CN114774111B - Preparation method of polyethylene glycol modified silver doped boron quantum dot as iron ion fluorescent nano probe - Google Patents
Preparation method of polyethylene glycol modified silver doped boron quantum dot as iron ion fluorescent nano probe Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 39
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000523 sample Substances 0.000 title claims abstract description 34
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 27
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 20
- 239000002096 quantum dot Substances 0.000 title claims abstract description 12
- -1 iron ion Chemical class 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 150000001638 boron Chemical class 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000010791 quenching Methods 0.000 claims abstract description 7
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000003378 silver Chemical class 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
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- 238000002189 fluorescence spectrum Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
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- 241001465754 Metazoa Species 0.000 description 1
- 102000036675 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a silver-doped boron quantum dot modified by polyethylene glycol PEG as iron ion Fe 3+ A preparation method of fluorescent nano-probe. Boron powder is used as a raw material, PEG is used as a stabilizer, an ultrasonic-assisted liquid phase stripping method is adopted to prepare a boron nano-sheet in the presence of silver ions, and then the silver-doped boron quantum dots Ag@BQDs with modified PEG surfaces are prepared through ultrasonic-assisted solvothermal treatment. And (3) adjusting the preparation conditions to obtain Ag@BQDs with blue-green fluorescence emission. When Fe is 3+ When present, fe 3+ Forms coordination and chelation interaction with PEG alcoholic hydroxyl groups, and non-radiative electrons of Ag@BQDs are transferred from an excited state to Fe under excitation 3+ And thus cause fluorescence quenching. Measurement of different Fe 3+ Fluorescence emission peak intensity of Ag@BQDs aqueous dispersion liquid under coexisting concentration, and fitting fluorescence intensity and Fe 3+ Linear relationship between concentrations, constructing Fe 3+ Fluorescent nanoprobes.
Description
Technical Field
The invention belongs to the technical field of preparation of water-dispersible silver-doped boron quantum dots and iron ion fluorescent nano probes, and particularly relates to a preparation method of a polyethylene glycol-modified silver-doped boron quantum dot serving as an iron ion fluorescent nano probe.
Background
The content of iron element in crust is arranged at 4 th position, the average abundance is 4.7%, and the iron element is next to oxygen, silicon and aluminum element. Iron has little toxicity to human and animals, and when the concentration of iron compounds in the water body is 0.1-0.3 mg/L, the color and smell of the water body can be changed, and peculiar smell appears. When the iron content in the water used in the printing and dyeing industry is too high, unsightly spots can appear on the product, and the iron content of the industrial water used in rubber, textile, paper making, brewing, food and the like has higher requirements than that of drinking water. The highest allowable concentration of iron content of drinking water regulated by China is 0.3 mg/L, and the ground water is 0.5 mg/L. The important role of elemental iron in the human body is to maintain erythrocyte metabolism and assist bone marrow hematopoiesis, with about 70% of the iron present in erythrocytes, about 30% carried in myoglobin, about 70% in hemoglobin, and about 15% stored iron. Stored iron is released once the body ingests too little or no iron.
Iron ions play an important role in maintaining erythrocyte metabolism, are mainly distributed in the liver, spleen, bone marrow and other parts, are closely related to hematopoiesis, and are key factors for maintaining normal erythrocyte function and metabolism. If the food is eaten or the intestinal tract has blood loss, iron deficiency anemia is often caused, which indicates that the iron ion content is obviously insufficient. Proper amounts of iron are required daily, and pregnant women have more iron demand due to the need to burden the marrow hematopoietic functions of the mother and fetus. If the human body lacks iron for a long time, the functions of the central system can be affected, and symptoms such as hypodynamia, dizziness and the like can also appear besides anemia. Therefore, the high-efficiency detection of the iron ions in the water body and the biological fluid has very important practical significance for water body environment protection and human health monitoring.
