CN111944523A - MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione - Google Patents

MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione Download PDF

Info

Publication number
CN111944523A
CN111944523A CN202010857024.4A CN202010857024A CN111944523A CN 111944523 A CN111944523 A CN 111944523A CN 202010857024 A CN202010857024 A CN 202010857024A CN 111944523 A CN111944523 A CN 111944523A
Authority
CN
China
Prior art keywords
glutathione
solution
quantum dots
mxene quantum
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010857024.4A
Other languages
Chinese (zh)
Other versions
CN111944523B (en
Inventor
卓淑娟
王静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Normal University
Original Assignee
Anhui Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Normal University filed Critical Anhui Normal University
Priority to CN202010857024.4A priority Critical patent/CN111944523B/en
Publication of CN111944523A publication Critical patent/CN111944523A/en
Application granted granted Critical
Publication of CN111944523B publication Critical patent/CN111944523B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Biophysics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses MXene quantum dots with peroxide mimic enzyme property, a preparation method thereof and a method for detecting glutathione, wherein the preparation method comprises the following steps: mixing Ti2C3Refluxing treatment is carried out in concentrated nitric acid, then the pH of the system is adjusted to be alkaline, and then post-treatment is carried out to obtain MXene quantum dots. The MXene quantum dot with the peroxide mimic enzyme property can be used as mimic enzyme to quantitatively detect glutathioneMeasuring to improve the accuracy of the detection of the glutathione; meanwhile, the preparation method has the characteristics of simple process and mild conditions.

