A method for detecting silver ion content with dual fluorescence and phosphorescence responses

Abstract

The present invention discloses a method for detecting silver ion content with dual fluorescence and phosphorescence responses, belonging to the technical field of heavy metal ion detection. The method includes the following steps: synthesis of polyaminosiloxane, establishment of a standard working curve for detecting silver ion concentration, and determination of actual samples. The method of the present invention determines the silver ion content by detecting the changes in the fluorescence and phosphorescence intensities of the detector, and can achieve rapid and efficient dual-response detection. This highly sensitive, rapid, and accurate detection method has strong practicability, is suitable for industrial production, and has broad application prospects in the field of heavy metal ion detection.

Description

Technical Field

[0001] The present invention belongs to the technical field of heavy metal ion detection, and particularly relates to a method for detecting silver ion content with dual fluorescence and phosphorescence responses. Background Art

[0002] With the continuous improvement of the world's industrial level, the prevention and control of heavy metal pollution has become an important task. Heavy metal pollution is one of the most serious environmental problems affecting global sustainable development. Heavy metal ions are generally non-biodegradable and will continuously accumulate in the food chain, posing a very serious threat to the environment and human health. The noble metal silver (Ag) and its derivatives play an important role in the long history of mankind and the development of modern civilization. Known for its scarcity and attractive appearance, silver is widely used in daily life for making jewelry, coins, silverware, etc. At the same time, due to the bactericidal property of silver ions in inactivating microorganisms such as Gram-positive bacteria, Gram-negative bacteria, and fungi, silver ions are also widely used as antibacterial drugs for sterilization and disinfection of body parts such as dentistry and nasal cavities. On the other hand, the large-scale use of silver in the fields of electronics and photographic imaging industries has led to the generation of a large amount of silver-containing industrial waste. Although silver has brought certain conveniences to human society, silver can also inactivate sulfhydryl enzymes, bind to imidazole, amine, and carboxyl groups of various metabolites, and replace Ca2+ and Zn2+ in hydroxyapatite, while hydroxyapatite is the main inorganic component of the bones of humans and animals. Therefore, excessive silver can cause various diseases such as growth retardation, anemia, cardiac enlargement, neurodegenerative diseases, etc. In addition, insoluble heavy metal deposits can also cause serious damage to the skin, kidneys, etc. It is very necessary to develop a method for rapidly, highly sensitively, and selectively detecting silver ions, which is of great significance to human health. However, currently, traditional detection methods mainly include atomic absorption or emission spectrometry, inductively coupled plasma mass spectrometry, etc. Such detection methods require complex and time-consuming pretreatment processes and expensive instrument equipment support. Fluorescent probes are a simple, rapid, highly sensitive, low-cost, and efficient detection method, with advantages such as real-time imaging and real-time tracking. However, in practical applications, due to the often very complex composition of actual water samples, in addition to dissolving a large number of non-target heavy metal ions, there are also a large number of soluble blending impurities, such as soluble dyes, etc. This will cause very serious fluorescence background interference to traditional optical probes. This will lead to deviations in the accuracy of the spectrum and affect the experimental precision. Therefore, to achieve the direct detection of heavy metal ions in polluted wastewater, the construction of anti-background interference probes is particularly important. Summary of the Invention

[0003] In view of the above situation, the present invention provides a method for detecting silver ion content with dual fluorescence and phosphorescence responses. Through the relationship between silver ion concentration and fluorescence / phosphorescence emission intensity, efficient and rapid detection is achieved. The dual-response probe can mutually corroborate the test results, effectively solve the problems existing in the prior art, and ensure the accuracy of the detection results.

[0004] To achieve the above object, the technical solution provided by the present invention is as follows:

[0005] A method for detecting silver ion content with dual fluorescence and phosphorescence responses, comprising the following steps:

[0006] (1) Synthesis of polyaminosiloxane: Mix aminosiloxane with dilute acid and deionized water, stir vigorously at room temperature for 3 h, then raise the temperature to 90 °C and age for 24 hours before stopping the reaction. After the reaction is completed, rinse with deionized water, filter, and dry in a vacuum oven at 80 °C for 24 h. The obtained white powder is polyaminosiloxane.

