CN108593614B - Application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection - Google Patents

Application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection Download PDF

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CN108593614B
CN108593614B CN201810399655.9A CN201810399655A CN108593614B CN 108593614 B CN108593614 B CN 108593614B CN 201810399655 A CN201810399655 A CN 201810399655A CN 108593614 B CN108593614 B CN 108593614B
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周海波
江正瑾
包芷君
胡紫微
袁凯松
简敬一
黄睿
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Abstract

The invention belongs to the technical field of analysis and detection, and discloses an application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection. The application process comprises the following steps: adding the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots into a phosphate buffer solution for dilution to serve as a probe solution, then adding a copper ion solution to be detected, detecting by using a fluorescence spectrometer, and obtaining the concentration of copper ions in the solution to be detected according to the relation between the fluorescence intensity ratio and the concentration of the copper ions. The method for detecting the copper ions by using the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots as the probe for the first time does not need to pre-conjugate or pre-assemble together through a complex procedure, can effectively reduce the influence caused by photobleaching and signal fluctuation, and has the advantages of simple operation, high detection speed and high sensitivity.

Description

Application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to an application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection.
Background
It is well known that copper ions play an important role in the fields of environmental, biological and chemical systems, and are an essential element of the growth of most living organisms. Particularly, a proper amount of copper ions is required for maintaining healthy bone formation, cellular respiration, connective tissue development, various metalloenzymes, and the like of a human body. At high concentrations, however, copper ions may become toxic. For humans, excessive copper intake can be a health hazard, such as gastrointestinal disorders, kidney damage, neurodegenerative diseases, and the like. Copper ions are commonly found in natural and environmental water sources such as tap water, river water and lake water, and the U.S. environmental protection agency has allowed a copper ion limit of 1.3ppm (about 20 μ M) in drinking water. Therefore, it is necessary to develop analytical techniques and strategies for trace amounts of copper ions in environmental samples. Instrumental analysis for high sensitivity copper ion determination has so far included atomic absorption spectroscopy, inductively coupled plasma mass spectrometry and some electrochemical-based methods. However, expensive specialized instruments and complex procedures limit their widespread use.
To ameliorate this problem, highly selective and sensitive fluorescent chemical sensors have been applied to rapid, low-cost, and easy-to-operate metal ion monitoring. Various fluorescence sensors have been proposed for copper ion sensing based on fluorescence quenching effects or recovery from quenched Quantum Dot (QDs) -copper complexes. Quantum dot probes have several incomparable advantages over organic fluorescence-based sensors, including superior fluorescence characteristics, high photochemical stability, and excellent photobleaching resistance. To date, great efforts have been reported to develop quantum dot sensors for ultrasensitive and fast copper ion detection, including ZnS quantum dots, CdTe quantum dots, CdS quantum dots, alloyed CdSeTe quantum dots, CdSe/ZnS quantum dots, and carbon/graphene dots, which produce only one single response signal in detection. Research shows that the fluorescence characteristics of the quantum dots are inevitably subjected to intensity fluctuation caused by instrument or environmental factors, and as a result, wrong read-out signals can occur in the analysis process. In order to improve the reliability of the detection, by constructing a ratiometric fluorescence sensor from a reference object by introducing another fluorophore, the negative fluctuations of the fluorescent probe can be eliminated by measuring the intensity ratio of the two different wavelengths. Several quantum dot-based ratiometric fluorescence sensors are currently used to measure copper ions. For example, dual fluorophore ratiometric probes constructed from graphene oxide in combination with CdTe quantum dots have been designed for copper ion detection, taking advantage of their distinct and independent fluorescence responses in the presence of copper ions. However, in such conventional ratiometric systems, the two luminophores (quantum dots plus the other) need to be pre-conjugated or pre-assembled together by a complex procedure, which is both time consuming and expensive. For high performance copper ion assays, there is still much room for developing novel ratiometric fluorescent quantum dot sensors.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide the application of the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection.
The invention also aims to provide a preparation method of the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot.
The purpose of the invention is realized by the following technical scheme:
the application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots in copper ion detection comprises the following application processes: adding the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots into a phosphate buffer solution for dilution to serve as a probe solution, then adding a copper ion solution to be detected, detecting by using a fluorescence spectrometer, and obtaining the concentration of copper ions in the solution to be detected according to the relation between the fluorescence intensity ratio and the concentration of the copper ions.
