CN110596061A - Method for rapidly detecting copper ions based on BPEI-CuNCs fluorescent probe - Google Patents
Method for rapidly detecting copper ions based on BPEI-CuNCs fluorescent probe Download PDFInfo
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- CN110596061A CN110596061A CN201910890759.4A CN201910890759A CN110596061A CN 110596061 A CN110596061 A CN 110596061A CN 201910890759 A CN201910890759 A CN 201910890759A CN 110596061 A CN110596061 A CN 110596061A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a method for rapidly detecting copper ions based on a BPEI-CuNCs fluorescent probe, which comprises the following steps: the branched polyethyleneimine BPEI reacts under the combined action of copper ions and ascorbic acid AA to generate BPEI-CuNCs with fluorescence; and adding a sample to be detected into a buffer solution containing BPEI-CuNCs, and detecting the concentration of copper ions based on a BPEI-CuNCs fluorescent probe. Detecting fluorescence intensity of 430nm emission wavelength at excitation wavelength of 360nm by fluorescence spectrometer according to Cu2+And (5) obtaining the concentration of the copper ions by a standard concentration gradient curve. The lowest detection limit of copper ions is 0.01 mu mol/L, and the recovery rate of the added standard reaches 96-99%. The method is simple, rapid, high in selectivity and high in sensitivity. Has wide application prospect in selectively measuring metal copper ions in the fields of biology and environment.
Description
Technical Field
The invention relates to the field of metal ion detection, in particular to a method for rapidly detecting copper ions based on a BPEI-CuNCs fluorescent probe.
Background
Copper (Copper) plays an important role in promoting the growth of animals and plants as a trace element necessary for the growth and development of animals, plants and human beings. The copper element is vital to human health, and has catalytic and auxiliary effects on a plurality of enzymes in the oxidation-reduction activity process of Cu (I)/Cu (II); it may also promote the generation of Reactive Oxygen Species (ROS), thereby interfering with the transduction of cell signals, disrupting cellular structures, and leading to apoptosis. High concentration of copper ions can also cause liver cirrhosis, vomiting, dyskinesia, and sensory nerve disorder, which affect the normal growth and development of organisms and may lead to death in severe cases. In addition, if copper accumulates in the neuronal cytoplasm for a long time, it causes dyskinesia and neurological disorders, and in severe cases, it causes diseases such as alzheimer's disease, parkinsonism and amyotrophic lateral sclerosis. Therefore, the detection of copper ions in a sample and the accurate determination of the content of the copper ions are of great significance for both environmental protection and human health.
The WHO of the world health organization specifies a maximum threshold value of 2mg/kg for copper content in drinking water and 1.0mg/L for EPA. The national sanitary standard for drinking water (GB5749-2006) also stipulates that the limit value of the copper content in the drinking water is 1.0mg/L
The detection methods of heavy metal copper ions are various, and in addition to the atomic absorption spectrophotometry specified by the environmental protection standard of the people's republic of china (HJ 486-. Thus, a simple, fast, highly selective, highly sensitive Cu is established2+Detection methods are necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for rapidly detecting copper ions based on a BPEI-CuNCs fluorescent probe, which has the advantages of simple operation, high selectivity, high sensitivity, no need of depending on large-scale equipment and instruments, and no strict requirements on detection environment and time.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the method for rapidly detecting the copper ions based on the BPEI-CuNCs fluorescent probe comprises the following steps:
1) the branched polyethyleneimine BPEI reacts under the combined action of copper ions and ascorbic acid AA to generate BPEI-CuNCs with fluorescence;
2) and adding a sample to be detected into a buffer solution containing BPEI-CuNCs, and detecting the concentration of copper ions based on a BPEI-CuNCs fluorescent probe.
In the step 1), the BPEI-CuNCs are prepared by the following steps: mixing deionized water and BPEI uniformly, and then adding CuSO4Placing the solution on an air constant temperature shaking table, and stirring for 10 min; and finally, adding AA, oscillating for two days at room temperature, and filtering to obtain a BPEI-CuNCs solution.
