CN114891502B - Method for synthesizing fluorescent probe with assistance of eutectic solvent and application - Google Patents
Method for synthesizing fluorescent probe with assistance of eutectic solvent and application Download PDFInfo
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- 239000002113 nanodiamond Substances 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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"
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- 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
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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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Abstract
The invention relates to a method for synthesizing a fluorescent probe with the assistance of a eutectic solvent and application thereof. The synthesis method comprises the following steps: (1) Mixing a hydrogen bond donor with a hydrogen bond acceptor to obtain a mixed solution, wherein the hydrogen bond acceptor comprises metal, and heating until the mixed solution becomes a uniform and transparent solution to obtain a metal eutectic solvent, namely MDES; (2) preparing MDES solution from MDES; (3) Heating and reacting the MDES solution, and cooling to obtain a carbon dot solution; (4) Filtering and dialyzing the carbon dot solution to obtain a solution containing the fluorescent probe. The probe synthesized by the invention can be used for detecting nitrite in food and monitoring pH of water environment. The invention has the advantages of environment protection, low cost, stable fluorescence, wide sources, simple preparation, high quantum yield, good water solubility, strong selectivity, wide linear range, good detection sensitivity and the like.
Description
Technical Field
The invention belongs to the technical fields of fluorescent nano material preparation, food and environmental science, and particularly relates to a method for synthesizing a fluorescent probe with the assistance of a eutectic solvent and application thereof.
Background
Nitrite is commonly known as industrial salt and is widely used as a colorant, a preservative, an antibacterial agent and an additive for the food industry. However, excessive intake of nitrite can be detrimental to human health. It can be converted into various nitrogen oxides in human body, and can be reacted with protein metabolites of amine, etc. in acid medium to form nitrosamine, so that it has serious carcinogenic risk. In addition, excess nitrite in the blood can also convert hemoglobin to methemoglobin, thereby interfering with the oxygen transport system in the body, leading to hypoxia and blood pressure reduction. Nitrite is widely used in food industry, and also widely exists in chemical fertilizer degradation, acid rain, industrial waste and the like. Therefore, monitoring nitrite ion content is becoming increasingly important to human health. This has prompted the need to establish a highly sensitive, highly selective approach. In addition, the addition of nitrite can greatly influence the pH value, and the stability and fluorescence performance of detection under different pH values are particularly important, so that a foundation is laid for the future application of nitrite in water environment pH monitoring.
Currently, methods for detecting nitrite include chromatography, capillary electrophoresis, electrochemical methods, fluorescence spectroscopy, and the like. Colorimetry is the most commonly used method among them, and has been used for decades. The method is simple, quick, low in cost and wide in application, but still has the defects of low sensitivity, high toxicity, easiness in interference by other matrixes and anions and the like. The chromatographic method and the electrochemical method have high sensitivity and good selectivity, but have long time consumption and are not suitable for trace detection.
Currently, fluorescent nanomaterials as fluorescent sensors are various in variety, such as semiconductor quantum dots, polymer dots, fluorescent nanodiamonds, fluorescent nanoclusters, and the like. However, a range of fluorescent materials that synthesize carbon dots are expensive and detrimental, and most fluorescent probes are required to meet acidic conditions when detecting nitrite ions. Therefore, it is still necessary to develop a green alternative material.
Therefore, aiming at the food problem caused by the large-scale production of nitrite, the development of the precursor preparation method of the green-friendly carbon quantum dots has important significance in realizing the effective detection of nitrite in food.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a method for synthesizing a fluorescent probe with the assistance of a eutectic solvent and application thereof, and the method has the advantages of environmental friendliness, environmental protection, low cost, stable fluorescence, wide sources, simple preparation, high quantum yield, good water solubility, strong selectivity, wide linear range, good detection sensitivity and the like.
The technical scheme for solving the technical problems is as follows:
the invention provides a method for synthesizing a fluorescent probe with the assistance of a eutectic solvent, which comprises the following steps:
(1) Mixing a hydrogen bond donor with a hydrogen bond acceptor to obtain a mixed solution, wherein the hydrogen bond acceptor comprises metal, and heating until the mixed solution becomes a uniform and transparent solution to obtain a metal eutectic solvent, namely MDES;
(2) Preparing MDES solution from MDES;
(3) Heating and reacting the MDES solution, and cooling to obtain a carbon dot solution;
(4) The carbon dot solution was filtered to obtain a solution containing a fluorescent probe.
The beneficial effects of adopting above-mentioned scheme include:
the fluorescent probe prepared by the invention is based on a metal type eutectic solvent which is a precursor and iron-doped carbon quantum dot fluorescent probe, has extremely high thermal stability, higher atom economy and biodegradability, accords with the concept of green chemistry, and is a strong substitute of toxic organic solvents.
The fluorescent probe synthesized by the method has the advantages of environment friendliness, low cost, stable fluorescence, wide source, simplicity in preparation, high quantum yield, good water solubility, strong selectivity, wide linear range, good detection sensitivity and the like. And can realize nitrite detection in food and environment, and can be used as an environmental pH indicator due to unique color change under different pH values.
Further, the hydrogen bond donor is DL-malic acid; the hydrogen bond acceptor includes ethylene glycol and metal; the molar ratio of DL-malic acid, ethylene glycol and metal is 2:8: (0.2-1.2).
