CN114705646A - Method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material and application thereof - Google Patents
Method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material and application thereof Download PDFInfo
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- 150000003943 catecholamines Chemical class 0.000 title claims abstract description 56
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- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims abstract description 10
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Abstract
The invention discloses a method for rapidly carrying out colorimetric analysis on catecholamine based on a MnCo @ C NCs active material and application thereof, belonging to the technical field of colorimetric sensing. The method comprises the steps of firstly preparing a MnCo @ C NCs active material with a core-shell structure, adding MnCo @ C NCs into a plurality of morpholine ethanesulfonic acid buffer solution samples containing catecholamine with different concentrations by utilizing the high catalytic activity of the MnCo @ C NCs active material, carrying out reaction, recording the absorbance value A of each sample at the wavelength of 485nm after the reaction, and obtaining the detection linear relation between the catecholamine concentration and the absorbance value A. And analyzing the concentration of the catecholamine in the sample to be detected according to the detection linear relation and the absorbance value of the sample to be detected containing the catecholamine. The colorimetric detection method has the advantages of low cost, simple and convenient operation, quick response, high sensitivity and the like, and can be applied to human health diagnosis.
Description
Technical Field
The invention belongs to the technical field of colorimetric sensing, relates to a catecholamine colorimetric analysis method, and particularly relates to a rapid catecholamine colorimetric analysis method based on MnCo @ C NCs active materials and application of the rapid colorimetric analysis catecholamine colorimetric analysis method to human health diagnosis.
Background
Catecholamines are a class of biogenic compounds, including dopamine, epinephrine and norepinephrine, which play important physiological roles in the human body as neurotransmitters and hormones, and are also important markers for the diagnosis of diseases and dysfunctions, such as parkinson's disease, schizophrenia and alzheimer's disease, etc. Therefore, the determination of catecholamine in human body has very important significance for the diagnosis of diseases and the research of pathophysiological mechanism. Current methods for their determination include: the method comprises high performance liquid chromatography, a liquid chromatography-mass spectrometry combined method, a non-damage imaging technology and the like, and the methods have the problems of complicated operation of instrument and equipment, complex pretreatment, higher detection cost, long detection period and the like. Therefore, there is an urgent need to develop a low-cost, simple, rapid, and highly sensitive method for quantitatively analyzing phenolic pollutants in the environment.
Colorimetric analysis based on nanomaterials has attracted considerable attention due to its simplicity, cost-effectiveness, visualization, and field applicability. Particularly, the nano material has been applied in the colorimetric sensing field due to its low cost, simple preparation, high stability and excellent catalytic performance, which can catalyze the oxidation of catecholamine substances and generate a color reaction visible to the naked eye. However, it remains a challenge to obtain nanomaterials with high catalytic activity, which greatly limits their widespread use.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for rapidly and colorimetrically analyzing catecholamine based on MnCo @ C NCs active materials, which has the advantages of low required reagent amount, rapid response, strong anti-interference capability and the like, is low in cost, simple and convenient to operate, visualized and high in sensitivity, and can be applied to human health diagnosis.
In order to solve the technical problems, the invention adopts the following technical scheme.
A rapid colorimetric analysis method for catecholamine based on MnCo @ C NCs active materials is provided, wherein the MnCo @ C NCs are of a core-shell structure, the inner core is a MnCo bimetallic oxide, and the shell is a porous carbon shell C NCs, and the method comprises the following steps:
(1) preparation of MnCo @ C NCs:
(1.1) dispersing manganese acetate and PVP in a mixed solution of ethanol and water, stirring, adding a potassium cobalt cyanide aqueous solution, and incubating at room temperature to obtain a MnCo precursor;
(1.2) re-dispersing the MnCo precursor into an aqueous solution, then adding a dopamine aqueous solution, and reacting at room temperature to obtain a MnCo precursor of the polydopamine coating;
(1.3) carrying out high-temperature pyrolysis on the MnCo precursor of the polydopamine coating to obtain a MnCo bimetal oxide porous carbon active material with a core-shell structure, namely MnCo @ C NCs;
(2) respectively adding the prepared MnCo @ C NCs into a plurality of morpholine ethanesulfonic acid buffer solution samples containing catecholamine with different concentrations to obtain a mixed system, and recording the absorbance value A of each sample at the wavelength of 485nm after reaction to obtain a detection linear relation between the catecholamine concentration and the absorbance value A;
(3) and obtaining the concentration of the catecholamine in the sample to be detected according to the detection linear relation between the concentration of the catecholamine and the absorbance value A and the absorbance value of the sample to be detected containing the catecholamine.
