CN115433572A - Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof - Google Patents

Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof Download PDF

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CN115433572A
CN115433572A CN202211014056.3A CN202211014056A CN115433572A CN 115433572 A CN115433572 A CN 115433572A CN 202211014056 A CN202211014056 A CN 202211014056A CN 115433572 A CN115433572 A CN 115433572A
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齐海燕
刘春彤
赵英楠
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Qiqihar University
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Abstract

The invention provides a method for preparing carbon quantum dots based on industrial hemp, the carbon quantum dots and application thereof. The invention takes industrial hemp as raw material, and two carbon quantum dots with different grain diameters are prepared by a one-time hydrothermal carbonization method and are respectively used for detecting Fe 3+ And tetracycline antibiotics. Compared with the respective preparation modes in the prior art, the method selects the environmental-friendly and pollution-free natural product industrial hemp as the carbon source, after pretreatment and hydrothermal carbonization reaction with ultrapure water, the reaction solution is dialyzed in the dialysis bag, and the liquid outside the dialysis bag enters into the dialysis bagAnd dialyzing in dialysis bags with different molecular weights once again to obtain two kinds of carbon quantum dots with different sizes, wherein the prepared carbon dots have good optical stability, the preparation process is simple and quick, and meanwhile, because the industrial hemp is low in cost, the cost is reduced, and the problem that the industrial hemp straw is difficult to treat is solved.

Description

Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a method for preparing carbon quantum dots based on industrial hemp, the carbon quantum dots and application thereof.
Background
Fe 3+ Is an important element for human beings, which has the ability to transport oxygen and also acts as a cofactor for various enzymatic activities. But excessive Fe 3+ Ions may have negative effects on human health, such as increasing oxidation of lipids, proteins and other biological components. Tetracyclines are commonly used antibiotics in pharmaceutical and food antiseptics. Despite their broad antimicrobial spectrum, their residue in food and the environment poses a significant threat to all living beings. Thus, for Fe 3+ And tetracycline antibiotics are of critical importance. Separate detection of Fe exists in the prior art 3+ And tetracycline antibiotics, but these instruments are expensive, complicated in operation steps, and cumbersome in sample pretreatment, making the instrumental analysis methods less suitable for field use.
Carbon quantum dots (CDs) are novel fluorescent carbon nano materials, have the characteristics of excellent water solubility, optical stability, good biocompatibility and the like compared with other fluorescent carbon nano materials, and can be applied to Fe 3+ And tetracycline antibiotics, but due to detection of Fe 3+ The mechanism of tetracycline antibiotics and the properties of the used carbon quantum dots are different, so different types of carbon quantum dots are generally required to be prepared respectively, the preparation process is complicated, and the cost is increased.
Disclosure of Invention
The invention aims at solving the problem of how to prepare the carbon quantum dots by aiming at Fe in the prior art 3+ And the detection of tetracycline antibiotics has the defects of expensive detection instrument, complex operation steps, complicated sample pretreatment and the like, the invention provides a preparation method of a carbon quantum dot, which can quickly and accurately detect Fe 3+ And tetracycline antibiotics.
In order to solve the above problems, the present invention provides a method for preparing carbon quantum dots based on industrial hemp, comprising:
after pretreatment, industrial hemp is mixed with ultrapure water, and a hydrothermal carbonization reaction is carried out to obtain a first solution;
centrifuging and filtering the first solution and separating the first solution by using a microporous filter membrane to obtain a second solution;
injecting the second solution into a first dialysis bag with the molecular weight of 1000Da, continuously dialyzing for 60-90 hours, taking out the liquid in the first dialysis bag to obtain first carbon quantum dots, wherein the first carbon quantum dots are used for detecting Fe 3+
And concentrating the liquid outside the first dialysis bag, injecting the concentrated liquid into a second dialysis bag with the molecular weight of 200Da, continuously dialyzing for 60-90 hours, and taking out the liquid in the second dialysis bag to obtain a second carbon quantum dot, wherein the second carbon quantum dot is used for detecting tetracycline antibiotics.
Preferably, the industrial hemp is mixed with ultrapure water after pretreatment, and subjected to hydrothermal carbonization reaction to obtain a first solution, wherein the first solution comprises:
and (3) mixing the pretreated industrial hemp with the ultrapure water, carrying out hydrothermal carbonization reaction for 6-10 hours at 150-200 ℃, naturally cooling to room temperature, centrifuging, and filtering to obtain the first solution.
Preferably, the pretreatment of industrial hemp comprises: drying the leaves and the skin fibers of the industrial hemp, preparing the leaves of the industrial hemp into powder, preparing the skin fibers of the industrial hemp into blocks, and mixing the leaves and the skin fibers of the industrial hemp according to a mass ratio of 1:1.