Further, the pH value of the phosphate buffer solution is 6-8, and the concentration of the phosphate buffer solution is 0.1-0.001M.
Further, the excitation wavelength of the fluorescence spectrometer for detection is 250-350 nm, and the fluorescence intensity ratio is the ratio of the fluorescence intensity at 420-430 nm to the fluorescence intensity at 580-600 nm.
Preferably, the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot is prepared by the following method:
(1) preparation of manganese stearate: adding stearic acid into excessive methanol, heating to be clear, adding tetramethyl ammonium hydroxide diluted by the methanol, stirring and mixing uniformly, then dropwise adding a methanol solution of manganese chloride under the stirring condition for reaction, filtering and collecting a white flocculation product, and drying to obtain manganese stearate;
(2) preparing the manganese-doped zinc sulfide quantum dots: adding zinc stearate, manganese stearate, sulfur powder, octadecylamine and octadecylene into a reactor A, heating to 100-150 ℃, removing water and oxygen by nitrogen replacement, heating to 270-280 ℃, keeping for 5-7 min, and annealing to 245-255 ℃; adding zinc stearate, stearic acid and octadecene into a reactor B, heating to 110-120 ℃, and removing water and oxygen by nitrogen replacement to obtain a mixed solution; adding the mixed solution in the reactor B into the reactor A, keeping the temperature at 245-255 ℃ for 30-40 min, finishing the reaction, cooling to room temperature, and purifying to remove unreacted substances to obtain manganese-doped zinc sulfide quantum dots;
(3) preparing the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots: dispersing the manganese-doped zinc sulfide quantum dots into chloroform, adding mercaptopropionic acid, stirring for reaction, separating and washing a solid product, and dispersing the solid product into aqueous solution containing tetramethylammonium hydroxide to obtain the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots.
Preferably, the molar ratio of the stearic acid and the tetramethylammonium hydroxide added in the step (1) is 2 (1-3).
Preferably, the molar ratio of the stearic acid to the manganese chloride added in the step (1) is 10 (5-7).
Preferably, the molar ratio of zinc stearate to sulfur powder added in the reactor A in the step (2) is 1 (4-6), the molar ratio of zinc stearate to sulfur powder added in the reactor B is (2-3): 1, the molar ratio of manganese stearate to sulfur powder added is 1 (80-120), and the molar ratio of stearic acid to sulfur powder added is (2-3): 1.
Preferably, the process for purifying and removing unreacted materials in the step (2) is as follows: precipitating the reaction solution cooled to room temperature by using excessive acetone, centrifuging, and removing octadecene; dissolving with chloroform, precipitating with acetone, and removing octadecene twice; dissolving the precipitate with chloroform, precipitating with methanol, and removing residual amine and acid twice; the precipitate was dissolved in hot cyclohexane, insoluble zinc stearate was removed by centrifugation, and the upper solution was retained and stored in a refrigerator at 4 ℃ until use.
Preferably, the stirring reaction time in the step (3) is 20-30 min, the separation refers to centrifugal separation, and the washing refers to washing with acetone and water in sequence.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the method provided by the invention is used for detecting copper ions by using mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots as a probe for the first time. The linear range is 0-3.0 mu mol/L, and the detection limit is 14.5 nmol/L.
(2) The probe used by the invention is a dual-emission-peak ratiometric fluorescent probe, and is not required to be pre-conjugated or pre-assembled together through a complex procedure, so that the influence caused by photobleaching and signal fluctuation can be effectively reduced.
(3) The method can carry out quantitative detection only by using a fluorescence photometer, and has the advantages of simple operation, high detection speed and high sensitivity.
(4) The method can effectively avoid the interference of other impurities in the sample, so the selectivity is good, and a complex sample pretreatment process is not needed.
Drawings
FIG. 1 is an emission spectrum of a mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot probe solution in example 1 under the condition of adding different copper ion concentrations.
