CN114011470A - Catalyst for hydrolyzing adenosine triphosphate and preparation method and application thereof - Google Patents
Catalyst for hydrolyzing adenosine triphosphate and preparation method and application thereof Download PDFInfo
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- CN114011470A CN114011470A CN202111435169.6A CN202111435169A CN114011470A CN 114011470 A CN114011470 A CN 114011470A CN 202111435169 A CN202111435169 A CN 202111435169A CN 114011470 A CN114011470 A CN 114011470A
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- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 title claims abstract description 139
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 17
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- 238000000835 electrochemical detection Methods 0.000 claims abstract description 48
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- IGRWTCFRZATNPW-UHFFFAOYSA-N 4-[6-(4-carboxyphenyl)-1,4-dihydro-1,2,4,5-tetrazin-3-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)C1=NNC(=NN1)c1ccc(cc1)C(O)=O IGRWTCFRZATNPW-UHFFFAOYSA-N 0.000 claims abstract description 19
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013543 active substance Substances 0.000 claims description 29
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- OQRXBXNATIHDQO-UHFFFAOYSA-N 6-chloropyridine-3,4-diamine Chemical compound NC1=CN=C(Cl)C=C1N OQRXBXNATIHDQO-UHFFFAOYSA-N 0.000 description 1
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- NBSCHQHZLSJFNQ-GASJEMHNSA-N D-Glucose 6-phosphate Chemical compound OC1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H](O)[C@H]1O NBSCHQHZLSJFNQ-GASJEMHNSA-N 0.000 description 1
- VFRROHXSMXFLSN-UHFFFAOYSA-N Glc6P Natural products OP(=O)(O)OCC(O)C(O)C(O)C(O)C=O VFRROHXSMXFLSN-UHFFFAOYSA-N 0.000 description 1
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- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
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- 238000001903 differential pulse voltammetry Methods 0.000 description 1
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
- C07H19/16—Purine radicals
- C07H19/20—Purine radicals with the saccharide radical esterified by phosphoric or polyphosphoric acids
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
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Abstract
The invention relates to the technical field of adenosine triphosphate detection, in particular to a catalyst for hydrolyzing adenosine triphosphate, a preparation method thereof and application thereof in electrochemical detection of adenosine triphosphate. The catalyst comprises a metal organic framework material, wherein a metal element in the metal organic framework material is cerium, and an organic ligand is 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid. The catalyst of the invention has adjustable adenosine triphosphate hydrolysis activity and can simultaneously realize adenosine triphosphate hydrolysis and electrochemical detection.
Description
Technical Field
The invention relates to the technical field of adenosine triphosphate detection, in particular to a catalyst for hydrolyzing adenosine triphosphate, a preparation method thereof and application thereof in electrochemical detection of adenosine triphosphate.
Background
Adenosine Triphosphate (ATP) hydrolysis materials are primarily cerium-based oxides, for example ceria can hydrolyze adenosine triphosphate to adenosine diphosphate and phosphate. Only one example of a cerium-based metal organic framework material with terephthalic acid as an organic ligand has been reported to hydrolyze adenosine triphosphate and adenosine diphosphate.
On the other hand, adenosine triphosphate electrochemical sensors are mainly classified into three major groups: (1) aptamer-based sensors, such as Fan et al, hybridize thiol and ferrocenyl labeled aptamer oligonucleotides to their complementary strands and then self-assemble on gold electrodes to prepare aptamer-based sensors for quantitative detection of adenosine triphosphate. Mao and the like construct a double recognition unit by combining the base recognition capability of an aptamer and the phosphate recognition capability of polyimidazole, and the selective and sensitive detection of adenosine triphosphate is realized. (2) Enzyme-based biosensors, where adenosine triphosphate is electrochemically inactive, require the use of natural enzymes to convert adenosine triphosphate into an electrochemically detectable substance. For example, Dale et al prepared an adenosine triphosphate biosensor by combining hexokinase with glucose oxidase, and read the change in adenosine triphosphate by the change in glucose signal when glucose is phosphorylated to glucose-6-phosphate; in addition, Hinzman et al utilize three enzymes (adenosine deaminase, nucleoside phosphorylase, xanthine oxidase) to convert adenosine to H which can be detected electrochemically2O2. (3) And (3) a sensor based on other micro-nano materials. The sensor realizes sensitive detection of adenosine triphosphate by utilizing the recognition of the adenosine triphosphate by micro-nano materials and the like. For example, the inventor wraps laccase in ZIF-90 in earlier work, and based on the damage effect of adenosine triphosphate on ZIF-90, dopamine is used as an electrochemical probe, so that sensitive detection of trace adenosine triphosphate in rat brain is realized. Mao et al, based on the competitive binding capacity of positively charged polyimidazole and adenosine triphosphate with negatively charged adenosine triphosphate aptamers, implemented sensitive detection of adenosine triphosphate using micron-scale ion current rectification (MICR).