Compared with the prior art, the method for preparing the carbon quantum dots based on the industrial hemp has the advantages that:
the invention takes industrial hemp as raw material, and two carbon quantum dots with different grain diameters are prepared by a one-time hydrothermal carbonization method and are respectively used for detecting Fe 3+ And tetracycline antibiotics. Compared with the respective preparation mode in the prior art, the invention selects the natural product industrial hemp which is environment-friendly and pollution-free as the carbon source, after the pretreatment, the reaction solution is jected to hydrothermal carbonization reaction with ultrapure water, the reaction solution is dialyzed in the dialysis bag for the first time, and then the dialysis solution is dialyzed for the second timeThe liquid outside the bag after dialysis is dialyzed again, and the dialysis of both sides adopts the dialysis bag of different molecular weights to obtain two kinds of different carbon quantum dots of size, the carbon dot of preparation has good optical stability, and the preparation process is simple, quick, simultaneously because industry hemp low cost, not only reduce cost, and make industry hemp straw can waste utilization.
The invention also provides a carbon quantum dot prepared by the method for preparing the carbon quantum dot based on the industrial hemp, which comprises a first carbon quantum dot and a second carbon quantum dot with different sizes.
Compared with the prior art, the advantages of the carbon quantum dots prepared by the method are the same as those of the method for preparing the carbon quantum dots based on industrial hemp, and the method is not repeated.
The invention also provides an application of the carbon quantum dot, which comprises the application of the carbon quantum dot in Fe detection 3+ And tetracycline antibiotics, specifically comprising:
diluting the first carbon quantum dots to a first set concentration to obtain a first detection solution;
respectively adding Fe with different concentrations into the first detection solution 3+ Obtaining a plurality of first detection samples;
respectively carrying out fluorescence measurement on a plurality of first detection samples under the set excitation wavelength of the first carbon quantum dots to obtain a first standard curve, wherein the abscissa of the first standard curve is Fe 3+ The ordinate is the fluorescence quenching efficiency;
adding a first sample to be detected into the first detection solution to obtain a first sample to be detected, and performing fluorescence measurement on the first sample to be detected under the set excitation wavelength of the first carbon quantum dots to obtain a first fluorescence quenching efficiency;
determining Fe in the first sample to be detected according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (c).
Preferably, the Fe in the first sample to be detected is determined according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (A) includes:
determining the fluorescence quenching efficiency with the Fe according to the first standard curve 3+ A first linear equation of concentration change;
substituting the first fluorescence quenching efficiency into the first linear equation to obtain Fe in the first sample to be detected 3+ The concentration of (c).
Preferably, the method further comprises:
diluting the second carbon quantum dots to a second set concentration to obtain a second detection solution;
adding tetracycline antibiotics with different concentrations into the second detection solution respectively to obtain a plurality of second detection samples;
respectively carrying out fluorescence measurement on a plurality of second detection samples under the set excitation wavelength of the second carbon quantum dots to obtain a second standard curve, wherein the abscissa of the second standard curve is the concentration of tetracycline antibiotics, and the ordinate of the second standard curve is fluorescence quenching efficiency;
adding a second sample to be detected into the second detection solution to obtain a second sample to be detected, and performing fluorescence measurement on the second sample to be detected under the set excitation wavelength of the second carbon quantum dots to obtain a second fluorescence quenching efficiency;
and determining the concentration of the tetracycline antibiotic in the second sample to be detected according to the second fluorescence quenching efficiency and the second standard curve.
Preferably, the determining the concentration of the tetracycline antibiotic in the second test sample according to the second fluorescence quenching efficiency and the second standard curve includes:
determining a second linear equation of the fluorescence quenching efficiency along with the change of the concentration of the tetracycline antibiotic according to the second standard curve;
and substituting the second fluorescence quenching efficiency into the second linear equation to obtain the concentration of the tetracycline antibiotics in the second sample to be detected.
Preferably, the test conditions for the fluorescence assay comprise: the slit width is 10nm, and the fluorescence measurement range is 300-700nm.
Preferably, the set excitation wavelength of the first carbon quantum dot is 445nm, and the set excitation wavelength of the second carbon quantum dot is 350nm.
Detection of Fe based on carbon quantum dots 3+ And tetracycline antibiotics, among the advantages over the prior art:
the invention respectively detects Fe by utilizing the size effect of two carbon quantum dots prepared based on industrial hemp 3+ And tetracycline antibiotics, first carbon quantum dots to detect Fe 3+ The mechanism of the second carbon quantum dot for detecting the tetracycline antibiotics is an inner filtering effect. As the carbon dots have good selectivity and optical stability, the detection method is convenient and quick, has high sensitivity and low detection limit, and Fe 3+ The actual sample concentration range of (2) is 0.1-60 mu mol/L, the actual sample concentration range for detecting tetracycline and oxytetracycline is 0.1-40 mu mol/L, and the actual sample concentration range for detecting aureomycin is 0.1-55 mu mol/L. The rest advantages are the same as the advantages of the method for preparing the carbon quantum dots based on the industrial hemp compared with the prior art, and are not described again.