Description

MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione
Technical Field
The invention relates to MXene quantum dots, in particular to MXene quantum dots with peroxide mimic enzyme property, a preparation method thereof and a method for detecting glutathione.
Background
The existing methods for detecting glutathione include fluorescence spectrometry, absorbance method, high performance liquid chromatography, mass spectrometry, colorimetry, absorbance method, capillary method and the like, and the absorbance method and the colorimetry are increasingly emphasized by people because of the advantages of simplicity, low cost, convenience and the like.
In many of the above detection methods, biological enzymes or mimetic enzymes are often used. Mimetic enzymes are nanomaterial-based artificial enzyme mimetics that have been of great interest in the past decade due to their significant advantages over traditional biological enzymes. Various nanomaterials such as noble metal nanoparticles, metal oxides and carbon-based nanomaterials have been developed as potential nanoenzymes.
However, the effect of the existing mimic enzyme is not ideal, for example, PB (Prussian blue) materials, such as the material synthesized by taking PB as a raw material and described in the literature "Colloids and Surfaces A physical and Engineering applications, 2019: 622-; firstly, the inherent blue color of the PB can generate strong background interference on colorimetric detection of a target substance, and secondly, the PB is aggregated in an aqueous solution due to poor dispersibility, so that the catalytic activity is further reduced.
Disclosure of Invention
The invention aims to provide MXene quantum dots with peroxide mimic enzyme property, a preparation method thereof and a method for detecting glutathione, wherein the MXene quantum dots with peroxide mimic enzyme property can be used as mimic enzyme to carry out quantitative detection on glutathione so as to improve the detection accuracy of glutathione; meanwhile, the preparation method has the characteristics of simple process and mild conditions.
In order to achieve the above object, the present invention provides a method for preparing MXene quantum dots having peroxide mimetic enzyme properties, the method comprising: mixing Ti2C3Refluxing treatment is carried out in concentrated nitric acid, then the pH of the system is adjusted to be neutral or alkaline, and then post-treatment is carried out to obtain MXene quantum dots.
The invention also provides a preparation method of the MXene quantum dots with peroxide mimic enzyme properties, and the MXene quantum dots are prepared by the preparation method.
The invention also provides a method for detecting glutathione, which comprises the following steps:
1) adding different amounts of glutathione into blank solutions with the same volume respectively to obtain multiple groups of solutions to be detected: wherein the blank solution contains water, sodium acetate buffer solution, and H2O2TMB and Mxene quantum dots;
2) after the system reacts for 15-25min, determining the absorbance 1 of each group of solution to be detected;
3) taking the final concentration of glutathione in the solution to be measured as an abscissa (the final concentration refers to the concentration of the glutathione mixed with the blank solution), taking the measured absorbance 1 as an ordinate, and performing linear fitting to obtain an equation;
4) adding a sample to be detected containing glutathione with unknown concentration into the blank solution, detecting the absorbance 2, and calculating the concentration of the glutathione in the sample to be detected according to the absorbance 2.
MXene is a novel two-dimensional transition metal carbide or nitride nano material, and has the advantages of good metal conductivity, stability, large surface area, easy functionalization, hydrophilicity, biocompatibility and the like. And the graphene also has a layered structure similar to graphene, and is widely researched in the fields of energy, nanomedicine, catalysis, sensing and the like.
In the technical scheme, the invention adopts Ti2C3The Mxene quantum dots prepared by refluxing in concentrated nitric acid not only have size advantage, strong quantum confinement and edge effect, but also have excellent luminescence property similar to that of common carbon quantum dots; the surface of the Mxene quantum dot prepared has rich oxygen-containing groups, such as hydroxyl and carboxyl groups, and the Mxene quantum dot is used as a peroxide mimic enzyme in H2O2In the presence of a catalyst, 3 ', 5, 5' -Tetramethylbenzidine (TMB) to give a blue product: (OXTMB) to enable its use as a peroxidase mimetic. Meanwhile, the Mxene quantum dot is a green pollution-free catalyst. In addition, the Mxene quantum dot also has the characteristics of high fluorescence quantum yield, good dispersibility, controllability, low production cost and good reproducibility.
In the invention, the detection principle of glutathione is as follows: under the catalysis of horseradish peroxidase or other appropriate peroxidase, TMB can be oxidized by hydrogen peroxide to generate a soluble blue product, and in the application, Mxene quantum dots can be competent for peroxide mimic enzyme; once glutathione is added, the system can fade due to the reduction of the glutathione, and the fading degree of the system is different along with the difference of the concentration of the glutathione, so that the concentration of the glutathione can be quantitatively detected according to a colorimetric method.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1-1 is a Transmission Electron Microscopy (TEM) picture of Mxene quantum dots prepared in example 1;
FIGS. 1-2 are particle size distribution plots for the preparation of Mxene quantum dots in example 1;
FIG. 2 is a Fluorescence excitation dependence graph (Fluorescence) of MXene quantum dots prepared in example 1;