In recent years, zero-dimensional single-element boron nano-materials attract wide research interest, and a large number of related reports of theoretical calculation and experimental research appear. Compared with the two-dimensional single-element boron nanomaterial, the zero-dimensional single-element boron nanomaterial, in particular to the experimental preparation and practical application research report of single-element boron quantum dots, are few. Experimental studies related to the elemental boron quantum dots mainly include: 1. crystalline semiconductor characterization studies of boron quantum dots (J.Hao, G.Tai, J.Zhou, R.Wang, C.Hou, W.Guo, crystalline semiconductor boron quantum dots, ACS Applied Materials & Interfaces,2020,12,17669.); 2. boron quantum dot edge defects induce photothermal effects (L.Wang, S.M.Xu, S.Guan, X.Qu, G.I.N.Waterhouse, S.He, S.Zhou, highly efficient photo-thermal heating via distorted edge-defects in boron quantum dots, journal ofMaterials ChemistryB,2020,8,9881); 3. photoacoustic imaging mediated photothermal therapy (T.Guo, Q.Tang, Y.Guo, H.Qiu, J.Dai, C.Xing, S.Zhuang, G.Huang, boron quantum dots for photo acoustic imaging-guided photothermal therapy, ACS Applied Materials & Interfaces,2021,13,306.) and the like. At present, no experimental preparation of polyethylene glycol modified silver doped boron quantum dots and domestic and foreign literature and patent reports of the polyethylene glycol modified silver doped boron quantum dots serving as fluorescent nano probes for efficient detection of iron ions exist.
Disclosure of Invention
The invention aims to develop a preparation method of an efficient polyethylene glycol modified silver-doped boron quantum dot serving as an iron ion fluorescent nano probe, and the prepared probe can be used for quantitative and visual detection of iron ions in water samples and biological fluids.
In order to achieve the above purpose, the invention relates to a fluorescent nano probe based on polyethylene glycol modified silver doped boron quantum dots as iron ions, and the preparation method specifically comprises the following steps:
(1) Measuring 50-100 ml of N-methylpyrrolidone NMP, adding 50-100 mg of block boron powder under stirring to form a dispersion liquid of the boron powder, then dropwise adding a silver nitrate aqueous solution to form a mixed liquid, adjusting the boron concentration to be 0.5-1.0 mg/ml, and adjusting the silver concentration to be 0.05-0.1 mg/ml;
(2) Ultrasonic processing the mixed solution by using a probe under the power of 500-1000 watts, firstly carrying out ultrasonic processing for 5 seconds, then suspending for 10 seconds, repeating the ultrasonic-suspended circulation operation, and maintaining the whole process for 30-60 minutes;
(3) Weighing 10 ml of secondary distilled water, adding 0.1-1.0 ml of polyethylene glycol PEG-400 under stirring to dilute into aqueous dispersion of PEG-400, dropwise adding the aqueous dispersion into the mixed solution subjected to ultrasonic probe treatment, and continuously treating the mixed solution for 3-6 hours under 1000-1200 watts of power by adopting bath ultrasound;
(4) Transferring the mixed solution after ultrasonic treatment in the bath into a miniature magnetic force containing polytetrafluoroethylene liningIn a high-pressure reaction kettle, in N 2 Stirring and reacting for 5-10 hours at 100-200 ℃, cooling a reaction product to room temperature, centrifuging for 10-20 minutes at 3500 rpm, absorbing upper liquid, centrifuging for 10-20 minutes at 12000 rpm, washing the obtained precipitate for 3-6 times by ethanol and secondary distilled water, and then vacuum drying at 60 ℃ to obtain PEG-400 surface-modified silver-doped boron quantum dots PEG-Ag@BQDs;
(5) Preparing aqueous dispersion of PEG-Ag@BQDs, dropwise adding an aqueous solution of ferric chloride under stirring to form a liquid to be detected, regulating the concentration of the PEG-Ag@BQDs to be 0.5-1.0 mg/ml, and regulating the concentration of iron ions Fe 3+ The concentration is 0.01 to 10 micromoles/milliliter, a fluorescence spectrometer is adopted to measure the fluorescence emission spectrum of the liquid to be measured, and different fluorescence emission peak intensities and corresponding Fe are fitted 3+ The linear relation between the concentrations constructs the fluorescent nano probe based on PEG-Ag@BQDs for Fe 3+ High efficiency detection of Fe in 3+ The linear detection range of the concentration is 0.01-10 micromoles/ml, the detection limit is 1-10 nanomoles/ml, and the concentration is based on Fe 3+ The induced PEG-Ag@BQDs blue-green fluorescence quenching probe is used for quantitative and visual detection of iron ions in water samples and biological fluids.
