CN112782104B - Platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid and preparation method and application thereof - Google Patents

Platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid and preparation method and application thereof Download PDF

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CN112782104B
CN112782104B CN201911089717.7A CN201911089717A CN112782104B CN 112782104 B CN112782104 B CN 112782104B CN 201911089717 A CN201911089717 A CN 201911089717A CN 112782104 B CN112782104 B CN 112782104B
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杨勇
程琴
杨莉莉
彭宇思
姚秀敏
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention discloses a platinum dendritic nanoparticle for visually and rapidly detecting ascorbic acid, and a preparation method and application thereof. The preparation method adopts a liquid phase synthesis method, polyvinylpyrrolidone is used as a surface end-capping agent, hydrochloric acid is used as an oxidation etching agent, and H is used as H2PtCl6·6H2O and HAuCl4·4H2And O is used as a precursor to prepare the Pt-Au DNPs. The invention also establishes a method for detecting the ascorbic acid by a colorimetric method, and can be widely applied to the detection of the ascorbic acid in foods and medicines.

Description

Platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and relates to platinum dendritic nanoparticles (Pt-Au DNPs) with high oxidation-simulated enzyme activity for detecting the content of Ascorbic Acid (AA) by catalytic oxidation of TMB, a preparation method and application thereof, which can be directly applied to visual rapid detection of ascorbic acid in food and environmental samples.
Background
Ascorbic acid is a nutrient essential to human body, and has effects of maintaining immune function, preventing gingival bleeding, and promoting metabolism of certain amino acids. However, the human body cannot self-synthesize ascorbic acid, and must be ingested from food, and both excessive intake and lack of intake can cause some diseases. Currently, the main sources of ascorbic acid required by the human body are vegetables and fruits. Therefore, it is very important to accurately know the content of ascorbic acid in food and medicine by a simple method.
At present, the main methods for measuring ascorbic acid are: gas chromatography, fluorescence, electrophoresis and the like, which have the disadvantages of complex process, time consumption and high cost. Therefore, it is very important to develop a method which is efficient, economical and easy to operate. Among all detection methods, the colorimetric method has unique advantages, intuitively displays the content of a substance to be detected through the change of the color of a reactant based on the relation between the color of the substance and the light absorption, has high sensitivity and low cost, and has the characteristic of visualization. Chinese patent (CN201811434227.1) uses Ag (I) ions to make 3,3 ', 5, 5' -tetramethyl benzidine (TMB) generate oxidation reaction to generate blue TMB imine salt, then adds a trace amount of reducing agent ascorbic acid to make the blue color of the system become light, and the degree of lightening is in direct proportion to the concentration of ascorbic acid, so the detection limit is 0.6 mu M according to the detection of ascorbic acid, and the sensitivity is lower. Chinese patent (CN201811435210.8) considers that Ce (IV) ions can cause oxidation reaction of 3,3 ', 5, 5' -Tetramethylbenzidine (TMB) to generate blue TMB imine salt, thereby establishing a color development system to detect ascorbic acid, and the detection limit is low, but the recovery of Ce (IV) is difficult to realize by virtue of the oxidation performance of the ions. Pradeep Kumar Yadav (Acs Biomaterials Science & Engineering,5(2019)623-632.) utilizes a synthesized carbon quantum dot with catalase-like activity to catalyze and oxidize 3,3 ', 5, 5' -Tetramethylbenzidine (TMB), a colorimetric ascorbic acid detection system is established, the selectivity is good, but unstable hydrogen peroxide needs to be added in the detection process to influence the detection stability.
Disclosure of Invention
The invention aims to provide a stable and accurate method for detecting Ascorbic Acid (AA), and synthesizes platinum dendritic nanoparticles (Pt-Au DNPs), the preparation method is simple to operate, the prepared nanoparticles have good oxidase-like activity, and the established colorimetric method has good selectivity and high sensitivity.