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
the existing adenosine triphosphate hydrolysis material has fixed types and performances, can only hydrolyze adenosine triphosphate, is not related to physiologically active substances in organisms, has no electrochemical activity, and cannot be applied to an adenosine triphosphate electrochemical sensor.
For adenosine triphosphate electrochemical sensors, aptamer-based sensors are less selective because they have similar forces for adenosine triphosphate, adenosine diphosphate, and adenosine monophosphate; the sensor based on natural enzyme needs the cascade of a plurality of enzymes, has complex operation and harsh enzyme survival conditions, so the sensor has poor stability; the sensor based on the micro-nano material may have the problems of non-uniformity of the size and volume of the micro-nano material and the like, so that the performances of the sensor such as reproducibility and sensitivity are reduced.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a catalyst for hydrolyzing adenosine triphosphate, a preparation method thereof and application in electrochemical detection of adenosine triphosphate, wherein the catalyst can realize the hydrolysis and the electrochemical detection of the adenosine triphosphate simultaneously.
The catalyst for hydrolyzing adenosine triphosphate comprises a metal organic framework material, wherein a metal element in the metal organic framework material is cerium, and an organic ligand is 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid.
The catalyst for hydrolyzing adenosine triphosphate according to the embodiment of the present invention brings advantages and technical effects: 1. after intensive and extensive research on organic ligands in metal-organic framework materials, the inventor finds that the catalytic activity of the metal-organic framework materials can be adjusted by adopting 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid as the organic ligand, and particularly, the metal-organic framework materials containing the ligand can be oxidized by physiologically active substances to enhance the electron-withdrawing capability of the metal-organic framework materials, so that the hydrolysis performance of the metal-organic framework materials on adenosine triphosphate is enhanced; 2. the organic ligand of the metal organic framework material of the embodiment of the invention has good electrochemical activity, and is particularly shown in that the metal organic framework material can be electrochemically oxidized and reduced, thereby realizing the electrochemical detection of adenosine triphosphate; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; 3. after the catalyst provided by the embodiment of the invention is oxidized by the physiologically active substance, the hydrolysis catalytic activity of adenosine triphosphate is enhanced, and by utilizing the characteristic, the catalyst provided by the embodiment of the invention can enhance the hydrolysis performance of the physiologically active substance with oxidation in a living body.
In some embodiments of the invention, the metal-organic framework material is optionally oxidized by a physiologically active substance comprising hydrogen peroxide.
The preparation method of the catalyst for hydrolyzing adenosine triphosphate comprises the following steps:
a. heating and refluxing 4-cyanobenzoic acid in a hydrazine solution, cooling, collecting a precipitate, and drying to obtain 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid;
b. and c, dissolving the 4,4'- (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid obtained in the step a in N' N-dimethylformamide, mixing with a metal salt solution for reaction, collecting a precipitate after the reaction, and drying to obtain the metal organic framework material, wherein a metal element of the metal salt solution is cerium.
The preparation method of the catalyst for hydrolyzing adenosine triphosphate according to the embodiment of the invention has the following advantages and technical effects: 1. after intensive and extensive research on organic ligands in metal-organic framework materials, the inventor finds that the catalytic activity of the metal-organic framework materials can be adjusted by adopting 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid as the organic ligand, and specifically, the metal-organic framework materials containing the ligand can be oxidized by physiologically active substances or electrochemically to enhance the electron-withdrawing capability of the metal-organic framework materials, so that the hydrolysis performance of the metal-organic framework materials on adenosine triphosphate is enhanced; 2. the organic ligand of the metal organic framework material of the embodiment of the invention has good electrochemical activity, and is particularly shown in that the metal organic framework material can be electrochemically oxidized and reduced, thereby realizing the electrochemical detection of adenosine triphosphate; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; 3. the preparation method of the catalyst for hydrolyzing adenosine triphosphate in the embodiment of the invention has the advantages of simple and controllable preparation process, low cost and easy realization of industrial production, and furthermore, the preparation method of the embodiment of the invention adopts metal materials with wide sources, easy obtainment and low cost.