The beneficial effects of adopting above-mentioned scheme include: the inventors have unexpectedly found that the proportion of doped metal can greatly influence the fluorescence intensity of MDES-CDs and the response of nitrite. The quality of the fluorescent probe is improved by adopting the proper proportion.
Further, the metal is selected from one or a combination of a plurality of Cu, mn, fe, zn, co.
Preferably, the hydrogen bond donor is selected from DL-malic acid, and the hydrogen bond acceptor comprises ethylene glycol and metal Fe.
The beneficial effects of adopting above-mentioned scheme include: the fluorescence probe prepared by the eutectic solvent synthesized by DL-malic acid-metal Fe-glycol has high fluorescence intensity, and can realize the determination of nitrite.
Further, in the step (1), the heating temperature is 60-80 ℃; in step (3), the conditions for the heating reaction include: the temperature is 120-200 ℃, and the reaction time is 2-10h; in step (4), filtration was performed using a 0.22 μm microporous filter membrane.
The beneficial effects of adopting above-mentioned scheme include:
the heating temperature is 60-80 ℃, which is favorable for accelerating the reaction speed, leading the reaction speed to be heated uniformly and leading the MDES to be synthesized relatively stably in the temperature range. The temperature is too low to be heated slowly, and the temperature requirement for forming MDES can not be met; too high a temperature is prone to sticking to the bottom or cracking, and safety problems can occur.
The temperature is 120-200 ℃, the reaction time is 2-10h, and the conditions are optimal conditions obtained by researching the influence of synthesis temperature and time variable on fluorescence intensity, so that MDES-CDs obtains higher fluorescence quantum yield.
The macromolecular impurities in the solution are removed by adopting a microporous filter membrane with the thickness of 0.22 mu m, so that the MDES-CDs solid has better luminous property.
Further, the method also comprises the steps of dialysis after filtration and freeze drying to obtain MDES-CDs; the conditions for lyophilization included: freeze drying at-80deg.C for 24-48 hr.
The beneficial effects of adopting above-mentioned scheme include: the MDES-CDs solid obtained has better luminous property.
Further, the method comprises the step of preparing MDES-CDs solution from MDES-CDs; in the MDES-CDs solution, the concentration of MDES-CDs is 10-50 mg.mL -1 。
The beneficial effects of adopting above-mentioned scheme include: is prepared into the concentration of 10-50 mg.mL -1 The MDES-CDs solution has too low concentration, too low fluorescence intensity and too large dosage; too high a concentration error becomes large and there is a possibility of self-quenching.
The invention provides a reagent or a kit for detecting nitrite and/or pH, which comprises a fluorescent probe synthesized by the method.
The beneficial effects of adopting the technical scheme include: the reagent or the kit provided by the invention has ultrahigh sensitivity, selectivity, excellent pH dependent luminescence and unique color change, and has wide application prospect.
The invention provides the application of the fluorescent probe in one or more of (1), (2), (3) and (4),
(1) Detecting nitrite;
(2) Detecting the pH;
(3) A reagent or kit for making or detecting nitrite;
(4) Reagents or kits for making or detecting pH.
The invention provides a method for detecting nitrite, which comprises the following steps: and (3) preparing a standard curve of fluorescence intensity relative to nitrite concentration, mixing the fluorescence probe with a sample to be detected for reaction, detecting the fluorescence intensity, and calculating the nitrite concentration of the sample to be detected according to the standard curve.
For example: whether to perform pretreatment or not can be selected according to actual needs. Then mixing the sample to be tested with MDES-CDs solution, wherein the concentration of MDES-CDs in the MDES-CDs solution can be 10-mg.mL -1 The volume of the sample to be tested and the MDES-CDs solution can be 1:10, and the reaction is carried out for 20min at 60 ℃ under the condition of pH=2, so that the fluorescence intensity of the reacted solution is tested. Substituting the value into a linear regression equation to calculate the concentration of nitrite in the sample to be detected.
The beneficial effects of adopting the technical scheme include: the fluorescent probe provided by the invention is environment-friendly, has ultrahigh sensitivity and selectivity to sodium nitrite, has a detection limit as low as 50nm, and can be used for large-scale production and detection of nitrite in food and environment.
The invention provides a method for detecting pH, which comprises the following steps: and (3) preparing a standard curve of fluorescence intensity with respect to pH, mixing the fluorescent probe with a sample to be detected for reaction, detecting the fluorescence intensity, and calculating the pH of the sample to be detected according to the standard curve.
For example: whether to perform pretreatment or not can be selected according to actual needs. Then mixing the sample to be tested with MDES-CDs solution, wherein the concentration of MDES-CDs in the MDES-CDs solution can be 10-mg.mL -1 The reaction was carried out at 60℃for 20 minutes, and the fluorescence intensity of the reacted solution was measured. Substituting the value into a linear regression equation to calculate the pH value in the sample to be detected.
The beneficial effects of adopting the technical scheme include: the fluorescent probe provided by the invention has excellent pH-dependent luminescence and unique color change, and can be used as a pH indicator for detecting water environment. And has good application value and prospect in the fields of food, environmental monitoring and the like.
Drawings
Fig. 1 is a schematic diagram of a preparation principle and a detection principle of an Fe-doped carbon quantum dot fluorescent probe for nitrite and pH detection in the present invention.
FIG. 2 is a plot of the optimization of synthesis conditions for MDES-CDs: metal species (a); iron doping ratio (B); synthesis temperature (C); time (D).
