CN115124998A - N, S, B-doped Chinese herbal medicine residue carbon dot, fluorescent probe and application - Google Patents
N, S, B-doped Chinese herbal medicine residue carbon dot, fluorescent probe and application Download PDFInfo
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Abstract
The invention provides N, S, B-doped Chinese herbal medicine residue carbon dots, a fluorescent probe and application. N, S, B preparation method of doped biomass carbon dots: carrying out hydrothermal reaction on the Chinese herbal medicine dregs, urea, thiourea and boric acid, centrifuging, filtering, dialyzing the obtained material to obtain a pure carbon dot solution, and freeze-drying to obtain a carbon dot solid. The method makes full use of the Chinese herbal medicine dregs, realizes the recycling of solid wastes, improves the quantum yield by adding the heteroatom, and has simple and convenient operation. According to the preparation method of the specific carbon point @ molecularly imprinted polymer, N, S, B-doped Chinese herbal medicine residue carbon points and orange-red carbon points are encapsulated in the molecularly imprinted polymer through a suspension polymerization method to form the specific carbon point fluorescent probe. The linear concentration range of furazolidone detected by the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe is 0-400mg/L, and the furazolidone detected by the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe is not easily influenced by other substances and has strong anti-interference capability.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to N, S, B-doped Chinese herbal medicine residue carbon dots, a fluorescent probe and application.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The carbon dots are luminescent quasi-spherical carbon-based nanomaterials with a size of less than 10 nm. The sources of carbon dots mainly comprise organic chemical molecules, natural organic small molecules and natural biomass, wherein the advantages of wide and easily-obtained natural biomass sources are gradually attracting attention. However, biomass carbon dots face many problems, such as the dependence of quantum yield on the intrinsic properties of the precursor, generally low quantum yield, and generally short wavelength. To solve the above problems, the addition of a heteroatom organic chemical reagent is a feasible means.
The herb residue is generally formed after active ingredients are extracted from Chinese herbs. A large amount of Chinese herbal medicine dregs are treated by a Chinese herbal medicine pharmacy factory or a pharmaceutical enterprise generally by burning, burying or stacking and the like, and are rarely recycled, wherein burning is the most common mode, and the treatment mode not only causes the increase of the treatment cost of enterprises and the pollution to the environment, but also causes the waste of resources.
Furazolidone is a common nitrofuran antibiotic, is commonly used for treating gastrointestinal diseases such as dysentery, enteritis, gastric ulcer and the like and bacterial livestock diseases, and can also be used together with other medicines for treating helicobacter pylori. Although it has the above advantages, excessive use may cause certain side effects, such as liver and kidney damage, allergic reactions, and gastrointestinal reactions such as nausea and vomiting. In 2008, nitrofurans such as furazolidone and the like cannot be detected in animal foods in the prohibition of China. Therefore, it is very necessary to accurately detect the concentration of furazolidone. At present, methods for detecting furazolidone comprise high performance liquid chromatography, enzyme-linked immunosorbent assay, high performance liquid chromatography-mass spectrometry, high performance liquid chromatography-tandem mass spectrometry and the like, but the methods have complex pretreatment modes, long time and higher cost.
Disclosure of Invention
In order to solve the problem of low quantum yield of the carbon dots and the problem of environmental pollution and resource waste caused by burning or stacking of Chinese herbal medicine residues, the N, S, B-doped Chinese herbal medicine residue carbon dots are prepared by using waste Chinese herbal medicine residues, urea, thiourea and boric acid as precursors through a solvothermal method. In order to solve the problems of complicated pretreatment mode and high cost of the existing means for detecting furazolidone and improve the sensitivity and specificity in the detection process, the ratiometric carbon point @ molecularly imprinted polymer fluorescent probe is formed by mainly adopting a suspension polymerization method to synthesize orange-red carbon points and Chinese herbal medicine residue carbon points in a thermal method by taking neutral red as a carbon source and thiourea as a sulfur source in a solvent, and encapsulating the orange-red carbon points and the Chinese herbal medicine residue carbon points in a molecularly imprinted polymer.
In order to achieve the above object, the present invention provides the following technical solutions.
The invention provides a preparation method of N, S, B-doped Chinese herbal medicine residue carbon dots, which comprises the following steps:
(1) dissolving the Chinese herbal medicine residue powder, urea, thiourea and boric acid in deionized water, and magnetically stirring to form a suspension;
(2) putting the suspension into a high-temperature hydrothermal kettle for hydrothermal reaction, and taking out the material after the reaction is cooled; centrifuging, filtering, dialyzing, collecting the liquid in the dialysis bag, and freeze-drying to obtain the product.