FIG. 2 is a graph showing the linear relationship between the concentration of copper ions added in example 1 and the ratio of fluorescence intensity corresponding to the probe.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
1. Preparation of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots
(1) Preparation of manganese stearate
10mmol of stearic acid was added to 15mL of methanol and heated to 40 ℃ until clear. 10mmol of tetramethylammonium hydroxide diluted with 5mL of methanol was added to the above solution, and the mixture was stirred for 20 min. 5mmol of manganese chloride was dissolved in methanol, the solution was added dropwise with vigorous stirring, and white flocculation was collected by filtration. Drying and storing for later use.
(2) Preparation of manganese-doped zinc sulfide quantum dots
0.063g of zinc stearate, 0.003g of manganese stearate, 0.016g of sulfur powder, 0.8g of octadecylamine and 10mL of octadecene are added into a 250mL three-neck flask A, the mixture is heated to 150 ℃, vacuumized, introduced with nitrogen, repeatedly heated for 3 times to remove water and oxygen, heated to 270 ℃ and kept for 5 minutes, and then annealed to 250 ℃. Adding zinc stearate, stearic acid and octadecene into a 150mL three-neck flask B, heating to 110-120 ℃, vacuumizing, introducing nitrogen, and repeating for 2-3 times to remove water and oxygen. Injecting the solution in the bottle B into the bottle A, keeping the temperature at 250 ℃ for 30min, finishing the reaction, cooling to room temperature, precipitating the obtained reaction solution by using excessive acetone, centrifuging, and removing octadecene; dissolving with chloroform, precipitating with acetone, and removing octadecene twice; dissolving the precipitate with chloroform, precipitating with methanol, and removing residual amine and acid twice; dissolving the precipitate in hot cyclohexane, centrifuging insoluble zinc stearate, collecting the upper solution, and storing in refrigerator at 4 deg.C.
(3) Preparation of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots
And (3) putting the manganese-doped zinc sulfide cyclohexane solution obtained in the step (2) into a round-neck flask, performing rotary evaporation to remove cyclohexane, adding chloroform to disperse the chloroform, adding mercaptopropionic acid, performing stirring reaction for 20-30 min, centrifuging, and removing the upper layer liquid. Washing the obtained precipitate with acetone for 2 times, then washing with water for 2 times, dispersing the precipitate in water, and adding a few drops of tetramethyl ammonium hydroxide aqueous solution to obtain the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot.
2. The mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot obtained in the embodiment is subjected to fluorescence detection in a cuvette
Adding 10 mu L of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots into a phosphate buffer solution (0.02M) with the pH value of 7.0 to serve as a probe solution, and carrying out fluorescence detection in a quartz cuvette. Adding copper ion solution successively to make the copper ion concentration in the probe solution be 0, 0.3, 0.6, 0.9, 1.2 and 1.5 respectively,1.8, 2.1, 2.4, 2.7 and 3.0. mu.M, the emission spectra after each addition of copper ions were recorded separately by means of a Perkin-Elmer LS-55 type fluorescence spectrometer, the excitation wavelength was chosen to be 310nm and the light was cut off at 390 nm. The fluorescence intensities at 430nm and 590nm were recorded, respectively, and the results are shown in FIG. 1. The concentration of added copper ions and the ratio (I) of the fluorescence intensities at 480nm and 590nm, respectively430/I590)/(I430/I590)0By making the linear relationship, one linear equation, y, 1.0373+0.5674x (R) can be obtained20.9871), see fig. 2. The content of copper ions in the sample can be quantitatively analyzed from a linear equation.
Example 2
In this embodiment, the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot solution fluorescent probe obtained in example 1 is applied to detection of copper ions in a real water sample.
Collected lake water and tap water were filtered twice with qualitative filter paper, and 1mM copper ion solution was prepared with the filtered lake water and tap water, respectively. mu.L of the mercaptopropionic acid-modified manganese-doped zinc sulfide quantum dots prepared in example 1 was added to 1990. mu.L of pH7.0, 0.02M phosphate buffer solution as a probe solution, and fluorescence detection was performed in a quartz cuvette using a Perkin-Elmer LS-55 type fluorescence spectrometer. The excitation wavelength was chosen to be 310nm, with light cut at 390 nm. The copper ion solutions were added successively so that the concentrations of copper ions in the solutions were 0.9. mu.M, 2.1. mu.M and 2.7. mu.M, respectively, and the emission spectra after each addition of the copper ion solution and the fluorescence intensities at 430nm and 590nm, respectively, were recorded. The fluorescence intensity ratio at each concentration was substituted into the linear relationship y of 1.0373+0.5674x (R) in FIG. 220.9871), calculating x as the concentration value of sample collection, repeating the experiment 3 times for each concentration, and calculating the recovery rate and RSD to obtain Table 1.