FIG. 3 is a graph showing the results of the morphology, composition and surface structure studies of MDES-CDs; a is a transmission electron microscope image of MDES-CDs and lattice analysis; b is the particle size distribution diagram of MDES-CDs; c is the infrared spectrum of MDES-CDs.
FIG. 4 is an X-ray photoelectron spectrum of MDES-CDs: a full scan spectrogram (A); c1s spectrogram (B); o1 s spectrogram (C); fe 2p spectrogram (D).
FIG. 5 is a graph showing the results of verifying the optical characteristics of MDES-CDs by ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence spectroscopy; ultraviolet absorption spectrum of MDES-CDs and optimal fluorescence excitation and emission spectrum (A) (the inset is the contrast graph of the solution color of MDES-CDs under sunlight and ultraviolet lamp); fluorescence emission patterns (B) of MDES-CDs at different excitation wavelengths (350-520 nm).
FIG. 6 is a graph showing the effect of high ionic strength and irradiation time on MDES-CDs fluorescence intensity; MDES-CDs in salt solutions of different concentrations (0.1-1 mol.L -1 ) Salt stability spectrum (A) and continuous excitation at optimal excitation wavelengthFrom 0 to 100 min).
FIG. 7 is a graph of the detection condition optimization of MDES-CDs for nitrite: pH value (A); temperature (B); time (C).
FIG. 8 is a graph of fluorescence emission spectra of MDES-CDs solutions at various nitrite concentrations.
FIG. 9 is a graph showing the linear relationship between the different concentrations of nitrite and the fluorescence intensity of MDES-CDs.
FIG. 10 is a graph showing the effect of different interfering ions on the fluorescence intensity of MDES-CDs solutions.
FIG. 11 is a graph showing fluorescence emission spectra of MDES-CDs at different pH.
FIG. 12 is a graph showing the linear relationship between the fluorescence intensity of MDES-CDs and various pH values.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
As shown in fig. 1, the invention provides a method for preparing a fluorescent probe with the assistance of a metal eutectic solvent and application thereof, and the prepared fluorescent probe is a metal doped fluorescent probe which is based on a metal eutectic solvent as a precursor and iron doped carbon quantum dot fluorescent probe, and can be used for detecting nitrite in food and monitoring pH of water environment.
The invention provides a method for preparing a fluorescent probe with the assistance of a metal eutectic solvent, which comprises the following steps:
(1) Preparing a metal type eutectic solvent: mixing a hydrogen bond donor and a hydrogen bond acceptor, and heating at 60-80 ℃ until the mixture becomes a uniform and transparent solution, namely the metal eutectic solvent; the hydrogen bond donors include: DL-malic acid; the hydrogen bond acceptor comprises glycol and metal (one or more selected from Cu, mn, fe, zn and Co). Preferably, DL-malic acid acts as a hydrogen bond donor and ethylene glycol acts as a hydrogen bond acceptor with metallic Fe. The fluorescence probe prepared by the eutectic solvent synthesized by DL-malic acid-metal Fe-glycol has high fluorescence intensity, and can realize the determination of nitrite. DL-malic acid: ethylene glycol: the molar ratio of the metal phase Fe is 2:8: (0.2-1.2).
(2) Precisely weighing 5mL of MDES, dissolving in 10mL of deionized water, and carrying out ultrasonic treatment until the system is uniformly mixed to obtain an MDES solution.
(3) And (3) placing the MDES solution mixed in the step (2) in a polytetrafluoroethylene liner high-pressure reaction kettle, reacting for 2-10h at the temperature of 120-200 ℃ in an oven, and cooling the system to room temperature to obtain a carbon dot solution.
(4) The carbon spot solution cooled to room temperature in step (3) was filtered with a 0.22 μm filter membrane and then dialyzed for 24 hours using a dialysis bag (MW: 500 Da).
(5) And (3) carrying out vacuum (-80 ℃) freeze drying on the solution in the step (4) for 24-48 hours to obtain the novel fluorescent probe (MDES-CDs), and placing the novel fluorescent probe at a low temperature of 4 ℃ for standby.
(6) Adding ultrapure water to the MDES-CDs solid obtained in the step (5) to prepare an MDES-CDs solution (concentration of 10-50 mg.mL) -1 ) Storing at 4deg.C for use.
The metal doped carbon quantum dot fluorescent probe (namely MDES-CDs fluorescent probe) can be prepared by the preparation method.
The MDES-CDs fluorescent probe prepared by the method can be applied to nitrite detection and environmental pH detection.
The invention provides a method for detecting nitrite, which comprises the following steps: and (3) preparing a standard curve of fluorescence intensity relative to nitrite concentration, mixing the fluorescence probe with a sample to be detected for reaction, detecting the fluorescence intensity, and calculating the nitrite concentration of the sample to be detected according to the standard curve.
For example: whether to perform pretreatment or not can be selected according to actual needs. Then mixing the sample to be tested with MDES-CDs solution, wherein the concentration of MDES-CDs in the MDES-CDs solution can be 10-mg.mL -1 The volume of the sample to be tested and the MDES-CDs solution can be 1:10, and the reaction is carried out for 20min at 60 ℃ under the condition of pH=2, so that the fluorescence intensity of the reacted solution is tested. Substituting the value into a linear regression equation to calculate the concentration of nitrite in the sample to be detected.
The invention provides a method for detecting pH, which comprises the following steps: and (3) preparing a standard curve of fluorescence intensity with respect to pH, mixing the fluorescent probe with a sample to be detected for reaction, detecting the fluorescence intensity, and calculating the pH of the sample to be detected according to the standard curve.