The invention has the effect of disclosing a preparation method of a silver-doped boron quantum dot based on polyethylene glycol modification as an iron ion fluorescent nano probe. Boron powder is used as an initial raw material, polyethylene glycol PEG is used as a surface coating agent and a stabilizer, probe-bath ultrasound is adopted to assist liquid phase stripping in the presence of silver ions to prepare a boron nano sheet, and then solvent heat treatment assisted by the bath ultrasound is carried out to prepare the PEG surface modified silver doped boron quantum dots PEG-Ag@BQDs. PEG-Ag@BQDs with blue-green fluorescence emission are prepared by adjusting the dosage and proportion of boron powder and silver ions, ultrasonic power, ultrasonic time, reaction time and reaction temperature in the preparation process. When Fe is an iron ion 3+ When present, fe 3+ Forms coordination and chelation interaction with the alcoholic hydroxyl groups of PEG on the surface of Ag@BQDs, and non-radiative electrons of the Ag@BQDs are transferred from an excited state to Fe under excitation 3+ Thereby causing fluorescence quenching of ag@bqds. Based on this, in PEG-Ag @Adding Fe into BQDs aqueous dispersion 3+ Measuring different Fe 3+ Corresponding Ag@BQDs fluorescence emission peak intensity in presence concentration, and fitting fluorescence intensity and Fe 3+ Linear relationship between concentrations, thereby establishing Fe based on PEG-Ag@BQDs 3+ Fluorescent nanoprobes.
Drawings
Fig. 1 is a schematic diagram of a preparation method of a polyethylene glycol modified silver doped boron quantum dot as an iron ion fluorescent nano probe and a process for detecting iron ions by using the same.
Detailed Description
The invention will now be described in detail by means of specific embodiments thereof with reference to the accompanying drawings.
Example 1
The preparation method and detection process of the polyethylene glycol modified silver-doped boron quantum dot as the iron ion fluorescent nano probe are shown in fig. 1, and the specific preparation steps are as follows:
55 ml of N-methylpyrrolidone NMP was measured, 60 mg of a bulk boron powder was added with stirring to form a dispersion of boron powder, then a silver nitrate aqueous solution was added dropwise to form a mixed solution, the boron concentration was adjusted to 1.0 mg/ml, and the silver concentration was adjusted to 0.05 mg/ml. The above mixture was sonicated with a probe at 600 watts of power, sonicated for 5 seconds and then paused for 10 seconds, and the ultrasound-pause cycle was repeated for 30 minutes. 10 ml of secondary distilled water is measured, 0.2 ml of polyethylene glycol PEG-400 is added under stirring to dilute into aqueous dispersion, the aqueous dispersion is added into the mixed solution after probe ultrasonic treatment drop by drop, and then the mixed solution is continuously treated by adopting bath ultrasonic for 3 hours under 1000 watts of power. Transferring the mixed solution after ultrasonic treatment in a bath into a miniature magnetic high-pressure reaction kettle with polytetrafluoroethylene lining, and adding the mixed solution into N 2 Stirring and reacting for 6 hours at the temperature of 120 ℃ under protection, cooling the reaction product to room temperature, centrifuging for 10 minutes at the rotating speed of 3500 revolutions per minute, absorbing the upper liquid, centrifuging for 10 minutes at the rotating speed of 12000 revolutions per minute, washing the obtained precipitate for 3 times by ethanol and secondary distilled water, and then vacuum drying at the temperature of 60 ℃ to obtain the PEG-400 surface modified silver doped boron quantum dots PEG-Ag@BQDs.