Further, the concentration of PEI in the BPEI-CuNCs solution is 0.36 mg/mL; CuSO4The molar ratio to AA was 1: 1.
In step 2), the buffer solution is 0.03% CTAB-containing citrate buffer, the pH value of the buffer solution is 4, and the concentration of the buffer solution is 20 mmol/L.
The step 2) specifically comprises the following steps: adding copper ions with different concentrations into BPEI-CuNCs and 20mmol/L citrate buffer solution with pH4 containing 0.03% CTAB, mixing uniformly, detecting the fluorescence intensity with emission wavelength of 430nm at excitation wavelength of 360nm after reaction, and plotting by taking the concentration of the copper ions as abscissa and the difference between the blank fluorescence intensity value and the fluorescence intensity value containing the copper ions as ordinate to obtain a linear regression equation to detect the concentration of the copper ions.
Furthermore, the volume ratio of the copper ions, the BPEI-CuNCs and the buffer solution is 1: 2: 16.
Further, the linear regression equation is that y is 1.3588x +10.744, R2The lowest detection limit of copper ions was 0.01 μmol/L, 0.9752.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1) the method has the advantages of simple operation, short time, sensitivity and convenience, no need of large-scale equipment and instruments, and no strict requirements on detection environment and time;
2) good specificity, good selectivity, and little interference to other metal ions, such as Al3+、Cd2+、Fe2+、Mg2+、Pb2+When the method is used for detecting the copper ions, the interference of other metal ions in the sample can be eliminated, and the result is more reliable;
3) the lowest detection limit of copper ions is 0.01 mu mol/L and is lower than the limit value of 1.0mg/L (about 15.74 mu mol/L) specified by the sanitary standard of drinking water (GB 5749-2006); the recovery rate of a copper ion labeling experiment reaches 96-99%, and the BPEI-CuNCs probe has accuracy and reliability in detecting ions in an actual sample and can be suitable for detecting Cu in life2+And (5) qualitatively and quantitatively detecting.
Drawings
FIG. 1 shows the detection of Cu by BPEI-CuNCs2+Working principle diagram of (1);
FIG. 2 is an electron micrograph of BPEI-CuNCs;
FIG. 3 is a fluorescence spectrum of BPEI-CuNCs; in the figure, A is a fluorescence spectrum obtained by diluting BPEI-CuNCs by 10 times; b is a fluorescence spectrum of BPEI-CuNCs (stock solution), and the set detection wavelength Em is 430nm and Ex is 360 nm;
FIG. 4 is a graph showing the relationship between the concentration of copper ions and the Δ fluorescence intensity;
FIG. 5 is a comparison graph of fluorescence intensity of BPEI-CuNCs detecting different heavy metal ions; in the figure, the concentrations of different heavy metal ions are all 50 mu mol/L;
FIG. 6 shows the recovery of each water sample in the copper ion labeling experiment; in the figure, the copper ion concentration of each water sample was 50. mu. mol/L.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to be limiting.
Example 1
1) Preparation of BPEI-CuNCs
The BPEI-CuNCs is prepared by adopting an ascorbic acid reduction method. 48.09mL of deionized water and 1.91mL of 9.4mmol/L BPEI are sequentially added into a cleaned and dried beaker, mixed uniformly, and then 835 mu L of 10mmol/L CuSO is added4The solution was stirred for 10min on an air constant temperature shaker. Finally, 835. mu.L of 100mmol/L AA was added, shaken at room temperature for two days, and filtered for use.
The color of the synthesized BPEI-CuNCs solution gradually becomes lighter from blue and finally becomes grass green along with the change of time, and the PEI concentration in the BPEI-CuNCs solution is 0.36mg/mL finally. The fluorescence spectrum of BPEI-CuNCs was measured by fluorescence spectrometer, and when Ex is 360nm, it has an absorption peak around 430 nm.