The Chinese herbal medicine residue powder in the step (1): urea: thiourea: the mass ratio of boric acid is 1.0: 0.5-1.5: 0.5-1.5: 0.5-1.5.
The hydrothermal reaction temperature in the step (2) is 180-240 ℃, and the reaction time is 6-14 h.
In the step (2), a dialysis bag with the cut-off molecular weight of 1kDa is used for dialysis in water for 24 hours.
In a second aspect of the invention, N, S, B-doped Chinese herbal medicine residue carbon dots prepared by the preparation method are provided.
The third aspect of the invention provides a preparation method of a ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe, which comprises the following steps:
(1) adding neutral red and thiourea into deionized water, dissolving by ultrasonic waves, and placing the mixture into a reaction kettle for reaction; taking out the materials after the reaction, centrifuging, filtering, dialyzing, and freeze-drying the liquid in the collected dialysis bag to obtain orange red carbon dots;
(2) n, S, B adding carbon dots of the doped Chinese herbal medicine residues and orange red carbon dots into acetonitrile, and ultrasonically dissolving; adding a target template, namely furazolidone and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), and stirring to enable a prepolymerization compound to be self-assembled;
(3) adding Ethylene Glycol Dimethacrylate (EGDMA) and Azobisisobutyronitrile (AIBN) into the mixture, stirring, introducing argon gas for purging, sealing the flask, placing the flask in a water bath, curing and mashing; washing with acetonitrile for multiple times, then performing ultrasonic-assisted elution for multiple times by using a mixed solution of methanol and acetic acid, and centrifuging to remove the solvent; finally, the polymer was washed with ethanol, dried in a vacuum oven and ground.
In the step (1), the mass ratio of neutral red to thiourea is 1: 1.
in the step (1), the taken material is centrifuged at 10000rpm for 20 min; the filtration is carried out by adopting a 0.2 mu m filter membrane; dialyzed in deionized water for 24 h.
In the step (2), the mass of the N, S, B-doped Chinese herbal medicine residue carbon dots and the orange-red carbon dots is 4-10mg and 1.5-3mg, and for example, the mass can be 10 mg: 1.5mg, 10 mg: 3mg, 6 mg: 3mg, 4 mg: 3 mg.
In the step (2), the dosage of the target template-furazolidone is 0.2mmol, and the dosage of the 2-acrylamide-2-methylpropanesulfonic acid is 1.2 mmol.
In the step (3), the dosage of Ethylene Glycol Dimethacrylate (EGDMA) is 2-6 mmol; azobisisobutyronitrile (AIBN) was used in an amount of 0.6 mmol.
In a fourth aspect of the invention, a method for detecting furazolidone by using a ratiometric carbon dot @ molecularly imprinted polymer is provided, which comprises the following steps: preparing a carbon dot @ molecularly imprinted polymer solution with the concentration of 0.5mg/mL by using a Bertany-Robinson buffer solution (B-R buffer solution) with the pH of 3.0-11.0, putting 4mL of the carbon dot @ molecularly imprinted polymer solution into a 5mL centrifuge tube, adding 100 mu L of furazolidone, uniformly mixing, incubating, and measuring the fluorescence intensity.
Compared with the prior art, the invention has the following obvious advantages:
1. the invention provides a preparation method for preparing blue biomass carbon dots by effectively utilizing Chinese herbal medicine dregs, which has the advantages that: the biomass carbon dots are synthesized by taking the Chinese herbal medicine residues as a carbon source, so that a new idea is provided for resource utilization of the Chinese herbal medicine residues; the quantum yield of the pure biomass carbon dots is low due to the fact that the impurity element proportion of the waste Chinese herbal medicine dregs is small, the quantum yield of the biomass carbon dots is improved by adding urea and thiourea, and the emission wavelength of the carbon dots is subjected to red shift to a certain degree by adding boric acid.