For example: whether to perform pretreatment or not can be selected according to actual needs. Then mixing the sample to be tested with MDES-CDs solution, wherein the concentration of MDES-CDs in the MDES-CDs solution can be 10-mg.mL -1 The reaction was carried out at 60℃for 20 minutes, and the fluorescence intensity of the reacted solution was measured. Substituting the value into a linear regression equation to calculate the pH value in the sample to be detected.
The fluorescent probe prepared based on the metal eutectic solvent is environment-friendly, low in cost, high in fluorescence intensity and good in stability. MDES-CDs have relatively uniform size and good dispersibility in aqueous solutions without significant aggregation. The surface of the fluorescent probe contains rich oxygen-containing functional groups, and the MDES-CDs can be used as a stable and excellent fluorescent probe for sensing and measuring.
Compared with the prior art, the invention has the following characteristics:
(1) The fluorescent probe prepared by the invention has wide sources of raw materials and is green.
(2) The fluorescent probe provided by the invention is simple to prepare, high in quantum yield and good in water solubility.
(3) The fluorescent probe provided by the invention has stronger photobleaching stability and keeps basically stable under higher salt concentration.
(4) The fluorescent probe of the invention is MDES-CDs with blue fluorescence, and the addition of nitrite can lead to the fluorescent quenching of the MDES-CDs. And the fluorescence intensity has good linear relation with nitrite concentration in a certain range.
(5) The fluorescent probe has super-strong selectivity to nitrite, wide linear range and good detection sensitivity, and is successfully used for detecting samples of food and environment.
(6) The MDES-CDs fluorescent probe also has unique pH sensitivity, can realize excellent linear relation with pH in the range of 2-7, the fluorescence intensity of the MDES-CDs is obviously quenched, and the solution is converted from pale yellow-green color under sunlight, so that the fluorescent probe can be used as a color indicator for pH detection.
(7) Based on the excellent sensing capability of MDES-CDs on nitrite and pH. So that the preparation method has good application value in the fields of food safety, environmental pollution and the like.
The following is presented by way of specific examples.
In the present invention, parameters of the fluorescence spectrophotometer may be set as: scanning speed (1000 nm/min), excitation bandwidth (10 nm), emission bandwidth (10 nm), gain (medium, 650V).
Example 1
The preparation method of the MDES-CDs fluorescent probe with the metal eutectic solvent as the precursor comprises the following steps:
(1) DL-malic acid is used as hydrogen bond donor, ethylene glycol and metal are used as hydrogen bond acceptor to prepare metal eutectic solvent (MDES). The molar ratio is DL-malic acid: ethylene glycol: metallic phase = 2:8:1. magnetically stirring the mixture at 80deg.C for 30min to obtain uniform transparent liquid phase which is MDES. And (5) after naturally cooling to room temperature, placing the mixture in a closed container for later use.
(2) 5mL of MDES is precisely weighed and dissolved in 10mL of deionized water, and the mixture is evenly mixed by ultrasonic treatment. The mixed solution was placed in an oven and reacted at 200℃for 6 hours, and after the system was cooled to room temperature, the product was filtered with a 0.22 μm filter membrane.
The synthesis conditions of MDES-CDs are optimized, the influence of the doping metal type, the doping metal proportion, the synthesis temperature and the synthesis time on the fluorescence property of the MDES-CDs is examined, and the experimental result is shown in figure 2.
The effect of the doping metal species on the fluorescent properties of MDES-CDs was examined. Different metals including Cu, mn, fe, zn and Co are selected, and are respectively mixed with DL-malic acid and ethylene glycol according to the same proportion as the steps, and the mixture is magnetically stirred for 30min at 80 ℃. After cooling to room temperature, 5mL each was taken and 10mL deionized water was added thereto and mixed well by sonication. Then placing the mixture in a polytetrafluoroethylene liner high-pressure reaction kettle to react for 6 hours at 200 ℃ in an oven, cooling the system to room temperature, filtering the mixture by using a 0.22 mu m filter membrane, and testing the fluorescence intensity of the mixture at the excitation wavelength of 410nm, wherein only MDES-CDs prepared and synthesized by Fe-DES has obvious quenching on nitrite (shown in figure 2A), the upper left-hand corner illustration of figure 2A shows that different MDES-CDs colors (from left to right are the colors of metal eutectic solvents prepared by Cu, mn, fe, zn, co respectively under the same condition of 180 ℃ and 6 hours under the sunlight) under sunlight, so that the fluorescent intensity is highest under the condition that metal Fe exists, and the effect of doping metal into Fe is best. The following experiment was performed with the doping metal Fe.
The effect of the doping metal ratio on the fluorescence properties of MDES-CDs was examined. DL-malic acid was studied: ethylene glycol: doping Fe element in a molar ratio of 2:8: (0.2-1.2) effect on the fluorescence intensity of MDES-CDs, the fluorescence intensities of Fe elements with doping ratios of 0.2, 0.4, 0.6, 0.8, 1.0 and 1.2 were tested under the same conditions (other steps are the same as the steps for synthesizing MDES-CDs), the experimental results are shown in FIG. 2B, and the result shows that when the Fe element ratio reaches 1.0, the fluorescence intensity of MDES-CDs is remarkably enhanced, the increasing trend is slowed down when the Fe element ratio reaches 1.2, and finally the doping Fe molar ratio is set to be 1.
