CN112763438B - Application of carbon dot peroxidase CDs@NC in detection of D-alanine and D-proline - Google Patents
Application of carbon dot peroxidase CDs@NC in detection of D-alanine and D-proline Download PDFInfo
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Abstract
The invention provides an application of carbon-point peroxidase CDs@NC in detecting D-alanine and D-proline, wherein D-Ala and D-Pro can generate H in the presence of DAAO 2 O 2 At H 2 O 2 Under the combined action of CDs@NC, colorless TMB is changed into blue TMB, and an obvious absorption peak appears at 652-nm part of an ultraviolet-visible spectrum, so that the rapid detection of D-Ala and D-Pro can be realized based on the change of the intensity of the ultraviolet absorption peak along with the concentration of D-Ala and D-Pro. The method has the advantages of no need of expensive large-scale instruments, wide application range and good environmental adaptability. The nano enzyme related by the method is a carbon material, has low price and good stability, and can be prepared in a large amount.
Description
Technical Field
The invention relates to an application of carbon point peroxidase CDs@NC in detecting D-alanine and D-proline, belonging to the technical field of non-noble metal catalysts in electrocatalysis.
Background
Research shows that the survival rate of gastric cancer after late treatment is far lower than that of early treatment, so that early detection and timely treatment of gastric cancer have important significance. However, most early gastric cancer patients have no specific symptoms, which makes timely diagnosis difficult. Traditional diagnostic methods for early gastric cancer include endoscopy, biopsy and blood examination. However, these methods are complex, time consuming, rely on well-equipped laboratory facilities and can cause trauma to human tissue, and thus there is a strong need for a convenient, rapid, non-invasive method of gastric cancer detection.
The concentrations of D-alanine (D-Ala) and D-proline (D-Pro) in gastric juice and saliva, respectively, of early stage gastric cancer patients were reported to be 126.3-285.3. Mu.M and 46.1-114.5. Mu.M, respectively, much higher than in healthy persons (7.3-18.3. Mu.M and 5.4-7.8. Mu.M, respectively). Thus, accurate monitoring of the concentrations of D-Ala and D-pro is of great importance for the diagnosis of gastric cancer. Currently, many detection methods have been reported, including chromatography, electrochemiluminescence, electrochemical biosensor methods, and the like. However, colorimetric detection of D-Ala and D-Pro is rarely reported. Previous studies have reported that D-amino oxidase (DAAO) can be selectedSelectively oxidizing D-Ala and D-Pro to H 2 O 2 In the case of peroxidases and H 2 O 2 Under the combined action of (a), colorless TMB changes to blue TMB. Thus, D-Ala and D-Pro can be potential biomarkers for gastric cancer detection.
The nano-enzyme as a combination of the mimic enzyme and the nano-material has undergone rapid development in the past few years, and has been widely used in the fields of analytical sensing and biomedicine, and compared with the natural enzyme, the nano-enzyme has lower production cost, easier mass production and better stability. Among them, carbon-based nano-enzymes are attractive due to their high stability, low cost and good biocompatibility. Carbon dots, which are a typical carbon material, have been widely paid attention to due to high stability, low toxicity and high biocompatibility, and have been found to have intrinsic peroxidase activity in the past. However, the peroxidase activity of the carbon dots is reduced due to factors such as easy agglomeration, uneven size and morphology, and the like. ZIF-8 is a typical metal-organic framework material, the framework is stable, the internal pore size is uniform (1.9 nm), and glucose molecules can be loaded into the pores of ZIF-8 in a liquid phase and carbonized at 200 ℃ to generate carbon points. In particular, the peroxidase activity of the carbon material may also be increased by nitrogen doping methods. However, the synergistic effect of carbon sites and nitrogen-doped carbon to increase peroxidase activity has not been previously reported.
Disclosure of Invention
Aiming at the problem of low peroxidase activity of the existing carbon material, ZIF-8 is used as a template, glucose is used as a carbon source, carbon points with uniform size are obtained at 200 ℃, then the carbon points coated by nitrogen-doped carbon (CDs@NC) are further carbonized at high temperature to obtain novel peroxidase, and the novel nano-enzyme is used for rapidly and efficiently detecting D-Ala and D-Pro by utilizing the peroxidase activity of the novel nano-enzyme. The detection mechanism is as follows: D-Ala and D-Pro can produce H in the presence of DAAO 2 O 2 And at H 2 O 2 Can change colorless TMB into blue TMB under the combined action of CDs@NC, and shows obvious absorption peak at 652 nm on ultraviolet-visible spectrum based on ultraviolet absorption peakThe intensity changes along with the concentration of D-Ala and D-Pro, so that the detection of D-Ala and D-Pro can be realized.
