CN115340615A - Fluorescent molecule based on cyclodextrin-amino acid and synthetic method and application thereof - Google Patents
Fluorescent molecule based on cyclodextrin-amino acid and synthetic method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
Abstract
The invention relates to a fluorescent molecule based on cyclodextrin-amino acid and a synthesis method and application thereof, wherein the preparation method comprises the following steps: adding aldehyde cyclodextrin and amino acid into water to prepare a mixed solution, and sequentially adjusting the pH, heating and stirring, and performing solid-liquid separation to obtain the fluorescent molecule based on cyclodextrin-amino acid; wherein the aldehyde cyclodextrin is obtained by pre-oxidizing beta-cyclodextrin with sodium periodate. Compared with the prior art, the cyclodextrin-histidine fluorescent molecule prepared by the invention can be used as a specificity identification fluorescent probe of aureomycin, has high sensitivity and strong selectivity, and can be used for visual portable detection based on a fluorescent image.
Description
Technical Field
The invention belongs to the technical field of fluorescent sensors, and relates to a fluorescent molecule based on cyclodextrin-amino acid, a synthetic method thereof and application thereof in aureomycin fluorescent detection.
Background
Organic fluorescent materials have been widely used in sensor, cell imaging and display technologies. The traditional fluorescent molecules have a chemical bond conjugated structure base based on a pi-conjugated aromatic structure, and have adjustable luminous color and high fluorescence efficiency. However, these materials generally have the characteristics of poor solubility, high biotoxicity, high cost, complex synthesis process and the like, and the practical application thereof is greatly limited. In contrast, unconventional luminophores without significant conjugated structures have the unique advantages of high biocompatibility, low toxicity, good processability and ease of synthesis. Unconventional emitters have electron-rich heteroatoms, such as nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), halogens (Cl, br and I) or unsaturated groups containing C = O, C = C and C ≡ N. They emit in concentrated and/or solid state, but tend not to emit light in dilute solutions. This phenomenon is known as Cluster Triggered Emission (CTE). Clustered illuminants in an aggregated state have been used for encryption and bio-imaging. However, the concentration of cluster luminophores used for cell imaging is 1000 times higher than that of conventional luminophores, which is a big obstacle to its practical application. In addition, in sensing applications, fluorescent probes need to interact efficiently with analytes. However, at present, the interaction between the solid-state cluster luminescent material based on cluster luminescence and the analyte in the aqueous solution is limited, and the reported unconventional luminophores have poor performance as sensors. Therefore, it is highly desirable to find new strategies to promote the CTE effect with strong luminescence even in dilute solutions.
The phenomenon of luminescence of mono-, di-, oligo-and polysaccharide crystals with abundant hydroxyl groups as non-conventional luminophores has been extensively studied. They are weakly emissive in dilute solutions and bright emission is only observed from concentrated solutions (> 8 wt.%) or the crystalline state. In dilute solutions, linear polysaccharides, such as sodium alginate, exhibit an extended worm-like conformation, which results in no luminescence due to lack of sufficient electron delocalization and active molecular motion. Therefore, the development of nonlinear molecules and enhanced molecular packing are of great importance for obtaining bright luminescence in dilute solutions.
Compared with the traditional detection method, the fluorescent probe technology is considered to be one of the most promising analysis methods for detecting trace pollutants due to the characteristics of simplicity, portability, high sensitivity, low cost and the like. At present, tetracycline is used as a novel pollutant which is often detected in a water body, and a plurality of fluorescent sensing materials are reported to be used for detecting tetracycline antibiotics. However, tetracycline antibiotics with very similar molecular host structures, such as chlortetracycline, oxytetracycline, minocycline, tetracycline, etc., are difficult to distinguish. Therefore, it is necessary to design a fluorescent probe for a specific tetracycline antibiotic for development and application.