2) Preparation of buffer solution
To make the buffer solution more stable, a small amount of cationic surfactant, i.e., CTAB solution, was added. First, 65.5mL of a 0.1M citric acid solution and 34.5mL of a 0.1M sodium citrate solution were thoroughly mixed, and the pH was adjusted to 4 using a gyromagnetic pH meter, whereby a citrate buffer solution (pH 4) was obtained at 100 mmol/L. Then 10mL of 100mmol/L citrate buffer solution, 15mL of 0.1% CTAB and 25mL of deionized water were mixed to prepare 20mmol/L citrate buffer solution (0.03% CTAB, pH 4) for later use.
3)Cu2+Drawing standard concentration gradient curve
A1.5 mL centrifuge tube was sequentially charged with 800. mu.L of 20mmol/L pH4 citrate buffer solution (0.03% CTAB), 100. mu.L of BPEI-CuNCs and 50. mu.L of Cu at various concentrations2+Ions, prepared three times per group concentration. Cu of Final inspection2+The ion concentration gradient ranges from 0 to 500. mu. mol/L. The fluorescence spectrum in the interval of 400 nm-650 nm is scanned by using the exciting light with the wavelength of 360nm of the fluorescence spectrometer. As shown in FIG. 4, the fluorescence intensity data at 430nm peak was extracted and 0. mu. mol/L Cu was added2+The fluorescence intensity at each concentration was subtracted from the fluorescence intensity at the ion concentration to obtain the fluorescence intensity for Cu2+The difference in fluorescence intensity of the ion concentration gradient, Δ F, was averaged and the standard deviation was calculated. Selecting Cu2+The concentration (0.1-10 mu mol/L) and the delta fluorescence intensity value are plotted to obtain a linear curve of the two, a trend line and an error bar are drawn, and the linear regression equation is that delta F is 1.3588x +10.744(R2 is 0.9752). The lowest detection limit of copper ions is 0.01 mu mol/L, which is lower than the limit of 1.0mg/L (about 15.74 mu mol/L) specified by the sanitary standard of drinking water (GB 5749-2006).
4) Heavy metal specificity experiments
A1.5 mL centrifuge tube was charged with 800. mu.L of 20mmol/L pH4 citrate buffer solution (0.03% CTAB), 100. mu.L of BPEI-CuNCs, and50 μ L of 50 μmol/L different heavy metal ions (Cu)2+、Al3+、Cr3+、Cd2+、Fe2+、Mg2+、Pb2 +) While a blank of ultrapure water was set. And scanning the fluorescence spectrum in the interval of 400 nm-650 m by using the exciting light with the wavelength of 360nm of the fluorescence spectrometer, and comparing the fluorescence intensity of each metal ion.
As shown in FIG. 5, Al3+、Cd2+、Fe2+、Mg2+、Pb2+The heavy metal ions do not substantially interfere with the fluorescence intensity of the BPEI-CuNCs; wherein Cr is3+Possibly reducing the fluorescence, but with a smaller reduction range, compared with Cu2+The comparison is negligible. Indicating that BPEI-CuNCs is coupled with Cu2+The ions have better selectivity.
5) Labeling experiment for copper ions in actual water sample
Selecting four water sample types: river water is sampled from the purple lake stream of Nanjing forestry university; selecting common farmer mountain spring brand bottled drinking water as mineral water; tap water is sampled from a tap water pipeline of Nanjing forestry university; and ultrapure water for laboratory use. Setting 50. mu. mol/L as Cu for final measurement2+And (3) measuring the fluorescence intensity of each water sample, and repeating three groups of experiments by taking ultrapure water as a control group. The fluorescence spectrum in the interval of 400 nm-650 nm is scanned by using exciting light with the wavelength of 360nm of a fluorescence spectrometer, the value of the peak value of an absorption peak is selected for comparison, and an error bar is made.