The effect of the synthesis temperature on the fluorescence properties of MDES-CDs was examined. We placed them in an oven 120℃at 140℃at 160℃at 180℃at 200℃for 6 hours, respectively (the other steps were the same as those for synthesizing MDES-CDs described above), and then tested for fluorescence intensity. As can be seen from FIG. 2C, the increase in fluorescence intensity of MDES-CDs at 120℃to 180℃is not significant, and when the reaction temperature reaches 200℃it gives rise to a qualitative jump, indicating that 200℃is its optimal reaction temperature.
The effect of synthesis time on the fluorescent properties of MDES-CDs was examined. The effect of synthesis time on the fluorescence intensity of MDES-CDs was investigated, and the reaction was carried out at 200℃for 2h, 4h, 6h, 8h, and 10h, respectively (the other steps were the same as those for the above-mentioned synthesis of MDES-CDs), and then the fluorescence intensities were measured, respectively. The experimental results are shown in FIG. 2D, and since the fluorescence difference after 6 hours is not obvious, the synthesis time of 6 hours was selected.
Example 2
The preparation method of the MDES-CDs fluorescent probe with the metal eutectic solvent as the precursor comprises the following steps:
(1) DL-malic acid is used as hydrogen bond donor, ethylene glycol and metal (Fe) are used as hydrogen bond acceptor to prepare metal eutectic solvent (MDES). The molar ratio is DL-malic acid: ethylene glycol: metallic phase = 2:8:1. magnetically stirring the mixture at 80deg.C for 30min to obtain uniform transparent liquid phase which is MDES. And (5) after naturally cooling to room temperature, placing the mixture in a closed container for later use.
(2) 5mL of MDES is precisely weighed and dissolved in 10mL of deionized water, and the mixture is evenly mixed by ultrasonic treatment. The mixed solution was placed in an oven and reacted at 200℃for 6 hours, after the system was cooled to room temperature, the product was filtered with a 0.22 μm filter membrane, and then dialyzed in a dialysis bag (MW: 500 Da) for 24 hours, and freeze-dried to obtain MDES-CDs. Then dispersing proper powder into ultrapure water to prepare the powder with the concentration of 30 mug.mL -1 MDES-CDs solution is stored at low temperature of 0-6deg.C for subsequent further characterization and application.
The morphology, composition and surface structure of MDES-CDs obtained by the above optimization method were studied, and the results are shown in FIG. 3. The morphology of MDES-CDs was analyzed by Transmission Electron Microscopy (TEM) and, as shown in FIG. 3A, MDES-CDs had relatively uniform size and good dispersibility in aqueous solutions without significant aggregation. Further, the carbon lattice distance thereof was 0.21nm, corresponding to the lattice spacing of the graphite structure, as analyzed by HR-TEM image (upper right-hand corner inset of FIG. 3A). FIG. 3B shows that the size distribution of MDES-CDs is predominantly in the range of 2-5nm and the average particle size is 3.72nm. The functional groups in MDES-CDs were then identified using Fourier transform infrared spectroscopy (FT-IR). In FIG. 3C, MDES-CDs and MDES-CDs+NO are shown from bottom to top 2 - Is a single crystal, and is a single crystal. Notably, 3423cm -1 The broad and strong absorption peak at this point is the O-H stretching vibration. In addition, MDES-CDs and MDES-CDs+NO due to out-of-plane bending vibration of O-H 2 - At 1398cm -1 1384cm -1 The presence of hydroxyl groups was further confirmed by the absorption peak at this position. 1635cm -1 And 1637cm -1 The infrared absorption peak at which is caused by stretching vibration of carbonyl C=O, and 1041cm -1 The absorption peak at this point can be classified as a tensile vibration of C-O, indicating that carboxyl groups may be present in the structure. At 626cm -1 The peak of (2) is the stretching vibration of the C-H bond. According toThe characterization results show that the surface of MDES-CDs may contain rich oxygen-containing groups, and the functional hydrophilic groups greatly improve the water solubility and stability of MDES-CDs and provide action sites for sensing nitrite.
X-ray photoelectron spectroscopy (XPS) also confirmed the elemental composition and chemical bonding of MDES-CDs (FIG. 4), and was substantially consistent with the elemental measurements of FT-IR measurements. As shown in fig. 4A, the three characteristic peaks centered about 285, 583 and 710eV can be attributed to the binding energies of C1s, O1 s and Fe 2p, respectively, indicating successful doping of the Fe element. Fig. 4B is a high resolution XPS spectrum of C1s (spectrum of c= C, C-O, C =o from left to right, respectively) showing three fitted peaks at 284.0, 285.1 and 287.2eV, respectively, which are assigned to c=c (sp 2 hybridized carbon), C-O and c=o, respectively. This indicates that the graphite structure of the prepared MDES-CDs has sp2 hybridized carbon atoms and confirms the presence of carbonyl functionality. As shown in fig. 4C, the three fitted peaks at 530.1, 531.1 and 532.2eV represent three types of oxygen containing functional groups, i.e., C-O, O-H and c=o bonds, respectively. As shown in fig. 4D, in the high resolution electron spectrum of Fe 2p, the absorption peaks at 710.8 and 722.2eV indicate the presence of iron in the oxidized form. These results further confirm the doping of the Fe element and the formation of oxygen-containing functional groups on the MDES-CDs surface.