At present, novel fluorescent molecules based on cyclodextrin-amino acid are not reported. Reported technologies such as chinese patent CN 201810866243.1 disclose a safe and simple method for preparing double-doped nitrogen and phosphorus carbon quantum dots, which comprises dissolving amino acid and carbon precursor (including glucose, citric acid monohydrate or cyclodextrin) in deionized water, adding phosphoric acid solution, and then performing ultrasonic treatment for 1-2 h; and heating the solution subjected to the ultrasonic treatment in an oil bath at 90-150 ℃ for 1-5 hours to prepare a nitrogen and phosphorus co-doped carbon dot solution. Through patent comparison, although raw materials such as amino acid, cyclodextrin and the like are also adopted in the patent, the preparation method is obviously different from a final product, and nitrogen and phosphorus double-doped carbon quantum dots obtained by the patent through methods such as ultrasound, high-temperature oil bath and the like have long synthesis time and complex treatment process. In contrast, the novel fluorescent molecule based on the amino acid grafted cyclodextrin, which is different from a carbon quantum dot, has definite molecular composition and spatial structure, mild synthesis conditions, synthesis temperature of 60-80 ℃ and reaction time of only 30-60min. In addition, the fluorescent molecule of histidine-grafted cyclodextrin can be used as a specificity recognition probe of aureomycin, so that the high-sensitivity and high-selectivity portable detection of aureomycin can be realized, and good application prospects are shown.
In the aspect of fluorescence analysis technology of aureomycin, reported technologies such as Chinese patent CN201710302455.2 disclose a gold/platinum bimetallic nano-cluster fluorescent probe based on polyethyleneimine protection and application thereof in aureomycin detection, and the method utilizes the bimetallic gold/platinum nano-cluster protected by polyethyleneimine as a fluorescent sensing material and is used for detecting tetracycline antibiotics based on a fluorescence quenching mechanism; however, it is still necessary to add Al 3+ Based on a fluorescence enhancement mechanism, the aureomycin can be distinguished from tetracycline, and the aim of specifically detecting aureomycin is fulfilled. The method is used for detecting aureomycin, the linear range is 0.5-30 mu M, and the detection limit is 0.5 mu M. But the detection method detectsThe limit is still higher, and the detection requirement of trace aureomycin in the existing sewage is difficult to meet.
Disclosure of Invention
The invention aims to provide a fluorescent molecule based on cyclodextrin-amino acid and a synthetic method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a method for synthesizing a fluorescent molecule based on cyclodextrin-amino acid, comprising:
adding aldehyde cyclodextrin and amino acid into water to prepare a mixed solution, and sequentially adjusting the pH, heating and stirring, and performing solid-liquid separation to obtain the cyclodextrin-amino acid based fluorescent molecule; the aldehyde cyclodextrin is obtained by pre-oxidizing beta-cyclodextrin with sodium periodate.
Further, the preparation method of the aldehyde cyclodextrin comprises the following steps:
stirring beta-cyclodextrin and sodium periodate in water in a dark place for reaction, performing nanofiltration, stirring and mixing with ethanol until precipitate is separated out, and then sequentially performing filtration, washing and freeze-drying to obtain aldehyde cyclodextrin;
wherein the mol ratio of the beta-cyclodextrin to the sodium periodate is 1 (1-4);
in the light-shielding stirring reaction, the reaction temperature is 30-50 ℃, and the reaction time is 3-5h;
the purification process adopts a water/ethanol mixed solution with the volume ratio of 1/4 for washing.
Furthermore, the molar ratio of the aldehyde cyclodextrin to the amino acid is 1 (2-6).
Further, the amino acid comprises at least one of glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine, phenylalanine, tryptophan, or histidine.
Further, when the amino acid is at least one of glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine or phenylalanine, adjusting the pH of the reaction system to 8-9;
when the amino acid is one or two of tryptophan or histidine, adjusting the pH of the reaction system to 6-7.
Further, in the heating and stirring process, the heating temperature is 60-80 ℃, and the stirring time is 30-60min.
Further, the solid-liquid separation comprises dialysis and freeze drying.
A cyclodextrin-amino acid based fluorescent molecule synthesized as described above.
The application of the cyclodextrin-amino acid-based fluorescent molecule comprises the step of using the fluorescent molecule as a fluorescent probe for qualitative and/or quantitative detection of aureomycin in a water body.