Drawings
FIG. 1 is a flow chart of a method for preparing carbon quantum dots based on industrial hemp in an embodiment of the present invention;
FIG. 2 shows that carbon quantum dots prepared based on industrial hemp in the embodiment of the present invention are respectively used for detecting Fe 3+ And a schematic flowsheet for tetracycline antibiotics;
FIG. 3 is a schematic transmission electron microscope of carbon quantum dots prepared based on industrial hemp in an embodiment of the present invention;
fig. 4 is an ultraviolet-visible absorption spectrum, an excitation spectrum and an emission spectrum of the first carbon quantum dot in example 1 of the present invention;
fig. 5 shows the uv-vis absorption spectrum and the excitation spectrum and the emission spectrum of the second carbon quantum dot in example 2 of the present invention;
FIG. 6 shows the first carbon quantum dot and Fe in example 1 of the present invention 3+ Quenching curve of action;
FIG. 7 shows the first carbon quantum dot and Fe in example 1 of the present invention 3+ Standard curve of action;
FIG. 8 is a quenching curve of the second carbon quantum dot effect with tetracycline in example 2 of the present invention;
FIG. 9 is a standard curve of the effect of a second carbon quantum dot on tetracycline in example 2 of the present invention;
FIG. 10 is a quenching curve of the effect of a second carbon quantum dot on chlortetracycline in example 2 of the present invention;
FIG. 11 is a standard curve of the effect of a second carbon quantum dot on chlortetracycline in example 2 of the present invention;
FIG. 12 is a quenching curve of the second carbon quantum dot interaction with oxytetracycline in example 2 of the present invention;
FIG. 13 is a standard curve of the effect of the second carbon quantum dot on oxytetracycline in example 2 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Referring to fig. 1 and 2, a method for preparing carbon quantum dots based on industrial hemp according to an embodiment of the present invention includes:
step 110, mixing the pretreated industrial hemp with ultrapure water, and carrying out hydrothermal carbonization reaction to obtain a first solution;
step 120, centrifuging, filtering and separating the first solution with a microporous filter membrane to obtain a second solution;
step 130, injecting the second solution into a first dialysis bag with the molecular weight of 1000Da, continuously dialyzing for 60-90 hours, and taking out the liquid in the first dialysis bag to obtain first carbon quantum dots, wherein the first carbon quantum dots are used for detecting Fe 3+
And 140, concentrating the liquid outside the first dialysis bag, injecting the concentrated liquid into a second dialysis bag with the molecular weight of 200Da, continuously dialyzing for 60-90 hours, and taking out the liquid in the second dialysis bag to obtain second carbon quantum dots, wherein the second carbon quantum dots are used for detecting tetracycline antibiotics.
In a specific embodiment, the industrial hemp is pretreated and mixed with ultrapure water to perform hydrothermal carbonization reaction, and the first solution is obtained by: mixing the pretreated industrial hemp with the ultrapure water, carrying out hydrothermal carbonization reaction at 150-200 ℃ for 6-10 hours, naturally cooling to room temperature, centrifuging, and filtering to obtain the first solution.
Wherein the pretreatment of industrial hemp comprises: drying the leaves and the skin fibers of the industrial hemp, preparing the leaves of the industrial hemp into powder, preparing the skin fibers of the industrial hemp into blocks, and mixing the leaves and the skin fibers of the industrial hemp according to a mass ratio of 1:1.
Specifically, leaf and bark fibers from the same industrial hemp plant are taken and placed in an air-blast drying oven to be dried to remove moisture, the dried leaves are placed in a mortar to be ground into fine powder, and the bark fibers are cut into blocks by scissors. Weighing leaf and skin fibers according to the mass ratio of 1:1, placing the leaf and skin fibers in a reaction kettle with a polytetrafluoroethylene lining, adding 15-20mL of ultrapure water, uniformly stirring, screwing the reaction kettle, placing the reaction kettle in a drying box with air blowing, performing hydrothermal carbonization at 150-200 ℃ for 6-10 hours, and naturally cooling to room temperature after the reaction is finished. The reaction solution was taken out, centrifuged, filtered and passed through a 0.22 μm microporous membrane to obtain a tan first solution.