In some embodiments of the present invention, in step a,
the mass ratio of the 4-cyanobenzoic acid to the hydrazine is 0.1-0.4;
and/or the heating reflux temperature is 80-90 ℃, the time is 3-5h, and the drying temperature is 50-60 ℃.
In some embodiments of the present invention, in step b,
the molar ratio of the 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid to the metal is (5-10): 1;
and/or the reaction temperature is 110-130 ℃, and the reaction time is 16-32 h.
In some embodiments of the invention, optionally, the method of preparing further comprises: c. standing the metal organic framework material in a water solution of a physiologically active substance for oxidation, and washing and drying a solid product after the oxidation is finished to obtain an oxidized metal organic framework material;
wherein the physiologically active substance comprises hydrogen peroxide.
In some embodiments of the present invention, in the step c, the concentration of the physiologically active substance is 0.01 to 1mol/L, and the oxidation reaction time is 1 to 5 hours.
The embodiment of the invention also provides an application of the catalyst or the catalyst obtained by the preparation method in adenosine triphosphate electrochemical detection, wherein the metal organic framework material is not oxidized.
The catalyst of the embodiment of the invention or the catalyst obtained by the preparation method has the advantages and technical effects brought by the application in the electrochemical detection of adenosine triphosphate: 1. the organic ligand of the catalyst has good electrochemical activity, and specifically shows that the metal organic framework material can be electrochemically oxidized and reduced, so that the electrochemical detection of adenosine triphosphate is realized; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; 2. the metal organic framework material provided by the embodiment of the invention can realize hydrolysis catalysis and electrochemical detection of adenosine triphosphate at the same time.
The working electrode for electrochemically detecting adenosine triphosphate comprises an electrode body, wherein the surface of the electrode body is modified with the catalyst or the catalyst obtained by the method, and the metal organic framework material is not oxidized.
The working electrode for electrochemically detecting adenosine triphosphate provided by the embodiment of the invention has the following advantages and technical effects: the surface of the working electrode of the embodiment of the invention is modified with a metal organic framework material with electrochemical activity, and the metal organic framework material can be used for the electrochemical detection of adenosine triphosphate.
The electrochemical detection system for adenosine triphosphate comprises the working electrode.
The electrochemical detection system for adenosine triphosphate of the embodiment of the invention has the following advantages and technical effects: the detection system provided by the embodiment of the invention takes the metal organic framework material provided by the embodiment of the invention as a sensor, realizes the selective detection of the adenosine triphosphate through the interaction of the adenosine triphosphate and the metal organic framework material, and has no participation of natural enzymes and aptamers, so that the electrochemical detection system provided by the embodiment of the invention has a simple structure and strong sensor stability.
Drawings
FIG. 1 is a schematic diagram of the enhancement of adenosine triphosphate hydrolysis by oxidation of a metal-organic framework material and the electrochemical detection of adenosine triphosphate by a metal-organic framework material according to an embodiment of the present invention;
FIG. 2 is Ce-MOF and Ce-MOF (H) prepared in example 12O2) Transmission electron microscopy images and scanning electron microscopy images of the two catalysts, wherein a is the transmission electron microscopy image of Ce-MOF; b is a scanning electron micrograph of Ce-MOF; c is Ce-MOF (H)2O2) Transmission electron microscope images of (a); d isCe-MOF(H2O2) Scanning electron microscopy images of (a);
FIG. 3 is a drawing of Ce-MOF and Ce-MOF (H) prepared in example 12O2) Structural characterization images of the two catalysts, wherein a is X-ray diffraction spectrum (XRD), B is thermogravimetric analysis (TGA), C is infrared spectroscopy (FTIR), and D is X-ray photoelectron spectroscopy (XPS).