Further, the detection method specifically comprises the following steps:
1) Drawing a standard curve: respectively mixing and uniformly stirring the fluorescent probes with a plurality of solutions containing aureomycin with different concentrations to obtain a standard solution with the aureomycin concentration range of 0-5 mu M, taking a 365nm ultraviolet lamp as an excitation light source, shooting in a dark environment to obtain a fluorescent image, analyzing the B value and the G value of the image, drawing a standard curve by taking B/G as a vertical coordinate and aureomycin concentration as a horizontal coordinate, and detecting the aureomycin to obtain a fitting equation;
2) And (3) detecting the aureomycin in the water sample: and (2) mixing the fluorescent probe with the water sample to be detected by adopting the dosage ratio of the fluorescent probe to the aureomycin solution in the step 1) to obtain a mixed sample, obtaining a fluorescent image by taking a 365nm ultraviolet lamp as an excitation light source, analyzing and calculating to obtain the B/G of the image, and then obtaining the corresponding aureomycin concentration according to a standard curve or a fitting equation.
Firstly, oxidizing and modifying beta-cyclodextrin with low solubility and low reaction activity by using sodium periodate to obtain aldehyde cyclodextrin with good water solubility and high reaction activity and containing a dialdehyde structure; then the aldehyde group of the aldehyde-based cyclodextrin reacts with amino groups in various amino acid molecules through Schiff base to obtain the novel fluorescent molecule of 12 amino acid grafted cyclodextrins based on different amino acids. The synthesized fluorescent molecule has excellent fluorescence performance in a dilute solution, good water solubility and excellent environmental compatibility based on a mechanism of enhancing cluster luminescence. The synthesized histidine-grafted cyclodextrin fluorescent molecule is used as a fluorescent probe of aureomycin, and can realize high-selectivity and high-sensitivity portable detection of aureomycin based on a visualization technology.
Compared with the prior art, the invention has the following characteristics:
1) The synthesis method is simple, the cyclodextrin is obtained by simply modifying cyclodextrin, the synthesis condition is mild, the reaction temperature can be controlled below 80 ℃, and the preparation environment requirement can be provided based on the conventional water bath condition;
2) Compared with the traditional fluorescent molecule with a conjugated structure, the novel fluorescent molecule of cyclodextrin-amino acid prepared by the invention has the advantages of simple structure, low synthesis cost, good water solubility, no biotoxicity, good environmental compatibility and the like.
3) The invention can synthesize a series of novel cyclodextrin-amino acid fluorescent molecules with abundant structures and performances, and provides a general method for synthesizing unconventional fluorescent materials based on amino acid-cyclodextrin.
4) The novel cyclodextrin-histidine fluorescent molecule prepared by the invention can directly identify the aureomycin molecule with high characteristics, realize high-sensitivity detection (the detection range is 0-5 mu M, the detection limit is 12 nM), is more suitable for accurate detection of low-concentration trace pollutants and high-selectivity detection, has no signal response to other tetracycline classes with very similar molecular main body structures, and can realize portable detection of the aureomycin by a visualization technology based on a fluorescent image.
Drawings
FIG. 1 is a three-dimensional fluorescence diagram of the fluorescent molecule of cyclodextrin-amino acid synthesized in examples 1 and 2;
FIG. 2 is a graph of the emission spectra of the cyclodextrin-amino acid fluorescent molecules synthesized in example 1 and example 2 at different excitation wavelengths;
FIG. 3 is a graph showing the fluorescence spectra of cyclodextrin-histidine in example 3 under different amounts of amino acid added;
FIG. 4 is a graph showing fluorescence emission spectra of example 4 after various concentrations of aureomycin were added;
FIG. 5 is a standard curve for aureomycin assay as set forth in example 4;
FIG. 6 is the effect of different small organic molecules on the fluorescence emission spectra of the synthesized cyclodextrin-histidine fluorescent molecule in example 5.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A fluorescent molecule based on cyclodextrin-amino acid, and the synthesis method comprises the following steps:
s1: mixing beta-cyclodextrin and sodium periodate in a molar ratio of 1 (1-4) in water, stirring and reacting for 3-5h at 30-50 ℃ in the dark, performing nanofiltration, stirring and mixing with ethanol until precipitation is separated out, and then sequentially performing filtration, purification and freeze-drying to obtain aldehyde cyclodextrin;
wherein, the purification process is to wash by adopting a water/ethanol mixed solution with the volume ratio of 1/4;
s2: preparing aldehyde cyclodextrin into an aqueous solution;
s3: adding amino acid into the above water solution, adjusting pH value of the system, heating to 60-80 deg.C, and continuously stirring for 30-60min to obtain product solution;
wherein the molar ratio of the aldehyde cyclodextrin to the amino acid is 1 (2-6);
when the amino acid is at least one of glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine or phenylalanine, adjusting the pH of the reaction system to 8-9;
when the amino acid is one or two of tryptophan or histidine, adjusting the pH value of the reaction system to 6-7;
s4: dialyzing the product liquid for 12h, and freeze-drying the obtained dialyzate to obtain the novel fluorescent material powder based on the cyclodextrin-amino acid.