2. The method for detecting furazolidone by using the ratiometric carbon dot @ molecularly imprinted polymer has the advantages that:
orange red carbon points synthesized by neutral red and thiourea are used as internal standard signals, blue Chinese herbal medicine residue carbon points are used as reaction signals, and the two are encapsulated in a molecularly imprinted polymer together to form a ratiometric carbon point @ molecularly imprinted polymer fluorescent probe. The molecularly imprinted polymer simulates an antigen-antibody recognition mode, specific binding to target template molecules is formed, blue Chinese herbal medicine residue carbon spots can be quenched by various substances without selectivity, interference of other substances can be reduced by forming the molecularly imprinted polymer with furazolidone as a target template, and specific detection of the furazolidone is realized. Compared with a single fluorescent alpha signal, the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe is less susceptible to factors such as solvent, temperature and substrate concentration, and the detection result is more reliable.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is a transmission electron micrograph and a particle size distribution plot of carbon dots of N, S, B-doped blue herbal residue prepared in example 9;
FIG. 2 is a graph of the fluorescence spectra of N, S, B-doped blue herbal residue carbon dots prepared in example 9 at different excitation wavelengths;
FIG. 3 is an X-ray photoelectron spectrum of carbon dots of N, S, B-doped blue herbal residue prepared in example 9;
FIG. 4 is a transmission electron micrograph and a particle size distribution of the orange-red carbon dots prepared in example 10;
FIG. 5 is a graph showing fluorescence spectra of orange-red carbon dots prepared in example 10 at different excitation wavelengths;
FIG. 6 is a transmission electron micrograph of the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe prepared in example 16;
FIG. 7 is a graph showing the effect of different pH buffer solutions on the detection of furazolidone by using a ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe solution prepared in example 16, wherein the abscissa is the pH value of the B-R buffer solution, and the ordinate is the ratio of the fluorescence intensities of absence and presence of furazolidone at 365nm and 520nm excitation wavelengths, respectively;
FIG. 8 is a fluorescence spectrum of the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe prepared in example 19 in a buffer solution with pH 7 as a function of the concentrations of furazolidone at different concentrations, wherein the excitation wavelengths are 365nm and 520 nm;
FIG. 9 shows the fluorescence intensity of the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe prepared in example 19 in a pH 7 buffer solution as a function of furazolidone concentration, with the abscissa representing the furazolidone concentration and the ordinate representing the fluorescence intensity at an excitation wavelength of 365nm, respectively, (F) 0-365 -F 365 )/F 0-365 And fluorescence intensity at excitation wavelength of 520 nm.
FIG. 10 is a schematic diagram showing the selectivity of N, S, B doped blue herbal medicine residue carbon dots prepared in example 9 and the ratiometric carbon dots @ molecularly imprinted polymer fluorescent probe prepared in example 16 for common substances and similar structures of furazolidone.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida Biotechnology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 1.0g of urea, 1.0g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And putting the suspension into a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 180 ℃ for 14 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 2
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida Biotechnology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 1.0g of urea, 1.0g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 240 ℃ for 6 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 3
N, S, B preparation of carbon dots of blue-doped Chinese herbal medicine residues:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida biological technology limited, drying the dried Chinese herbal medicine residue in a drying oven at 65 ℃ to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to be below 80 meshes.
(2) 1.0g of Chinese herbal medicine residue powder, 1.0g of urea, 1.0g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 240 ℃ for 10 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 4
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida Biotechnology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 0.5g of urea, 1.0g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 220 ℃ for 10 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 5
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida biological technology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 1.5g of urea, 1.0g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 220 ℃ for 10 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 6
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida Biotechnology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 0.5g of urea, 0.5g of thiourea and 0.5g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and performing hydrothermal treatment at 220 ℃ for 10 hours.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 7
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida Biotechnology limited, drying at 65 deg.C in a drying oven to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to below 80 mesh.
(2) 1.0g of Chinese herbal medicine residue powder, 0.5g of urea, 1.5g of thiourea and 0.5g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 220 ℃ for 10 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 8
N, S, B preparation of carbon dots of blue-doped Chinese herbal medicine residues:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida biological technology limited, drying the dried Chinese herbal medicine residue in a drying oven at 65 ℃ to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to be below 80 meshes.
(2) 1.0g of Chinese herbal medicine residue powder, 0.5g of urea, 1.5g of thiourea and 1.5g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and stirred magnetically for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 220 ℃ for 10 h.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
Example 9
N, S, B preparation of blue-doped Chinese herbal medicine residue carbon dots:
(1) drying most of water in Chinese herbal medicine residue obtained from Shandong Furuida biological technology limited, drying the dried Chinese herbal medicine residue in a drying oven at 65 ℃ to obtain dried Chinese herbal medicine residue, and grinding the dried Chinese herbal medicine residue to be below 80 meshes.