The raw materials for synthesizing the quantum dots are various, and at present, in order to control the luminous performance of the carbon quantum dots, most of the chemicals are selected as the raw materials for synthesis, but many chemicals are toxic and harmful to human bodies. In the embodiment, the industrial hemp is used as a raw material, the used industrial hemp is derived from a field cultivated land of the subordination of Qiqi Harr city of Heilongjiang province, the industrial hemp is an environment-friendly pollution-free natural product, juice contains various complex components, two carbon dots with different particle sizes can be prepared at one time by utilizing a one-pot hydrothermal method, the carbon dots prepared on the basis of the industrial hemp have good optical stability, and the carbon dots can be respectively used for detecting Fe 3+ And tetracycline antibiotics.
At present, common methods for preparing carbon quantum dots comprise a microwave method and a hydrothermal synthesis method, and compared with the microwave method, the particle size of the carbon quantum dots prepared by the hydrothermal synthesis method is more uniform. In order to enable the prepared carbon quantum dot to have the property of long-wavelength luminescence, most of the prior art uses an organic solvent as a synthetic solvent, and in this case, a purification method of column chromatography is basically selected, however, the operation of the column chromatography is complex, the solvent is consumed, and the volatilized reagent may generate toxic effects on human bodies. In the embodiment of the invention, the used synthetic solvent is ultrapure water, so that the method is harmless to human bodies and is simple to operate.
The natural product is used as a raw material, the carbon quantum dots are synthesized by a hydrothermal method, generally, a solution of a hydrothermal reaction is purified by dialysis or other separation means, and the purification purpose is realized by one-time dialysis, so that the required carbon quantum dots are obtained. However, the carbon quantum dots synthesized by using natural products can only obtain one carbon quantum dot after purification. In the embodiment of the invention, industrial hemp raw materials and ultrapure water are used as a synthetic solvent, after hydrothermal reaction, a reaction solution is subjected to primary dialysis to obtain first carbon quantum dots, then, the dialyzed residual liquid is subjected to secondary dialysis, and the sizes of the two dialyzed residual liquids are respectively controlled to be 1000Da and 200Da, so that two carbon quantum dots with different sizes are respectively obtained, wherein the two carbon quantum dots are basically the same in structure, but have slightly different silicon-containing groups. Because the grain diameters of two kinds of carbon quantum dots are different, the two kinds of carbon quantum dots have different properties based on quantum size effect, and because of Fe 3+ And the response mode of the tetracycline antibiotics to the two carbon quantum dots is different, so that the carbon quantum dots prepared by the embodiment at one time have good selectivity. In addition, the two carbon dots prepared in this embodiment have other differences in optical properties, for example, the first carbon quantum dot is not acid-base resistant, and the second carbon quantum dot is acid-base resistant; the second carbon quantum dots are more easily subjected to concentration regulation and the like than the first carbon quantum dots.
The embodiment of the invention also provides application of the carbon quantum, and the carbon quantum dots are used for detecting Fe 3+ And a tetracycline antibiotic, the method comprising:
diluting the first carbon quantum dots to a first set concentration to obtain a first detection solution;
respectively adding Fe with different concentrations into the first detection solution 3+ Obtaining a plurality of first detection samples;
respectively carrying out fluorescence measurement on a plurality of first detection samples under the set excitation wavelength of the first carbon quantum dots to obtain a first standard curve, wherein the abscissa of the first standard curve is Fe 3+ The ordinate is the fluorescence quenching efficiency;
adding a first sample to be detected into the first detection solution to obtain a first sample to be detected, and performing fluorescence measurement on the first sample to be detected under the set excitation wavelength of the first carbon quantum dots to obtain a first fluorescence quenching efficiency;
determining Fe in the first sample to be detected according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (c).
Wherein, the Fe in the first sample to be detected is determined according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (A) includes:
determining the fluorescence quenching efficiency as a function of the Fe according to the first standard curve 3+ A first linear equation of concentration change;
substituting the first fluorescence quenching efficiency into the first linear equation to obtain Fe in the first sample to be detected 3+ The concentration of (c).
The detection of Fe based on carbon quantum dots 3+ And a tetracycline antibiotic, further comprising:
diluting the second carbon quantum dots to a second set concentration to obtain a second detection solution;
adding tetracycline antibiotics with different concentrations into the second detection solution respectively to obtain a plurality of second detection samples;
respectively carrying out fluorescence measurement on a plurality of second detection samples under the set excitation wavelength of the second carbon quantum dots to obtain a second standard curve, wherein the abscissa of the second standard curve is the concentration of tetracycline antibiotics, and the ordinate of the second standard curve is fluorescence quenching efficiency;
adding a second sample to be detected into the second detection solution to obtain a second sample to be detected, and performing fluorescence measurement on the second sample to be detected under the set excitation wavelength of the second carbon quantum dots to obtain a second fluorescence quenching efficiency;
and determining the concentration of the tetracycline antibiotics in the second sample to be detected according to the second fluorescence quenching efficiency and the second standard curve.