The application of the cyclodextrin-amino acid-based fluorescent molecule comprises the step of using the fluorescent molecule as a fluorescent probe for qualitative and/or quantitative detection of aureomycin in a water body.
Further, the detection method specifically comprises the following steps:
1) Drawing a standard curve: respectively mixing and uniformly stirring a fluorescent probe and a plurality of solutions containing aureomycin with different concentrations to obtain a standard solution with the aureomycin concentration range of 0-5 mu M, taking a 365nm ultraviolet lamp as an excitation light source, shooting in a dark environment to obtain a fluorescent image, carrying out image color homogenization treatment by using a software image J, then directly reading an average B value and an average G value of the image by using an F color taking device, drawing a standard curve by using B/G as a vertical coordinate and aureomycin concentration as a horizontal coordinate, and carrying out aureomycin detection fitting equation;
2) And (3) detecting the aureomycin in the water sample: and (2) mixing the fluorescent probe with the water sample to be detected by adopting the dosage ratio of the fluorescent probe to the aureomycin solution in the step 1) to obtain a mixed sample, obtaining a fluorescent image by taking a 365nm ultraviolet lamp as an excitation light source, analyzing and calculating to obtain the B/G of the image, and then obtaining the corresponding aureomycin concentration according to a standard curve or a fitting equation.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
a cyclodextrin-amino acid (histidine/tryptophan) -based fluorescent molecule, the synthesis method of which comprises the following steps:
s1: adding 15g of beta-cyclodextrin into 100mL of deionized water, uniformly stirring, adding 6g of sodium periodate, reacting for 4 hours at 40 ℃ in a dark state, filtering by a 220nm filter membrane, taking filtrate, mixing the filtrate with excessive absolute ethyl alcohol (800 mL) until precipitate is separated out, and sequentially filtering, washing with ethanol/water (V/V = 80/20) for multiple times, and freeze-drying to obtain aldehyde cyclodextrin with good water solubility and high reaction activity and containing a dialdehyde structure;
s2: dissolving 0.1mmol (114 mg) of aldehyde cyclodextrin and 0.6mmol (93 mg) of histidine or 0.6mmol (82 mg) of tryptophan in 20mL of water, and adjusting the pH value of the system to be 6-7;
s3: stirring the solution at 80 ℃ for reacting for 60min to obtain cyclodextrin-amino acid fluorescent molecules, dialyzing (molecular weight cut-off is 1000 Da), and freeze-drying to obtain 2 kinds of fluorescent material powder based on cyclodextrin-amino acid (histidine/tryptophan).
Example 2:
a fluorescent molecule based on cyclodextrin-amino acids (glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine or phenylalanine) whose synthesis differs from example 1 only in that:
in step S2, the amino acids used were 0.6mmol (45 mg) glycine or 0.6mmol (79 mg) isoleucine, 0.6mmol (105 mg) arginine, 0.6mmol (79 mg) asparagine, 0.6mmol (73 mg) cysteine, 0.6mmol (88 mg) glutamine, 0.6mmol (88 mg) glutamic acid, 0.6mmol (88 mg) lysine, 0.6mmol (90 mg) methionine, 0.6mmol (99 mg) phenylalanine; adjusting the pH value of the system to 8-9;
in the step S3, stirring and reacting for 30min to finally obtain 10 fluorescent material powders based on cyclodextrin-amino acid;
the rest is the same as example 1.
As shown in FIG. 1, the three-dimensional fluorescence of 12 cyclodextrin-amino acid-based novel fluorescent molecules (5 mM aqueous solution) synthesized in examples 1 and 2 is shown. As can be seen from the figure, based on the enhanced cluster luminescence effect in the cyclodextrin-limited space, the synthesized cyclodextrin-amino acid novel fluorescent molecule has a remarkable fluorescence signal although not having pi-conjugated groups, and the emission wavelength is concentrated in the range of 350-550 nm.