(2) 1.0g of Chinese herbal medicine residue powder, 0.5g of urea, 1.5g of thiourea and 1.0g of boric acid were weighed into a beaker and dispersed in 60mL of deionized water, and magnetically stirred for 20min to form a suspension.
(3) And (3) placing the suspension in a polytetrafluoroethylene hydrothermal kettle, and performing hydrothermal treatment at 220 ℃ for 10 hours.
(4) And (3) taking out the materials in the step (2), centrifuging the materials at a high speed of 10000rpm for 20min and performing suction filtration by using a filter membrane of 0.22 mu m to remove large-particle impurities, collecting filtrate, dialyzing the filtrate in water by using a dialysis bag with the cut-off molecular weight of 1kDa for 24h to remove unreacted substances and fluorescent small molecules, collecting liquid in the dialysis bag, and performing freeze drying to obtain a dark brown solid.
FIG. 1 is a Transmission Electron Microscope (TEM) N, S, B doped Chinese herbal medicine residue carbon dot for morphology and particle size analysis, and the prepared carbon dot has a nearly spherical morphology, a lattice spacing of 0.21nm, and an average particle size of 5.37 nm. FIG. 2 shows the optical properties of N, S, B doped blue carbon dots of herb residue, wherein N, S, B doped carbon dots of herb residue show excitation wavelength dependence, the fluorescence peak is red shifted with the increase of excitation wavelength, the fluorescence intensity is strongest when the excitation wavelength is 344nm, and the emission peak is 424 nm. FIG. 3 is an X-ray photoelectron spectrum of N, S, B doped carbon dots of Chinese herbal medicine residue, the surface of the carbon dots contains N, S and B peaks, and N, S and B elements are successfully doped.
Example 10
Preparation of orange-red carbon dots:
1) 0.3g of neutral red and 0.3g of thiourea are added into 60mL of deionized water and are subjected to ultrasonic treatment for 20min to be uniformly dispersed.
(2) And transferring the solution into a high-temperature polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 3 hours, and taking out the material after the reaction is cooled.
(3) Centrifuging the taken materials at 10000rpm for 20min, taking out supernate, performing suction filtration by using a 0.22 mu m filter membrane, collecting filtrate, dialyzing in deionized water for 24h, and freeze-drying the liquid in the collected dialysis bag to obtain black solid.
FIG. 4 is a transmission electron microscope used for analyzing the appearance and the particle size of orange-red carbon dots, wherein the prepared carbon dots are dispersed and spherical, the average particle size is 5.06nm, and the lattice spacing is 0.21 nm. FIG. 5 is a representation of the optical properties of a fluorospectrophotometer F-4700 for measuring orange-red carbon dots. The orange-red carbon dot shows the independence of the excitation wavelength, the position of an emission peak is irrelevant to the excitation wavelength, the wavelength of the emission peak is about 630nm, and red fluorescence is shown.
Example 11
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, 10mg of N, S, B doped blue herbal residue carbon dots and 1.5mg of orange-red carbon dots were added, and it was ultrasonically dissolved and uniformly dispersed.
(2) 0.2mmol of target template-furazolidone and 1.2mmol of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) are added into a three-neck flask, and the mixture is magnetically stirred for 1 hour, so that the prepolymerization compound is subjected to self-assembly.
(3) Then 4mmol of Ethylene Glycol Dimethacrylate (EGDMA) and 0.6mmol of Azobisisobutyronitrile (AIBN) were added to stir, argon was introduced to purge for 30min at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath to polymerize for 24h, and triturated using a mortar.
(4) To remove unreacted polymer, wash 3 times with acetonitrile, then 100mL of methanol: performing ultrasonic-assisted elution for multiple times with the ultrasonic-assisted elution time of 40min on acetic acid (9:1, v: v), and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
Example 12
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, 10mg of N, S, B doped blue biomass carbon dot and 3mg of orange-red carbon dot were added, and they were ultrasonically dissolved and uniformly dispersed.
(2) And (3) adding 0.2mmol of target template-furazolidone and 1.2mmol of AMPS into a three-neck flask, and magnetically stirring for 1h to perform self-assembly on the pre-polymerized compound.
(3) Then 4mmol of EGDMA and 0.6mmol of AIBN were added and stirred, argon was introduced and purged for 30min at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath and polymerized for 24h, and crushed in a mortar.