FIG. 4 is a representation of Ce-MOF and Ce-MOF (H) prepared in example 12O2) The method comprises the following steps of (1) testing the hydrolysis catalytic performance of adenosine triphosphate of two catalysts, wherein A is a hydrolysis performance test, and B is a hydrolysis rate test;
FIG. 5 is a schematic diagram of the detection method of the adenosine triphosphate electrochemical detection system of example 2;
FIG. 6 is a test of the system for electrochemical detection of adenosine triphosphate of example 2, wherein A is a performance test, B is an interference test, and C, D is a linear test.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The catalyst for hydrolyzing adenosine triphosphate comprises a metal organic framework material, wherein a metal element in the metal organic framework material is cerium, and an organic ligand is 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid.
According to the catalyst for hydrolyzing adenosine triphosphate provided by the embodiment of the invention, after intensive and extensive research on an organic ligand in a metal organic framework material, the inventor finds that the catalytic activity of the metal organic framework material can be adjusted by adopting 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid as the organic ligand, and specifically, the metal organic framework material containing the ligand can be oxidized by a physiologically active substance so that the electron-withdrawing capability of the metal organic framework material is enhanced, so that the hydrolysis performance of the metal organic framework material on adenosine triphosphate is enhanced; the organic ligand of the metal organic framework material of the embodiment of the invention has good electrochemical activity, and is particularly shown in that the metal organic framework material can be electrochemically oxidized and reduced, thereby realizing the electrochemical detection of adenosine triphosphate; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; after the catalyst provided by the embodiment of the invention is oxidized by the physiologically active substance, the hydrolysis catalytic activity of adenosine triphosphate is enhanced, and by utilizing the characteristic, the catalyst provided by the embodiment of the invention can enhance the hydrolysis performance of the physiologically active substance with oxidation in a living body.
In some embodiments of the invention, the metal-organic framework material is optionally oxidized by a physiologically active substance comprising hydrogen peroxide.
In the catalyst of the embodiment of the invention, after the catalyst is oxidized by the physiologically active substance, the hydrolysis catalytic activity of adenosine triphosphate is enhanced. This is because the valence of the metal element is increased and the cerium element is changed from positive trivalent to positive quadrivalent after the metal-organic framework material is oxidized by the physiologically active substance. The high valence metal element is the main site of nucleophilic reaction between the metal organic framework material and adenosine triphosphate; therefore, the high valence metal element is increased, and the reactivity of the metal-organic framework is enhanced. Meanwhile, after the organic ligand part of the metal organic framework material is oxidized by hydrogen peroxide, the dihydrotetrazine of the metal organic framework material is changed into a tetrazine structure, the electron-withdrawing capability is enhanced, and adenosine triphosphate with negative charges can be adsorbed more quickly.
The preparation method of the catalyst for hydrolyzing adenosine triphosphate comprises the following steps:
a. heating and refluxing 4-cyanobenzoic acid in a hydrazine solution, cooling, collecting a precipitate, and drying to obtain 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid;
b. and c, dissolving the 4,4'- (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid obtained in the step a in N' N-dimethylformamide, mixing with a metal salt solution for reaction, collecting a precipitate after the reaction, and drying to obtain the metal organic framework material, wherein a metal element of the metal salt solution is cerium.
According to the preparation method of the catalyst for hydrolyzing adenosine triphosphate, the inventor conducts intensive and extensive research on organic ligands in the metal-organic framework material, and then finds that the catalytic activity of the metal-organic framework material can be adjusted by adopting 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid as the organic ligand, and specifically, the metal-organic framework material containing the ligand can be oxidized by a physiologically active substance and the electron-withdrawing capability of the metal-organic framework material is enhanced, so that the hydrolysis performance of the metal-organic framework material on adenosine triphosphate is enhanced; the organic ligand of the metal organic framework material of the embodiment of the invention has good electrochemical activity, and is particularly shown in that the metal organic framework material can be electrochemically oxidized and reduced, thereby realizing the electrochemical detection of adenosine triphosphate; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; the preparation method of the catalyst for hydrolyzing adenosine triphosphate in the embodiment of the invention has the advantages of simple and controllable preparation process, low cost and easy realization of industrial production, and furthermore, the preparation method of the embodiment of the invention adopts metal materials with wide sources, easy obtainment and low cost.