As shown in fig. 2, the emission spectra of the synthesized 12 novel cyclodextrin-amino acid-based fluorescent molecules (5 mM aqueous solution) at different excitation wavelengths are shown. As can be seen from the figure, the synthesized novel fluorescent molecule has excitation wavelength dependence, and the emission peak gradually red shifts with the increase of the excitation wavelength.
Example 3: influence of different amino acid addition amounts
A cyclodextrin-amino acid (histidine) -based fluorescent molecule whose synthesis method differs from that of example 1 only in that:
in the step S2, the used amounts of histidine are 31mg,62mg,93mg and 124mg, respectively (the molar ratio of aldehyde cyclodextrin to amino acid is 1; the rest is the same as example 1.
The fluorescence emission curve at a concentration of 5mM (in water) was measured using a 365nm UV lamp as an excitation light source, and the results are shown in FIG. 3, in which the fluorescence intensity gradually increased as the amount of histidine added was increased. When the molar ratio is 1.
Example 4:
in the embodiment, the cyclodextrin-histidine-based fluorescent molecule prepared in example 1 is used as a fluorescent probe for detecting aureomycin in a water sample, and the specific detection process is as follows:
1) Drawing a standard curve: dispersing cyclodextrin-amino acid-based fluorescent molecules into deionized water at a concentration of 200 mu M to serve as fluorescent probes;
respectively preparing aureomycin standard solutions with the concentrations of 0, 1, 2, 4, 6, 8 and 10 mu M, mixing 0.5mL of aureomycin standard solutions with a fluorescent probe with the same volume to obtain a mixed solution, measuring a fluorescence emission curve of the obtained mixed solution by using a 365nm ultraviolet lamp as an excitation light source in a dark environment, and as shown in a figure 4, the fluorescence intensity of the system is gradually enhanced along with the increase of the concentration of the added aureomycin;
taking a picture of the mixed solution to obtain a fluorescence image, gradually increasing the brightness of the image along with the increase of the concentration of the aureomycin, analyzing the B value and the G value of the image by using image analysis software, drawing a standard curve (as shown in figure 5) by taking B/G as a vertical coordinate and the concentration (mu M) of the aureomycin as a horizontal coordinate, and obtaining an aureomycin detection fitting equation: y =0.1431x +1.3319, (R2 = 0.998); the detection limit calculated according to the detection limit LOD =3 σ/N (where σ is the standard deviation of the blank sample and N is the slope of the linear equation) was 12nM using the cyclodextrin-histidine fluorescent molecule as the probe.
2) Pretreatment of a water sample to be detected: filtering a water sample to be detected, and adjusting the pH of the water sample to be detected to be neutral;
3) And (3) detecting the aureomycin in the water sample: and (3) mixing 0.5mL of the pre-treated water sample with 0.5mL of the fluorescent probe solution to obtain a mixed sample, obtaining a fluorescent image by taking a 365nm ultraviolet lamp as an excitation light source, obtaining B/G of the image by using image analysis software, and obtaining the corresponding aureomycin concentration according to a fitting equation. College university campus water and tap water were collected for benchmarking recovery experiments, and 1 μ M, 3 μ M, 4 μ M and 7 μ M aureomycin were added, respectively, and the aureomycin recovery rate was 97.25% -101.67% by the above method, with the specific results as shown in table 1.