Preparing an aqueous dispersion of PEG-Ag@BQDs, dropwise adding an aqueous solution of ferric chloride under stirring to form a liquid to be measured, adjusting the concentration of the PEG-Ag@BQDs to 0.5 mg/ml, and adjusting the Fe ion 3+ The concentration is 0.01 to 1 micromole/ml. Measuring fluorescence emission spectrum of the liquid to be measured by adopting a fluorescence spectrometer, and fitting different fluorescence emission peak intensities and corresponding Fe 3+ The linear relation between the concentrations constructs the fluorescent nano probe based on PEG-Ag@BQDs for Fe 3+ High efficiency detection of Fe in 3+ The linear detection range of the concentration is 0.01-1 micromole/ml, the detection limit is 2 nanomole/ml, based on Fe 3+ The PEG-Ag@BQDs blue-green fluorescence quenching is caused, and the probe can be used for quantitative and visual detection of iron ions in water samples and biological fluids.
Example 2
The preparation method and detection process of the polyethylene glycol modified silver-doped boron quantum dot as the iron ion fluorescent nano probe are shown in fig. 1, and the specific preparation steps are as follows:
90 ml of N-methylpyrrolidone NMP was measured, 70 mg of a bulk boron powder was added with stirring to form a dispersion of boron powder, then a silver nitrate aqueous solution was added dropwise to form a mixed solution, the boron concentration was adjusted to 0.7 mg/ml, and the silver concentration was adjusted to 0.08 mg/ml. The above mixture was sonicated with a probe at 700 watts for 5 seconds followed by a pause of 10 seconds, and the ultrasound-pause cycle was repeated for 45 minutes. 10 ml of secondary distilled water is measured, 0.5 ml of polyethylene glycol PEG-400 is added under stirring to dilute into aqueous dispersion, the aqueous dispersion is added into the mixed solution after probe ultrasonic treatment drop by drop, and then the mixed solution is continuously treated by adopting bath ultrasonic for 4 hours under the power of 1100 watts. Transferring the mixed solution after ultrasonic treatment in a bath into a miniature magnetic high-pressure reaction kettle with polytetrafluoroethylene lining, and adding the mixed solution into N 2 Stirring at 160deg.C for 7 hr under protection, cooling to room temperature, centrifuging at 3500 rpm for 15 min, collecting supernatant, centrifuging at 12000 rpm for 10 min, washing the precipitate with ethanol and secondary distilled water for 4 times, and vacuum drying at 60deg.C to obtain PEG-400 surface-modified silver-doped boron quantum dots PEG-ag@bqds.
Preparing an aqueous dispersion of PEG-Ag@BQDs, dropwise adding an aqueous solution of ferric chloride under stirring to form a liquid to be measured, adjusting the concentration of the PEG-Ag@BQDs to 0.8 mg/ml, and adjusting the Fe ion 3+ The concentration is 0.1-10 micromoles/ml. Measuring fluorescence emission spectrum of the liquid to be measured by adopting a fluorescence spectrometer, and fitting different fluorescence emission peak intensities and corresponding Fe 3+ The linear relation between the concentrations constructs the fluorescent nano probe based on PEG-Ag@BQDs for Fe 3+ High efficiency detection of Fe in 3+ The linear detection range of the concentration is 0.1-10 micromoles/ml, the detection limit is 5 nanomoles/ml, and the concentration is based on Fe 3+ The induced PEG-Ag@BQDs blue-green fluorescence quenching probe is used for quantitative and visual detection of iron ions in water samples and biological fluids.