The invention is realized by the following technical scheme:
application of carbon dot peroxidase CDs@NC in detecting D-alanine and D-proline. D-Ala and D-Pro can produce H in the presence of DAAO 2 O 2 At H 2 O 2 The colorless TMB is changed into blue TMB under the combined action of CDs@NC, and a visible absorption peak appears at 652-nm on an ultraviolet-visible spectrum, so that the detection of D-Ala and D-Pro can be realized based on the change of the intensity of the ultraviolet absorption peak along with the concentration of D-Ala and D-Pro.
Further, the preparation method of the CDs@NC comprises the following steps:
(1) preparation of ZIF-8: dissolving 4 g dimethyl imidazole in 60 mL methanol solution; 1.68 g Zn (NO) 3 ) 2 ·6H 2 Dissolving O into 20 mL methanol solution, adding the solution, and stirring vigorously at room temperature for 1 h; incubating the mixture at room temperature for 24 h without stirring; centrifugal washing and drying to obtain ZIF-8;
(2) preparation of G@ZIF-8: immersing 200 mg ZIF-8 powder in glucose solution, stirring at room temperature for 6H, centrifuging to separate white precipitate, and concentrating with EtOH/H 2 O=9: 1, washing the solution for three times, and drying at 60 ℃ under vacuum overnight;
(3) preparation of CDs@ZIF-8: heating the G@ZIF-8 powder to 200 ℃, preserving heat, and cooling to room temperature to obtain CDs@ZIF-8;
(4) preparation of CDs@NC: the powder of CDs@ZIF-8 is heated to 900 ℃ and incubated to obtain CDs@NC.
Further, the concentration of the glucose solution is 1-3 mM, and the solution is EtOH/H 2 O=9: 1 by volume ratio.
Further, the atmosphere of heating the G@ZIF-8 powder to 200 ℃ is N 2 The temperature rising rate is 5 ℃ for min -1 The heat preservation time is 3h.
Further, the CDs@ZIF-8 powder is heated to 900 ℃ and the atmosphere is N 2 The temperature rising rate is 5 ℃ for min -1 When preserving heatThe interval is 3h.
Advantageous effects
The invention discloses an application of carbon dot peroxidase CDs@NC in detecting D-alanine and D-proline, which comprises the following steps:
(1) The method has the advantages of no need of expensive large-scale instruments, wide application range and good environmental adaptability.
(2) The nano enzyme related by the method is a carbon material, has low price and good stability, and can be prepared in a large amount.
(3) The method can detect the concentration of D-alanine (D-Ala) and D-proline (D-Pro), and has important significance for further using the system for detecting saliva samples of human bodies, causing no harm to the human bodies, being simpler to operate and carrying out noninvasive diagnosis on early gastric cancer patients.
Drawings
A transmission electron micrograph of (a) nitrogen-doped carbon-coated carbon dots in fig. 1; (B) High resolution transmission electron microscopy images of nitrogen doped carbon coated carbon dots; (C) lattice fringe image of carbon dots;
FIG. 2 (A) shows the UV-visible absorption spectrum after adding D-Ala at different concentrations to the detection system, wherein the concentrations of D-Ala are 0, 10, 20, 30, 50, 100, 200, 300, 400, 500, 600, 800, 1000. Mu.M from top to bottom; (B) The relationship between the absorbance of the reaction system at 652 nm and the concentration of D-Ala, the inset shows the linear range;
FIG. 3 (A) is a graph showing the ultraviolet-visible absorption spectrum after adding D-Pro at different concentrations to the detection system, wherein the concentrations of D-Pro are 0, 10, 20, 30, 40, 50, 100, 150, 200, 300, 400, 600, 800, 1000. Mu.M from top to bottom; (B) The relationship between absorbance of the reaction system at 652 nm and D-Pro concentration, the inset shows the linear range;
FIG. 4 (A) test of tamper resistance of the detection system; (B) Testing of human saliva samples, samples 1,2,3 from healthy persons; samples 4,5,6 were from gastric cancer patients;
the absorbance of different samples in FIG. 5 is CDs@NC-3, CDs@NC-2, CDs@NC-1, ZIF-8-900+CDs, CDs, ZIF-8-900 in sequence from top to bottom, and CDs@NC-1 represents that the glucose concentration is 1 mM; CDs@NC-2 represents a glucose concentration of 2 mM; CDs@NC-3 represents a glucose concentration of 3 mM; CDs means carbon spots obtained by immersing the prepared cds@zif-8 in a 1 mM KOH solution for etching and then filtering and extracting with diethyl ether; ZIF-8-900 represents a material heated directly to 900℃without glucose addition; ZIF-8-900+CDs are materials obtained by mechanically mixing ZIF-8-900 with CDs.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
(1) Preparation and characterization of nitrogen-doped carbon-coated carbon dots:
(1) preparation of ZIF-8. Dissolving 4 g dimethyl imidazole in 60 mL methanol solution; 1.68 g Zn (NO) 3 ) 2 ·6H 2 Dissolving O into 20 mL methanol solution, adding the solution, and stirring vigorously at room temperature for 1 h; incubating the mixture at room temperature for 24 h without stirring; and (5) centrifugal washing and drying.