The optical properties of MDES-CDs were verified by ultraviolet-visible absorption spectroscopy (UV-Vis) and fluorescence spectroscopy (FIG. 5). MDES-CDs exhibit excellent water solubility without any further chemical modification. As shown in FIG. 5A (results for MDES-CDs, excitation, emission, respectively, from left to right), the MDES-CDs solution was transparent yellowish in sunlight and emitted bright bluish fluorescent light under excitation of a 410nm ultraviolet lamp. UV-Vis spectra (black line in fig. 5A) show different characteristic absorption bands of MDES-CDs, including two ultraviolet absorption peaks at 241 and 351nm, due to pi-pi transitions of c=c bonds and n-pi transitions of c=o bonds, respectively. As shown in FIG. 5B, to investigate whether the fluorescence emission wavelength of MDES-CDs depends on the excitation wavelength, its fluorescence properties at different excitation wavelengths of 350nm to 520nm were tested. The results indicate that MDES-CDs have a maximum emission at 410nm of about 473nm and are characterized by a significant dependence of excitation wavelength. While the absolute quantum yield (Abs-QY) of MDES-CDs was 15.59%.
In addition, the effect of high ionic strength and irradiation time on MDES-CDs fluorescence intensity was examined (FIG. 6). MDES-CDs were mixed with NaCl solutions at 0mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L and 1.0mol/L, respectively, and after vortexing to homogenize the mixture, the fluorescence intensity was measured. FIG. 6A shows that the fluorescence intensity can be kept substantially stable at NaCl concentrations as high as 1M. For the irradiation time, we put it under the ultraviolet lamp with the wavelength of 410nm for continuous irradiation for 90min, and test the fluorescence intensity every 5min, it can be seen from fig. 6B that the fluorescence intensity can be maintained above 75% within 90min of the ultraviolet irradiation with the wavelength of 410 nm. It is demonstrated that MDES-CDs can be used as a stable and excellent fluorescent probe for sensing assays.
Example 3
A method of detecting nitrite comprising the steps of:
3.0mg of MDES-CDs is precisely weighed and placed in a 100mL volumetric flask, and the volume is fixed, so as to obtain corresponding stock solution. mu.L of MDES-CDs solution (30. Mu.g.mL concentration) -1 ) Mix with 200. Mu.L of the sample to be tested in a centrifuge tube, adjust pH, and add water to 1mL. The reaction solution is subjected to fluorescence test after shaking for 20min in a constant temperature water bath.
Detection conditions: 410nm as excitation wavelength and 475nm fluorescence value as NO 2 - The emission slit width was set at 10nm and the test conditions were performed in triplicate (i.e., three parallel samples were prepared for the measurement).
When a standard curve is produced, the sample to be measured can be NaNO with different concentrations 2 A solution. After the reaction by adopting the method, the fluorescence intensity is detected, and a standard curve of the fluorescence intensity relative to the nitrite concentration is drawn. According to the fluorescence intensity of the sample to be measured with unknown concentration, the nitrite concentration in the sample to be measured can be calculated by combining the standard curve.
In carrying out the measurement of the actual sample, the actual sample may be first subjected to appropriate pretreatment such as pulverization, centrifugation, filtration, dilution, and the like. This was then mixed with MDES-CDs and reacted at 60℃for 20min at pH=2 to test the fluorescence intensity. Substituting the value into a linear regression equation to calculate the concentration of nitrite in the actual sample.
Example 4
(1) MDES-CDs probe systems were prepared for optimization of nitrite detection conditions. The effect of the solution acidity, reaction time, temperature and other variables on the performance of MDES-CDs in detecting nitrite was examined, and the results are shown in FIG. 7.
To examine the effect of acidity of the solution on nitrite detection performance, we prepared solutions with pH of 2.08, 2.59, 3.15, 3.64, 3.93, 4.26, 4.66, 5.40, 5.90, 6.50, 6.98 with HCl solution, added MDES-CDs and nitrite solution, vortexed and mixed uniformly, reacted at 60℃for 20min, and then tested its fluorescence intensity with a fluorescence spectrophotometer. The effect of solution acidity (pH) is shown in FIG. 7A, where the fluorescence intensity of MDES-CDs itself decreases rapidly over the pH range of 2-7. When pH reached 7, its autofluorescence disappeared, since ph=2 was chosen as the optimal condition for analytical detection.
For optimization of the reaction temperature, we mixed MDES-CDs with nitrite solution, reacted at 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃,60 ℃ for 20min, respectively, under the condition of ph=2, and then tested the fluorescence intensity thereof. As shown in FIG. 7B, the quenching degree of MDES-CDs by nitrite is increased with the increase of temperature, the reaction speed is promoted at a higher temperature, and the fluorescence quenching degree is maximum at 60 ℃, so that we finally select 60 ℃ as the optimal reaction temperature.
Fig. 7C studies the trend of fluorescence intensity over time after adding nitrite, we mixed MDES-CDs with nitrite solution and reacted for 0min, 0.66min, 3min, 5min, 10min, 15min, 19min, 22min, 25min, 27min, 29min, 32min at ph=2, at 60 ℃ respectively, and found that fluorescence intensity at 473nm quenched 59% within 5min, up to 96% after 20min, indicating that the reaction was completed within 20 min. Thus, 20min was chosen as the optimal reaction time.