FIG. 3 is the UV absorption, fluorescence Excitation and Emission patterns (Absorbance, Excitation spectra, Emission spectra) of MXene quantum dots prepared in example 1;
fig. 4 is an infrared spectrum (FTIR) of MXene quantum dots prepared in example 1;
fig. 5 is an X-ray diffraction pattern (XRD) of the MXene quantum dots and precursor prepared in example 1;
FIG. 6 is an X-ray photoelectron spectroscopy (XPS) of MXene quantum dots prepared in example 1;
FIG. 7 is a graph of UV absorption for comparison of different simulated peroxidases;
FIG. 8-1 is a graph showing the phenomenon of UV absorption of Mxene quantum dots prepared as peroxidase in example 1 under different concentrations of glutathione;
fig. 8-2 is a line graph of fig. 8-1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of MXene quantum dots with peroxide mimic enzyme property, which comprises the following steps: mixing Ti2C3Refluxing treatment is carried out in concentrated nitric acid, then the pH of the system is adjusted to be neutral or alkaline, and then post-treatment is carried out to obtain MXene quantum dots.
In the above-mentioned production method, the concentration of the concentrated nitric acid can be selected within a wide range, but in order to improve the catalytic performance of the resulting Mxene quantum dots, it is preferable that the concentration of the concentrated nitric acid is 60 to 75 wt%.
In the above-mentioned production method, the amount of each material may be selected within a wide range, but in order to improve the catalytic performance of the resulting Mxene quantum dot, preferably, Ti2C3The dosage of the concentrated nitric acid is respectively 0.1 g: 140 and 160 mL.
In the above-mentioned production method, the conditions of the reflux treatment can be selected within a wide range, but in order to improve the catalytic performance of the resulting Mxene quantum dot, it is preferable that the reflux treatment satisfies at least the following conditions: the temperature is 110-150 ℃, and the time is 36-60 h; more preferably, the reflow process satisfies at least the following conditions: the temperature is 120-140 ℃ and the time is 45-50 h.
In the above-mentioned production method, the pH of the system after the reflux treatment can be selected within a wide range, but in order to improve the catalytic performance of the resulting Mxene quantum dot, it is preferable that the pH of the system after the reflux treatment is adjusted to 7 to 8.
In the above embodiment, the manner of adjustment of the pH of the system can be selected within a wide range, but in order to further improve the adjustment effect, it is preferable that the pH adjustment of the system is performed by adding a basic compound; more preferably, the basic compound is selected from at least one of potassium hydroxide, sodium hydroxide and ammonia water.
In the present invention, Ti2C3It may be commercially available or prepared by itself for increasing Ti content2C3Preferably, Ti2C3Prepared by the following method: mixing Ti2AlC3And performing contact reaction with HF, centrifuging, taking precipitate, washing with water to pH 7, and performing ultrasonic treatment and vacuum drying in ice water bath.
In the above Ti2C3In the production method of (1), in order to further improve the yield, preferably, Ti2AlC3And HF in a molar ratio of 1: 200-250; more preferably, the contact reaction satisfies at least the following conditions: the temperature is 60-80 ℃ and the time is 15-30 h.
The invention also provides a preparation method of the MXene quantum dots with peroxide mimic enzyme properties, and the MXene quantum dots are prepared by the preparation method.
The invention also provides a method for detecting glutathione, which comprises the following steps:
1) adding different amounts of glutathione into blank solutions with the same volume respectively to obtain multiple groups of solutions to be detected: wherein the blank solution contains water, sodium acetate buffer solution, and H2O2TMB and Mxene quantum dots;
2) after the system reacts for 15-25min, determining the absorbance 1 of each group of solution to be detected;
3) taking the final concentration of glutathione in the solution to be measured as an abscissa and the measured absorbance 1 as an ordinate, and performing linear fitting to obtain an equation;
4) adding a sample to be detected containing glutathione with unknown concentration into the blank solution, detecting the absorbance 2, and calculating the concentration of the glutathione in the sample to be detected according to the absorbance 2.
In the above-mentioned detection method, the content of each component in the blank solution can be selected within a wide range, but in order to improve the accuracy of detection, it is preferable that in the blank solution, sodium acetate buffer solution, H2O2And the dosage ratio of the TMB to the Mxene quantum dots to the water is 1 mL: 0.9. mu. mol: 0.3-0.5. mu. mol: 15-25 μ g: 700-900 μ L;
in the above detection method, each component in the blank solution can be provided in pure form or in other forms, such as solution form, preferably, the pH of the sodium acetate buffer solution is 3-4, the TMB is provided by the solution with the concentration of 8-10mmol/L, the Mxene quantum dot is provided by the solution of 350-2O2Is provided by a solution with the concentration of 8-10 mol/L.
In the present invention, in order to further improve the accuracy of the detection of glutathione, preferably, in step 3), the equation obtained by linear fitting is: y is 0.02755x-0.0284, x is the molar concentration of glutathione and y is the absorbance value.