In the aforementioned method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material, preferably, in the step (2), when MnCo @ C NCs are added to morpholine ethanesulfonic acid buffer solution without catecholamine, the reaction system is almost colorless. When a sample to be detected containing catecholamine is added, a reaction system generates a color reaction, so that whether the sample to be detected contains the catecholamine or not is qualitatively detected.
Preferably, the catecholamine comprises Epinephrine (EP), as described above for the rapid colorimetric analysis of catecholamines based on MnCo @ C NCs-based active materials. The linear regression equation for detecting the EP concentration and the absorbance value A is as follows:
when the concentration of 2,4-DP is 0.54-109.2. mu.M, A is 0.0035CEP+0.0153(1)；
When the concentration of 2,4-DP is 109.2-272.9. mu.M, A is 0.0005CEP+0.33(2)；
In the formulae (1) and (2), A represents an absorbance value, CEPIs the concentration value of adrenalin in the solution to be detected, the unit corresponding to the concentration value is mu M, and the correlation coefficient R of the formula (1)2Correlation coefficient R of formula (2) 0.9912The linear range of detection for epinephrine was 0.54 μ M to 272.9 μ M with a limit of detection of 0.68 μ M at 0.994.
Preferably, in the step (1.1), the mass ratio of manganese acetate to PVP is 1: 5-10, and the molar ratio of Mn to Co is 1: 1 to 3.
Preferably, in the step (1.2), the mass ratio of the dopamine to the MnCo precursor is 1: 1-3.
Preferably, in the step (2), the reaction time is 3min to 10 min. In the step (2) and the step (3), the concentration of the morpholine ethanesulfonic acid is 30 mM-50 mM.
As a general technical concept, the invention also provides an application of the method for rapidly and colorimetrically analyzing catecholamine based on the MnCo @ C NCs active material in human health diagnosis medical materials.
In the present invention, the unit M means mol/L.
In the invention, the concentrations of manganese acetate, PVP and potassium cobalt cyanide in water are not limited, and the manganese acetate, PVP and potassium cobalt cyanide can be dissolved in water.
The detection principle of the invention mainly lies in that: the MnCo @ C NCs prepared by the invention have excellent catalytic activity, can catalyze the oxidation and color development of epinephrine under the air condition and in the presence of epinephrine, change the solution into yellowish brown visible to the naked eye, have darker color along with the increase of the concentration of the epinephrine, and show the increase of the absorbance value at 485 nm. The detection of epinephrine is achieved based on a chromogenic strategy that catalyzes epinephrine oxidation.
Compared with the prior art, the invention has the advantages that:
the invention provides a rapid colorimetric analysis method for catecholamine based on MnCo @ C NCs active materials. The preparation method of the material has the advantages of simple preparation process, low cost, high stability, environmental friendliness and the like, and is suitable for large-scale preparation. Meanwhile, the Mn and Co have high catalytic activity due to the synergistic effect and reversible multiple valence states, catecholamine can be catalytically oxidized and developed to generate a red product under the air condition, and the detection sensitivity is improved. In the reaction system, other color developing agents are not needed to be added, only MnCo @ C NCs are added to catalyze the substrate to develop color, the content of the catalyst is extremely low, the catalyst can be efficiently catalyzed only at the level of mu g/mL, and the detection cost is greatly reduced. Meanwhile, the response is rapid, the color change visible to the naked eye can be observed within 3min by the colorimetric analysis method, and the detection time is greatly shortened.