The invention provides a preparation method of platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid, which adopts a liquid phase synthesis method, takes polyvinylpyrrolidone as a surface capping agent, hydrochloric acid as an oxidation etching agent and H2PtCl6·6H2O and HAuCl4·4H2O is used as a precursor to prepare the platinum dendritic nano-particleThe daughter Pt-Au DNPs.
Preferably, the preparation method of the platinum dendritic nanoparticles Pt-Au DNPs comprises the following steps:
(1) adding ethylene glycol, stirring, condensing and refluxing under the heating condition of 170-200 ℃, and then adding hydrochloric acid; the volume of the hydrochloric acid accounts for 10-15% of the volume of the ethylene glycol;
(2) then, adding a precursor solution and a polyvinylpyrrolidone solution; the precursor solution is prepared from H2PtCl6·6H2O and HAuCl4·4H2The O solution is composed of 5: 1-9: 1 in volume ratio; the precursor solution accounts for 10 to 15 percent of the volume of the total reaction solution; the polyvinylpyrrolidone solution is a solution of polyvinylpyrrolidone with the concentration of 0.02-0.04M in glycol; the polyvinylpyrrolidone solution accounts for 35-50% of the total volume of the reaction solution;
(3) the reaction is carried out at the temperature of 170-200 ℃, and the solution turns black after the reaction is carried out for 18-25 min;
(4) and after the reaction is finished, naturally cooling to room temperature, and alternately centrifuging and washing the acetone and the ethanol to obtain a sample.
Preferably, said H2PtCl6·6H2O and HAuCl4·4H2The concentration of the O solution is 0.05-0.07M respectively; preferably, said H2PtCl6·6H2O and HAuCl4·4H2The concentration of the O solution was the same.
Preferably, the concentration of the hydrochloric acid is 30 to 37 wt%.
Preferably, the condensing reflux time is 4-8 min.
Preferably, the precursor solution and the polyvinylpyrrolidone solution are added once every 25-45 s, and the process needs to be completed within 4-7 min.
Preferably, the preparation method further comprises: the sample was ultrasonically dispersed into the dispersant.
Preferably, the method further comprises the following steps: a step of ultrasonically dispersing a sample into a dispersant; preferably, the dispersant is ethanol or water; more preferably, the time for ultrasonically dispersing the sample is 20-30 min; further preferably, the dispersion concentration of the sample in the dispersant is 0.25 mg/mL-1 mg/mL.
The preparation method of the platinum dendritic nanoparticles is simple, and the product dispersibility is good.
In a second aspect, the invention provides platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid, which are obtained by the preparation method.
In a third aspect, the invention further provides an application of the platinum dendritic nanoparticles in colorimetric ascorbic acid detection.
Preferably, the detection method comprises: mixing 3,3 ', 5, 5' -Tetramethylbenzidine (TMB) solution, platinum dendritic nanoparticle solution and acetic acid-sodium acetate buffer solution for reaction, adding ascorbic acid solutions with different amounts respectively, measuring absorbance respectively, constructing a linear relation between the absorbance and the ascorbic acid concentration, and detecting the ascorbic acid with unknown concentration by using the linear relation.
Preferably, the pH of the mixed reaction solution is 3.5 to 4.5, preferably 4.0.
Preferably, the concentration of the platinum dendritic nanoparticles in the mixed reaction solution is 10-20 μ g/mL, preferably 15 μ g/mL.
Preferably, the reaction temperature is 30-40 ℃, and preferably 35 ℃; the reaction time is 8-12 min, preferably 10 min.
Preferably, the concentration of the acetic acid-sodium acetate buffer solution is 0.2M, and the pH value is 3.5-4.5.
The platinum dendritic nanoparticles (Pt-Au DNPs) have the following advantages:
(1) the preparation method (liquid phase synthesis method) adopted by the invention is simple, and the product has uniform size, good dispersibility and good stability.
