Peach gum polysaccharide polymer dot fluorescence / colorimetric probe as well as preparation method and application thereof

Abstract

The invention discloses a peach gum polysaccharide polymer dot fluorescence / colorimetric probe and a preparation method and application thereof.The preparation method comprises the following steps that peach gum raw materials and 3-aminophenylboronic acid are dissolved in water, the peach gum raw materials are at least one of peach gum polysaccharide, aldehydelated peach gum and carboxylated peach gum, a hydrothermal reaction is conducted, filtering, dialysis and drying are conducted, and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is obtained. The peach gum polysaccharide polymer dot fluorescence / colorimetric probe is obtained. The peach gum polysaccharide polymer dot fluorescence / colorimetric probe prepared by the invention has the advantages of good biocompatibility, strong environmental stability, fluorescence and colorimetric dual response characteristics and the like, and can specifically recognize catechol in a complex environment through multiple detection modes, and finally realize instant, rapid, quantitative and high-sensitivity detection of catechol.

Description

Technical Field

[0001] The invention belongs to the field of biomass conversion and nanosensing, and particularly relates to a peach gum polysaccharide polymer dot fluorescence / colorimetric probe and a preparation method and application thereof. Background Art

[0002] Catechol, a representative derivative of phenol, is widely used in the manufacture of photosensitive chemicals, hair dyes, developers, pesticides, secondary colorants, and flavorings. As a highly toxic and poorly degradable pollutant, catechol is classified as a human carcinogen and a Class II B periodic environmental pollutant due to its potential skin irritation and carcinogenicity to the human central nervous system. The lethal dose of catechol for humans is 50-500 mg / kg, or one ounce for a 70-kg person, posing a significant threat to human safety. Therefore, detecting and quantifying the catechol content in daily drinking water is of great importance. Currently, the main methods for detecting catechol include spectrophotometry, electrochemistry, and high-performance liquid chromatography. However, these methods are highly instrument-dependent, lack portability, and have limited application in the environment.

[0003] Polymer dots (PDOs) are a new type of fluorescent carbon dot, less than 10 nm in size, that retain polymer surface groups while possessing a carbonized core. Compared to organic molecular dyes and traditional semiconductor quantum dots, PDOs offer advantages such as ease of synthesis, low cost, high chemical stability, resistance to photobleaching, good biocompatibility, and low toxicity. They exhibit significant potential in a wide range of fields, including sensing, detection, bioimaging, and medical diagnosis and treatment. Therefore, the development of a PDO fluorescent / colorimetric probe with excellent biocompatibility, strong environmental stability, and both fluorescent and colorimetric responses is of great practical significance for the rapid and accurate detection of catechol in complex environments. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a peach gum polysaccharide polymer dot fluorescence / colorimetric probe with good biocompatibility, strong environmental stability, and dual fluorescence and colorimetric responses, as well as a preparation method and application thereof.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions.

[0006] A method for preparing a peach gum polysaccharide polymer dot fluorescence / colorimetric probe comprises the following steps: dissolving a peach gum raw material and 3-aminophenylboronic acid in water, performing a hydrothermal reaction, filtering, dialyzing, and drying to obtain a peach gum polysaccharide polymer dot fluorescence / colorimetric probe; the peach gum raw material is at least one of peach gum polysaccharide, aldehyde-modified peach gum, and carboxylated peach gum.

[0007] The above preparation method is further improved, wherein the mass ratio of the peach gum raw material to 3-aminophenylboronic acid is 1:0.5-16; the temperature of the hydrothermal reaction is 90°C-180°C, and the time of the hydrothermal reaction is 6h-8h; the filtration is performed using a filter membrane with a pore size of 0.22μm-0.45μm, the dialysis is performed using a dialysis bag with a molecular weight cutoff of 200Da-3500Da, the dialysis time is 12h-24h, and the drying is freeze-drying.