In some embodiments of the present invention, in step a,
the mass ratio of the 4-cyanobenzoic acid to the hydrazine is 0.1-0.4, preferably 0.15;
and/or the heating reflux temperature is 80-90 ℃, the time is 3-5h, and the drying temperature is 50-60 ℃.
In some embodiments of the present invention, in step b,
the molar ratio of the 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid to the metal is (5-10):1, preferably 8: 1;
and/or the reaction temperature is 110-130 ℃, and the reaction time is 16-32 h.
In some embodiments of the invention, optionally, the method of preparing further comprises: c. standing the metal organic framework material in a water solution of a physiologically active substance for oxidation, and washing and drying a solid product after the oxidation is finished to obtain an oxidized metal organic framework material;
wherein the physiologically active substance comprises hydrogen peroxide.
In some embodiments of the present invention, in the step c, the concentration of the physiologically active substance is 0.01 to 1mol/L, and the oxidation reaction time is 1 to 5 hours.
The embodiment of the invention also provides an application of the catalyst or the catalyst obtained by the preparation method in adenosine triphosphate electrochemical detection, wherein the metal organic framework material is not oxidized.
The catalyst or the catalyst obtained by the preparation method of the embodiment of the invention is applied to the electrochemical detection of adenosine triphosphate, and the organic ligand of the catalyst of the embodiment of the invention has good electrochemical activity, and specifically shows that the metal organic framework material can be electrochemically oxidized and reduced, so that the electrochemical detection of adenosine triphosphate is realized; adenosine triphosphate is a non-electrochemical active substance, while the ligand in the existing adenosine triphosphate hydrolysis catalyst has no electrochemical activity or poor electrochemical activity and cannot be used for electrochemical detection of the adenosine triphosphate; the metal organic framework material provided by the embodiment of the invention can realize hydrolysis catalysis and electrochemical detection of adenosine triphosphate at the same time.
In the application of the embodiment of the present invention, as shown in fig. 1, the catalyst of the embodiment of the present invention can be applied to the electrochemical detection of adenosine triphosphate due to its electrochemical activity, and its principle is as follows: the negative charge carried by the adenosine triphosphate can be combined with positively charged metal ions through electrostatic interaction so that the adenosine triphosphate is combined with the metal organic framework material, the adenosine triphosphate is an organic molecule without electrochemical activity, and after the adenosine triphosphate is combined with the metal ions, the generated steric hindrance can block the electron transmission of the metal organic framework material and influence the electrochemical redox of a ligand in the metal organic framework material, so that the metal organic framework material provided by the embodiment of the invention can also be used for detecting the electrochemical content of the adenosine triphosphate.
Further, in the application of the embodiment of the present invention, the metal organic framework material which is not oxidized or not completely oxidized can be used for the electrochemical detection of adenosine triphosphate. If the organic ligand of the metal-organic framework material is completely oxidized, the electrochemical detection of the adenosine triphosphate can only show a weaker oxidation peak or not show an oxidation peak, and the electrochemical detection of the adenosine triphosphate in the embodiment of the invention depends on the oxidation peak of the organic ligand of the metal-organic framework material, so that the completely oxidized metal-organic framework material cannot be used for the electrochemical detection of the adenosine triphosphate, but the metal-organic framework material can enhance the hydrolysis catalytic performance of the adenosine triphosphate.
The working electrode for electrochemically detecting adenosine triphosphate comprises an electrode body, wherein the surface of the electrode body is modified with the catalyst or the catalyst obtained by the method, and the metal organic framework material is not oxidized.
The working electrode for electrochemically detecting adenosine triphosphate provided by the embodiment of the invention is modified with a metal organic framework material with electrochemical activity on the surface, and can be used for electrochemically detecting adenosine triphosphate.
Preferably, the preparation method of the working electrode for electrochemical detection of adenosine triphosphate in the embodiment of the present invention comprises: uniformly dispersing a metal organic framework material in an aqueous solution to prepare a dispersion liquid with the concentration of 2g/L, polishing the glassy carbon electrode by using 0.05 mu m and 1 mu m of aluminum oxide polishing powder respectively, then dripping 5 mu L of the dispersion liquid on the surface of the polished glassy carbon electrode, and airing at room temperature for later use.