Wherein the determining the concentration of the tetracycline antibiotic in the second test sample according to the second fluorescence quenching efficiency and the second standard curve comprises:
determining a second linear equation of the fluorescence quenching efficiency along with the change of the concentration of the tetracycline antibiotic according to the second standard curve;
and substituting the second fluorescence quenching efficiency into the second linear equation to obtain the concentration of the tetracycline antibiotics in the second sample to be detected.
In a specific embodiment, analytically pure iron sulfate and tetracycline antibiotics such as tetracycline, aureomycin, terramycin and the like are dissolved to prepare standard series solutions with different concentrations.
Diluting the prepared first carbon quantum dots to a first set concentration, and adding prepared Fe with different concentrations 3+ Observing the change of the fluorescence curve on a fluorescence spectrometer, and recording the corresponding spectral data, wherein the Fe is used 3+ Concentration of ions as abscissa, in terms of fluorescence quenching efficiency (F) 0 -F)/F 0 And drawing a corresponding first standard curve for the ordinate.
Adding a first sample to be detected into the diluted first carbon quantum dots, observing the change of a fluorescence curve, extracting corresponding fluorescence data and bringing the fluorescence data into a first standard curve to obtain Fe in the first sample to be detected 3+ The content of (a).
Diluting the prepared second carbon quantum dots to a second set concentration, adding prepared tetracycline, aureomycin and oxytetracycline solutions with different concentrations, observing the change of a corresponding fluorescence curve on a fluorescence spectrometer, and recording corresponding spectral data, wherein the concentration of tetracycline antibiotics (tetracycline, aureomycin and oxytetracycline) is taken as an abscissa, and the fluorescence quenching efficiency (F) is taken as 0 -F)/F 0 For the ordinate, each is plottedFrom the corresponding second standard curve.
And adding a second sample to be detected into the diluted second carbon quantum dots, observing the change of the fluorescence curve, extracting corresponding fluorescence data, and substituting the fluorescence data into the obtained second standard curve of tetracycline, aureomycin and oxytetracycline to obtain the content of the tetracycline antibiotics in the second sample to be detected.
Ultrapure water was used for the preparation of the solutions.
Wherein the test conditions of the fluorescence assay comprise: the width of the slit is 10nm, and the fluorescence measurement range is 300-700nm. The excitation wavelength of a first sample to be detected in the actual detection of the first carbon quantum dot is 445nm, and the excitation wavelength of a second sample to be detected in the actual detection of the second carbon quantum dot is 350nm.
The carbon quantum dots of the embodiment have good selectivity and anti-interference capability, wherein the actual sample suitable for detection of the first carbon quantum dots is a water sample, and the actual sample suitable for detection of the second carbon quantum dots is a milk sample or a cosmetic sample.
In this example, the first carbon quantum dot detection contains Fe 3+ The actual sample concentration range of the second carbon quantum dot detection contains tetracycline and oxytetracycline is 0.1-40 mu mol/L, and the actual sample concentration range of the second carbon quantum dot detection contains aureomycin is 0.1-55 mu mol/L.
The detection method of the embodiment is convenient and rapid, has high sensitivity and low detection limit, and can be used for rapidly detecting Fe required at present 3+ And the prospect of tetracycline antibiotics provides a new scheme and thought, and has good application prospect.
The present invention will be described in detail below with reference to specific examples.
Example 1:
method for detecting Fe in water sample by using carbon dots prepared from industrial hemp 3+ The method comprises the following steps:
(1) Preparation of industrial hemp based first carbon quantum dots
Taking leaves and skin fibers on the same industrial hemp plant, putting the leaves and the skin fibers into a drying box to be blown, fully drying, removing water, putting the leaves into a mortar, grinding into powder, cutting the skin fibers into fine pieces by using scissors, respectively weighing 0.7g of the leaves and the skin fibers, putting the leaves and the skin fibers into a reaction kettle with a polytetrafluoroethylene lining, adding 15mL of ultrapure water, carrying out hydrothermal reaction for 10h at 170 ℃ in an electric heating blowing drying box, naturally cooling to room temperature, centrifuging for 30min at the rotating speed of 8000r/min, filtering, passing through a microporous filter membrane of 0.22 mu m to obtain a tan solution, injecting the solution into a dialysis bag with the molecular weight of 1000Da, continuously dialyzing for 72h, taking out the solution in the bag, putting the solution in a refrigerator with the temperature of 4 ℃ for standby, putting first carbon quantum dots under a transmission electron microscope, observing the appearance of the first carbon quantum dots as shown in a picture A in a picture 3, and obtaining 6.838 +/-62 nm particle size.
(2)Fe 3+ Preparation of Standard solutions
Accurately weighing analytically pure ferric sulfate and preparing into 10mmol/L solution as mother liquor, diluting the mother liquor to 100 mu mol/L, finally preparing into 0-60 mu mol/L gradient standard series solution, and storing the solution in a refrigerator at 4 ℃ for later use.