(2) Has excellent oxidase-like activity, the Michaelis constant Km of catalyzing TMB oxidation can be 0.22mM, the maximum reaction rate Vmax can reach 282nM S-1
(3) The detection limit of the detection method can be 78nM, and the selectivity is good.
Drawings
FIG. 1 is a transmission electron microscope image of platinum dendritic nanoparticles (Pt-Au DNPs) according to the present invention; wherein, the graph a is a morphology graph of Pt-Au DNPs, the graph b is an HAADF-STEM photo of the Pt-Au DNPs, the graph b-1 is a platinum element surface scanning graph, and the graph b-2 is a gold element surface scanning graph.
FIG. 2 is a graph showing the results of the oxidase-like activity experiments of platinum dendritic nanoparticles (Pt-Au DNPs) according to the present invention.
FIG. 3 is a graph showing the results of the catalytic reaction kinetics of platinum dendritic nanoparticles (Pt-Au DNPs) according to the present invention, wherein a is a Michaelis-Menten curve, and b is a Lineweaver-Burk reciprocal double curve.
FIG. 4 is a schematic diagram of the platinum dendritic nanoparticles (Pt-Au DNPs) for colorimetric AA detection.
FIG. 5 is a diagram showing the results of the selectivity of platinum dendritic nanoparticles (Pt-Au DNPs) for colorimetric AA detection.
FIG. 6 is a standard curve diagram of platinum dendritic nanoparticles (Pt-Au DNPs) for colorimetric AA detection according to the present invention.
FIG. 7 is a graph showing the AA degradation catalyzed by platinum dendritic nanoparticles (Pt-Au DNPs) according to the present invention.
FIG. 8 is a graph showing the effect of different concentrations of PVP on the catalytic oxidation of TMB by platinum dendritic nanoparticles (Pt-Au DNPs) according to the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention discloses a platinum nanoparticle for visually and rapidly detecting ascorbic acid. The method adopts a liquid phase synthesis method, takes polyvinylpyrrolidone (PVP) as a surface end capping agent, takes hydrochloric acid with a certain concentration as an oxidation etching agent, and prepares platinum dendritic nanoparticles (Pt-Au DNPs) by regulating and controlling the conditions of precursor proportion, reaction temperature and the like. The preparation method is simple, and the product has good dispersibility.
Polyvinylpyrrolidone, PVP for short, is a commonly used stabilizer in the controllable preparation of noble metal nanostructures to prevent the agglomeration of particles; also commonly referred to as a surface covering agent, can guide an anisotropic growth process, and for platinum metal, PVP is preferentially adsorbed on a {100} crystal plane or a {111} crystal plane, and the proportion of PVP adsorbed on different crystal planes is different according to the proportion of PVP and a reactant. Thus, by varying the concentration of PVP, the morphology of the seed and its process of anisotropic growth can be controlled.
The growth process of the nanocrystals (i.e. platinum dendritic nanoparticles) can be generally divided into 3 stages: the metal ions are reduced to form nuclei; evolution of the nucleus particles to seeds; the seed crystal grows into the final nanocrystal. Researches find that the oxidation etching effect can influence any one of the three processes through the control of conditions, so that the shape of the final product is regulated and controlled. The oxidation etching process is a process of oxidizing zero-valent metal atoms obtained by reduction into metal ions, oxygen and chloride ion pairs (O)2/Cl-) An oxide etch may be induced.
The preparation method of platinum dendritic nanoparticles for visual rapid detection of ascorbic acid is exemplarily described below.
In some embodiments, the platinum dendritic nanoparticles (Pt-Au DNPs) are prepared by:
firstly, adding ethylene glycol, stirring, and carrying out condensation reflux for 4-8 min under heating of 170-200 ℃ in an oil bath. In some embodiments, the ethylene glycol is added in an amount of 2 to 4 mL.