Table 1 sample recovery example of copper ions in real water sample (n ═ 3)
Figure BDA0001645408520000061
As can be seen from the data in Table 1, the recovery rate of the copper ion concentration in the real water sample detected by the method can reach 92.0% -100.4%, which shows that the method has better accuracy.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. The application of the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection is characterized by comprising the following application processes: adding the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots into a phosphate buffer solution for dilution to serve as a probe solution, then adding a copper ion solution to be detected, detecting by using a fluorescence spectrometer, and obtaining the concentration of copper ions in the solution to be detected according to the relation between the fluorescence intensity ratio and the concentration of the copper ions;
the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot is prepared by the following method:
(1) preparation of manganese stearate: adding stearic acid into excessive methanol, heating to be clear, adding tetramethyl ammonium hydroxide diluted by the methanol, stirring and mixing uniformly, then dropwise adding a methanol solution of manganese chloride under the stirring condition for reaction, filtering and collecting a white flocculation product, and drying to obtain manganese stearate;
(2) preparing the manganese-doped zinc sulfide quantum dots: adding zinc stearate, manganese stearate, sulfur powder, octadecylamine and octadecylene into a reactor A, heating to 100-150 ℃, removing water and oxygen by nitrogen replacement, heating to 270-280 ℃, keeping for 5-7 min, and annealing to 245-255 ℃; adding zinc stearate, stearic acid and octadecene into a reactor B, heating to 110-120 ℃, and removing water and oxygen by nitrogen replacement to obtain a mixed solution; adding the mixed solution in the reactor B into the reactor A, keeping the temperature at 245-255 ℃ for 30-40 min, finishing the reaction, cooling to room temperature, and purifying to remove unreacted substances to obtain manganese-doped zinc sulfide quantum dots;
(3) preparing the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots: dispersing the manganese-doped zinc sulfide quantum dots into chloroform, adding mercaptopropionic acid, stirring for reaction, separating and washing a solid product, and dispersing the solid product into aqueous solution containing tetramethylammonium hydroxide to obtain mercaptopropionic acid modified manganese-doped zinc sulfide quantum dots;
the pH value of the phosphate buffer solution is 6-8, and the concentration of the phosphate buffer solution is 0.1-0.001M;
the excitation wavelength of the fluorescence spectrometer for detection is 250-350 nm, and the fluorescence intensity ratio is the ratio of the fluorescence intensity at 420-430 nm to the fluorescence intensity at 580-600 nm.
2. The application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection according to claim 1 is characterized in that: in the step (1), the molar ratio of stearic acid to tetramethylammonium hydroxide is 2 (1-3).
3. The application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection according to claim 1 is characterized in that: the molar ratio of stearic acid to manganese chloride added in the step (1) is 10 (5-7).
4. The application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection according to claim 1 is characterized in that: in the step (2), the molar ratio of zinc stearate to sulfur powder in the reactor A is 1 (4-6), the molar ratio of zinc stearate to sulfur powder in the reactor B is (2-3): 1, the molar ratio of manganese stearate to sulfur powder is 1 (80-120), and the molar ratio of stearic acid to sulfur powder is (2-3): 1.
5. The application of the mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection according to claim 1, wherein the process for purifying and removing unreacted substances in the step (2) is as follows: precipitating the reaction solution cooled to room temperature by using excessive acetone, centrifuging, and removing octadecene; dissolving with chloroform, precipitating with acetone, and removing octadecene twice; dissolving the precipitate with chloroform, precipitating with methanol, and removing residual amine and acid twice; the precipitate was dissolved in hot cyclohexane, insoluble zinc stearate was removed by centrifugation, and the upper solution was retained and stored in a refrigerator at 4 ℃ until use.
6. The application of mercaptopropionic acid modified manganese-doped zinc sulfide quantum dot in copper ion detection according to claim 1 is characterized in that: and (3) stirring and reacting for 20-30 min, wherein the separation refers to centrifugal separation, and the washing refers to washing with acetone and water in sequence.
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