[0008] The above preparation method is further improved. The preparation method of the aldehyde-modified peach gum is specifically as follows: peach gum polysaccharide, sodium periodate and water are mixed, reacted, and dialyzed to obtain aldehyde-modified peach gum; the mass ratio of the peach gum polysaccharide to sodium periodate is 1:1-3, and the mass volume ratio of the peach gum polysaccharide to water is 1g:30mL-80mL; the reaction time is 1h-5h, and the reaction is carried out under light-proof conditions;

[0009] The preparation method of the carboxylated peach gum is specifically as follows: peach gum polysaccharide and an organic solvent are mixed, 4-dimethylaminopyridine and succinic anhydride are added, reacted, and washed and dried to obtain the carboxylated peach gum; the mass ratio of the peach gum polysaccharide, 4-dimethylaminopyridine, and succinic anhydride is 1:0.5-1.5:1-4, the mass volume ratio of the peach gum polysaccharide to the organic solvent is 1g:5mL-20mL, and the organic solvent is N,N-dimethylformamide; the mixing temperature is 50°C-90°C, the reaction temperature is 45°C-75°C, the reaction time is 8h-12h, and the reaction is carried out under an argon atmosphere.

[0010] As a general technical concept, the present invention also provides a peach gum polysaccharide polymer dot fluorescent / colorimetric probe prepared by the above-mentioned preparation method of the peach gum polysaccharide polymer dot fluorescent / colorimetric probe.

[0011] The above-mentioned peach gum polysaccharide polymer dot fluorescence / colorimetric probe is further improved. The particle size of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is 1nm to 10nm, the emission peak of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is 475nm to 575nm, and the fluorescence of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is green fluorescence.

[0012] As a general technical concept, the present invention also provides a use of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe in detecting catechol.

[0013] The above application is further improved, wherein the detection method (1) comprises the following steps:

[0014] (1.1) Mixing peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution;

[0015] (1.2) mixing the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (1.1) with catechol solutions of different concentrations to obtain mixed solutions, performing fluorescence detection, and establishing a linear equation for the fluorescence intensity of the mixed solution and the catechol concentration based on the linear relationship between the fluorescence intensity of the mixed solution and the concentration of catechol in the catechol solution;

[0016] (1.3) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (1.1) to obtain a mixed solution to be tested, detecting the fluorescence intensity of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested according to the detection linear equation obtained in step (1.2), thereby realizing the detection of catechol in water;

[0017] Alternatively, the detection method (ii) comprises the following steps:

[0018] (2.1) Mixing peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution;

[0019] (2.2) mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution obtained in step (2.1) with catechol solutions of different concentrations to obtain mixed solutions, performing UV detection, and establishing a linear equation for the relationship between the UV absorbance of the mixed solution and the catechol concentration in the catechol solution based on the linear relationship between the UV absorbance of the mixed solution and the catechol concentration;

[0020] (2.3) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (2.1) to obtain a mixed solution to be tested, detecting the ultraviolet absorbance of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested according to the detection linear equation obtained in step (2.2), thereby realizing the detection of catechol in water;

[0021] Alternatively, the detection method (iii) comprises the following steps:

[0022] (3.1) Mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain a peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution;

[0023] (3.2) Mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution obtained in step (3.1) with catechol solutions of different concentrations to obtain mixed solutions, performing RGB identification, and establishing a linear equation for the detection of the RGB parameters of the mixed solution and the catechol concentration based on the linear correspondence between the RGB parameters of the mixed solution and the catechol concentration in the catechol solution;

[0024] (3.3) Mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (3.1) to obtain a mixed solution to be tested, detecting the RGB parameters of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested based on the detection linear equation obtained in step (3.2), thereby realizing the detection of catechol in water.

[0025] The above application is further improved, in the detection method (I), the detection linear equation of the fluorescence intensity of the mixed solution and the catechol concentration is shown in formula (1);

[0026] F / F0=0.9577-0.0096C cc (1);

[0027] In formula (1), F is the fluorescence intensity of the mixed solution, F0 is the fluorescence intensity of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution, that is, F / F0 is the fluorescence intensity ratio of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9919, the linear range of catechol detection is 0-72 μM, and the minimum detection limit is 0.25 nM.

[0028] The above application is further improved, in the detection method (II), the detection linear equation of the ultraviolet absorbance of the mixed solution and the catechol concentration is shown in formula (2);

[0029] A 490 =0.0423+0.0033C cc (2);

[0030] In formula (2), A 490 is the UV absorbance of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9901, the linear range of catechol detection was 0-81 μM, and the minimum detection limit was 4.9 nM.