(2) The response capacity of MDES-CDs to nitrite was investigated under optimal synthesis conditions (200 ℃,6h, molar ratio DL-malic acid: ethylene glycol: fe=2:8:1). MDES-CDs were mixed with nitrite at different concentrations at ph=2, reacted at 60 ℃ for 20min, and then tested for fluorescence intensity. FIG. 8 shows the fluorescence spectra of kb (blank), 0.2. Mu.M, 1. Mu.M, 5. Mu.M, 10. Mu.M, 20. Mu.M, 30. Mu.M, 40. Mu.M, 50. Mu.M, 60. Mu.M, 80. Mu.M, 100. Mu.M, 150. Mu.M, 300. Mu.M, respectively, in the presence of nitrite at different concentrations, and it can be seen from FIG. 8 that the fluorescence intensity of MDES-CDs gradually decreases as the nitrite concentration (0-300. Mu.M) increases.
(3) As shown in FIG. 9, we plotted fluorescence intensity values against nitrite concentration, and found that fluorescence intensity follows nitrite concentration to exhibit a linear response (0.2. Mu.M, 3. Mu.M, 7. Mu.M, 15. Mu.M, 20. Mu.M, 30. Mu.M, 40. Mu.M, 50. Mu.M, 60. Mu.M, 70. Mu.M, 80. Mu.M) in the range of 0.2 to 80. Mu.M, and the regression equation obtained was y= -39.62[ NO 2 - ]+4212, linear coefficient R 2 0.9932. Limit of detection (LOD, s/n=3).
The detection limit for nitrite concentration was calculated as 50nM by parallel measurement of 11 blank solutions, calculating their 3-fold standard deviation and then the slope of the linear equation.
When detecting an actual sample, such as sausage, firstly carrying out proper pretreatment on the sausage, then adding the sausage into a mixed solution of nitrite and MDES-CDs, carrying out reaction under the same condition as the step (2), testing the fluorescence value of the sausage, and substituting the fluorescence value for a linear equation to obtain the concentration of nitrite in the sausage. This allows us to accurately quantify the nitrite in the actual sample.
(4) A comparison of the effect of different interfering ions on the fluorescence intensity of MDES-CDs solutions is shown in FIG. 10.
Considering the selectivity of MDES-CDs sensing platform in nitrite detection, taking a plurality of 1mL centrifuge tubes, adding 20 mu L and 200 mu L five-fold concentration of interfering substances in MDES-CDs solution in example 2 into the 1mL centrifuge tubes, wherein the interfering substances comprise anions, metal ions and some additives, and the anionsFor example: NO (NO) 2 - 、F - 、Cl - 、Br - 、I - 、OH - 、NO 3 - 、SO 4 2- 、SO 3 2- 、CO 3 - 、CH 3 COO - 、 HCO 3 - Etc., metal ions such as: fe (Fe) 3+ 、Mg 2 、K + 、Na + 、Cu 2+ 、Zn 2+ 、Ca 2+ 、Fe 2+ Etc., additives such as: DL-malic acid, L-cysteine, lactic acid, ascorbic acid, citric acid, glucose, glutamic acid, glutathione, etc., and fluorescence intensity was measured and recorded.
As shown in fig. 10A, it was observed that only nitrite could cause a sharp decrease in fluorescence intensity, while no significant change in fluorescence was observed in the presence of other anions.
Further, in the case where the above-mentioned interfering substances including anions, metal ions, additives, and the like were added thereto at a concentration of 200. Mu.L of five times, respectively, under the coexistence of MDES-CDs and nitrite, and fluorescence intensities were measured and recorded, it was observed that the degree of quenching was not much different from that in the case where only nitrite was present, as shown in FIG. 10B, indicating that the interference experiment was conducted under the coexistence of nitrite and interfering ions, the fluorescence intensity of MDES-CDs was affected little. This indicates that the prepared MDES-CDs have high selectivity for detection of nitrite.
Example 5
A method of detecting pH comprising the steps of:
3.0mg of MDES-CDs is precisely weighed and placed in a 100mL volumetric flask, and the volume is fixed, so as to obtain corresponding stock solution. This experiment was performed using 20. Mu.L of MDES-CDs solution (30. Mu.g.mL concentration) -1 ) Placing the sample into a centrifuge tube containing a sample to be tested, and fixing the volume to 1mL. Detection conditions: the emission slit width was set to 10nm using 410nm as excitation wavelength and fluorescence at 475nm as measurement of pH, and the test conditions were performed in triplicate (i.e., three parallel samples were prepared for measurement).
When a standard curve is produced, the samples to be measured are solutions with different pH values. After the reaction by the method, the fluorescence intensity is measured, and a standard curve of the fluorescence intensity with respect to the pH is drawn. According to the fluorescence intensity of the sample to be measured with unknown pH value, the pH value of the sample to be measured can be calculated by combining the standard curve.
When the actual sample is detected, the actual sample (e.g., water) may be first subjected to appropriate pretreatment (centrifugation, filtration, dilution, etc.), and then mixed with MDES-CDs, reacted with 60℃for 20 minutes, and tested for fluorescence intensity. And (5) bringing the value into a linear regression equation to obtain the pH value of the actual sample.
Example 6
MDES-CDs probe systems were prepared for pH optimization and detection.