Then, hydrochloric acid which accounts for 10-15% of the volume ratio of the ethylene glycol and has the concentration of 30-37 wt% is added. Hydrochloric acid as oxidizing etching agent to oxidize the reduced zero-valent metal atom into metal ion, oxygen and chlorine ion pair (O)2/Cl-) Can induce the oxidation etching effect, thereby controlling the appearance. The proper amount of hydrochloric acid can maintain the oxide etching speed in a good range.
Then, the precursor mixed solution and the PVP-ethylene glycol solution were added. The precursor mixed solution is prepared from H2PtCl6·6H2O and HAuCl4·4H2And (4) O solution. H2PtCl6·6H2O and HAuCl4·4H2The concentration of the O solution is consistent, and both the O solution and the O solution can be 0.05-0.07M. H2PtCl6·6H2O:HAuCl4·4H2The volume ratio of the O solution can be (5-9):1, and is preferably 5: 1. The proper proportion of the precursor solution is beneficial to regulating and controlling the activity of the similar oxidase of the Pt-Au DNPs. The concentration of the PVP glycol solution is 0.02-0.04M, and the PVP glycol solution accounts for 35-50% of the volume of the total reaction solution, and preferably 50%. For metal platinum, PVP is preferentially adsorbed on a {100} crystal face or a {111} crystal face, and the proportion of PVP adsorbed on different crystal faces is different with the proportion of PVP and reactants. Thus, by varying the concentration of PVP, the morphology of the seed and its process of anisotropic growth can be controlled. In some embodiments, the precursor solution and PVP solution are added once every 30s, completing the process within 5 min.
The reaction is carried out at 170-200 ℃, and the solution turns black after the reaction is carried out for 18-25 min.
And after the reaction is finished, naturally cooling to room temperature, and alternately centrifuging and washing the acetone and the ethanol to obtain a sample. In some embodiments, the sample is ultrasonically dispersed into an ethanol dispersant. In some embodiments, the dispersant may be ethanol or water. The time for dispersing the sample by ultrasonic can be 20-30 min. The dispersion concentration of the sample in the dispersing agent can be 0.25-1 mg/mL.
The method has short reaction time, the average reaction time is about 20min, and the method is different from the method of controlling the morphology by CTAB singly, the PVP and HCl act simultaneously, in the reaction process, the additive plays a main role, the deposition rate and the diffusion rate are controlled simultaneously, the anisotropic growth process of the seed crystal is induced, the growth process becomes a process of dynamic control, and the reaction process is clear and controllable.
The morphology and performance of the prepared platinum dendritic nanoparticle (Pt-Au DNPs) catalyst are characterized.
The performance characterization result shows that the material has good oxidase-like activity, can catalyze TMB to oxidize to generate a blue product (ox-TMB), can reduce the ox-TMB by AA, can detect AA by a colorimetric method established on the basis, and has good sensitivity.
TMB is used as a chromogenic substrate, the oxidase-like activity of platinum dendritic nanoparticles (Pt-Au DNPs) is tested, the reaction conditions are optimized, and the platinum dendritic nanoparticles have good performance when reacting for 10min at 35 ℃ and pH4.0 and with the catalyst concentration of 15 mu g/mL; the kinetic parameters are tested, and the oxidation TMB mie constant Km of the platinum dendritic nanoparticles (Pt-Au DNPs) is 0.22 mM; ascorbic Acid (AA) was found to inhibit the oxidase-like activity of platinum dendritic nanoparticles (Pt-Au DNPs) and AA can reduce TMB that has been oxidized; based on the findings, a colorimetric method for detecting AA is established, and the detection limit is 78nM., so that the colorimetric method can be widely applied to detection of AA in food and medicines.