[0031] The above application is further improved, in the detection method (III), the detection linear equation of the mixed solution RGB parameters and catechol concentration is shown in formula (3);

[0032] Y=668.21-2.40x (3);

[0033] In formula (3), Y is the RGB parameter of the mixed solution, x is the concentration of catechol in the catechol solution, the unit is μM, and the correlation coefficient R is 2 =0.9917, the linear range of catechol detection was 0-162 μM, and the minimum detection limit was 2.18 μM.

[0034] Compared with the prior art, the advantages of the present invention are:

[0035] The present invention provides a method for preparing a peach gum polysaccharide polymer dot fluorescent / colorimetric probe. Using a hyperbranched peach gum raw material (peach gum polysaccharide, aldehyde-modified peach gum, or carboxylated peach gum) and 3-aminophenylboronic acid as a carbon precursor, a hydrothermal reaction is performed to prepare a core-shell structured peach gum polysaccharide polymer dot fluorescent / colorimetric probe. This preparation method, on the one hand, utilizes a polymer material, allowing the resulting polymer dot to retain polymer chains on its surface, resulting in excellent biocompatibility and low biotoxicity. On the other hand, the introduction of the boronic acid group from 3-aminophenylboronic acid imparts the polymer dot with the ability to capture catechol, further enhanced by the electronegativity of the benzene ring. Furthermore, nitrogen doping modulates the intrinsic electronic and surface properties of the polymer dot, imparting high catalytic activity to the polymer dot, thereby demonstrating specific recognition of catechol and catalytic colorimetric properties. The preparation method of the present invention has the advantages of low cost, simple preparation, and environmental friendliness. The peach gum polysaccharide polymer dot fluorescence / colorimetric probe prepared therefrom has the advantages of good biocompatibility, strong environmental stability, and dual fluorescence and colorimetric response characteristics. It can specifically identify catechol in complex environments, and ultimately achieve instant, rapid, quantitative, and highly sensitive detection of catechol. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a transmission electron microscopy image of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention.

[0037] Figure 2 This is a Fourier transform infrared spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention.

[0038] Figure 3 The UV-vis spectrum, fluorescence excitation and emission spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention.

[0039] Figure 4This is the UV-vis spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) and catechol (CC) in Example 4 of the present invention.

[0040] Figure 5 This is a linear equation diagram for detecting the fluorescence intensity of a mixed solution of peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) and catechol (CC) versus catechol concentration in Example 4 of the present invention.

[0041] Figure 6 This is a linear equation diagram for detecting the ultraviolet absorbance of a mixed solution of peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) and catechol (CC) and the catechol concentration in Example 5 of the present invention.

[0042] Figure 7 This is a linear equation diagram for detecting the RGB parameters of a mixed solution of peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) and catechol (CC) and the catechol concentration in Example 6 of the present invention. DETAILED DESCRIPTION

[0043] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but the scope of protection of the present invention is not limited thereby. The materials and instruments used in the following examples are all commercially available.

[0044] Example 1:

[0045] A method for preparing a peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention comprises the following steps:

[0046] Peach gum polysaccharide (PGP) and 3-aminophenylboronic acid were dissolved in water at a mass ratio of 1:0.5 and stirred until completely dissolved to obtain a mixed solution. The mixed solution was transferred to a 50 mL stainless steel reactor lined with polypropylene, reacted at 120°C for 8 h, and cooled to room temperature to obtain a reaction product. The reaction product was filtered through a 0.22 μM filter membrane and transferred to a dialysis bag (molecular weight cutoff 500 Da) for dialyzation for 12 h. The dialyzate was then rotary evaporated and freeze-dried to obtain peach gum polysaccharide polymer dot fluorescent / colorimetric probe, denoted as B,N-CPDs.

[0047] The peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in this example has a particle size of 1 nm to 10 nm, an emission peak at 475 nm to 575 nm, and green fluorescence.