(4) To remove unreacted polymer, wash 3 times with acetonitrile, then 100mL of methanol: performing ultrasonic-assisted elution for multiple times with the ultrasonic-assisted elution time of 40min on acetic acid (9:1, v: v), and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
Example 13
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, and 4mg of N, S, B doped blue biomass carbon dot and 3mg of orange-red carbon dot were added and ultrasonically dissolved and uniformly dispersed.
(2) And (3) adding 0.2mmol of target template-furazolidone and 1.2mmol of AMPS into a three-neck flask, and magnetically stirring for 1h to perform self-assembly on the pre-polymerized compound.
(3) Then, 4mmol of EGDMA and 0.6mmol of AIBN were added thereto, and the mixture was stirred, purged with argon gas for 30min at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath, polymerized for 24 hours, and crushed using a mortar.
(4) To remove unreacted polymer, wash 3 times with acetonitrile, then 100mL of methanol: performing ultrasonic-assisted elution for multiple times with the ultrasonic-assisted elution time of 40min on acetic acid (9:1, v: v), and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
Example 14
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, and 6mg of N, S, B doped blue biomass carbon dot and 3mg of orange-red carbon dot were added and ultrasonically dissolved and uniformly dispersed.
(2) And (3) adding 0.2mmol of target template-furazolidone and 1.2mmol of AMPS into a three-neck flask, and magnetically stirring for 1h to perform self-assembly on the pre-polymerized compound.
(3) Then, 2mmol of EGDMA and 0.6mmol of AIBN were added thereto, and the mixture was stirred, purged with argon gas for 30min at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath, polymerized for 24 hours, and crushed using a mortar.
(4) To remove unreacted polymer, wash 3 times with acetonitrile, then 100mL of methanol: performing ultrasonic-assisted elution for multiple times with the ultrasonic-assisted elution time of 40min on acetic acid (9:1, v: v), and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
Example 15
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, 6mg of N, S, B doped blue biomass carbon dot and 3mg of orange-red carbon dot were added, and they were ultrasonically dissolved and uniformly dispersed.
(2) Adding 0.2mmol of target template-furazolidone and 1.2mmol of AMPS into a three-necked flask, and magnetically stirring for 1h to perform self-assembly on the pre-polymerized compound.
(3) Then 6mmol of EGDMA and 0.6mmol of AIBN were added and stirred, argon was purged for 30min at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath and polymerized for 24h, and crushed using a mortar.
(4) To remove unreacted polymer, wash 3 times with acetonitrile, then 100mL of methanol: performing ultrasonic-assisted elution on acetic acid (9:1, v: v) for multiple times, wherein the ultrasonic-assisted elution time is 40min, and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
Example 16
Preparation of a specific carbon dot @ molecularly imprinted polymer fluorescent probe:
(1) 50mL of acetonitrile was placed in a 250mL brown three-necked flask, and 6mg of N, S, B doped blue biomass carbon dot and 3mg of orange-red carbon dot were added and ultrasonically dissolved and uniformly dispersed.
(2) Adding 0.2mmol of target template-furazolidone and 1.2mmol of AMPS into a three-necked flask, and magnetically stirring for 1h to perform self-assembly on the pre-polymerized compound.
(3) Then, 4mmol of EGDMA and 0.6mmol of AIBN were added thereto, and the mixture was stirred, purged with argon gas for 30 minutes at a flow rate of 300mL/min, the flask was sealed, placed in a 65 ℃ water bath, polymerized for 24 hours, and crushed using a mortar.
(4) To remove unreacted polymer, 3 washes with acetonitrile were followed by 100mL of methanol: performing ultrasonic-assisted elution on acetic acid (9:1, v: v) for multiple times, wherein the ultrasonic-assisted elution time is 40min, and centrifuging to remove the solvent. Finally, the polymer was washed several times with ethanol, dried in a vacuum oven at 65 ℃ for 24h, and ground using a mortar.
FIG. 6 is a representation of the morphology of the comparative molecularly imprinted polymer fluorescent probe by Transmission Electron Microscopy (TEM), and the TEM image shows that the particle size of the composite material is greater than 50nm, which proves the synthesis of the composite material.