(3) Detection of Fe by determining first carbon quantum dots of industrial hemp 3+ Standard curve of
Fig. 4 shows the optimal excitation Wavelength and the corresponding emission Wavelength of the first carbon quantum dot, where the abscissa Wavelength in fig. 4 is the Wavelength, the ordinate Absorbance is the Absorbance, and the ordinate Fluorescence intensity is the Fluorescence intensity, and it can be seen from fig. 4 that the optimal excitation Wavelength of the first carbon quantum dot is 445nm and the corresponding emission Wavelength is 510nm.
Diluting the first carbon quantum dot with ultrapure water to 6000-8000 μ g/mL concentration to maximize the fluorescence intensity in the fluorescence spectrum, adding the prepared standard series solutions into the first carbon quantum dot solution respectively after the optimal spectrum condition is adjusted, recording the change of the fluorescence curve at the excitation wavelength of 445nm as shown in FIG. 6, and using Fe 3+ Concentration of (d) is plotted on the abscissa as fluorescence quenching efficiency (F) 0 -F)/F 0 A standard curve is plotted for the ordinate as shown in fig. 7, and the linear equation and the respective correlation coefficient for each concentration are shown in table 1.
TABLE 1 internal Fe of 0-60. Mu. Mol/L 3+ Concentration and fluorescence quenching ofEfficiency (F) 0 -F)/F 0 The relationship between
Figure BDA0003811334920000111
Wherein [ Fe ] in Table 1 3+ ]Represents Fe 3+ The concentration of (c).
(4) Pretreatment of real water samples
A20 mL water sample was taken as a stock solution of an actual sample, the stock solution was filtered to remove large-particle impurities, and the filtrate was stored in a refrigerator at 4 ℃ through a 0.22 μm microporous filter for later use.
(5) Detection of first carbon quantum dot of industrial hemp on actual water sample
Adding the processed actual sample into the first carbon quantum dot solution, recording spectral data after the system completely reacts, and obtaining the fluorescence quenching efficiency (F) 0 -F)/F 0 Putting the standard curve into the obtained Fe content of the actual sample 3+ The content of (a).
Example 2:
a method for detecting tetracycline antibiotics in an actual sample by using carbon spots prepared from industrial hemp comprises the following steps:
(1) Preparation of industrial hemp-based second carbon quantum dots
And (2) taking out the liquid outside the dialysis bag with the molecular weight of 1000Da in the step (1) of the example 1, concentrating, injecting the liquid into the dialysis bag with the molecular weight of 200Da, continuously dialyzing for 72 hours, taking out the solution in the bag, storing the solution in a refrigerator at 4 ℃ for later use, placing the second carbon quantum dots under a transmission electron microscope, observing the appearance of the second carbon quantum dots as shown in a B picture in figure 3, and observing the particle size of the second carbon quantum dots to be 1.978 +/-0.2783 nm.
(2) Preparation of tetracycline antibiotic standard solution
Tetracycline, aureomycin and oxytetracycline were prepared into gradient standard series solutions of 0 to 50. Mu. Mol/L, 0 to 55. Mu. Mol/L and 0 to 40. Mu. Mol/L, respectively, according to the method in step (2) of example 1, and the solutions were stored in a refrigerator at 4 ℃ until use.
(3) Standard curve for detecting tetracycline antibiotics by measuring secondary carbon quantum dots of industrial hemp
Fig. 5 shows that the optimal excitation wavelength and the corresponding emission wavelength of the second carbon quantum dot are measured, and as can be seen from fig. 5, the optimal excitation wavelength and the corresponding emission wavelength of the second carbon quantum dot are 350nm and 435nm, respectively.
Diluting the second carbon quantum dots to 2000 μ g/mL with ultrapure water, making the fluorescence intensity in the fluorescence spectrum reach the maximum value, respectively adding the standard series solutions prepared in step (2) into the second carbon quantum dot solutions after the optimal spectrum conditions are adjusted, recording the change of the fluorescence curve at the excitation wavelength of 350nm as shown in FIG. 8, FIG. 10 and FIG. 12, and taking the concentration of tetracycline antibiotics as the abscissa and the fluorescence quenching efficiency (F) 0 -F)/F 0 Standard curves are plotted for the ordinate as shown in fig. 9, 11, 13, and the linear equation and the respective correlation coefficient for each substance are shown in table 2.
TABLE 2 Tetracycline antibiotic concentration and fluorescence quenching efficiency (F) 0 -F)/F 0 The relationship between
Figure BDA0003811334920000121
In Table 2, [ TC ] represents the tetracycline concentration, [ CTC ] represents the aureomycin concentration, and [ OTC ] represents the oxytetracycline concentration.
