invention This invention provides a method for preparing nitrogen-containing phosphate resin monomers and their application in indicating iron ions. This compound is not only simple and readily available, with low manufacturing costs and high fluorescence quantum yield, but also causes minimal environmental pollution.
[0003] Preparation of a nitrogen-containing phosphate resin monomer and its application as an indicator of iron ions, wherein the chemical structural formula of the compound is as follows:
[0004] A method for synthesizing the nitrogen-containing phosphate resin monomer, the method comprising the following synthetic route:
[0005] The method specifically includes the following steps: (1) Compound Z+3, trimethylbromosilane, was added to the reaction flask at room temperature. After dissolving in dichloromethane, the temperature was raised to 40°C and the reaction was carried out for 12 hours to obtain the reaction solution. The reaction process was monitored in real time using TLC (thin-layer chromatography). (2) Cool the reaction solution in step (1) to room temperature, remove the solvent under reduced pressure, and finally purify it by silica gel column chromatography [eluent is V(ethyl acetate)∶V(acetic acid)=100∶1]. After rotary evaporation, a series of yellow compounds I, namely nitrogen-containing phosphate resin monomers, are obtained.
[0006] The raw material is Z+3 in the application CN118994249A, entitled "Preparation of a Phosphorus-Containing Seven-Member Fluoroboron Compound and Its Application in Fluorescent Ink". It reacts under the action of trimethylbromosilane; the feed ratio of Z+3 to trimethylbromosilane is 1:3~5.
[0007] The heating temperature in step (1) is 20~60℃ and the heating time is 9~15 hours.
[0008] The solvents include dichloromethane and DMSO.
[0009] The eluent used in the silica gel column chromatography purification process is V(ethyl acetate):V(acetic acid) = 100-150:1.
[0010] The present invention also provides a fluorescent probe for iron ion detection, comprising the aforementioned nitrogen-containing phosphate resin monomer.
[0011] A method for detecting Fe in aqueous phase 3+ The method includes the following steps: The nitrogen-containing phosphate resin monomer is dissolved in the aqueous phase to form a probe solution; Add the sample to be tested to the probe solution; Measure the change in fluorescence intensity and determine the Fe based on the fluorescence quenching effect. 3+ The existence of.
[0012] The nitrogen-containing phosphate resin monomer has a positive effect on Fe 3+ The detection limit is 9.5 μM.
[0013] The beneficial effects of this invention are as follows: The nitrogen-containing phosphate resin monomer described in this invention has great potential in the field of iron ion indication and can be used for Fe 3+ It exhibits selective detection and high detection sensitivity. Attached Figure Description
[0014] Figure 1 This is the proton NMR spectrum of compound I obtained in Example 1.
[0015] Figure 2 This is a fluorescence intensity detection graph of compound I after the addition of various ions.
[0016] Figure 3 This is a graph showing the fluorescence intensity ratio (F / F0) of compound I with different added metal ions compared to the blank group.
[0017] Figure 4 Different concentrations of Fe 3+ The fluorescence emission spectrum of compound I.
[0018] Figure 5The fluorescence intensity of compound I in the range of (66~6000) μM is related to Fe 3+ Linear relationship graph of concentration. Detailed Implementation
[0019] The present invention will be further illustrated below with reference to the embodiments, but the scope of protection of the present invention is not limited to the scope described in the embodiments.
[0020] Example 1 Weigh out compound Z+3 (112 mg, 0.25 mmol), add trimethylbromosilane (0.61 mL, 1.25 mmol), dissolve it in 5.00 mL of dichloromethane, heat and stir at 40 °C for 12 hours. After the reaction is complete, cool to room temperature, remove the solvent under reduced pressure, and finally purify by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). After rotary evaporation, obtain the yellow compound compound I with a yield of 56.8%.
[0021]
[0022] Example 2 Compound Z+3 (112 mg, 0.25 mmol) was weighed and dissolved in 5.00 mL of dichloromethane. The mixture was heated and stirred at 60 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Finally, the mixture was purified by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). The yellow compound, compound I, was obtained by rotary evaporation. Compared to Example 1, the temperature was increased by 20 °C. C, its yield decreased by 12.4%.
[0023]
[0024] Example 3 Compound Z+3 (112 mg, 0.25 mmol) was weighed and then trimethylbromosilane (0.61 mL, 1.25 mmol) was added. The solution was dissolved in 5.00 mL of dichloromethane. The mixture was heated and stirred at 20 °C for 12 hours. After the reaction was complete, it was cooled to room temperature, and the solvent was removed under reduced pressure. Finally, the mixture was purified by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). Rotary evaporation yielded the yellow compound, compound I. Compared to Example 2, the temperature decreased by 40 °C. C, its yield decreased by 8.6%.