In some embodiments, a method for determining AA content using platinum dendritic nanoparticles, comprising the steps of:
(1) dispersing the platinum dendritic nano particles into deionized water to prepare an aqueous solution of the platinum dendritic nano particles;
(2) uniformly mixing a TMB solution, a platinum dendritic nanoparticle aqueous solution and an acetic acid-sodium acetate buffer solution;
(3) reacting the mixed solution at a certain temperature for a period of time, terminating the reaction, adding 0 to 100 mu mol/L of AA standard solutions with different concentrations, oscillating to fully and uniformly mix the solutions, measuring absorbance, and drawing a working curve according to the relation between the absorbance and the concentration of AA;
(4) and (3) replacing the AA standard solution with the sample solution, oscillating to fully and uniformly mix the sample solution, measuring the absorbance, and substituting the absorbance into the working curve to obtain the concentration of the AA.
In some embodiments, the platinum dendritic nanoparticle has a detection limit of AA of 78nM.
In some embodiments, the linear range of AA detection of the platinum dendritic nanoparticles is 1-15 μmol/L, and the correlation coefficient can reach 0.995.
The Pt-Au DNPs of the present invention can directly catalyze ascorbic acid degradation and have ascorbic acid oxidase activity (ascorbate oxidase), as shown in fig. 7 below. The test procedure was as follows: adding 50uL of AA solution with certain concentration of 6mM into a mixed solution containing 60uL of Pt-Au DNPs solution with 0.75mg/mL and 2.89mL of 0.2M acetic acid-sodium acetate buffer solution (pH is 4.0), and uniformly mixing; the absorbance of the solution at 264nm was measured every 15 s.
In addition, as can be seen from the schematic diagram in fig. 4, in the detection process, TMB is catalyzed and oxidized into a blue product ox-TMB by Pt-Au DNPs with stable PVP, the blue product ox-TMB is reduced by Ascorbic Acid (AA), and the continuous oxidation of the TMB catalyzed by the Pt-Au DNPs is inhibited, so that the accurate detection of AA is realized; the high specific surface area of Pt-Au DNPs can provide more active sites, so that the Pt-Au DNPs have strong catalytic oxidation effect on TMB; meanwhile, the catalytic activity of the Pt-Au DNPs (PVP may occupy active sites) can be regulated by regulating the amount of PVP attached to the surface of the Pt-Au DNPs, as shown in the following figure 8.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation process of the platinum dendritic nanoparticles (Pt-Au DNPs) comprises the following specific steps:
(1) adding 2.5mL of glycol into a 50mL three-neck flask, stirring (the speed is 300r/min), and carrying out condensation reflux for 5min at the oil bath heating temperature of 180 ℃; (2) then 0.35mL of 35 wt% hydrochloric acid was added; (3) then, 1mL of the precursor mixed solution (precursor mixed solution H) was added2PtCl6·6H2O and HAuCl4·4H2O solution, the concentration of both is 0.06M, and the volume ratio is: h2PtCl6·6H2O:HAuCl4·4H2O5: 1) and 4mL of PVP solution with the concentration of 0.04M, wherein 100 μ L of the precursor mixed solution is added each time, 400 μ L of PVP is added each time, and the precursor mixed solution is added once every 30s, and the process is completed within 5 min; (4) the reaction is kept at 180 ℃, and after the reaction is carried out for 20min, the solution turns into black; (5) and after the reaction is finished, taking down the three-neck flask, naturally cooling to room temperature, washing by alternately centrifuging acetone and ethanol (6000r/min) to obtain a sample, and ultrasonically dispersing the sample (20-30 min) into dispersant ethanol.
The morphology of the prepared platinum dendritic nanoparticles (Pt-Au DNPs) is shown in FIG. 1. Wherein a shows a TEM image of the synthesized Pt-Au DNPs, and the image shows that the synthesized nano particles have the diameter of about 40nm and good dispersibility, and the TEM image can clearly see that the nano particles have obvious dendritic structures which have the function of increasing the surface area of the prepared nano material; EDS surface scanning results (figure b-1, figure b-2) show that Pt and Au elements are uniformly distributed, and an alloy structure is formed.
Example 2
The platinum dendritic nanoparticles (Pt-Au DNPs) have oxidase-like activity.