[0007] (2) Establishment of the standard working curve for silver ion concentration detection: Immerse the polyaminosiloxane prepared in step (1) in silver ion standard solutions with different concentrations for a period of time. After heating at 100 °C for 1 min, conduct subsequent fluorescence and phosphorescence spectrum acquisition experiments, and respectively establish the standard working curve of silver ion concentration vs. the relative intensity of any fluorescence emission peak before and after polyaminosiloxane treatment and the standard working curve of silver ion concentration vs. the relative intensity of any phosphorescence emission peak before and after polyaminosiloxane treatment;

[0008] (3) Determination of the actual sample: First, obtain the fluorescence and phosphorescence emission spectra of the polyaminosiloxane without adding the analyte to be measured for standby using a spectrometer. Then, after centrifuging and filtering the insoluble substances of the analyte to be measured, immerse the polyaminosiloxane prepared in step (1) in the analyte to be measured for a period of time, fish out and dry the moisture, conduct fluorescence and phosphorescence spectrum tests to obtain the spectrum of the treated polyaminosiloxane, take the intensity of any fluorescence and phosphorescence emission peaks, compare the peak intensity here with the emission intensity before treatment to obtain the relative intensity, and use the standard working curves obtained in step (2) and the relative fluorescence and phosphorescence emission intensities to calculate the silver ion content in the experimental sample solution respectively. The average value of the test results of the two methods is the finally measured silver ion concentration.

[0009] In the above step (1), the purity of aminosiloxane and dilute acid is chemically pure, with a content greater than 98%, and no further purification is carried out; the usage amounts of the aminosiloxane, dilute acid, and deionized water are 10:0.1:0.28 (molar ratio).

[0010] In the above step (1), the aminosiloxane includes but is not limited to one of the compounds with the following structural formulas:

[0011] .

[0012] The dilute acid used in the above step (1) is dilute hydrochloric acid or dilute hydrobromic acid, and the concentration of the dilute acid is 0.1 - 0.5 mol / L.

[0013] The minimum dosage of the polyaminosiloxane in the above step (2) is 10 mg, there is no upper limit on the dosage, and the optimal dosage is 10 - 100 mg.

[0014] The insoluble matter obtained by centrifugal filtration of the analyte in the above step (3) is: the analyte needs to be centrifugally filtered to remove insoluble matters such as sand, dust, and paper scraps and then reserved for use.

[0015] In the above steps (2) and (3), the polyaminosiloxane is immersed in the insoluble matter obtained by centrifugal filtration for 1 minute.

[0016] In the above steps (2) and (3), the fluorescence emission peaks are the same, and the phosphorescence emission peaks are also the same.

[0017] The beneficial effects of the present invention are as follows:

[0018] (1) The present invention first proposes to use fluorescence and phosphorescence dual-response detection for the rapid sensing analysis method of silver ions, and obtains an efficient, rapid, and accurate single-ion dual-response detection material. In the concentration range of 2×10 -9 mol / L – 2×10 -3 mol / L, a standard working curve of the silver ion concentration and the fluorescence and phosphorescence emission intensities of the polyaminosiloxane is established, and the lowest detection limit of silver ions is 2.65×10 -11 mol / L.

[0019] (2) Compared with the traditional sensors, the determination method provided by the present invention realizes dual-response detection, can deduct the influence of soluble fluorescent dyes on the spectrum through mutual verification of data, achieves the effect of multiple verifications in one test, and has the advantages of rapidity and high precision. Description of the Drawings

[0020] Figure 1 is the standard curve of the fluorescence emission of the polyaminosiloxane by silver ions with different concentrations;

[0021] Figure 2 is the standard curve of the phosphorescence emission of the polyaminosiloxane by silver ions with different concentrations. Detailed Embodiments

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.

[0023] The specific embodiments of the present invention are as follows:

[0024] Formulation of the standard working curve

[0025] (1) Instruments and Reagents

[0026] Steady-state / transient fluorescence spectrometer that can test the visible light range;

[0027] Polyaminosiloxane: Self-synthesized;

[0028] Standard application solutions of silver ions with different concentrations, self-prepared.

[0029] (2) Experimental Procedures

[0030] Take 10 mg of polyaminosiloxane and soak it in 1 mL of silver nitrate solutions with different concentrations. After leaving it at room temperature for 1 minute, take it out and conduct subsequent fluorescence and phosphorescence spectroscopy experiments. Respectively establish the standard working curves of silver ion concentration x and the intensity y of any emission peak of polyaminosiloxane fluorescence and phosphorescence.

[0031] Example 1

[0032] A method for detecting silver ion content with dual fluorescence and phosphorescence responses, including the following steps:

[0033] (1) Synthesis of polyaminosiloxane: Mix amino siloxane (10 mmol), 1 mL of 0.1 N HCl solution, and 5 mL of deionized water, and stir vigorously at room temperature for three hours. After three hours, raise the temperature to 90 °C and age for 24 hours to stop the reaction. After the reaction, rinse with deionized water and dry in a vacuum oven at 80 °C. The obtained white powder is polyaminosiloxane;