As shown in table 1 and fig. 6, the measurement results of the copper ion concentrations of the three water samples of river water, mineral water and tap water were not particularly significantly different in numerical values. Meanwhile, Cu in the environmental water sample is found through calculation2+The quantitative peak recovery rate is higher: cu in river water samples2+The recovery rate of the quantitative peak is 96.15 percent, and Cu in mineral water samples2+Recovery of 97.93%, Cu in tap water sample2+The recovery of (D) was 99.49%. The result shows that the BPEI-CuNCs probe has accuracy and reliability for detecting ions in an actual sample and can be suitable for detecting Cu in life2+And (5) qualitatively and quantitatively detecting.
TABLE 1 sources and recovery of different water samples
It is to be noted that the above-mentioned list is only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. The method for rapidly detecting the copper ions based on the BPEI-CuNCs fluorescent probe is characterized by comprising the following steps of:
1) the branched polyethyleneimine BPEI reacts under the combined action of copper ions and ascorbic acid AA to generate BPEI-CuNCs with fluorescence;
2) and adding a sample to be detected into a buffer solution containing BPEI-CuNCs, and detecting the concentration of copper ions based on a BPEI-CuNCs fluorescent probe.
2. The method of claim 1, wherein the BPEI-CuNCs are prepared by the following steps in step 1): mixing deionized water and BPEI uniformly, and then adding CuSO4Placing the solution on an air constant temperature shaking table, and stirring for 10 min; and finally, adding AA, oscillating for two days at room temperature, and filtering to obtain a BPEI-CuNCs solution.
3. The method of claim 2, wherein the concentration of PEI in the BPEI-CuNCs solution is 0.36 mg/mL; the CuSO4The molar ratio to the AA is 1: 1.
4. The method according to claim 1, wherein in step 2), the buffer solution is a citrate buffer solution containing 0.03% CTAB, and has a pH value of 4 and a concentration of 20 mmol/L.
5. The method according to claim 4, wherein the step 2) comprises the following steps: adding copper ions with different concentrations into BPEI-CuNCs and 20mmol/L citrate buffer solution with pH4 containing 0.03% CTAB, mixing uniformly, detecting the fluorescence intensity with emission wavelength of 430nm at excitation wavelength of 360nm after reaction, and plotting by taking the concentration of the copper ions as abscissa and the difference between the blank fluorescence intensity value and the fluorescence intensity value containing the copper ions as ordinate to obtain a linear regression equation to detect the concentration of the copper ions.
6. The method of claim 5, wherein the volume ratio of the copper ions, BPEI-CuNCs and the buffer solution is 1: 2: 16.
7. The method of claim 5, wherein the linear regression equation is y 1.3588x +10.744, R2The lowest detection limit of copper ions was 0.01 μmol/L, 0.9752.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113281331A (en) * | 2021-05-17 | 2021-08-20 | 福州大学 | Machine learning-based rapid detection method for copper ions in water environment |
| CN113980672A (en) * | 2021-11-16 | 2022-01-28 | 江西省科学院微生物研究所 | Fluorescent probe for detecting copper ions and preparation method, detection method and application thereof |
| CN115505386A (en) * | 2022-09-15 | 2022-12-23 | 西南交通大学 | Tetracycline detection material based on BPEI and SDS, and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113281331A (en) * | 2021-05-17 | 2021-08-20 | 福州大学 | Machine learning-based rapid detection method for copper ions in water environment |
| CN113980672A (en) * | 2021-11-16 | 2022-01-28 | 江西省科学院微生物研究所 | Fluorescent probe for detecting copper ions and preparation method, detection method and application thereof |
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| CN115505386A (en) * | 2022-09-15 | 2022-12-23 | 西南交通大学 | Tetracycline detection material based on BPEI and SDS, and preparation method and application thereof |
| CN115505386B (en) * | 2022-09-15 | 2024-03-19 | 西南交通大学 | BPEI and SDS-based tetracycline detection material and preparation method and application thereof |
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