CN114426845A - Fluorescent carbon quantum dot-based probe and application thereof in detecting water content in organic solvent - Google Patents
Fluorescent carbon quantum dot-based probe and application thereof in detecting water content in organic solvent Download PDFInfo
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- CN114426845A CN114426845A CN202111653667.8A CN202111653667A CN114426845A CN 114426845 A CN114426845 A CN 114426845A CN 202111653667 A CN202111653667 A CN 202111653667A CN 114426845 A CN114426845 A CN 114426845A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
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- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Abstract
The invention relates to a fluorescent carbon quantum dot-based probe and application thereof in detecting water content in an organic solvent. The technical scheme is as follows: dissolving o-phenylenediamine and nitric acid in water, and performing ultrasonic treatment to form a uniformly dispersed mixed solution; transferring the obtained mixed solution into a polytetrafluoroethylene high-pressure reaction kettle, transferring the reaction kettle into a drying oven, and carrying out hydrothermal reaction; and centrifuging, dialyzing and freeze-drying the obtained reaction solution to obtain the fluorescent carbon quantum dot-based probe. The fluorescent carbon quantum dot-based probe prepared by the invention breaks through the limitations of large toxicity, need of professional operators and the like of the traditional Karl-Fischer titration method, and opens up a novel detection system for detecting the water content in the organic solvent under a ratio and colorimetric dual mode.
Description
Technical Field
The invention belongs to the field of organic solvent detection, and particularly relates to a method for detecting water content in an organic solvent based on a fluorescent carbon quantum dot-based probe, which establishes a novel detection system under a ratio and colorimetric dual mode.
Background
Water is a common impurity in organic solvents, and water contamination in organic solvents can cause hydrolysis and the formation of harmful oxidation products that destroy the organic solvent during storage. The karl-fischer titration method is a conventional method for determining the moisture content in organic solvents, but has a number of disadvantages: for example, it requires toxic reagents, precise sample handling and specified equipment. Fluorescent organic dyes, conjugated fluorescent polymers and fluorescent metal organic frameworks are ideal substitutes for detecting trace amounts of water by the classical Karl-Fischer titration method. For example, the water content is detected by a fluorescent organic dye method; the synthesized Eu-MOF nano hybrid is used for detecting water in an organic solvent. However, these methods also have the disadvantages of toxicity, complicated synthesis process, long synthesis period, poor photostability, etc. Therefore, there is an increasing interest in the synthesis of new carbon dot type fluorescence sensors with tunable emission spectra.
Carbon Dots (CDs) have the advantages of low toxicity, high light stability, good dispersibility in various solvents, biocompatibility, easy preparation from less toxic chemical substances or eco-friendly natural resources, good Photoluminescence (PL) performance and the like, and are an excellent multifunctional material which is widely researched in recent years. Because of the superior characteristics of CDs compared to semiconductor quantum dots and organic dyes, CDs have found wide applications in sensing, bio-imaging, photocatalysis, medical imaging, light emitting diodes, photovoltaics, antibacterial agents, and drug delivery. To date, synthetic substrates for CDs include natural biological substances, small non-aromatic open/closed chain molecules, weak organic acids, carbohydrates, amino acids, urea, ethylenediamine, and the like. However, there are disadvantages in that: the CDs prepared have low Quantum Yields (QYs) and exhibit excitation-dependent PL emission characteristics, thereby limiting the use of CDs in many fields. Currently, substituted polycyclic hydrocarbons/substituted benzenes are used as carbon sources for increasing QYs, such as folic acid, diaminonaphthalene, 1, 3-dihydroxynaphthalene, phenylenediamine, and 1,3, 5-trihydroxybenzene. CDs derived from these compounds generally exhibit a large red-shift and excitation independent luminescence. Through years of efforts, high QYs CDs with blue (94.5%), green (73%), yellow (76%) and red (53%) emissions are successfully synthesized by taking substituted benzene/substituted polycyclic hydrocarbon as a raw material.
At present, a carbon quantum dot system for detecting the water content in an organic solvent in a ratio and a colorimetric dual mode with near infrared luminescence is not reported.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to prepare a fluorescent carbon quantum dot-based probe emitting near-infrared light by a one-pot hydrothermal method using o-phenylenediamine and nitric acid, and to use the fluorescent carbon quantum dot-based probe for detecting the water content in an organic solvent in a ratiometric and colorimetric dual mode.
The technical scheme adopted by the invention is as follows: a fluorescent carbon quantum dot-based probe is prepared by the following steps:
1) dissolving o-phenylenediamine and nitric acid in water, and performing ultrasonic treatment to form a uniformly dispersed mixed solution;
2) transferring the obtained mixed solution into a polytetrafluoroethylene high-pressure reaction kettle, transferring the reaction kettle into a drying oven, and carrying out hydrothermal reaction;
3) centrifuging and dialyzing the reaction solution obtained in the step 2);
4) and (3) freezing and drying the product obtained in the step 3) to obtain the fluorescent carbon quantum dot-based probe.