TABLE 1 spiking recovery test results
Example 5:
the cyclodextrin-histidine-based fluorescent probe synthesized in example 1 is used for selectively detecting different coexisting or structurally similar small molecular organic matters, and the specific method is as follows:
dispersing cyclodextrin-amino acid-based fluorescent molecules into deionized water at a concentration of 200 mu M to serve as fluorescent probes; meanwhile, a plurality of 200 mu M different small molecular organic matter solutions are prepared, wherein the different small molecular organic matter solutions respectively comprise aureomycin (CTC), acetic Acid (AC) Glucose (Glucose), ampicillin (Amp), chloramphenicol (CAP), streptomycin (Str), nalidixic acid (Nal), glycine (Gly), histidine (His), phenylalanine (Phe), tryptophan (Trp), trichloroacetamide (TCAM), tetracycline (TC), oxytetracycline (OTC) and Minocycline (MOC), 1mL of the small molecular organic matter solutions are respectively mixed with equal volume of fluorescent probe solutions, after a reaction system is kept stable, a fluorescent spectrum (with a 365nm ultraviolet lamp as an excitation light source) is tested, and the selective recognition capability of the small molecular organic matter solutions is inspected, as shown in FIG. 6, after aureomycin is added, the fluorescent signal of the system is obviously enhanced, the blue shift of an emission peak is simultaneously performed, and the fluorescent response of the system is not obviously changed after other small molecular organic matters are added, so that the method has good selectivity and the specific recognition of the aureomycin-histidine fluorescent probe is realized.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for synthesizing a fluorescent molecule based on cyclodextrin-amino acid, comprising:
adding aldehyde cyclodextrin and amino acid into water to prepare a mixed solution, and sequentially adjusting the pH, heating and stirring, and performing solid-liquid separation to obtain the cyclodextrin-amino acid based fluorescent molecule; the aldehyde cyclodextrin is obtained by pre-oxidizing beta-cyclodextrin with sodium periodate.
2. The method for synthesizing cyclodextrin-amino acid-based fluorescent molecules of claim 1, wherein the method for preparing aldehyde cyclodextrin comprises:
stirring beta-cyclodextrin and sodium periodate in water in a dark place for reaction, performing nanofiltration, stirring and mixing with ethanol until precipitate is separated out, and then sequentially performing filtration, washing and freeze-drying to obtain aldehyde cyclodextrin;
wherein the mol ratio of the beta-cyclodextrin to the sodium periodate is 1 (1-4);
in the light-shielding stirring reaction, the reaction temperature is 30-50 ℃, and the reaction time is 3-5h.
3. The method for synthesizing a fluorescent molecule based on cyclodextrin-amino acid as claimed in claim 1, wherein the molar ratio of aldehyde cyclodextrin to amino acid is 1 (2-6).
4. The method of claim 1, wherein the amino acid comprises at least one of glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine, phenylalanine, tryptophan, or histidine.
5. The method for synthesizing the fluorescent molecule based on cyclodextrin-amino acid as claimed in claim 4, wherein when the amino acid is at least one of glycine, isoleucine, methionine, cysteine, glutamic acid, glutamine, asparagine, arginine, lysine or phenylalanine, the pH of the reaction system is adjusted to 8-9;
when the amino acid is one or two of tryptophan or histidine, the pH value of the reaction system is adjusted to 6-7.
6. The method for synthesizing fluorescent molecules based on cyclodextrin-amino acid as claimed in claim 1, wherein the heating temperature is 60-80 ℃ and the stirring time is 30-60min during the heating and stirring process.
7. The method of claim 1, wherein the solid-liquid separation comprises dialysis and freeze-drying.
8. A fluorescent molecule based on cyclodextrin-amino acids, characterised in that it is synthesized using the method according to any one of claims 1 to 7.
9. Use of a cyclodextrin-amino acid-based fluorescent molecule according to claim 8 as a fluorescent probe for qualitative and/or quantitative detection of aureomycin in a body of water.
10. Use of a cyclodextrin-amino acid-based fluorescent molecule according to claim 9, wherein the detection method comprises the steps of:
1) Drawing a standard curve: respectively mixing and uniformly stirring the fluorescent probe and a plurality of solutions containing aureomycin with different concentrations to obtain a standard solution with the aureomycin concentration range of 0-5 mu M, taking a 365nm ultraviolet lamp as an excitation light source, shooting in a dark environment to obtain a fluorescent image, analyzing a B value and a G value of the image, drawing a standard curve by taking B/G as a vertical coordinate and taking the aureomycin concentration as a horizontal coordinate, and detecting the aureomycin to fit an equation;
2) And (3) detecting the aureomycin in the water sample: and (2) mixing the fluorescent probe with the water sample to be detected by adopting the dosage ratio of the fluorescent probe to the aureomycin solution in the step 1) to obtain a mixed sample, obtaining a fluorescent image by taking a 365nm ultraviolet lamp as an excitation light source, analyzing and calculating to obtain the B/G of the image, and then obtaining the corresponding aureomycin concentration according to a standard curve or a fitting equation.
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