[0025]
[0026] Example 4 Weigh out compound Z+3 (112 mg, 0.25 mmol), add trimethylbromosilane (0.61 mL, 1.25 mmol), dissolve it in 5.00 mL of dichloromethane, heat and stir at 40 °C for 9 hours. After the reaction is complete, cool to room temperature, remove the solvent under reduced pressure, and finally purify by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). After rotary evaporation, obtain yellow compound I with a yield of 39.4%.
[0027]
[0028] Example 5 Compound Z+3 (112 mg, 0.25 mmol) was weighed and then trimethylbromosilane (0.61 mL, 1.25 mmol) was added. After dissolving it in 5.00 mL of dichloromethane, the mixture was heated and stirred at 40 °C for 15 hours. After the reaction was complete, it was cooled to room temperature, and the solvent was removed under reduced pressure. Finally, it was purified by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). After rotary evaporation, the yellow compound compound I was obtained. Compared with Example 4, the reaction time was 6 hours longer and the yield decreased by 5.1%.
[0029]
[0030] Example 6 Compound Z+3 (112 mg, 0.25 mmol) was weighed and then trimethylbromosilane (0.38 mL, 0.75 mmol) was added. After dissolving it in 5.00 mL of dichloromethane, the mixture was heated and stirred at 40 °C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Finally, the mixture was purified by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). After rotary evaporation, the yellow compound compound I was obtained with a yield of 43.1%.
[0031]
[0032] Example 7 Compound Z+3 (112 mg, 0.25 mmol) was weighed, and trimethylbromosilane (0.5 mL, 1 mmol) was added. After dissolving it in 5.00 mL of dichloromethane, the mixture was heated and stirred at 40 °C for 12 hours. After the reaction was complete, it was cooled to room temperature, and the solvent was removed under reduced pressure. Finally, it was purified by silica gel column chromatography (eluent: V(ethyl acetate):V(acetic acid) = 100:1). After rotary evaporation, the yellow compound compound I was obtained. Compared with Example 6, the amount of trimethylbromosilane was increased, and its yield increased by 17.6%.
[0033]
[0034] Example 8: Application of nitrogen-containing phosphate resin monomers Example 8-1 Weigh out 0.01 mmol of compound I and dissolve it in 1 mL of deionized water; take 18.0 μL of the solution from the mother liquor and add 3.0 mL of deionized water to prepare a solution with a concentration of 6 × 10⁻⁶ mmol / L. -5 The test solution was prepared at a concentration of mmol / mL. Then, a solution with a concentration of 6.6 × 10⁻⁶ mmol / mL was added to the above solution. - 5 Different types of metal ion solutions (Mn) at mmol / mL 2+ Fe 2+ Ni 2+ K + Cu 2+ Fe 3+ Na + Zn 2+ Ca 2+ Co2+ and Al 3 + After shaking for 30 seconds, transfer the solution to a cuvette. Finally, place the cuvette in a fluorescence spectrophotometer to detect fluorescence (e.g., Figure 2 ).
[0035] Therefore, the selective detection of I for various metal ions was studied by fluorescence spectroscopy. Figure 2 These are several common metal ions (Mn 2+ Fe 2+ Ni 2+ K + Cu 2+ Fe 3+ Na + Zn 2+ Ca 2+ Co 2+ And Al 3+ The effect of I concentration on fluorescence intensity (I concentration is 6 × 10⁻⁶) -5 (mmol / mL, all measured under 440 nm excitation), at an ion concentration of 6.6 × 10⁻⁶. -5 Under the same conditions of mmol / mL, the fluorescence intensity of I increased with Fe 3+ The addition of ions significantly reduced the effect. Figure 3 The graph shows the fluorescence intensity ratio (F / F0) of I after the addition of different metal ions. The changes in fluorescence intensity of I after the addition of various metal ions are clearly observed, indicating that I affects Fe... 3+ Ions exhibit high selectivity.
[0036] Example 8-2 To investigate the effect of I on different concentrations of Fe 3+ The response was measured at different concentrations of Fe. 3+The effect on the fluorescence intensity of I.
[0037] Weigh out 0.01 mmol of compound I and dissolve it in 1 mL of deionized water; take 18.0 μL of the solution from the mother liquor and add 3.0 mL of deionized water to prepare a solution with a concentration of 6 × 10⁻⁶ mmol / L. -5 The test solution was prepared at a concentration of mmol / mL. Then, a solution with a concentration of 6.6 × 10⁻⁶ mmol / mL was added to the above solution. - 5 mmol / mL Fe 3+ The fluorescence intensity of compound I in the solution was measured to be 843.2.