Preferably, in the above fluorescent carbon quantum dot-based probe, in step 2), the hydrothermal reaction is carried out at 180 ℃ for 12 hours.
Preferably, in the fluorescent carbon quantum dot-based probe, in the step 3), the centrifugation is performed at 8000r/min for 5 min.
Preferably, in the above fluorescent carbon quantum dot-based probe, in step 3), the dialysis is performed by using a dialysis bag with a molecular weight cut-off of 500D and a dialysis time of 48 h.
The invention provides an application of a fluorescent carbon quantum dot-based probe in detecting water content in an organic solvent.
A method for detecting water content in an organic solvent based on a fluorescent carbon quantum dot-based probe comprises the following steps: adding a fluorescent carbon quantum dot-based probe into an organic solvent, uniformly mixing, and testing the fluorescence spectrum and the ultraviolet spectrum of the mixed solution.
Preferably, the organic solvent is ethanol.
The invention has the beneficial effects that:
1. in the invention, o-phenylenediamine contains a benzene ring structure, and forms fluorescent carbon quantum dots by a hydrothermal method, thereby further becoming a fluorescent carbon quantum dot-based probe. The fluorescent carbon quantum dot-based probe of the present invention can be obtained by inexpensive materials and simple procedures.
2. The fluorescent carbon quantum dot-based probe provided by the invention can be used as a new detection system in a dual mode, is used for detecting the water content in an organic solvent, and has a great application prospect.
3. The fluorescent carbon quantum dot-based probe provided by the invention can be used for detecting in a fluorescence and colorimetric dual mode, overcomes the defects of high toxicity, need of professional technicians and the like of the traditional Karl Fischer titration method, and provides a novel system for detecting the water content in an organic solvent.
Drawings
FIG. 1 is a transmission electron micrograph of a fluorescent carbon quantum dot based probe.
FIG. 2a is a graph of the fluorescence spectrum of a fluorescent carbon quantum dot based probe in ethanol solvent.
FIG. 2b shows the UV absorption peak and fluorescence excitation peak of a fluorescent carbon quantum dot based probe.
FIG. 3a is an infrared spectrum of o-phenylenediamine and fluorescent carbon quantum dot based probes.
FIG. 3b is a XPS summary of fluorescent carbon quantum dot based probes.
FIG. 4a is a fluorescence spectrum of fluorescent carbon quantum dot based probes in ethanol of different water content.
FIG. 4b is a CIE graph corresponding to the fluorescence spectra of fluorescent carbon quantum dot based probes in ethanol at different water contents.
FIG. 5a is a graph of the color change of fluorescent carbon quantum dot based probes in ethanol with different water contents under daylight.
Fig. 5b is a graph of the ultraviolet absorption of fluorescent carbon quantum dot based probes in ethanol at different water contents.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are to be construed as being better understood and not as imposing any limitation on the scope thereof.
Example 1 a fluorescent carbon quantum dot-based probe (a) was prepared by the following steps:
1) dissolving 0.3g of o-phenylenediamine and 0.24mL of nitric acid in 10mL of water, and performing ultrasonic treatment for 15min to form a uniformly dispersed mixed solution;
2) transferring the obtained mixed solution into a polytetrafluoroethylene high-pressure reaction kettle, transferring the reaction kettle into a drying oven, and carrying out hydrothermal reaction for 12 hours at 180 ℃ to obtain a reaction solution;
3) centrifuging the reaction solution obtained in the step 2) for 5min at the rotating speed of 8000r/min, and dialyzing the supernatant for 48h by using a 500D dialysis bag;
4) and (3) freeze-drying the dialyzed product obtained in the step 3) in a freeze dryer for 48 hours to obtain the solid powdery fluorescent carbon quantum dot-based probe.
(II) detection
FIG. 1 is a transmission electron micrograph of a fluorescent carbon quantum dot based probe. As can be seen from FIG. 1, the fluorescent carbon quantum-based probes were uniformly dispersed in the ethanol solution, and had an average diameter of 4nm, which is shown by the inset, having a lattice spacing of 0.21 nm.
FIG. 2a is a graph of the fluorescence spectrum of a fluorescent carbon quantum dot based probe in ethanol solvent. FIG. 2b shows the UV absorption peak and fluorescence excitation peak of a fluorescent carbon quantum dot based probe. As can be seen from FIG. 2a, the fluorescent carbon quantum dot-based probe exhibited an emission behavior in ethanol solution independent of the excitation wavelength, and as can be seen from FIG. 2b, the absorption at 284nm represents π - π*Transition, absorption at 534nm and 578nm for n- π*And (4) transition.
FIG. 3a is an IR spectrum of o-phenylenediamine and fluorescent carbon quantum dot based probes, as seen in FIG. 3a, where the peaks represent the groups: N-H (3430 cm)-1),C＝N/C＝C(1602cm-1),C-N(1499 and 1350cm-1),C-O(1110cm-1)。
Fig. 3b is an XPS summary of the fluorescent carbon quantum dot based probe, as can be seen from fig. 3b, indicating the elemental ratio C: n: o70.09%: 19.58%: 10.33 percent.