Example 17
Influence of solution pH contrast ratio carbon dot @ molecularly imprinted polymer fluorescent probe on detection of furazolidone
Weighing 5mg of the ratiometric carbon dot @ molecularly imprinted polymer into a 15mL centrifuge tube, preparing a 4mg/L furazolidone solution by using B-R buffer solution with the pH value of 3-11, adding 10mL of the solution into the centrifuge tube to prepare a 0.5mg/mL solution of the ratiometric carbon dot @ molecularly imprinted polymer, and transferring the solution into a cuvette to measure the fluorescence intensity at an excitation wavelength of 365nm and 520 nm. FIG. 7 is a graph showing the effect of different pH buffer solutions on the detection of furazolidone by using the ratiometric molecularly imprinted polymer fluorescent probe solution prepared in example 20, wherein the abscissa is the pH value of the B-R buffer solution, and the ordinate is the ratio of the fluorescence intensity of absence and presence of furazolidone at the excitation wavelengths of 365nm and 520nm, respectively. It can be seen from the figure that F at 365nm excitation wavelength, pH 4 and 11 0-365 /F 365 The ratio of (A) is the largest, the quenching efficiency is the highest, but F 0-520 /F 520 The ratio of (a) to (b) is higher than 1.1, which indicates that the fluorescence intensity of the orange-red carbon dot is changed obviously, and finally, a buffer solution with the pH value of 7 is selected in consideration of the fact that the orange-red carbon dot is used as an internal standard signal and basically keeps unchanged and the quenching efficiency is high.
Example 18
Application of specific carbon dot @ molecularly imprinted polymer fluorescent probe in detection of furazolidone
Preparing a 0.5mg/mL ratio carbon dot @ molecularly imprinted polymer solution by using a B-R buffer solution with the pH value of 7, placing 4mL of the solution into a 5mL centrifuge tube, adding 100 mu L of furazolidone with different concentrations, uniformly mixing, incubating for 15min, transferring the solution into a cuvette, measuring fluorescence intensity at an excitation wavelength of 365nm and 520nm, and finding out that the fluorescence intensity of a carbon dot at the wavelength of 365nm is in a linear relation with the furazolidone with a certain concentration according to an experimental result. Wherein the furazolidone concentration is 0mg/L, 5mg/L, 10mg/L, 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L, 150mg/L, 200mg/L, 250mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 800mg/L, 900mg/L and 1000mg/L respectively. Drawing (A)8 is a fluorescence spectrum diagram of the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe prepared in example 18 in a buffer solution with pH 7, wherein the fluorescence spectrum varies with the concentration of furazolidone with different concentrations, and the intensity of a fluorescence peak at 420nm gradually decreases with the increase of the concentration of the furazolidone. FIG. 9 shows the fluorescence intensity of the ratiometric molecularly imprinted polymer fluorescent probe prepared in example 18 in a buffer solution with pH 7 as a function of the concentration of furazolidone at different concentrations, with the abscissa representing the concentration of furazolidone and the ordinate representing the change in fluorescence intensity at the excitation wavelength 365, respectively, (F) 0-365 -F 365 )/F 0-365 And fluorescence intensity at an excitation wavelength of 520 nm. It can be seen from the graph that the intensity of the orange-red fluorescence does not vary much, (F) 0-365 -F 365 )/F 0-365 Has a linear relation (R) with the furazolidone concentration within the range of 0-400mg/L 2 ＝0.9857)。
Example 19
Adding 4mL of N, S, B doped blue Chinese herbal medicine residue carbon point solution with concentration of 0.1mg/mL into a 5mL centrifuge tube, and adding 100 μ L of 21 common substances with concentration of 2.0mM respectively, wherein Al is 3+ 、Ca 2+ 、Co 2+ 、Cr 6+ 、Cr 3+ 、Fe 2+ 、Fe 3+ 、K + 、Mn 2+ 、Ni 2+ 、Pb 2+ 、Zn 2+ D (-) -fructose (Fru), DL-tartaric acid (Tar), L-glutamic acid (Glu), L-ascorbic acid (Asc), L-lysine (Lys), L-histidine (His), glycine (Gly), citric acid (Cit), sucrose (Suc), 2 structurally similar substances to Furazolidone (FZD) were nitrofurantoin (Nit) and furazoline (Lin), respectively, and the change in fluorescence intensity was measured at an excitation wavelength of 344 nm. To a 5mL centrifuge tube, 4mL of 0.5mg/mL ratiometric carbon dot @ molecularly imprinted polymer solution was added, and then 100. mu.L of the above interfering substance was added at a concentration of 1.0mM, and changes in fluorescence intensity were measured at 365nm and 520nm excitation wavelengths. FIG. 10 shows the effect of different interfering substances on the fluorescence intensity of carbon dots and carbon dots @ molecularly imprinted polymer of N, S, B-doped blue herb residue, wherein furazolidone, furazolidone and nitrofurantoin have a greater effect on the fluorescence intensity of carbon dots of N, S, B-doped blue herb residue and a greater effect on carbon dots @ moleculeThe impact of the imprinted polymer is relatively small, which demonstrates that the molecularly imprinted polymeric layer helps to improve selectivity.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of N, S, B doped Chinese herbal medicine residue carbon dots is characterized by comprising the following steps:
(1) dissolving the Chinese herbal medicine residue powder, urea, thiourea and boric acid in deionized water, and magnetically stirring to form a suspension;
(2) putting the suspension into a high-temperature hydrothermal kettle for hydrothermal reaction, and taking out the material after the reaction is cooled; centrifuging, filtering, dialyzing, collecting the liquid in the dialysis bag, and freeze-drying to obtain the product.