The electrochemical detection system for adenosine triphosphate comprises the working electrode.
According to the electrochemical detection system for adenosine triphosphate provided by the embodiment of the invention, the metal organic frame material provided by the embodiment of the invention is used as a sensor, the selective detection of the adenosine triphosphate is realized through the interaction of the adenosine triphosphate and the metal organic frame material, and no natural enzyme or aptamer is involved, so that the electrochemical detection system provided by the embodiment of the invention has a simple structure and strong sensor stability.
Preferably, the electrochemical detection system of the embodiment of the present invention comprises: the working electrode modified with the catalyst of the embodiment of the invention through adsorption, a silver/silver chloride reference electrode, a platinum wire counter electrode, an electrochemical workstation, an adenosine triphosphate solution to be detected and a Tris (hydroxymethyl) aminomethane hydrochloride buffer solution (Tris, pH 7.4). The detection method of the detection system of the embodiment of the invention comprises the following steps: suspending the working electrode in a blank secondary aqueous solution/adenosine triphosphate solution to be detected, standing for one minute, and taking out; cleaning the electrode in a secondary aqueous solution; the working, reference and counter electrodes were then placed in tris hydrochloride buffer (pH 7.4) and connected to an electrochemical workstation for electrochemical testing.
The present invention will be described in detail below with reference to examples and the accompanying drawings.
Example 1
(1) Preparation of non-oxidized cerium-based metal organic framework materials
a. Weighing 6.0g of 4-cyanobenzoic acid, adding the 4-cyanobenzoic acid into a 100mL round-bottom flask, then adding 40.0mL of 35% hydrazine solution, and then heating the mixed solution to 85 ℃ for refluxing for 4 hours with continuous stirring; after the reaction is finished, cooling to room temperature, filtering and collecting yellow solid, washing with deionized water, and drying in vacuum at 60 ℃ overnight to obtain 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid;
b. 0.2746g of 4,4'- (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid were weighed out and dissolved in 20mL of N' N-dimethylformamide as solution A; 0.0584g of ammonium cerium nitrate were weighed out and dissolved in 200. mu.L of deionized water as solution B. And mixing the two solutions, stirring for 24 hours at 120 ℃, centrifuging, washing, and vacuum-drying overnight at 60 ℃ to obtain a yellow cerium-based metal organic framework material, which is recorded as Ce-MOF.
(2) Preparation of oxidized cerium-based metal organic framework materials
Adding 0.005g of Ce-MOF into 2mL of hydrogen peroxide with the concentration of 0.1mol/L, standing for 2H, centrifuging, washing with deionized water, and drying to obtain the hydrogen peroxide-treated cerium-based metal organic framework material, which is marked as Ce-MOF (H-MOF)2O2)。
Ce-MOF and Ce-MOF (H) prepared in this example2O2) Two catalysts were characterized, wherein transmission electron microscopy images and scanning electron microscopy are shown in the figure2, XRD, TGA, FTIR, XPS images are shown in FIG. 3.
Ce-MOF and Ce-MOF (H) prepared in this example2O2) The adenosine triphosphate hydrolysis performance of the two catalysts is tested, and the test method specifically comprises the following steps: 50 μ g/mL Ce-MOF, Ce-MOF (H)2O2) Separately, 100. mu. mol/L of adenosine triphosphate was mixed at a volume ratio of 1:1, incubated in a constant temperature shaker (37 ℃ C., 150rpm), and the concentration of free phosphate in the solution was measured using a phosphate kit or the concentration of adenosine triphosphate was measured using an adenosine triphosphate kit. The test results are shown in FIG. 4, both catalysts have good adenosine triphosphate hydrolysis, Ce-MOF (H)2O2) The hydrolysis capability and the hydrolysis efficiency are better.
Example 2
(1) Preparation of working electrode for electrochemical detection of adenosine triphosphate
Uniformly dispersing 2mg of Ce-MOF obtained in example 1 in 1mL of secondary aqueous solution to prepare a material dispersion liquid, polishing the glassy carbon electrode by using 0.05 mu m and 1 mu m of alumina polishing powder respectively, then dripping 5 mu L of the material dispersion liquid on the surface of the polished glassy carbon electrode, and airing at room temperature for later use to obtain the working electrode modified with Ce-MOF.