[0048] Figure 1 This is a transmission electron microscopy image of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention. Figure 1It shows that the B,N-CPDs prepared in the present invention have uniform and well-dispersed particles, are approximately spherical, and have a particle size of about 3.3 nm.

[0049] Figure 2 This is a Fourier transform infrared spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention. Figure 2 The results show that the infrared spectra of peach gum polysaccharide (PGP) and B, N-CPDs have similar characteristic peaks, indicating that the B, N-CPDs prepared by the present invention retain the polymer structure of PGP and successfully prepare peach gum polysaccharide polymer dots; in addition, the peaks at 3386, 1565, and 1331 cm -1 There are nitrogen-containing groups (-NH, CN) at 1166 cm -1 The characteristic peak of BC stretching vibration was observed at , confirming the successful doping of B and N elements.

[0050] Figure 3 The UV-vis spectrum, fluorescence excitation and emission spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) prepared in Example 1 of the present invention. Figure 3 The UV absorption spectrum of B,N-CPDs (blue) is shown, revealing a distinct absorption peak around 275 nm. This peak is attributed to the carbonization of B,N-CPDs, which forms C=C bonds and causes π-π* transitions. The optimal excitation (pink) and emission wavelengths (violet) for B,N-CPDs are 490 nm and 532 nm, respectively, indicating that the detected fluorescence of B,N-CPDs is green.

[0051] In this example, peach gum polysaccharide polymer dot fluorescence / colorimetric probes with different mass ratios were also prepared. The preparation method was basically the same as the preparation method of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B,N-CPDs) in Example 1, with the only difference being that the mass ratios of peach gum polysaccharide to 3-aminophenylboronic acid were 1:1, 1:2, 1:4, 1:8, and 1:16, respectively.

[0052] Example 2:

[0053] A method for preparing a peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention comprises the following steps:

[0054] (1) Preparation of aldehyde-modified peach gum

[0055] Take 1g of peach gum polysaccharide and dissolve it in 50mL of deionized water, stir until the peach gum polysaccharide is completely dissolved; then add 1.5g of sodium periodate, stir at room temperature in the dark for 3h, and load the obtained product into a 1000Da dialysis membrane and dialyze it in the dark for 24h to obtain aldehyde-modified peach gum, which is recorded as OPGP.

[0056] (2) The aldehyde-modified peach gum (OPGP) and 3-aminophenylboronic acid obtained in step (1) were dissolved in water at a mass ratio of 1:0.5, and stirred until completely dissolved to obtain a mixed solution; the mixed solution was transferred to a 50 mL stainless steel reactor lined with polypropylene, reacted at 120°C for 8 h, and cooled to room temperature to obtain a reaction product; the reaction product was filtered with a 0.22 μM filter membrane, transferred to a dialysis bag (molecular weight cutoff 500 Da) and dialyzed for 12 h, and then the dialyzate was rotary evaporated and freeze-dried to obtain a peach gum polysaccharide polymer dot fluorescence / colorimetric probe, which was recorded as B,N-CPDs-1.

[0057] In this example, peach gum polysaccharide polymer dot fluorescence / colorimetric probes with different mass ratios were also prepared. The preparation method was basically the same as the preparation method of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B,N-CPDs-1) in Example 2, with the only difference being that in step (2), the mass ratios of aldehyded peach gum and 3-aminophenylboronic acid were 1:1, 1:2, 1:4, 1:8, and 1:16, respectively.

[0058] Example 3:

[0059] A method for preparing a peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention comprises the following steps:

[0060] (1) Preparation of carboxylated peach gum

[0061] 1 g of peach gum polysaccharide was dissolved in 10 mL of N,N-dimethylformamide (DMF) and heated to 70°C until the peach gum polysaccharide was completely dissolved. 0.9 g of 4-dimethylaminopyridine and 1.5 g of succinic anhydride were then added, and argon was introduced. The mixture was stirred at 55°C for 10 h. The resulting product was washed several times with ethanol and then centrifuged to remove the supernatant. The solid product was dried in a vacuum drying oven at 60°C overnight to obtain carboxylated peach gum, which was recorded as HPGP.