The present invention will be described in detail below by way of examples. In the following examples, Ti2C3The compound is prepared by a method described in the document 'advanced Materials,2017,29(15): 1604847.1-1604847.6', and specifically comprises the following steps: taking Ti2AlC3Dissolving HF (molar ratio of 1: 200) in a polytetrafluoroethylene reaction kettle, stirring at 60 ℃ for 24h, taking out, washing and centrifuging with deionized water until the pH value is 7, and then carrying out ultrasonic treatment in ice-water bath and vacuum drying to obtain Ti2C3And (3) solid powder.
Example 1
0.1g of Ti was weighed2C3Adding into 150mL concentrated nitric acid (68 wt%), stirring at 25 deg.C for 20min, refluxing at 130 deg.C for 48h, naturally cooling, adjusting pH to 7.5 with NaOH solution (8mol/L), purifying, filtering with 0.22 μm microporous membrane, dialyzing for 12h to obtain solution, concentrating by rotary evaporation, vacuum drying to obtain solid particles, and quantitatively diluting.
Example 2
The procedure is as in example 1, except that the reflux temperature is 110 ℃ and the amount of concentrated nitric acid used is 160mL, and the other conditions are unchanged.
Example 3
The procedure was as in example 1, except that the reflux temperature was 120 ℃ and the amount of concentrated nitric acid used was 155mL, and the other conditions were not changed.
Example 4
The procedure is as in example 1, except that the reflux temperature is 140 ℃ and the amount of concentrated nitric acid used is 145mL, the other conditions being unchanged.
Example 5
The procedure is as in example 1, except that the reflux temperature is 150 ℃ and the amount of concentrated nitric acid used is 140mL, and the other conditions are not changed.
Detection example 1
1) The synthesized samples were examined by Hitachi HT 7700 transmission electron microscopy. The Mxene quantum dots in the detection example 1 are detected by a transmission electron microscope, and the result is shown in figure 1-1 and figure 1-2.
As can be seen from the figure: the MXene quantum dots are uniformly dispersed, are particles which are approximately spherical, have the average size of about 3.5nm, and have the same size distribution characteristics with the common carbon nano material, namely the carbon quantum dots (1-10 nm).
2) Fluorescence excitation detection is carried out on Mxene quantum dots in the detection example 1 by an FS5 fluorescence spectrometer of Edinburgh Limited company in USA, and the results are shown in figure 2, and curves represented from top to bottom in figure 2 are respectively 330nm, 320nm, 310nm, 340nm, 350nm, 360nm, 370nm and 380 nm.
As can be seen from fig. 2: the optimal excitation wavelength for Mxene quantum dots is at 330 nm.
3) The results of ultraviolet absorption, fluorescence excitation and emission detection of Mxene quantum dots in detection example 1 were shown in fig. 3 by Hitachi U-3010 ultraviolet-visible spectrophotometer of japan and FS5 fluorescence spectrometer of edinburg ltd, usa, and in fig. 3, the curves represented from left to right are the ultraviolet absorption spectrum, the optimum excitation wavelength and the optimum emission wavelength of Mxene quantum dots, respectively.
As can be seen from fig. 3: the Mxene quantum dot has wide light absorption in an ultraviolet region, and the optimal excitation wavelength and the optimal emission wavelength of the Mxene quantum dot are respectively 330nm and 430nm as can be seen from a fluorescence spectrum.
4) The Mxene quantum dots in detection example 1 were characterized by infrared spectrum by Japanese Shimadzu Fourier infrared spectrometer IR-21, and the results are shown in FIG. 4.
As can be seen from fig. 4: 3445cm in infrared spectrogram of Mxene quantum dot-11638cm of telescopic vibration attributed to O-H-1Vibration of 1385cm, ascribed to C ═ O-1Telescopic vibration attributed to C-O.
5) Mxene quantum dots and Ti in example 1 were detected by X-ray powder diffractometer D8 Adance pair of Bruker, Germany2C3The solid powder was characterized by X-ray diffraction and the results are shown in figure 5.
As can be seen from fig. 5: the Mxene quantum dot contains an unsaturated carbon peak, the characteristic peak of the precursor is obviously weakened after HF acid treatment, the 39-degree peak basically disappears, the interlayer Al disappears to indicate that etching is successful, and only the peak of amorphous carbon can be basically seen when the Mxene quantum dot is reached along with the increase of the carbonization degree.
6) Mxene quantum dots and Ti in example 1 were detected by the American thermal electric Co., Ltd. X-ray photoelectron spectrometer ESCALB 250 pair2C3The solid powder was subjected to X-ray photoelectron spectroscopy, and the results are shown in FIG. 6.
From fig. 6, it can be seen that the Mxene quantum dot mainly contains three elements, i.e., C, Ti, and O, and the contents thereof are 57.88%, 0.15%, and 41.97%, respectively.
The products of examples 2-5 were characterized in the same manner as described above, and the characterization results were substantially identical to those of the product of example 1.
Application example 1
Taking 800 mu LH2O, 1mL HAc/NaAc buffer solution at pH 3.5, 50. mu.L TMB (9mmol/L), 100. mu.LH2O2(9mmol/L), 50. mu.L (400. mu.g/mL) MXene quantum dots (prepared in example 1), reacted for 20min, and the absorption spectrum of TMB at 652nm was measured under different ambient conditions, as shown in FIGS. 7-8Wherein the three curves in FIG. 7 represent TMB + H2O2TMB + Mxene Quantum dots, TMB + H2O2The change of TMB absorbance under three environmental conditions of + Mxene quantum dots can be seen from FIGS. 7-8: only the quantum dots and hydrogen peroxide are present at the same time to cause significant color change of the TMB.
Application example 2