(4) Pretreatment of the actual sample
Milk samples were treated according to GBT 22990-2008 and cosmetic samples were treated according to SN/T3897-2014.
(5) Detection of second carbon quantum dot of industrial hemp on tetracycline antibiotics in actual samples
Adding the processed actual sample into a second carbon quantum dot solution, recording spectral data after the system completely reacts, and obtaining the fluorescence quenching efficiency (F) 0 -F)/F 0 And (5) bringing the standard curve to obtain the content of the tetracycline antibiotics in the actual sample.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. A method for preparing carbon quantum dots based on industrial hemp is characterized by comprising the following steps:
after pretreatment, industrial hemp is mixed with ultrapure water, and a hydrothermal carbonization reaction is carried out to obtain a first solution;
centrifuging and filtering the first solution and separating the first solution by using a microporous filter membrane to obtain a second solution;
injecting the second solution into a first dialysis bag with the molecular weight of 1000Da, continuously dialyzing for 60-90 hours, taking out liquid in the first dialysis bag to obtain first carbon quantum dots, wherein the first carbon quantum dots are used for detecting Fe 3+
And concentrating the liquid outside the first dialysis bag, injecting the concentrated liquid into a second dialysis bag with the molecular weight of 200Da, continuously dialyzing for 60-90 hours, and taking out the liquid in the second dialysis bag to obtain a second carbon quantum dot, wherein the second carbon quantum dot is used for detecting tetracycline antibiotics.
2. The method for preparing carbon quantum dots based on industrial hemp according to claim 1, wherein the industrial hemp is pretreated and then mixed with ultrapure water to perform hydrothermal carbonization reaction, and the obtaining of the first solution comprises:
and (3) mixing the pretreated industrial hemp with the ultrapure water, carrying out hydrothermal carbonization reaction for 6-10 hours at 150-200 ℃, naturally cooling to room temperature, centrifuging, and filtering to obtain the first solution.
3. The method for preparing carbon quantum dots based on industrial hemp according to claim 1, wherein the pretreatment of industrial hemp comprises: drying the leaves and the skin fibers of the industrial hemp, preparing the leaves of the industrial hemp into powder, preparing the skin fibers of the industrial hemp into blocks, and mixing the leaves and the skin fibers of the industrial hemp according to a mass ratio of 1:1.
4. A carbon quantum dot produced by the method for producing a carbon quantum dot based on industrial hemp according to any one of claims 1 to 3, comprising a first carbon quantum dot and a second carbon quantum dot having different sizes.
5. Use of the carbon quantum dot according to claim 4 in detecting Fe 3+ And tetracycline antibiotics, specifically including:
diluting the first carbon quantum dots to a first set concentration to obtain a first detection solution;
respectively adding Fe with different concentrations into the first detection solution 3+ Obtaining a plurality of first detection samples;
respectively carrying out fluorescence measurement on a plurality of first detection samples under the set excitation wavelength of the first carbon quantum dots to obtain a first standard curve, wherein the abscissa of the first standard curve is Fe 3+ The ordinate is the fluorescence quenching efficiency;
adding a first sample to be detected into the first detection solution to obtain a first sample to be detected, and performing fluorescence measurement on the first sample to be detected under the set excitation wavelength of the first carbon quantum dots to obtain a first fluorescence quenching efficiency;
determining Fe in the first sample to be detected according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (c).
6. The carbon quantum-based application of claim 5, wherein the Fe in the first test sample is determined according to the first fluorescence quenching efficiency and the first standard curve 3+ The concentration of (A) includes:
determining the fluorescence quenching efficiency as a function of the Fe according to the first standard curve 3+ A first linear equation of concentration change;
quenching the first fluorescenceSubstituting the extinguishing efficiency into the first linear equation to obtain Fe in the first sample to be detected 3+ The concentration of (c).
7. The use of carbon quantum according to claim 6, characterized in that the method further comprises:
diluting the second carbon quantum dots to a second set concentration to obtain a second detection solution;
adding tetracycline antibiotics with different concentrations into the second detection solution respectively to obtain a plurality of second detection samples;
respectively carrying out fluorescence measurement on a plurality of second detection samples under the set excitation wavelength of the second carbon quantum dots to obtain a second standard curve, wherein the abscissa of the second standard curve is the concentration of tetracycline antibiotics, and the ordinate of the second standard curve is fluorescence quenching efficiency;
adding a second sample to be detected into the second detection solution to obtain a second sample to be detected, and performing fluorescence measurement on the second sample to be detected under the set excitation wavelength of the second carbon quantum dots to obtain a second fluorescence quenching efficiency;
and determining the concentration of the tetracycline antibiotic in the second sample to be detected according to the second fluorescence quenching efficiency and the second standard curve.