[0062] (2) The carboxylated peach gum (HPGP) and 3-aminophenylboronic acid obtained in step (1) were dissolved in water at a mass ratio of 1:0.5, and stirred until completely dissolved to obtain a mixed solution; the mixed solution was transferred to a 50 mL stainless steel reactor lined with polypropylene, reacted at 120°C for 8 h, and cooled to room temperature to obtain a reaction product; the reaction product was filtered with a 0.22 μM filter membrane, transferred to a dialysis bag (molecular weight cutoff 500 Da) and dialyzed for 12 h, and then the dialyzate was rotary evaporated and freeze-dried to obtain a peach gum polysaccharide polymer dot fluorescence / colorimetric probe, recorded as B,N-CPDs-2.

[0063] In this example, peach gum polysaccharide polymer dot fluorescence / colorimetric probes with different mass ratios were also prepared. The preparation method was basically the same as the preparation method of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B,N-CPDs-2) in Example 3, with the only difference being that in step (2), the mass ratios of carboxylated peach gum and 3-aminophenylboronic acid were 1:1, 1:2, 1:4, 1:8, and 1:16, respectively.

[0064] Example 4:

[0065] An application of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention in detecting catechol comprises the following steps:

[0066] (1) The peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B,N-CPDs) in Example 1 was dissolved in PBS buffer solution with a pH of 8-12 to obtain a peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution with a concentration of 0.5 mg mL -1 100 μL of peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution was added to 3 mL of catechol solutions of different concentrations, with the concentration range of the catechol solution being 0 to 288 μM (interval of 12 μM). The mixture was reacted for 4 minutes to obtain a mixed solution. Fluorescence detection was performed to obtain the fluorescence intensity of the mixed solution under different catechol concentration conditions. Based on the linear relationship between the fluorescence intensity of the mixed solution and the concentration of catechol in the catechol solution, a linear equation for the fluorescence intensity of the mixed solution and the concentration of catechol was established. Figure 5 , as shown in formula (1).

[0067] F / F0=0.9577-0.0096C cc (1);

[0068] In formula (1), F is the fluorescence intensity of the mixed solution, F0 is the fluorescence intensity of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution, that is, F / F0 is the fluorescence intensity ratio of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9919, the linear range of catechol detection is 0-72 μM, and the minimum detection limit is 0.25 nM.

[0069] (2) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe to obtain a mixed solution to be tested; detecting the fluorescence intensity of the mixed solution to be tested, and calculating the concentration of catechol in the catechol solution to be tested according to the detection linear equation obtained in step (1), thereby achieving quantitative detection of catechol in water.

[0070] Figure 4This is the UV-vis spectrum of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe (B, N-CPDs) and catechol (CC) in Example 4 of the present invention. Figure 4 In the figure, B,N-CPDs represents the peach gum polysaccharide polymer dot fluorescence / colorimetric probe, CC represents catechol, and B,N-CPDs+CC represents the mixed solution of peach gum polysaccharide polymer dot fluorescence / colorimetric probe and catechol. Figure 4 It can be seen that after CC and B,N-CPDs are mixed, the solution changes from colorless to pink, and a new ultraviolet absorption peak appears at 500 nm, indicating that the two interact to generate a color-developing substance.

[0071] Example 5:

[0072] An application of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention in detecting catechol comprises the following steps:

[0073] (1) Take 100 μL of 0.5 mg mL -1 The peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution, which is the same as the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution in Example 4, was added to 3 mL of catechol solutions of different concentrations, the concentration range of the catechol solution was 0 to 198 μM (interval of 9 μM), and the reaction was carried out for 2 minutes to obtain a mixed solution. The ultraviolet detection was performed to obtain the ultraviolet absorbance of the mixed solution under different catechol concentration conditions; based on the linear correspondence between the ultraviolet absorbance of the mixed solution and the concentration of catechol in the catechol solution, a linear equation for the detection of the ultraviolet absorbance of the mixed solution and the catechol concentration was established, see Figure 6 , as shown in formula (2).

[0074] A 490 =0.0423+0.0033C cc (2);

[0075] In formula (2), A 490 is the UV absorbance of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9901, the linear range of catechol detection was 0-81 μM, and the minimum detection limit was 4.9 nM.