Example 3
The preparation method and detection process of the polyethylene glycol modified silver-doped boron quantum dot as the iron ion fluorescent nano probe are shown in fig. 1, and the specific preparation steps are as follows:
80 ml of N-methylpyrrolidone NMP was measured, 70 mg of a bulk boron powder was added with stirring to form a dispersion of boron powder, then a silver nitrate aqueous solution was added dropwise to form a mixed solution, the boron concentration was adjusted to 0.8 mg/ml, and the silver concentration was adjusted to 0.06 mg/ml. The above mixture was sonicated with a probe at 780 watts for 5 seconds and then paused for 10 seconds, and the ultrasound-pause cycle was repeated for 60 minutes. 10 ml of secondary distilled water is measured, 0.8 ml of polyethylene glycol PEG-400 is added under stirring to dilute into aqueous dispersion, the aqueous dispersion is added dropwise into the mixed solution after probe ultrasonic treatment, and then the mixed solution is continuously treated for 5 hours under 1050 watt power by adopting bath ultrasonic. Transferring the mixed solution after ultrasonic treatment in a bath into a miniature magnetic high-pressure reaction kettle with polytetrafluoroethylene lining, and adding the mixed solution into N 2 The reaction was carried out for 8 hours under stirring at 150℃under protection, the reaction product was cooled to room temperature, centrifuged at 3500 rpm for 15 minutes, the supernatant was aspirated, and the precipitate obtained was centrifuged at 12000 rpm for 15 minutes, and the precipitate was purified by ethanolWashing with alcohol and secondary distilled water for 5 times, and then vacuum drying at 60 ℃ to obtain the PEG-400 surface modified silver doped boron quantum dots PEG-Ag@BQDs;
preparing an aqueous dispersion of PEG-Ag@BQDs, dropwise adding an aqueous solution of ferric chloride under stirring to form a liquid to be measured, adjusting the concentration of the PEG-Ag@BQDs to be 1.0 mg/ml, and adjusting the Fe ion 3+ The concentration is 0.01-5 micromoles/ml. Measuring fluorescence emission spectrum of the liquid to be measured by adopting a fluorescence spectrometer, and fitting different fluorescence emission peak intensities and corresponding Fe 3+ The linear relation between the concentrations constructs the fluorescent nano probe based on PEG-Ag@BQDs for Fe 3+ High efficiency detection of Fe in 3+ The linear detection range of the concentration is 0.01-5 micromoles/ml, the detection limit is 3 nanomoles/ml, and the concentration is based on Fe 3+ The induced PEG-Ag@BQDs blue-green fluorescence quenching probe is used for quantitative and visual detection of iron ions in water samples and biological fluids.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The preparation method of the polyethylene glycol modified silver-doped boron quantum dot is characterized by comprising the following steps of:
(1) Measuring 50-100 ml of N-methylpyrrolidone NMP, adding 50-100 mg of block boron powder under stirring to form a boron powder dispersion, then dropwise adding a silver nitrate aqueous solution to form a mixed solution, adjusting the boron concentration to 0.5-1.0 mg/ml, and adjusting the silver concentration to 0.05-0.1 mg/ml;
(2) Ultrasonic processing the mixed solution by using a probe under the power of 500-1000 watts, firstly carrying out ultrasonic processing for 5 seconds, then suspending for 10 seconds, repeating the ultrasonic-suspended circulation operation, and maintaining the whole process for 30-60 minutes;
(3) Weighing 10 ml of secondary distilled water, adding 0.1-1.0 ml of polyethylene glycol PEG-400 under stirring to dilute into aqueous dispersion of PEG-400, dropwise adding the aqueous dispersion into the mixed solution subjected to ultrasonic probe treatment, and continuously treating the mixed solution for 3-6 hours under 1000-1200 watts of power by adopting bath ultrasound;
(4) Transferring the mixed solution after ultrasonic treatment in a bath into a miniature magnetic high-pressure reaction kettle with polytetrafluoroethylene lining, and adding the mixed solution into N 2 And (3) protecting and stirring at 100-200 ℃ for reaction for 5-10 hours, cooling the reaction product to room temperature, centrifuging for 10-20 minutes at the rotation speed of 3500 rpm, absorbing the upper liquid, centrifuging for 10-20 minutes at the rotation speed of 12000 rpm, washing the obtained precipitate with ethanol and secondary distilled water for 3-6 times, and then vacuum drying at 60 ℃ to obtain the PEG-400 surface-modified silver-doped boron quantum dots PEG-Ag@BQDs.