2. The preparation method according to claim 1, wherein the Chinese herbal medicine residue powder in the step (1): urea: thiourea: the mass ratio of boric acid is 1.0: 0.5-1.5: 0.5-1.5: 0.5-1.5.
3. The preparation method according to claim 1, wherein the hydrothermal reaction temperature in the step (2) is 180-240 ℃, and the reaction time is 6-14 h;
in the step (2), dialyzing in water for 24h by using a dialysis bag with the cut-off molecular weight of 1 kDa.
4. An N, S, B-doped herbal residue carbon dot prepared by the method of any one of the preceding claims.
5. A preparation method of a ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe is characterized by comprising the following steps of:
(1) adding neutral red and thiourea into deionized water, dissolving by ultrasonic, and placing into a reaction kettle for reaction; taking out the materials after reaction, centrifuging, filtering, dialyzing, and freeze-drying the liquid in the collected dialysis bag to obtain orange-red carbon dots;
(2) adding the N, S, B doped Chinese herbal medicine residue carbon dots and orange-red carbon dots into acetonitrile, and ultrasonically dissolving; adding a target template, namely furazolidone and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), and stirring to enable a prepolymerization compound to be self-assembled;
(3) adding Ethylene Glycol Dimethacrylate (EGDMA) and Azobisisobutyronitrile (AIBN) into the mixture, stirring, introducing argon gas for purging, sealing the flask, placing the flask in a water bath, curing and mashing; washing with acetonitrile for multiple times, then performing ultrasonic-assisted elution for multiple times by using a mixed solution of methanol and acetic acid, and centrifuging to remove the solvent; finally, the polymer was washed with ethanol, dried in a vacuum oven and ground.
6. The method according to claim 5, wherein in the step (1), the taken material is centrifuged at 10000rpm for 20 min; the filtration adopts a 0.2 μm filter membrane for filtration; dialyzed against deionized water for 24 h.
7. The preparation method according to claim 5, wherein in the step (1), the mass ratio of the neutral red to the thiourea is 1: 1.
8. the preparation method according to claim 5, wherein in the step (2), the N, S, B-doped carbon points of the herb residue and the orange-red carbon points have mass of 4-10mg and 1.5-3mg respectively; in the step (2), the dosage of the target template-furazolidone is 0.2mmol, and the dosage of the 2-acrylamide-2-methylpropanesulfonic acid is 1.2 mmol; preferably, in the step (3), the dosage of Ethylene Glycol Dimethacrylate (EGDMA) is 2-6 mmol; azobisisobutyronitrile (AIBN) was used in an amount of 0.6 mmol. .
9. The ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe prepared by the preparation method according to any one of claims 5 to 8.
10. A method for detecting furazolidone by using a ratiometric carbon dot @ molecularly imprinted polymer is characterized by comprising the following steps of:
the birutan-robinson buffer solution (B-R buffer solution) with pH of 3.0-11.0 is used to configure the ratiometric carbon dot @ molecularly imprinted polymer fluorescent probe of claim 9 into a carbon dot @ molecularly imprinted polymer solution with a concentration of 0.5mg/mL, 4mL of the carbon dot @ molecularly imprinted polymer solution is put into a 5mL centrifuge tube, 100 μ L of furazolidone is added, mixed evenly, incubated, and fluorescence intensity measurement is carried out.
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