[0034] (2) Establishment of the standard working curve for silver ion concentration detection: Prepare standard solutions of silver ions with different concentrations (2×10 -3 , 2×10 -4 , 2×10 -5 , 2×10 -6 , 2×10 -7 , 2×10 -8 , 2×10 -9 mol / L). Take the polyaminosiloxane prepared in step (1) and soak it in 1 mL of silver ion standard solutions with different concentrations. After standing at room temperature for 1 minute, take it out, heat it at 100 °C to evaporate the surface moisture, and then conduct subsequent fluorescence and phosphorescence spectroscopy tests. Establish the standard working curves of silver ion concentration x and the peak intensity y of polyaminosiloxane at 440 nm (fluorescence) and 496 nm (phosphorescence); The standard curve of the fluorescence emission of polyaminosiloxane by silver ions with different concentrations is shown in Figure 1 ; The standard curve of the phosphorescence emission of polyaminosiloxane by silver ions with different concentrations is shown in Figure 2 .

[0035] (3)Determination of actual samples: The fluorescence and phosphorescence emission spectra of untreated polyaminosiloxane powder were obtained using a spectrometer. Then, after the solution sample was pretreated, the polyaminosiloxane powder prepared in step (1) was immersed in 1 mL of the solution sample to be tested. After 1 minute, it was fished out, and the surface moisture was evaporated at 100 °C. Then, fluorescence and phosphorescence spectra were measured to obtain the fluorescence and phosphorescence emission spectra of the treated polyaminosiloxane. The relative intensities of the emission peaks of polyaminosiloxane at 440 nm (fluorescence) and 496 nm (phosphorescence) before and after treatment were calculated. The silver ion contents calculated by the two methods were obtained using the fluorescence and phosphorescence standard working curves described in step (2). The average of the results of the two methods was the silver ion content in the actual solution sample given by the test.

[0036] Application Example 1

[0037] Collection of environmental water samples: One portion of tap water was collected from the laboratory faucet and operated according to the steps and detection methods described in Example 1. The results are shown in Table 1.

[0038]

[0039] Application Example 2

[0040] Collection of environmental water samples: A certain brand of silver ion bacteriostatic agent was operated according to the steps and detection methods described in Example 1. The results are shown in Table 2.

[0041]

[0042] As described above, the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for detecting silver ion content with dual fluorescence and phosphorescence responses, characterized in that, It includes the following steps: (1) Synthesis of polyaminosiloxane: Mix aminosiloxane, dilute acid and deionized water, stir vigorously at room temperature, then heat to 90 °C and age for 24 h. After the reaction, rinse with deionized water, filter, and dry in a vacuum oven at 80 °C for 24 h. The obtained white powder is polyaminosiloxane; The aminosiloxane includes one of the compounds with the following structural formulas: ； (2) Establishment of the standard working curve for silver ion concentration detection: Immerse the polyaminosiloxane prepared in step (1) in silver ion standard solutions with different concentrations, heat at 100 °C for 1 min, and then conduct fluorescence and phosphorescence spectrum acquisition experiments to establish the standard working curve of silver ion concentration vs. the relative intensity of any fluorescence emission peak before and after polyaminosiloxane treatment and the standard working curve of silver ion concentration vs. the relative intensity of any phosphorescence emission peak before and after polyaminosiloxane treatment; (3) Actual measurement: First, obtain the fluorescence and phosphorescence emission spectra of the polyaminosiloxane without the analyte to be measured using a spectrometer for standby. Then, after the analyte is centrifuged to filter out insoluble substances, immerse the polyaminosiloxane prepared in step (1) in the analyte, take it out, dry the moisture, conduct fluorescence and phosphorescence spectrum tests to obtain the spectrum of the polyaminosiloxane after treatment, take the intensity of any fluorescence and phosphorescence emission peaks, compare the peak intensity here with the emission intensity before treatment to obtain the relative intensity, and use the standard working curves obtained in step (2) and the relative intensities of fluorescence and phosphorescence emissions to calculate the silver ion content in the experimental sample solution respectively. The average value of the test results of the two methods is the finally measured silver ion concentration.

2. The silver ion content detection method with dual fluorescence and phosphorescence responses according to claim 1, characterized in that: In step (1), the molar ratio of aminosiloxane, dilute acid, and deionized water is 10:0.1:0.

28.

3. The silver ion content detection method with dual fluorescence and phosphorescence responses according to claim 1, characterized in that: The type of dilute acid used in step (1) is dilute hydrochloric acid or dilute hydrobromic acid, and the concentration of the dilute acid is 0.1 - 0.5 mol / L.

4. The silver ion content detection method with dual fluorescence and phosphorescence responses according to claim 1, characterized in that: In step (2), the minimum amount of polyaminosiloxane used is 10 mg.

5. The silver ion content detection method with dual fluorescence and phosphorescence responses according to claim 1, characterized in that: In steps (2) and (3), the immersion time of polyaminosiloxane is 1 min.

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