1) 3.0mg of MDES-CDs is precisely weighed and placed in a 100mL volumetric flask, and the volume is fixed, so as to obtain corresponding stock solution. This experiment was performed using 20. Mu.L of MDES-CDs solution (30. Mu.g.mL concentration) -1 ) Placing the mixture into a centrifuge tube containing solutions with different pH values, and fixing the volume to 1mL. Detection conditions: the emission slit width was set to 10nm using 410nm as excitation wavelength and fluorescence at 475nm as measurement of pH, and the test conditions were performed in triplicate (i.e., three parallel samples were prepared for measurement).
2) Under the optimal synthesis conditions of MDES-CDs (200 ℃,6h, DL-malic acid: ethylene glycol: fe=2:8:1, and the fluorescence of MDES-CDs synthesized under this condition was best), and the response ability of MDES-CDs to pH was studied. The fluorescence spectra are shown in FIG. 11, and from top to bottom are curves with pH values of 2.08, 2.59, 3.64, 3.96, 4.26, 4.66, 5.30, 5.91, 6.50 and 6.98, respectively, and as can be seen from FIG. 11, the fluorescence intensity of MDES-CDs is obviously quenched as the pH value increases from 2 to 7, and the solution is converted from pale yellow-green to provide excellent characteristics for the sample, and can be used as a color indicator for pH detection.
3) As shown in FIG. 12, the fluorescence intensity of MDES-CDs decreases linearly with pH between 2 and 7 (pH 2.08, 2.59, 3.15, 3.64, 3.93, 4.26, 4.66, 5.40, 5.90, 6.50, 6.98, which can be adjusted with HCl and NaOH to obtain different pH solutions), and the linear equation is y= -923.2 [ pH]+6660，R 2 ＝0.9931。
For the sample to be measured, the same operation as described above is adopted, and the fluorescence intensity is detected, and the pH can be obtained by the linear equation described above. The method lays a foundation for pH detection of practical samples such as various water environments.
The above embodiments are provided to illustrate the technical solution of the present invention only to facilitate the person skilled in the art to understand and use the present invention and not to limit it; modifications of the specific embodiments of the invention or equivalent replacement of parts of the technical features will be apparent to those skilled in the art; and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A reagent or kit for detecting nitrite and/or pH, comprising a fluorescent probe; the synthesis method of the fluorescent probe comprises the following steps:
(1) Mixing a hydrogen bond donor with a hydrogen bond acceptor to obtain a mixed solution, wherein the hydrogen bond acceptor comprises metal, the metal is Fe, and heating until the mixed solution becomes a uniform and transparent solution to obtain a metal eutectic solvent, namely MDES; the hydrogen bond donor is DL-malic acid;
(2) Preparing MDES solution from MDES;
(3) Heating and reacting the MDES solution, and cooling to obtain a carbon dot solution;
(4) The carbon dot solution was filtered to obtain a solution containing a fluorescent probe.
2. The reagent or kit of claim 1, wherein the hydrogen bond acceptor further comprises ethylene glycol; the molar ratio of DL-malic acid, ethylene glycol and metal is 2:8:0.2-1.2.
3. The reagent or kit according to claim 1, wherein in step (1), the heating temperature is 60 to 80 ℃; in step (3), the conditions for the heating reaction include: the temperature is 120-200 ℃, and the reaction time is 2-10h; in the step (4), a microporous filter membrane with the size of 0.22 mu m is adopted for filtering.
4. A reagent or kit according to any one of claims 1 to 3, further comprising the steps of dialysis after filtration, freeze-drying to obtain MDES-CDs; the conditions for lyophilization included: freeze drying at-80deg.C under vacuum for 24-48h.
5. The reagent or kit according to claim 4, further comprising the step of preparing an MDES-CDs solution from MDES-CDs; in the MDES-CDs solution, the concentration of MDES-CDs is 10-mg.mL -1 。
6. The fluorescent probe is applied to one or more of (1), (2), (3) and (4),
(1) The detection of the nitrite is carried out,
(2) The pH was measured and the pH was measured,
(3) A reagent or a kit for preparing or detecting nitrite,
(4) Reagents or kits for preparing or detecting pH;
the synthesis method of the fluorescent probe is characterized by comprising the following steps:
(1) Mixing a hydrogen bond donor with a hydrogen bond acceptor to obtain a mixed solution, wherein the hydrogen bond acceptor comprises metal, the metal is Fe, and heating until the mixed solution becomes a uniform and transparent solution to obtain a metal eutectic solvent, namely MDES; the hydrogen bond donor is DL-malic acid;
(2) Preparing MDES solution from MDES;
(3) Heating and reacting the MDES solution, and cooling to obtain a carbon dot solution;
(4) The carbon dot solution was filtered to obtain a solution containing a fluorescent probe.
7. The use of claim 6, wherein the hydrogen bond acceptor further comprises ethylene glycol; the molar ratio of DL-malic acid, ethylene glycol and metal is 2:8:0.2-1.2.
8. The use according to claim 6, wherein in step (1) the heating temperature is 60-80 ℃; in step (3), the conditions for the heating reaction include: the temperature is 120-200 ℃, and the reaction time is 2-10h; in the step (4), a microporous filter membrane with the size of 0.22 mu m is adopted for filtering.
9. The use according to any one of claims 6 to 8, further comprising the steps of dialysis after filtration, freeze-drying to obtain MDES-CDs; the conditions for lyophilization included: freeze drying at-80deg.C under vacuum for 24-48h.
10. The use according to claim 9, further comprising the step of preparing MDES-CDs into a solution of MDES-CDs; in the MDES-CDs solution, the concentration of MDES-CDs is 10-mg.mL -1 。
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