(2) Construction of an electrochemical detection System for adenosine triphosphate
The electrochemical detection system of adenosine triphosphate comprises: a working electrode modified with Ce-MOF, a silver/silver chloride reference electrode, a platinum wire counter electrode, an electrochemical workstation, an adenosine triphosphate solution to be detected and a Tris (hydroxymethyl) aminomethane hydrochloride buffer solution (Tris, pH 7.4). As shown in fig. 5, the detection method of the detection system is as follows: suspending the working electrode in a blank secondary aqueous solution/adenosine triphosphate solution to be detected, standing for one minute, and taking out; cleaning the electrode in a secondary aqueous solution; the working, reference and counter electrodes were then placed in tris hydrochloride buffer (pH 7.4) and connected to an electrochemical workstation for electrochemical testing.
The electrochemical detection system of this example was subjected to performance testing, and the results are shown in FIG. 6.
The performance of Ce-MOF for detecting ATP was tested using Differential Pulse Voltammetry (DPV). As shown in fig. 6A, when ATP is present, the peak current decreases, and since ATP and metal ions in MOF are bonded together through electrostatic interaction, the larger molecular structure of ATP generates a certain steric hindrance, which affects the electron conduction in MOF, resulting in reduced oxidation of dihydrotetrazine in MOF ligand.
The anti-interference capability of the detection system is tested, and as shown in FIG. 6B, the influence of ADP, AMP, Pi and PPi is negligible relative to the current response of ATP.
The concentration response range of the detection system was tested and fig. 6C and 6D show that the system responded well in the 0.2-15 μ M concentration range.
Therefore, the Ce-MOF prepared by the embodiment of the invention can realize the electrochemical detection of adenosine triphosphate.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The catalyst for hydrolyzing adenosine triphosphate is characterized by comprising a metal organic framework material, wherein a metal element in the metal organic framework material is cerium, and an organic ligand is 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid.
2. The catalyst of claim 1, wherein the metal organic framework material is optionally oxidized by a physiologically active substance comprising hydrogen peroxide.
3. A preparation method of a catalyst for hydrolyzing adenosine triphosphate is characterized by comprising the following steps:
a. heating and refluxing 4-cyanobenzoic acid in a hydrazine solution, cooling, collecting a precipitate, and drying to obtain 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid;
b. and c, dissolving the 4,4'- (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid obtained in the step a in N' N-dimethylformamide, mixing with a metal salt solution for reaction, collecting a precipitate after the reaction, and drying to obtain the metal organic framework material, wherein a metal element of the metal salt solution is cerium.
4. The method according to claim 3, wherein in the step a,
the mass ratio of the 4-cyanobenzoic acid to the hydrazine is 0.1-0.4;
and/or the heating reflux temperature is 80-90 ℃, the time is 3-5h, and the drying temperature is 50-60 ℃.
5. The production method according to claim 3, wherein in the step b,
the molar ratio of the 4,4' - (1, 4-dihydro-1, 2,4, 5-tetrazine-3, 6-diyl) dibenzoic acid to the metal element is (5-10): 1;
and/or the reaction temperature is 110-130 ℃, and the reaction time is 16-32 h.
6. The method of claim 3, wherein optionally the method further comprises: c. placing the metal organic framework material in a water solution of a physiologically active substance for oxidation, and washing and drying a solid product after the oxidation is finished to obtain an oxidized metal organic framework material;
wherein the physiologically active substance comprises hydrogen peroxide.
7. The method according to claim 6, wherein the concentration of the physiologically active substance in the step c is 0.01 to 1mol/L, and the oxidation reaction time is 1 to 5 hours.
8. Use of the catalyst of claim 1 or the catalyst obtained by the preparation method of any one of claims 3 to 5 in the electrochemical detection of adenosine triphosphate, characterized in that the metal organic framework material is not oxidized.
9. A working electrode for electrochemical detection of adenosine triphosphate, comprising an electrode body, wherein the surface of the electrode body is modified with the catalyst of claim 1 or the catalyst obtained by the method of any one of claims 3 to 5, wherein the metal organic framework material is not oxidized.
10. An electrochemical detection system for adenosine triphosphate, comprising the working electrode according to claim 9.
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