The colorimetric sensing strategy is developed based on the oxidation of catecholamine, has the advantages of simplicity and convenience in operation, low cost, visualization, field application and the like, the catecholamine with different concentrations is added into a colorimetric sensing system, the detection linear relation between the catecholamine concentration and the absorbance value is established, the concentration of the catecholamine in a sample to be detected is calculated according to the detection linear regression equation, the rapid detection of the catecholamine in human body fluid (such as blood and urine) can be realized, and the colorimetric sensing strategy has good use value and market prospect.
Drawings
FIG. 1 is a scanning electron micrograph of MnCo @ C NCs prepared in example 1 of the present invention.
FIG. 2 is a graph of UV-vis of MnCo @ C NCs prepared in example 1 of the present invention catalyzing various concentrations of epinephrine.
FIG. 3 is a linear regression plot showing the absorbance values and the concentration of epinephrine measured in example 1.
FIG. 4 is a graph showing the anti-interference ability of MnCo @ C NCs for detecting epinephrine in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. In the following examples, all the raw materials and instruments used are commercially available unless otherwise specified.
Example 1
A method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active materials comprises the following steps:
(1) preparation of MnCo @ C NCs:
(1.1) dispersing manganese acetate and PVP in a mixed solution of ethanol and water, stirring, and then adding a potassium cobalt cyanide aqueous solution, wherein the mass ratio of the manganese acetate to the PVP is 1: 6, and the molar ratio of Mn to Co elements is 1: 1, incubating at room temperature to obtain a MnCo precursor;
(1.2) re-dispersing the prepared MnCo precursor into an aqueous solution, and then adding a dopamine aqueous solution, wherein the mass ratio of dopamine to the MnCo precursor is 1: 1, so as to obtain a MnCo precursor of the polydopamine coating;
and (1.3) carrying out high-temperature pyrolysis on the MnCo precursor of the polydopamine coating obtained in the step (1.2) to obtain the MnCo @ C NCs nano material. As shown in figure 1, electron microscope imaging analysis is carried out on MnCo @ C NCs, and the result shows that the MnCo @ C NCs are in a regular hollow structure, the diameter is about 150nm, and the specific surface area is increased and more active sites are provided due to the unique hollow structure. Thus, the preparation of hollow MnCo @ C NCs was successful.
(3) MnCo @ C NCs were added to a plurality of 30mM morpholine ethanesulfonic acid buffers containing adrenaline at different concentrations of 0.54. mu.M, 1.09. mu.M, 2.73. mu.M, 5.46. mu.M, 16.38. mu.M, 27.23. mu.M, 38.21. mu.M, 54.58. mu.M, 81.88. mu.M, 109.17. mu.M, 163.76. mu.M, 218.34. mu.M, 272.92. mu.M, 327.51. mu.M and 436.68. mu.M, respectively, and then reacted for 3min to obtain a reaction system.
FIG. 2 is a graph of UV-Vis of the present example in which MnCo @ C NCs catalyze various concentrations of epinephrine, and it can be seen that the absorbance value at 485nm gradually increases with increasing epinephrine concentration, and when the concentration exceeds 272.92 μ M, the absorbance value hardly changes significantly, indicating that the catalytic ability of MnCo @ C NCs has reached saturation.
(4) And recording the absorbance value A of each sample at the wavelength of 485nm after reaction to obtain the detection linear relation between the epinephrine concentration and the absorbance value A. And obtaining the concentration of the epinephrine in the sample to be detected according to the detection linear relation between the concentration of the epinephrine and the absorbance value A and the absorbance value of the sample to be detected containing the epinephrine.
In this example, the method for measuring absorbance was as follows: the sample was placed in an ultraviolet-visible spectrophotometer and the absorbance value at 485nm was measured.