[0076] (2) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe to obtain a mixed solution to be tested; detecting the ultraviolet absorbance of the mixed solution to be tested, and calculating the concentration of catechol in the catechol solution to be tested according to the detection linear equation obtained in step (1), thereby achieving quantitative detection of catechol in water.

[0077] Example 6:

[0078] An application of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe of the present invention in detecting catechol comprises the following steps:

[0079] (1) Take 100 μL of 0.5 mg mL -1 The peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution, which is the same as the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution in Example 4, was added to 3 mL of catechol solutions of different concentrations, the concentration range of the catechol solution was 0 to 207 μM (interval of 9 μM), and the reaction was carried out for 2 minutes to obtain a mixed solution. Color recognition was performed and RGB parameters were recorded to obtain RGB parameters of the mixed solution under different catechol concentration conditions; based on the linear correspondence between the RGB parameters of the mixed solution and the concentration of catechol in the catechol solution, a linear equation for the detection of the RGB parameters of the mixed solution and the catechol concentration was established, see Figure 7 , as shown in formula (1).

[0080] Y=668.21-2.40x (3);

[0081] In formula (3), Y is the RGB parameter of the mixed solution, x is the concentration of catechol in the catechol solution, the unit is μM, and the correlation coefficient R is 2 =0.9917, the linear range of catechol detection was 0-162 μM, and the minimum detection limit was 2.18 μM.

[0082] (2) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe to obtain a mixed solution to be tested; detecting the RGB parameters of the mixed solution to be tested, and calculating the concentration of catechol in the catechol solution to be tested according to the detection linear equation obtained in step (1), thereby achieving quantitative detection of catechol in water.

[0083] The above description is only a preferred embodiment of the present invention and does not constitute any formal limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the spirit and technical solution of the present invention, use the methods and technical contents disclosed above to make many possible changes and modifications to the technical solution of the present invention, or modify it into an equivalent embodiment of equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention, still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing a peach gum polysaccharide polymer dot fluorescence / colorimetric probe, characterized in that: The method comprises the following steps: dissolving peach gum raw material and 3-aminophenylboronic acid in water, carrying out hydrothermal reaction, filtering, dialyzing and drying to obtain peach gum polysaccharide polymer dot fluorescence / colorimetric probe; the peach gum raw material is at least one of peach gum polysaccharide, aldehyde-modified peach gum and carboxylated peach gum.

2. The method for preparing the peach gum polysaccharide polymer dot fluorescence / colorimetric probe according to claim 1, characterized in that: The mass ratio of the peach gum raw material to 3-aminophenylboronic acid is 1:0.5-16; the temperature of the hydrothermal reaction is 90°C-180°C, and the time of the hydrothermal reaction is 6h-8h; the filtration is performed using a filter membrane with a pore size of 0.22μm-0.45μm, the dialysis is performed using a dialysis bag with a molecular weight cutoff of 200Da-3500Da, the dialysis time is 12h-24h, and the drying is freeze-drying.

3. The method for preparing the peach gum polysaccharide polymer dot fluorescence / colorimetric probe according to claim 1, characterized in that: The preparation method of the aldehyde-modified peach gum comprises the following steps: mixing peach gum polysaccharide, sodium periodate and water, reacting the mixture, and dialyzing the mixture to obtain the aldehyde-modified peach gum; the mass ratio of the peach gum polysaccharide to the sodium periodate is 1:1-3, and the mass volume ratio of the peach gum polysaccharide to the water is 1 g:30 mL-80 mL; the reaction time is 1 h-5 h, and the reaction is carried out in a dark environment; The preparation method of the carboxylated peach gum is specifically as follows: peach gum polysaccharide and an organic solvent are mixed, 4-dimethylaminopyridine and succinic anhydride are added, reacted, and washed and dried to obtain the carboxylated peach gum; the mass ratio of the peach gum polysaccharide, 4-dimethylaminopyridine, and succinic anhydride is 1:0.5-1.5:1-4, the mass volume ratio of the peach gum polysaccharide to the organic solvent is 1g:5mL-20mL, and the organic solvent is N,N-dimethylformamide; the mixing temperature is 50°C-90°C, the reaction temperature is 45°C-75°C, the reaction time is 8h-12h, and the reaction is carried out under an argon atmosphere. 4 . A peach gum polysaccharide polymer dot fluorescent / colorimetric probe prepared by the method for preparing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe according to any one of claims 1 to 3 .