(2) Preparation of G@ZIF-8. 200 mg ZIF-8 powder was immersed in a glucose (G) solution (1-3 mM EtOH/H 2 O=9: 1) In the above, stirring at room temperature for 6H, centrifuging to separate white powder, and using EtOH/H 2 O=9: 1, and finally drying under vacuum at 60 ℃ overnight.
(3) Preparation of CDs@ZIF-8. Placing G@ZIF-8 powder in a tube furnace, heating to 200deg.C from room temperature under nitrogen, and maintaining the temperature at 200deg.C for 3h at a heating rate of 5deg.C for min -1 . Cooling to room temperature to obtain CDs@ZIF-8.
(4) Preparation of CDs@NC. Transferring the powder of CDs@ZIF-8 into a tube furnace, heating to 900 ℃ from room temperature under nitrogen, and preserving heat for 3h at a heating rate of 5 ℃ for min -1 And obtaining the carbon point coated by the nitrogen-doped carbon.
The prepared nano-enzyme is characterized by a transmission electron microscope and an ultraviolet-visible absorption spectrum. The size of the prepared nano-enzyme is about 250 nm as can be seen from the characterization result of the transmission electron microscope in fig. 1. Many black dots of about 1.9 nm size and lattice fringes of carbon dots (d=0.21 nm) can be seen at high resolution, indicating that we were successful in preparing nitrogen-doped carbon-coated carbon dots.
Preparing CDs@NC materials with different concentrations of glucose content respectively, preparing different materials by using different heating temperatures, and comparing the absorbance of the materials; see FIG. 5 for absorbance of different samples, CDs@NC-1 representing a glucose concentration of 1 mM; CDs@NC-2 represents a glucose concentration of 2 mM; CDs@NC-3 represents a glucose concentration of 3 mM; CDs means carbon spots obtained by immersing the prepared cds@zif-8 in a 1 mM KOH solution for etching and then filtering and extracting with diethyl ether; ZIF-8-900 represents a material heated directly to 900℃without glucose addition; ZIF-8-900+CDs are materials obtained by mechanically mixing ZIF-8-900 with CDs. The difference in absorbance represents the difference in the peroxidase-like activity of the material, and the higher the absorbance, the better the peroxidase-like activity of the material.
(2) Determination of D-Ala (or D-Pro): first, a solution containing 10. Mu.L of DAAO (10U mL -1 ) Incubation of a mixture of solution, 20 μl of different concentrations of D-Ala (or D-Pro) solution and 170 μl of PBS buffer (ph=6.8) at 37 ℃ for 45 min resulted in H 2 O 2。 Then 50. Mu.L of TMB (5 mM) solution, 20. Mu.L of CDs@NC (0.5 mg mL) were added to the above solution -1 ) And 730 μl of acetic acid-sodium acetate buffer (ph=4.0, 0.2M). Then incubated at 30℃for 30 minutes, and UV-visible absorption spectra were collected.