FIG. 3 is a linear regression graph of the absorbance values A and the concentration of epinephrine in this example. As can be seen from fig. 3, the absorbance value a increases with the increase of epinephrine concentration, and the absorbance value a and epinephrine concentration show a good linear relationship. The detection linear regression equation is:
A＝0.0035CEP+0.0153(0.54 μ M to 109.2 μ M) and a ═ 0.0005CEP+0.33(109.2μM～272.9μM)
(1)
In the formula (1), A represents an absorbance value, CEPIs the concentration value of adrenalin in the solution to be detected, the unit corresponding to the concentration value is mu M, and the correlation coefficient R of the formula (1)2The linear range of detection for epinephrine was 0.54 μ M to 272.9 μ M with a limit of detection of 0.68 μ M, 0.991 and 0.994.
In this example, when MnCo @ C NCs were added to a morpholine ethanesulfonic acid buffer solution containing no epinephrine to give a reaction system in the case of performing step (3), the reaction system was almost colorless. When a sample to be detected containing adrenaline is added, the reaction system is in yellow brown, so that whether the sample to be detected contains adrenaline or not is qualitatively detected, and the change trend of the concentration of the adrenaline can be qualitatively judged according to the color depth of the reaction system.
Example 2
Example 2
Wherein in the step (1), the mass ratio of manganese acetate to PVP is 1: 10, the molar ratio of Mn to Co is 1: 3, incubating at room temperature to obtain a MnCo precursor; the mass ratio of the dopamine to the MnCo precursor is 1: 3.
The rest is the same as example 1.
It should be noted that the properties of MnCo @ C NCs prepared in example 2 are the same as those of MnCo @ C NCs prepared in example 1, and the MnCo @ C NCs also have better catalytic activity for epinephrine.
Therefore, the rapid colorimetric analysis method based on the MnCo @ C NCs active material can be used for detecting catecholamine.
Analysis of actual sample feasibility
The feasibility of the method for rapid colorimetric analysis of catecholamine based on the MnCo @ C NCs active material in example 1 was evaluated by using a real sample, and a standard addition method was used to detect a target in the real sample by using the colorimetric detection method, and a recovery rate experiment was performed.
(1) The method for colorimetric analysis of the concentration of epinephrine in the serum sample of example 1 comprises the following steps: different serum samples are treated by adding 10% perchloric acid to remove proteins in the serum, after the serum is filtered by a 0.22 mu m membrane, supernatant is taken and diluted by morpholine ethanesulfonic acid buffer solution, the colorimetric detection method of the embodiment 1 is adopted to detect epinephrine in a solution to be detected, and the detection results are listed in the table 1. The concentrations of adrenaline added to the samples are referred to in table 1.
As can be seen from Table 1, the method for rapidly and colorimetrically analyzing catecholamine based on the MnCo @ C NCs active material has the advantages that the recovery rate is basically 93-103.5% in a measurable concentration range, and the measurement result is ideal, so that the colorimetric detection method has the feasibility of detecting actual samples.
Interference rejection capability investigation
Evaluation of interference rejection of the MnCo @ C NCs active material-based method for rapid colorimetric analysis of catecholamines of example 1, the colorimetric detection method of example 1 was used to detect common interferents (uric acid, urea, glucose, fructose, K) in serum+、Na+、Ca2+、Mg2+Glutamic acid, histidine, cysteine) were measured for absorbance at higher concentrations A, numbered Blank, Urea, UA, Glu, Fru, K, respectively+、Na+、Ca2+、Mg2+His, Glut and Cys, the results of which are shown in fig. 4. As can be seen from the figure, the rapid colorimetric analysis method based on the active material for epinephrine has strong anti-interference capability, the absorbance of the added other interferents hardly changes, and except cysteine, the interference of cysteine can be shielded by adding an N-ethylmaleimide masking agent in the actual detection process. This shows that the colorimetric detection method of the present invention has good anti-interference capability.