Example 2a method for detecting water content in organic solvents based on fluorescent carbon quantum dot based probes,
the fluorescent carbon quantum dot-based probe prepared in example 1 was used as a fluorescent probe to detect the water content in ethanol in a colorimetric and ratiometric manner.
The method comprises the following steps: mixing 0.01mg of fluorescent carbon quantum dot-based probe with 3mL of mixed solution of ethanol and water with different water contents (the volume percentages of the water are 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 percent respectively), stirring uniformly, placing into a four-way transmission cuvette, testing in a fluorescence spectrophotometer, fixing the excitation wavelength to 290nm, and collecting a fluorescence emission spectrogram.
The method comprises the following steps: 0.01mg of a fluorescent carbon quantum dot-based probe was mixed with 3mL of a mixed solution of ethanol and water having different water contents (the volume percentages of water were 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100%), stirred uniformly, placed in a two-pass transmission cuvette, tested in an ultraviolet spectrophotometer, the maximum absorption value of the mixed solution was collected, and the color of the mixed solution was recorded under sunlight.
FIG. 4a is a fluorescence spectrum of fluorescent carbon quantum dot based probes in ethanol of different water content. The peak at 360nm remained constant and the peak at 605 gradually decreased with increasing water content. Fig. 4b is a CIE coordinate diagram of the fluorescence spectra of fluorescent carbon quantum dot-based probes in ethanol with different water contents, and it can be seen from fig. 4b that the corresponding fluorescence color also changes from red to pink to blue.
FIG. 5a is a graph of the color change of fluorescent carbon quantum dot based probes in ethanol with different water contents under daylight. Fig. 5b is a graph of the ultraviolet absorption of fluorescent carbon quantum dot based probes in ethanol at different water contents. As can be seen from fig. 5a, the color also shifts from dark red to light red to colorless in daylight. As can be seen from fig. 5b, the normalized equation is, Y ═ 0.318x +0.477 (R), respectively20.996) and y-0.824 x +0.892 (R)2＝0.990)。
Claims (7)
1. A fluorescent carbon quantum dot-based probe, characterized by: the preparation method comprises the following steps:
1) dissolving o-phenylenediamine and nitric acid in water, and performing ultrasonic treatment to form a uniformly dispersed mixed solution;
2) transferring the obtained mixed solution into a polytetrafluoroethylene high-pressure reaction kettle, transferring the reaction kettle into a drying oven, and carrying out hydrothermal reaction;
3) centrifuging and dialyzing the reaction solution obtained in the step 2);
4) and (4) freezing and drying the product obtained in the step 3) to obtain the fluorescent carbon quantum dot-based probe.
2. A fluorescent carbon quantum dot based probe according to claim 1, wherein: in the step 2), the hydrothermal reaction is carried out for 12 hours at 180 ℃.
3. A fluorescent carbon quantum dot based probe according to claim 1, wherein: in the step 3), the centrifugation is carried out for 5min at the rotating speed of 8000 r/min.
4. A fluorescent carbon quantum dot based probe according to claim 1, wherein: in the step 3), the dialysis is that the cut-off molecular weight of a dialysis bag is 500D, and the dialysis time is 48 h.
5. Use of the fluorescent carbon quantum dot-based probe of any one of claims 1 to 4 for detecting water content in an organic solvent.
6. A method for detecting water content in organic solvent based on fluorescent carbon quantum dot based probe, characterized in that, the fluorescent carbon quantum dot based probe of any one of claims 1-4 is used, the method is as follows: adding a fluorescent carbon quantum dot-based probe into an organic solvent, uniformly mixing, and testing the fluorescence spectrum and the ultraviolet spectrum of the mixed solution.
7. The method of claim 6, wherein the organic solvent is ethanol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114907845A (en) * | 2022-06-15 | 2022-08-16 | 辽宁大学 | Three-primary-color fluorescent carbon quantum dot and preparation method and application thereof |
| CN116410746A (en) * | 2023-04-03 | 2023-07-11 | 郑州中科生物医学工程技术研究院 | Preparation method of fluorescent probe for beta-carotene detection |
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| CN110184053A (en) * | 2019-07-12 | 2019-08-30 | 青岛大学 | A kind of preparation method and applications of N doping feux rouges carbon quantum dot |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907845A (en) * | 2022-06-15 | 2022-08-16 | 辽宁大学 | Three-primary-color fluorescent carbon quantum dot and preparation method and application thereof |
| CN116410746A (en) * | 2023-04-03 | 2023-07-11 | 郑州中科生物医学工程技术研究院 | Preparation method of fluorescent probe for beta-carotene detection |
| CN116410746B (en) * | 2023-04-03 | 2024-03-22 | 郑州中科生物医学工程技术研究院 | Preparation method of fluorescent probe for beta-carotene detection |
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