In FIG. 2 (A), the ultraviolet-visible absorption spectrum after adding D-Ala at different concentrations to the detection system is shown, wherein the concentrations of D-Ala are 0, 10, 20, 30, 50, 100, 200, 300, 400, 500, 600, 800, 1000. Mu.M from top to bottom. (B) The relationship between absorbance and D-Ala concentration of the reaction system at 652 nm is plotted as a linear range. FIG. 3 (A) is a graph showing the ultraviolet-visible absorption spectrum after adding D-Pro at different concentrations to the detection system, wherein the concentrations of D-Pro are 0, 10, 20, 30, 40, 50, 100, 150, 200, 300, 400, 600, 800, 1000. Mu.M from top to bottom; (B) The relationship between absorbance and D-Pro concentration of the reaction system at 652 nm is plotted as a linear range. The linear range for D-Ala was: 20-400. Mu.M, the detection limit is 20. Mu.M. The linear range of D-Pro is: 20-300 mu M, and the detection limit is 20 mu M.
FIG. 4 shows the anti-interference capability test and the test results, wherein the content of D-Ala (or D-Pro) in saliva of early gastric cancer patients is above the detection limit of the detection system of the early gastric cancer patients, and the content of saliva of healthy people is below the detection limit of the detection system of the early gastric cancer patients.
The substances possibly influencing the detection system in saliva are detected, and researches show that the substances can not influence the detection system after being added, so that the method has better selectivity.
(3) Measurement of human saliva samples: we measured saliva from three healthy persons and three gastric cancer patients. Directly taking a saliva sample of a human body for testing. Specific test methods are as for the detection of D-Ala (or D-Pro). The detection result shows that saliva of healthy people does not develop color in the detection system, and saliva of gastric cancer patients develops color in the detection system, which has important significance for diagnosing gastric cancer patients.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (3)
1. The application of carbon-point peroxidase CDs@NC in detecting D-alanine and D-proline is characterized in that D-Ala and D-Pro can generate H in the presence of DAAO 2 O 2 At H 2 O 2 Under the combined action of CDs@NC, colorless TMB is changed into blue TMB, and an obvious absorption peak appears at 652-nm on an ultraviolet-visible spectrum, so that the detection of D-Ala and D-Pro can be realized based on the change of the intensity of the ultraviolet absorption peak along with the concentration of D-Ala and D-Pro;
the preparation method of the CDs@NC comprises the following steps:
(1) preparation of ZIF-8: dissolving 4 g dimethyl imidazole in60 In mL of methanol solution; 1.68 g Zn (NO) 3 ) 2 ·6H 2 Dissolving O into 20 mL methanol solution, adding the solution, and stirring vigorously at room temperature for 1 h; incubating the mixture at room temperature for 24 h without stirring; centrifugal washing and drying to obtain ZIF-8;
(2) preparation of G@ZIF-8: immersing 200 mg ZIF-8 powder in glucose solution, stirring at room temperature for 6H, centrifuging to separate white precipitate, and concentrating with EtOH/H 2 O=9: 1, washing the solution for three times, and drying at 60 ℃ under vacuum overnight; the concentration of the glucose solution is 1-3 mM, and the solution is EtOH/H 2 O=9: 1 by volume ratio;
(3) preparation of CDs@ZIF-8: heating the G@ZIF-8 powder to 200 ℃, preserving heat, and cooling to room temperature to obtain CDs@ZIF-8;
(4) preparation of CDs@NC: the powder of CDs@ZIF-8 is heated to 900 ℃ and incubated to obtain CDs@NC.
2. The use of the carbon-point peroxidase CDs@NC according to claim 1, wherein the atmosphere in which the G@ZIF-8 powder is heated to 200 ℃ is N 2 The temperature rising rate is 5 ℃ for min -1 The heat preservation time is 3h.
3. The use of the carbon-point peroxidase CDs@NC as defined in claim 1 for detecting D-alanine and D-proline, wherein the powder of CDs@ZIF-8 is heated to 900 ℃ in an atmosphere of N 2 The temperature rising rate is 5 ℃ for min -1 The heat preservation time is 3h.
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| CN113460993B (en) * | 2021-06-29 | 2022-07-05 | 湘潭大学 | Zinc-nitrogen modified dual-carbon catalytic material, preparation method thereof and application thereof in zinc-air battery |
| CN113493197B (en) * | 2021-07-22 | 2022-06-21 | 哈尔滨工程大学 | Preparation method of carbon dot/porous silica nanoenzyme with peroxidase-like activity |
| CN114479113B (en) * | 2022-03-18 | 2023-04-21 | 中国农业科学院蔬菜花卉研究所 | Two-dimensional fluorescent MOFs composite material, preparation method and application thereof, and method for detecting iron ions through fluorescence |
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