8. The application of the carbon quantum as claimed in claim 7, wherein the determining the concentration of the tetracycline antibiotic in the second test sample according to the second fluorescence quenching efficiency and the second standard curve comprises:
determining a second linear equation of the fluorescence quenching efficiency along with the change of the concentration of the tetracycline antibiotic according to the second standard curve;
and substituting the second fluorescence quenching efficiency into the second linear equation to obtain the concentration of the tetracycline antibiotics in the second sample to be detected.
9. The use of carbon quanta according to claim 8, wherein the fluorometric test conditions include: the width of the slit is 10nm, and the fluorescence measurement range is 300-700nm.
10. The use of the carbon quantum as claimed in claim 5 or 7, wherein the set excitation wavelength of the first carbon quantum dot is 445nm, and the set excitation wavelength of the second carbon quantum dot is 350nm.
CN202211014056.3A 2022-08-23 2022-08-23 Method for preparing carbon quantum dots based on industrial hemp, carbon quantum dots and application thereof Pending CN115433572A (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482609A (en) * 2013-10-15 2014-01-01 浙江师范大学 Preparation method of carbon quantum dots for detecting Fe<3+> in lake water
CN104449696A (en) * 2014-12-12 2015-03-25 安徽师范大学 Fluorescence probe and preparation method thereof, and detection method for oxytetracycline in milk
CN106753354A (en) * 2016-12-05 2017-05-31 广西师范学院 The preparation method of the Water-soluble carbon quantum dot with sisal hemp as raw material
CN108584916A (en) * 2018-06-05 2018-09-28 桂林理工大学 The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber
CN108822840A (en) * 2018-08-29 2018-11-16 济南大学 A kind of fiber crops are the preparation method of carbon source neodymium doped carbon quantum dot composite material
CN110155984A (en) * 2019-06-12 2019-08-23 浙江科技学院 Using soybean slag as the method and application of raw material hydro-thermal method synthesising biological matter fluorescent carbon point
CN112300796A (en) * 2020-10-20 2021-02-02 山西大学 Yellow fluorescent carbon dot and preparation method and application thereof
CN112322280A (en) * 2020-10-26 2021-02-05 南开大学 Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection
CN112795378A (en) * 2020-12-28 2021-05-14 南昌大学 Method for preparing carbon quantum dots by using waste culture medium and Fe-doped carbon quantum dots prepared by using method3+Application in linear detection
CN113372901A (en) * 2021-05-27 2021-09-10 桂林理工大学 Preparation method of fluorescence double-enhanced sisal fiber carbon quantum dots
CN113549450A (en) * 2021-07-28 2021-10-26 山西大学 Potassium-nitrogen co-doped carbon dots based on flint pericarp and preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482609A (en) * 2013-10-15 2014-01-01 浙江师范大学 Preparation method of carbon quantum dots for detecting Fe<3+> in lake water
CN104449696A (en) * 2014-12-12 2015-03-25 安徽师范大学 Fluorescence probe and preparation method thereof, and detection method for oxytetracycline in milk
CN106753354A (en) * 2016-12-05 2017-05-31 广西师范学院 The preparation method of the Water-soluble carbon quantum dot with sisal hemp as raw material
CN108584916A (en) * 2018-06-05 2018-09-28 桂林理工大学 The method for preparing the luminous water-solubility fluorescent carbon quantum dot of visible region with sisal fiber
CN108822840A (en) * 2018-08-29 2018-11-16 济南大学 A kind of fiber crops are the preparation method of carbon source neodymium doped carbon quantum dot composite material
CN110155984A (en) * 2019-06-12 2019-08-23 浙江科技学院 Using soybean slag as the method and application of raw material hydro-thermal method synthesising biological matter fluorescent carbon point
CN112300796A (en) * 2020-10-20 2021-02-02 山西大学 Yellow fluorescent carbon dot and preparation method and application thereof
CN112322280A (en) * 2020-10-26 2021-02-05 南开大学 Preparation method of piperazine functionalized carbon quantum dots and application of piperazine functionalized carbon quantum dots in oxytetracycline detection
CN112795378A (en) * 2020-12-28 2021-05-14 南昌大学 Method for preparing carbon quantum dots by using waste culture medium and Fe-doped carbon quantum dots prepared by using method3+Application in linear detection
CN113372901A (en) * 2021-05-27 2021-09-10 桂林理工大学 Preparation method of fluorescence double-enhanced sisal fiber carbon quantum dots
CN113549450A (en) * 2021-07-28 2021-10-26 山西大学 Potassium-nitrogen co-doped carbon dots based on flint pericarp and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAIYAN QI等: "Two kinds of biomass-derived carbon dots with one-step synthesis for Fe3+ and tetracyclines detection", DYES AND PIGMENTS, vol. 206, pages 110555 *

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