[0038] Example 8-3 Weigh out 0.01 mmol of compound I and dissolve it in 1 mL of deionized water; take 18.0 μL of the solution from the mother liquor and add 3.0 mL of deionized water to prepare a solution with a concentration of 6 × 10⁻⁶ mmol / L. -5 The test solution was prepared at a concentration of mmol / mL. Then, a solution with a concentration of 9.0 × 10⁻⁶ mmol / mL was added to the above solution. -4 mmol / mL Fe 3+ The fluorescence intensity of compound I in the solution was measured to be 836.9.
[0039] Example 8-4 Weigh out 0.01 mmol of compound I and dissolve it in 1 mL of deionized water; take 18.0 μL of the solution from the mother liquor and add 3.0 mL of deionized water to prepare a solution with a concentration of 6 × 10⁻⁶ mmol / L. -5 The test solution was prepared at a concentration of mmol / mL. Then, a solution with a concentration of 1.2 × 10⁻⁶ mmol / mL was added to the above solution. - 3 mmol / mL Fe 3+ The fluorescence intensity of compound I in the solution was measured to be 722.1.
[0040] Example 8-5 Weigh out 0.01 mmol of compound I and dissolve it in 1 mL of deionized water; take 18.0 μL of the solution from the mother liquor and add 3.0 mL of deionized water to prepare a solution with a concentration of 6 × 10⁻⁶ mmol / L. -5 The test solution was prepared at a concentration of mmol / mL. Then, a solution with a concentration of 1.5 × 10⁻⁶ mmol / mL was added to the above solution. - 3 mmol / mL Fe 3+ The fluorescence intensity of compound I in the solution was measured to be 687.9.
[0041] Figure 4 It involves adding different concentrations of Fe 3+ The fluorescence emission spectrum of I after Figure 5 The fluorescence intensity F and Fe in the range of (66~6000) μM are 3+The linear relationship between concentrations. The linear equation is F = -0.58867C + 784.34241 (R 2 =0.951), where C is Fe 3+ The concentration, calculated using the limit of detection formula LOD = 3σ / k (σ: blank standard deviation of I, k: slope of the fitted curve), yielded a limit of detection of 9.5 μM. The results indicate that I has a significant effect on Fe... 3+ It exhibits high sensitivity.
[0042] The above embodiments are merely preferred technical solutions of the present invention and should not be considered as limitations on the present invention. The embodiments and features described in this application can be arbitrarily combined with each other without conflict. The scope of protection of the present invention should be limited to the technical solutions described in the claims, including equivalent substitutions of the technical features described in the claims. That is, equivalent substitutions and improvements within this scope are also within the scope of protection of the present invention.
Claims
1. A nitrogen-containing phosphate resin monomer, characterized in that, The structural formula of the compound is shown below: Ⅰ。 2. The method for synthesizing nitrogen-containing phosphate resin monomers according to claim 1, characterized in that, This can be achieved through the following method: The method includes the following steps: (1) Compound Z+3 and trimethylbromosilane were added to the reaction flask at room temperature. After the solvent dissolved the compound, the reaction was heated to obtain the reaction solution. The reaction process was monitored in real time by TLC. (2) Cool the reaction solution in step (1) to room temperature, remove the solvent under reduced pressure, and finally purify it by silica gel column chromatography. After rotary evaporation, a series of yellow compounds I, namely nitrogen-containing phosphate resin monomers, are obtained.
3. The method for synthesizing nitrogen-containing phosphate resin monomers according to claim 2, characterized in that, In step (1), the molar ratio of Z+3 and trimethylbromosilane is 1:3~5, and the solvents include dichloromethane and DMSO.
4. The method for synthesizing nitrogen-containing phosphate resin monomers according to claim 2, characterized in that, The heating temperature in step (1) is 20~60℃ and the heating time is 9~15 hours.
5. The method for synthesizing nitrogen-containing phosphate resin monomers according to claim 2, characterized in that, The eluent used in the silica gel column chromatography purification process is V(ethyl acetate):V(acetic acid) = 100-150:
1.
6. A fluorescent probe for iron ion detection, characterized in that, It contains the nitrogen-containing phosphate resin monomer as described in claim 1.
7. A method for detecting Fe in an aqueous phase 3+ The method is characterized by, Includes the following steps: The nitrogen-containing phosphate resin monomer of claim 1 is dissolved in an aqueous phase to form a probe solution; Add the sample to be tested to the probe solution; Measure the change in fluorescence intensity and determine the Fe based on the fluorescence quenching effect. 3+ The existence of.
8. The method according to claim 9 or 10, characterized in that, The nitrogen-containing phosphate resin monomer has a positive effect on Fe 3+ The detection limit is 9.5 μM.