In order to explore the catalytic activity of the catalyst mimic enzyme, TMB was chosen as a chromogenic substrate, and the experimental procedure was as follows: 0.75mg of platinum dendritic nanoparticles (Pt-Au DNPs) was ultrasonically dispersed in 1mL of deionized water, 60 μ L (control group without catalyst, 60 μ L of deionized water) was added to 2900 μ L of a buffer solution (acetic acid-sodium acetate buffer solution (0.2M, pH 4.0)), followed by 40 μ L of TMB (5mM) in ethanol. The reaction was terminated by allowing the reaction mixture to stand in an ice bath at 37 ℃ for 5min after 10 min. And finally, measuring the absorbance value of the final solution at 400-800 nm. As a result, as shown in FIG. 2, it can be seen that the catalytic oxidation of TMB by platinum dendritic nanoparticles (Pt-Au DNPs) produces a typical blue product and has a strong absorption peak at 652 nm. Under the condition of no adding a catalyst, TMB is almost not oxidized completely, which shows that the platinum dendritic nano particles (Pt-Au DNPs) have good oxidase-like activity and can catalyze and oxidize the TMB.
Example 3
The platinum dendritic nanoparticles (Pt-Au DNPs) provided by the invention oxidize kinetic parameters of mimic enzymes.
And (3) dynamic experiments: 60 μ L of 0.75mg mL at 35 ℃-1A catalyst solution (i.e., a dispersion of 0.75mg of platinum dendritic nanoparticles dispersed ultrasonically in 1mL of deionized water), 40. mu.L of TMB (5mM), was added to 2.9mL of acetate-acetate buffer (0.2M, pH 4.0). The kinetic measurements were performed in a time course mode using a spectrophotometer to detect the absorbance of the reaction system every 15s at 652nm for the first 3 min. As shown in FIG. 3, the Michaelis-Menten constants were calculated using a Lineweaver-Burk plot. The calculated Michaelis constant Km was 0.22mM and the maximum reaction rate Vmax was 282nM S-1The result shows that the platinum dendritic nanoparticles (Pt-Au DNPs) have high affinity and catalytic reaction rate to TMB and good catalytic activity similar to oxidase.
Example 4
The principle of colorimetric detection of AA using platinum dendritic nanoparticles (Pt-Au DNPs) prepared in example 1 is shown in FIG. 4. As can be seen from the principle diagram of FIG. 4, in the detection process, TMB is catalyzed and oxidized into a blue product ox-TMB by Pt-Au DNPs with stable PVP, Ascorbic Acid (AA) reduces the blue product ox-TMB, and meanwhile, TMB is inhibited from being catalyzed and continuously oxidized by the Pt-Au DNPs, so that accurate detection of AA is realized.
The experimental procedure is as follows.
40uL of 5mM TMB, 60uL of 0.75mg/mL catalyst solution (namely, 0.75mg of platinum dendritic nanoparticles are dispersed in 1mL of deionized water by ultrasonic wave), 2.85mL of 0.2M acetic acid-sodium acetate buffer solution (0.2M, pH4.0), and then the mixture is mixed, reacted in a water bath kettle at 37 ℃ for 10min, then kept still in an ice bath for 5min to stop the reaction, 50uL of AA solution with certain concentration is added into the mixed solution, and the absorbance at 652nm is measured. As shown in FIG. 6, the linear range of 1-15 μ M was found by analyzing the curve, and the linear relationship was good (R)20.995). The detection limit was calculated to be 78nM (S/N-3), the detection limit being low.
Example 5
The platinum dendritic nanoparticles (Pt-Au DNPs) are used for colorimetric detection of the selectivity of AA.
To test the selectivity of this assay, glucose, lysine and several ions (Na) were selected+,K+,Al3 +,NO3 -,Cu2+,Cl-,SO4 2-,Zn2+,CH3COO-) All interfering substances were present at a concentration of 25. mu.M. 40uL of 5mM TMB, 60uL of 0.75mg/mL catalyst solution (i.e., a dispersion of 0.75mg of platinum dendritic nanoparticles dispersed in 1mL of deionized water by ultrasonic wave), 2.85mL of 0.2M acetic acid-sodium acetate buffer solution (0.2M, pH4.0) were mixed, reacted in a 37 ℃ water bath for 10min, then allowed to stand in an ice bath for 5min, the reaction was terminated, 50uL of interfering solution was added to the mixed solution, and the absorbance at 652nm was measured. Tests show that the substances have little influence on the oxidase-like activity for reducing ox-TMB and inhibiting platinum dendritic nanoparticles (Pt-Au DNPs), and can be ignored (figure 5), which shows that the method has good selectivity.
Example 6
The platinum dendritic nanoparticles (Pt-Au DNPs) are applied to colorimetric detection of AA in food samples.
40uL of 5mM TMB, 60uL of 0.75mg/mL catalyst solution (i.e., a dispersion of 0.75mg of platinum dendritic nanoparticles dispersed in 1mL of deionized water by sonication), 2.85mL of 0.2M acetic acid-sodium acetate buffer solution (0.2M, pH4.0) were mixed, reacted in a 37 ℃ water bath for 10min, then allowed to stand in an ice bath for 5min, the reaction was terminated, 50uL of fruit juice (purchased in a supermarket) was added, and the absorbance at 652nm was measured. The results of measuring the AA content in the juice are shown in Table 1.
TABLE 1 determination of AA content in fruit juices
Figure BDA0002266492010000081
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. A preparation method of platinum dendritic nanoparticles for visual and rapid detection of ascorbic acid is characterized by adopting a liquid phase synthesis method, taking polyvinylpyrrolidone as a surface capping agent, hydrochloric acid as an oxidation etching agent, and H2PtCl6·6H2O and HAuCl4·4H2Taking O as a precursor, and preparing platinum dendritic nano particles Pt-Au DNPs;
the preparation method of the platinum dendritic nanoparticle Pt-Au DNPs comprises the following steps:
(1) adding ethylene glycol, stirring, condensing and refluxing under the heating condition of 170-200 ℃, and then adding hydrochloric acid; the volume of the hydrochloric acid accounts for 10-15% of the volume of the ethylene glycol;
(2) then, adding a precursor solution and a polyvinylpyrrolidone solution; the precursor solution is prepared from H2PtCl6·6H2O and HAuCl4·4H2The O solution is composed of 5: 1-9: 1 in volume ratio; the precursor solution accounts for 10-15% of the total volume of the reaction solution; the polyvinylpyrrolidone solution is a solution of polyvinylpyrrolidone with the concentration of 0.02-0.04M in glycol; the polyvinylpyrrolidone solution accounts for 35-50% of the total volume of the reaction solution;
(3) the reaction is carried out at the temperature of 170-200 ℃, and the solution turns black after the reaction is carried out for 18-25 min;
(4) after the reaction is finished, naturally cooling to room temperature, and alternately centrifuging and washing acetone and ethanol to obtain a sample;
said H2PtCl6·6H2O and HAuCl4·4H2The concentration of the O solution is 0.05-0.07M; the concentration of the hydrochloric acid is 30-37 wt%.
2. The method of claim 1, wherein the H is2PtCl6·6H2O and HAuCl4·4H2The concentration of the O solution was the same.
3. The preparation method according to claim 1, wherein the condensing reflux time is 4-8 min.
4. The method according to claim 1, wherein the precursor solution and the polyvinylpyrrolidone solution are added every 25-45 s, and the process is completed within 4-7 min.
5. The method of claim 1, further comprising: a step of ultrasonically dispersing a sample into a dispersant; the dispersant is ethanol or water; the ultrasonic sample dispersing time is 20-30 min; the dispersion concentration of the sample in the dispersant is 0.25 mg/mL-1 mg/mL.
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