2. Detecting Fe by using polyethylene glycol modified silver doped boron quantum dots prepared by the preparation method of claim 1 as iron ion fluorescent nanoprobe 3+ Is characterized by comprising the following steps: preparing the aqueous dispersion of PEG-Ag@BQDs prepared in claim 1, dropwise adding an aqueous solution of ferric chloride under stirring to form a liquid to be tested, adjusting the concentration of the PEG-Ag@BQDs to be 0.5-1.0 mg/ml, and adjusting the concentration of iron ions Fe 3+ The concentration is 0.01-10 micromoles/milliliter, a fluorescence spectrometer is adopted to measure the fluorescence emission spectrum of the liquid to be measured, and different fluorescence emission peak intensities and corresponding Fe are fitted 3+ The linear relation between the concentrations constructs the fluorescent nano probe based on PEG-Ag@BQDs for Fe 3+ High efficiency detection of Fe in 3+ The linear detection range of the concentration is 0.01-10 micromoles/ml, the detection limit is 1-10 nanomoles/ml, and the concentration is based on Fe 3+ The induced PEG-Ag@BQDs blue-green fluorescence quenching probe is used for quantitative and visual detection of iron ions in water samples and biological fluids.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194464A (en) * | 2019-06-25 | 2019-09-03 | 中北大学 | A kind of preparation method and application of boron quantum dot |
| CN112251223A (en) * | 2020-09-14 | 2021-01-22 | 西华大学 | Nitrogen-doped fluorescent carbon dot based on citric acid and benzoylurea as well as preparation method and application thereof |
| CN113292989A (en) * | 2021-06-04 | 2021-08-24 | 青岛大学 | Preparation method of lactic acid fluorescence nano biological probe based on enzyme catalytic reaction of cobalt ion coordination type boron quantum dot |
| WO2021203567A1 (en) * | 2020-04-08 | 2021-10-14 | 青岛大学 | Preparation method for iron ion coordinated black phosphorus quantum dot having high stability and strong fluorescence emission |
| CN113697822A (en) * | 2020-05-20 | 2021-11-26 | 中国科学院理化技术研究所 | Boron quantum dot and preparation method and application thereof |
| CN113827734A (en) * | 2021-09-22 | 2021-12-24 | 青岛大学 | Preparation method of metal ion coordination boron quantum dot composite carrier with various biomedical functions |
-
2022
- 2022-06-02 CN CN202210621623.5A patent/CN114774111B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194464A (en) * | 2019-06-25 | 2019-09-03 | 中北大学 | A kind of preparation method and application of boron quantum dot |
| WO2021203567A1 (en) * | 2020-04-08 | 2021-10-14 | 青岛大学 | Preparation method for iron ion coordinated black phosphorus quantum dot having high stability and strong fluorescence emission |
| CN113697822A (en) * | 2020-05-20 | 2021-11-26 | 中国科学院理化技术研究所 | Boron quantum dot and preparation method and application thereof |
| CN112251223A (en) * | 2020-09-14 | 2021-01-22 | 西华大学 | Nitrogen-doped fluorescent carbon dot based on citric acid and benzoylurea as well as preparation method and application thereof |
| CN113292989A (en) * | 2021-06-04 | 2021-08-24 | 青岛大学 | Preparation method of lactic acid fluorescence nano biological probe based on enzyme catalytic reaction of cobalt ion coordination type boron quantum dot |
| CN113827734A (en) * | 2021-09-22 | 2021-12-24 | 青岛大学 | Preparation method of metal ion coordination boron quantum dot composite carrier with various biomedical functions |
Non-Patent Citations (2)
| Title |
|---|
| Boron Quantum Dots for Photoacoustic Imaging-Guided Photothermal Therapy;T. Guo er al.;《ACS Appl. Mater. Interfaces》;第13卷;第306-311页 * |
| Experimental synthesis, functionalized modifications and potential applications of monoelemental zero-dimensional boron nanomaterials;M. Yang er al.;《J. Mater. Chem. A》;第10卷;第5111-5146页 * |
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