The method comprises the steps of firstly selecting three samples to be detected containing glutathione to prepare blank liquid, measuring the concentration of the glutathione in the blank liquid (the concentration of the glutathione in the samples to be detected is obtained through calculation and is recorded as a first concentration), then measuring the concentration in a mixed liquid formed by the blank liquid and a glutathione standard solution (the glutathione in the standard solution is removed, the concentration of the glutathione in the samples to be detected is obtained through calculation and is recorded as a second concentration), further calculating the recovery rate, carrying out three parallel experiments on each group of experiments, and averaging the results.
The concentration of glutathione in the glutathione standard solution is 1 mu mol/L.
The blank liquid consists of the following components: 1000. mu.L HAc/NaAc (0.2mol/L), 100. mu.L TMB (9mmol/L), 200. mu. L H2O2(9mmol/L), 50. mu.L MXene quantum dots (400. mu.g/mL), 100. mu.L of sample to be tested and 550. mu.L of LH2O。
The blank liquid and glutathione standard solution consists of the following components: 1000. mu.L HAc/NaAc (0.2mol/L), 100. mu.L TMB (9mmol/L), 200. mu.L LH2O2(9mmol/L), 50. mu.L MXene quantum dots (400. mu.g/mL), 100. mu.L of sample to be tested, 200. mu.L of GSH glutathione (1. mu. mol/L) and 350. mu.L of glutathione2O。
And (3) measuring the absorbance of the two solutions after the two solutions react for 20min, and calculating the standard addition recovery rate by using a standard addition recovery formula. The specific detection results of the concentrations of the three standards are shown in table 1.
TABLE 1
Figure BDA0002646718280000091
Figure BDA0002646718280000101
From the above table, it can be seen that: the content of GSH in the standard sample is detected and verified by adopting a standard addition method, the recovery rate of GSH measurement is between 95 and 105 percent, and the Relative Standard Deviation (RSD) is less than 2.5 percent. The method can be used for measuring the GSH in the sample to be measured in the laboratory.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of MXene quantum dots with peroxide simulation enzyme properties is characterized by comprising the following steps: mixing Ti2C3And (3) carrying out reflux treatment in concentrated nitric acid, then adjusting the pH of the system to be neutral or alkaline, and then carrying out post-treatment to obtain the MXene quantum dots.
2. The method of claim 1, wherein the concentrated nitric acid has a concentration of 60 to 75 wt.%.
3. The production method according to claim 2, wherein the Ti2C3The dosage ratio of the concentrated nitric acid is 0.1 g: 140 and 160 mL.
4. The production method according to any one of claims 1 to 3, wherein the reflow treatment satisfies at least the following condition: the temperature is 110-150 ℃, and the time is 36-60 h;
preferably, the reflow process satisfies at least the following conditions: the temperature is 120-140 ℃ and the time is 45-50 h.
5. The production method according to any one of claims 1 to 3, wherein, after the reflux treatment, the pH of the system is adjusted to 7 to 8;
preferably, the pH adjustment of the system is performed by adding a basic compound;
preferably, the alkaline compound is selected from at least one of potassium hydroxide, sodium hydroxide and ammonia water.
6. The production method according to any one of claims 1 to 3, wherein the Ti is present2C3Prepared by the following method: mixing Ti2AlC3Performing contact reaction with HF, centrifuging, collecting precipitate, washing with water until pH is 7, and sequentially performing ice-water bath ultrasound and vacuum drying;
preferably, the Ti2AlC3And HF in a molar ratio of 1: 200-250;
preferably, the contact reaction satisfies at least the following conditions: the temperature is 60-80 ℃ and the time is 15-30 h.
7. A method for preparing MXene quantum dots with peroxide-simulated enzyme properties, wherein the MXene quantum dots are prepared by the preparation method of any one of claims 1-6.
8. A method for detecting glutathione, comprising:
1) adding different amounts of glutathione into blank solutions with the same volume respectively to obtain multiple groups of solutions to be detected: wherein the blank solution contains water, sodium acetate buffer solution, and H2O2TMB and Mxene quantum dots;
2) after the system reacts for 15-25min, the absorbance of each group of solution to be measured is measured;
3) taking the final concentration of glutathione in the solution to be measured as an abscissa and the measured absorbance value as an ordinate, and performing linear fitting to obtain an equation;
4) adding a sample to be detected containing glutathione with unknown concentration into the blank solution, detecting the absorbance 2, and calculating the concentration of the glutathione in the sample to be detected according to the absorbance 2.
9. The method for detecting glutathione according to claim 8, wherein in the blank solution, the sodium acetate buffer solution, H2O2And the dosage ratio of the TMB to the Mxene quantum dots to the water is 1 mL: 0.9. mu. mol: 0.3-0.5. mu. mol: 15-25 μ g: 700-900 μ L;
preferably, the pH of the sodium acetate buffer solution is 3-4, the TMB is provided by a solution with the concentration of 8-10mmol/L, the Mxene quantum dot is provided by a solution of 350-450 mu g/mL, and the H is provided by a solution of 450 mu g/mL2O2Is provided by a solution with the concentration of 8-10 mol/L.
10. The method for detecting glutathione according to claim 8, wherein in step 3), the equation obtained by linear fitting is: and y is 0.02755x-0.0284, wherein x is the concentration of glutathione and y is the absorbance value.
CN202010857024.4A 2020-08-24 2020-08-24 MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione Active CN111944523B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010857024.4A CN111944523B (en) 2020-08-24 2020-08-24 MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010857024.4A CN111944523B (en) 2020-08-24 2020-08-24 MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione

Publications (2)

Publication Number Publication Date
CN111944523A true CN111944523A (en) 2020-11-17
CN111944523B CN111944523B (en) 2022-08-30

Family

ID=73360309

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010857024.4A Active CN111944523B (en) 2020-08-24 2020-08-24 MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione

Country Status (1)

Country Link
CN (1) CN111944523B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112630179A (en) * 2020-12-09 2021-04-09 安徽师范大学 Prussian blue quantum dot with oxide mimic enzyme property, preparation method thereof and method for detecting L-cysteine
CN113913183A (en) * 2021-09-24 2022-01-11 山东师范大学 Oxidized TMB nano material and application thereof in detection of glutathione
CN115475642A (en) * 2022-09-01 2022-12-16 温州市工业科学研究院 V 2 N MXene synthesis method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258218A (en) * 2018-01-15 2018-07-06 青岛大学 A kind of preparation method and application of the titanium carbide hydrogel composite material of carbon dots doping
CN110371979A (en) * 2019-07-31 2019-10-25 北京科技大学 A kind of method that lye etching prepares MXene quantum dot
CN110726707A (en) * 2019-10-30 2020-01-24 南京医科大学 Based on N-Ti3C2Composite nano probe of QDs and o-phenylenediamine oxide and ratiometric fluorescence detection method thereof
CN111187619A (en) * 2020-02-27 2020-05-22 北京科技大学 MXene quantum dot fluorescence enhancement method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258218A (en) * 2018-01-15 2018-07-06 青岛大学 A kind of preparation method and application of the titanium carbide hydrogel composite material of carbon dots doping
CN110371979A (en) * 2019-07-31 2019-10-25 北京科技大学 A kind of method that lye etching prepares MXene quantum dot
CN110726707A (en) * 2019-10-30 2020-01-24 南京医科大学 Based on N-Ti3C2Composite nano probe of QDs and o-phenylenediamine oxide and ratiometric fluorescence detection method thereof
CN111187619A (en) * 2020-02-27 2020-05-22 北京科技大学 MXene quantum dot fluorescence enhancement method