The detection results show that the anti-interference capability of the method for rapidly colorimetric-analyzing catecholamine based on the MnCo @ C NCs active material has the advantages of high stability, strong universality, high sensitivity and the like, and can be used for detecting human body fluid epinephrine so as to diagnose the health of human bodies.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (7)
1. The method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material is characterized in that the MnCo @ C NCs are of a core-shell structure, the core is a MnCo bimetallic oxide, the shell is a porous carbon shell C NCs, and the method comprises the following steps:
s1, preparation of MnCo @ C NCs active material:
s1.1, dispersing manganese acetate and PVP in a mixed solution of ethanol and water, stirring, adding a potassium cobalt cyanide aqueous solution, and incubating at room temperature to obtain a MnCo precursor;
s1.2, re-dispersing the MnCo metal organic complex into an aqueous solution, then adding a dopamine aqueous solution, and reacting at room temperature to obtain a MnCo precursor of the polydopamine coating;
s1.3, carrying out high-temperature pyrolysis on the MnCo precursor of the polydopamine coating to obtain a MnCo bimetal oxide porous carbon active material with a core-shell structure, namely MnCo @ C NCs;
s2, adding the prepared MnCo @ C NCs active material into a plurality of morpholine ethanesulfonic acid buffer solution samples containing catecholamine with different concentrations respectively to obtain a mixed system, recording the absorbance value A of each sample at the wavelength of 485nm after reaction, and obtaining the detection linear relation between the catecholamine concentration and the absorbance value A;
and S3, obtaining the concentration of the catecholamine in the sample to be detected according to the detection linear relation between the concentration of the catecholamine and the absorbance value A and the absorbance value of the sample to be detected containing the catecholamine.
2. The method for rapid colorimetric analysis of catecholamines based on MnCo @ C NCs active material according to claim 1, wherein, in step S2, when MnCo @ C NCs is added to morpholine ethanesulfonic acid buffer without catecholamines, the reaction system is almost colorless; when a sample to be detected containing catecholamine is added, a reaction system generates a color development reaction and turns red, thereby qualitatively detecting whether the sample to be detected contains the catecholamine.
3. The method for rapid colorimetric analysis of catecholamines based on MnCo @ C NCs active material according to claim 1, wherein the catecholamines comprise epinephrine EP; the linear regression equation for detecting the EP concentration and the absorbance value A is as follows:
when the concentration of 2,4-DP is 0.54-109.2. mu.M, A is 0.0035CEP+0.0153 (1)；
When the concentration of 2,4-DP is 109.2-272.9. mu.M, A is 0.0005CEP+0.33 (2)；
In the formulae (1) and (2), A represents an absorbance value, CEPIs the concentration value of adrenalin in the solution to be tested, and the concentration valueCorresponding unit is mu M, and the correlation coefficient R of the formula (1)2Correlation coefficient R of formula (2) of 0.9912The linear range of detection for EP is 0.54 μ M to 272.9 μ M with a limit of detection of 0.68 μ M, 0.994.
4. The method for rapid colorimetric analysis of catecholamines based on MnCo @ C NCs active material according to any one of claims 1 to 3, wherein in step S1.1, the mass ratio of manganese acetate to PVP is 1: 5 to 10, the molar ratio of Mn to Co is 1: 1 to 3.
5. The method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material according to any one of claims 1 to 3, wherein the mass ratio of dopamine to MnCo precursor in step S1.2 is 1: 1 to 3.
6. The method for rapid colorimetric analysis of catecholamine based on MnCo @ C NCs active material according to any one of claims 1 to 3, wherein the reaction time is 3 to 10min and the concentration of morpholine ethanesulfonic acid is 30 to 50mM in step S2.
7. Use of the MnCo @ C NCs active material-based rapid colorimetric catecholamine analysis method according to any one of claims 1 to 4 or 5 to 7 in a human health diagnostic medical material.
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