5. The peach gum polysaccharide polymer dot fluorescence / colorimetric probe according to claim 4, characterized in that: The particle size of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is 1nm-10nm, the emission peak of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is 475nm-575nm, and the fluorescence of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe is green fluorescence.

6. Use of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe as claimed in claim 4 or 5 in detecting catechol.

7. The use according to claim 6, characterized in that The detection method (1) comprises the following steps: (1.1) Mixing peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution; (1.2) mixing the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (1.1) with catechol solutions of different concentrations to obtain mixed solutions, performing fluorescence detection, and establishing a linear equation for the fluorescence intensity of the mixed solution and the catechol concentration based on the linear relationship between the fluorescence intensity of the mixed solution and the concentration of catechol in the catechol solution; (1.3) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (1.1) to obtain a mixed solution to be tested, detecting the fluorescence intensity of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested according to the detection linear equation obtained in step (1.2), thereby realizing the detection of catechol in water; Alternatively, the detection method (ii) comprises the following steps: (2.1) Mixing peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution; (2.2) mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution obtained in step (2.1) with catechol solutions of different concentrations to obtain mixed solutions, performing UV detection, and establishing a linear equation for the relationship between the UV absorbance of the mixed solution and the catechol concentration in the catechol solution based on the linear relationship between the UV absorbance of the mixed solution and the catechol concentration; (2.3) mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (2.1) to obtain a mixed solution to be tested, detecting the ultraviolet absorbance of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested according to the detection linear equation obtained in step (2.2), thereby realizing the detection of catechol in water; Alternatively, the detection method (iii) comprises the following steps: (3.1) Mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe and PBS buffer to obtain a peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution; (3.2) Mixing the peach gum polysaccharide polymer dot fluorescent / colorimetric probe solution obtained in step (3.1) with catechol solutions of different concentrations to obtain mixed solutions, performing RGB identification, and establishing a linear equation for the detection of the RGB parameters of the mixed solution and the catechol concentration based on the linear correspondence between the RGB parameters of the mixed solution and the catechol concentration in the catechol solution; (3.3) Mixing the catechol solution to be tested and the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution obtained in step (3.1) to obtain a mixed solution to be tested, detecting the RGB parameters of the mixed solution to be tested, and calculating the catechol concentration in the catechol solution to be tested based on the detection linear equation obtained in step (3.2), thereby realizing the detection of catechol in water.

8. The use according to claim 7, characterized in that In the detection method (1), the detection linear equation of the fluorescence intensity of the mixed solution and the catechol concentration is shown in formula (1); F / F0=0.9577-0.0096C cc (1); In formula (1), F is the fluorescence intensity of the mixed solution, F0 is the fluorescence intensity of the peach gum polysaccharide polymer dot fluorescence / colorimetric probe solution, that is, F / F0 is the fluorescence intensity ratio of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9919, the linear range of catechol detection is 0-72 μM, and the minimum detection limit is 0.25 nM.

9. The use according to claim 7, characterized in that In the detection method (II), the detection linear equation of the mixed solution ultraviolet absorbance and catechol concentration is shown in formula (2); A 490 =0.0423+0.0033C cc (2); In formula (2), A 490 is the UV absorbance of the mixed solution, C cc is the concentration of catechol in the catechol solution, in μM, and the correlation coefficient R 2 =0.9901, the linear range of catechol detection was 0-81 μM, and the minimum detection limit was 4.9 nM.

10. The use according to claim 7, characterized in that In the detection method (III), the detection linear equation of the mixed solution RGB parameters and catechol concentration is shown in formula (3); Y=668.21-2.40x (3); In formula (3), Y is the RGB parameter of the mixed solution, x is the concentration of catechol in the catechol solution, the unit is μM, and the correlation coefficient R is 2 =0.9917, the linear range of catechol detection was 0-162 μM, and the minimum detection limit was 2.18 μM.

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