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MINGWANG LIU ET AL.: "A "naked-eye" colorimetric and ratiometric fluorescence probe for uric acid based on Ti3C2 MXene quantum dots", 《ANALYTICA CHIMICA ACTA》 *
QINGWEN GUAN ET AL.: "Highly fluorescent Ti3C2 MXene quantum dots for macrophage labeling and Cu2+ ion sensing", 《NANOSCALE》 *
YING HE ET AL.: "Self-Reducing Prussian Blue on Ti3C2Tx MXene Nanosheets as a Dual-Functional Nanohybrid for Hydrogen Peroxide and Pesticide Sensing", 《IND. ENG. CHEM. RES.》 *
YUNLONG QIN ET AL.: "High-yield fabrication of Ti3C2Tx MXene quantum dots and their electrochemiluminescence behavior", 《NANOSCALE》 *
ZHAOYONG JIN ET AL.: "Ti3C2Tx MXene-derived TiO2/C-QDs as oxidase mimics for the efficient diagnosis of glutathione in human serum", 《J. MATER. CHEM. B》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112630179A (en) * 2020-12-09 2021-04-09 安徽师范大学 Prussian blue quantum dot with oxide mimic enzyme property, preparation method thereof and method for detecting L-cysteine
CN113913183A (en) * 2021-09-24 2022-01-11 山东师范大学 Oxidized TMB nano material and application thereof in detection of glutathione
CN113913183B (en) * 2021-09-24 2023-10-20 山东师范大学 Oxidized TMB nano material and application thereof in detection of glutathione
CN115475642A (en) * 2022-09-01 2022-12-16 温州市工业科学研究院 V 2 N MXene synthesis method and application thereof

Also Published As

Publication number Publication date
CN111944523B (en) 2022-08-30

Similar Documents

Publication Publication Date Title
CN111944523B (en) MXene quantum dot with peroxide mimic enzyme property, preparation method thereof and method for detecting glutathione
Jiao et al. Well-redispersed ceria nanoparticles: promising peroxidase mimetics for H 2 O 2 and glucose detection
Dayakar et al. Novel synthesis and structural analysis of zinc oxide nanoparticles for the non enzymatic glucose biosensor
CN106044743B (en) A kind of preparation method and applications of the Water-soluble carbon quantum dot based on egg shell membrane
Liu et al. Facile one-pot preparation of Pd–Au/PEDOT/graphene nanocomposites and their high electrochemical sensing performance for caffeic acid detection
Meng et al. Effects of crystal structure on the activity of MnO 2 nanorods oxidase mimics
Yang et al. PB@ Co 3 O 4 nanoparticles as both oxidase and peroxidase mimics and their application for colorimetric detection of glutathione
CN106111181B (en) Porous graphene-zeolite-BiOX catalysis material and preparation and application
Zou et al. Enhanced photocatalytic activity of bismuth oxychloride by in-situ introducing oxygen vacancy
Kakuta et al. Shape effects of goethite particles on their photocatalytic activity in the decomposition of acetaldehyde
Sawant et al. Biogenic capped selenium nano rods as naked eye and selective hydrogen peroxide spectrometric sensor
CN103926234A (en) Single-layer nanogold surface-enhanced Raman activity substrate and preparation method thereof
Li et al. Fluorometric detection of tyrosine and cysteine using graphene quantum dots
Deng et al. Iron and nitrogen co-doped graphene quantum dots as highly active peroxidases for the sensitive detection of l-cysteine
Murmu et al. Graphene wrapped nickel phthalocyanine nanohybrid: Efficient electrocatalyst for nitrogen reduction reaction
Singh et al. Decoration of GO with Fe spinel-Naf/DMAP: an electrochemical probe for sensing H 2 O 2 reduction
Li et al. In situ Ba2+ exchange in amorphous TiO2 hollow sphere for derived photoelectrochemical sensing of sulfur dioxide
Wang et al. Ultrafine V2O5-anchored 3D N-doped carbon nanocomposite with augmented dual-enzyme mimetic activity for evaluating total antioxidant capacity
Harshavardhan et al. Synthesis of Tin oxide nanoparticles using Nelumbo nucifera leaves extract for electrochemical sensing of dopamine
CN112717934B (en) Attapulgite-loaded transition metal oxide composite material and preparation method and application thereof
CN112823885B (en) Gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material and preparation method and application thereof
Wang et al. Facile synthesis of nitrogen-doped carbon dots and its application as sensing probes for serum iron
CN110237870B (en) Polyphenolic/titanium dioxide composite material and preparation method and application thereof
CN110031448B (en) Preparation method of nano tin dioxide/carbon base point/nano silver surface enhanced Raman substrate
Lei et al. Highly sensitive and selective detection of butachlor based on the resonance light scattering of doped carbon quantum dots

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant