CN112162024A - Black phosphorus/hemin composite material, preparation method thereof and electrochemical biosensor - Google Patents
Black phosphorus/hemin composite material, preparation method thereof and electrochemical biosensor Download PDFInfo
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- CN112162024A CN112162024A CN202010987291.3A CN202010987291A CN112162024A CN 112162024 A CN112162024 A CN 112162024A CN 202010987291 A CN202010987291 A CN 202010987291A CN 112162024 A CN112162024 A CN 112162024A
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- black phosphorus
- hemin
- composite material
- dispersion liquid
- isopropanol
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 title claims abstract description 70
- 229940025294 hemin Drugs 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 206010028980 Neoplasm Diseases 0.000 claims description 3
- 201000011510 cancer Diseases 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 2
- -1 heme chloride Chemical class 0.000 claims 2
- 150000003278 haem Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000000835 electrochemical detection Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 2
- 229960004373 acetylcholine Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 206010008342 Cervix carcinoma Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 description 1
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 201000010881 cervical cancer Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- 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
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a black phosphorus/hemin composite material and a preparation method thereof, wherein the preparation method comprises the following steps: and mixing the black phosphorus nanosheet dispersion liquid and the hemin dispersion liquid under the protection of inert gas atmosphere, stirring, and then carrying out centrifugal separation to obtain the black phosphorus/hemin composite material. The invention also discloses an electrochemical biosensor comprising the black phosphorus/hemin composite material. The black phosphorus/hemin composite material improves the stability of the black phosphorus and can be applied to a water system solution.
Description
Technical Field
The invention relates to the technical field of electrochemical biosensors, in particular to a black phosphorus/hemin composite material, a preparation method thereof and an electrochemical biosensor comprising the black phosphorus/hemin composite material.
Background
Black phosphorus is one of the four allotropes common to phosphorus, and is also the most stable, having a metallic luster and good electrical conductivity. The black phosphorus nanosheet is a novel two-dimensional material, has a layered fold structure, has high electron migration speed, obvious anisotropy and good biocompatibility, is discovered for the first time in 2014, and is used in optoelectronic devicesThe fields of biomedicine, biosensing and the like are intensively studied. The black phosphorus layer is a good electron donor, has a low oxidation-reduction potential and excellent electron transfer characteristics, and has unique advantages in the construction of electrochemical sensors. The black phosphorus nanosheet can enhance the reducibility of the catalyst in the oxygen reduction reaction, so that the sensitivity of the sensor is improved. The material based on the black phosphorus nanosheet can be used for electrochemical detection of large molecules such as enzymes, growth factors and pathogenic bacteria, and small molecules such as heavy metal ions, amino acids and hydrogen peroxide. It is a very potential electrochemical sensing material. In the prior art, because a pair of lone electrons exist in phosphorus atoms of the black phosphorus nanosheet, the black phosphorus nanosheet can be rapidly degraded to generate nontoxic P when being exposed to ambient air or aqueous solutionxOyGradually lose the original performance, which becomes a key problem for hindering the application of black phosphorus in the sensor.
The stability of the black phosphorus nanosheet can be effectively improved by isolating water and oxygen by using organic solvents such as N, N' -dimethyl propylene urea (DMPU), N-cyclohexyl-2-pyrrolidone (CHP), N-methyl pyrrolidone (NMP), Isopropanol (IPA), N-Dimethylformamide (DMF) and the like, but the application range of the black phosphorus nanosheet is also limited, especially the intracellular electrochemical detection is limited. The black phosphorus protected by the organic solvent can only be applied to an anhydrous and oxygen-free environment generally, and the application of the black phosphorus in a water system is greatly limited.
Disclosure of Invention
The invention aims to provide a composite material which can improve the stability of black phosphorus and can be applied to a water system solution.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of a black phosphorus/hemin composite material, which comprises the following steps:
and mixing the black phosphorus nanosheet dispersion liquid and the hemin dispersion liquid under the protection of inert gas atmosphere, stirring, and then carrying out centrifugal separation to obtain the black phosphorus/hemin composite material.
In the present invention, the inert gas is preferably argon gas or nitrogen gas.
Hemin is a natural metal iron porphyrin, is a two-dimensional lamellar macromolecule, and belongs to a metal organic complex. The two-dimensional lamellar macromolecular structure of the chlorhematin is utilized to be compounded with the black phosphorus nanosheet to form a sandwich structure, and the black phosphorus is protected in the chlorhematin thin layer, so that the stability of the black phosphorus is effectively improved, the chlorhematin can be applied to a water system environment, and the application range of the black phosphorus nanosheet is expanded.
Further, the black phosphorus nanosheet dispersion liquid is an isopropanol solution or an N-methyl pyrrolidone solution of the black phosphorus nanosheets, and the concentration is 0.1-0.5mg/mL, preferably 0.2 mg/mL.
Further, the chlorhematin dispersion is isopropanol solution or N-methyl pyrrolidone solution of chlorhematin, and the concentration is 3-7mg/mL, preferably 5 mg/mL.
Further, the preparation method of the hemin dispersion liquid comprises the following steps: dispersing hemin in isopropanol, ultrasonic treating, centrifuging, and collecting supernatant.
Further, the volume ratio of the black phosphorus nanosheet dispersion liquid to the hemin dispersion liquid is 1: 2-1: 8.
further, when the black phosphorus nanosheet dispersion liquid and the hemin dispersion liquid are mixed, the stirring time is 48-72h, the centrifugal rotation speed is 10000-15000rpm, and the centrifugal time is 10-15 min.
In a second aspect, the invention provides a black phosphorus/hemin composite material prepared by the method of the first aspect.
Because the hemin internally contains the electrochemical active substance Fe, the hemin can show excellent electrochemical sensing performance on nitric oxide based on the redox couple (Fe (III)/Fe (II)). Based on the above, the third aspect of the present invention provides an electrochemical biosensor, comprising an electrode and the black phosphorus/hemin composite material of the second aspect modified on the electrode.
Further, the preparation method of the electrochemical biosensor comprises the following steps: dispersing the black phosphorus/hemin composite material in a mixed solution of isopropanol and Nafion, wherein the volume ratio of the isopropanol to the Nafion in the mixed solution is 6:1-7:1, and then dispersing the obtained dispersion material on an electrode to obtain the electrode.
Preferably, the volume ratio of isopropanol to Nafion in the mixed solution is 25: 4.
In a fourth aspect, the present invention provides the use of an electrochemical biosensor as described in the third aspect for the in situ detection of NO in drug-stimulated cancer cells.
Further, the cancer cell is a cervical cancer cell (Hela cells). The drug that stimulates cells to produce NO is acetylcholine, and the drug that impedes cells from producing NO is hemoglobin.
Compared with the prior art, the invention has the beneficial effects that:
1. the black phosphorus/hemin composite material prepared by the invention improves the stability of the black phosphorus nanosheet, and can be used in a water system solution.
2. The black phosphorus/hemin composite material prepared by the invention can be used for detecting nitric oxide in-situ cells, and is favorable for promoting the application of the black phosphorus in electrochemical biosensing.
Drawings
FIG. 1 is a transmission electron micrograph of a Black Phosphorus (BP) and a black phosphorus/hemin composite (H-BP);
FIG. 2 is a graph of the black phosphorus and black phosphorus/hemin composite material in air at room temperature for different periods of time;
FIG. 3 is a CV diagram of the response of different ratios of the Hemiphos/Hemiphene composite material to nitric oxide;
FIG. 4 is a time-series current response curve of the optimal ratio of the black phosphorus/hemin composite material for in situ detection of NO produced by cells.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1
(1) Preparing a black phosphorus/hemin composite material: introducing nitrogen into 2mL of isopropanol solution of hemin for 5min, adding 1mL of isopropanol dispersion liquid (0.2mg/mL) of black phosphorus nanosheet, and stirring for 48h under the nitrogen protection atmosphere. After the reaction, the sample is treated by ultrasonic treatment through an ultrasonic cleaning machine, is centrifuged through a centrifuge (the rotating speed: 10000rpm, the time: 10min), and finally the centrifuged sample is sealed in isopropanol solution, so that the black phosphorus/hemin composite material with the ratio of 1:2 is obtained.
(2) Preparing an electrochemical sensor: and modifying the prepared black phosphorus/hemin 7 composite material on the surface of the electrode, and carrying out electrochemical test.
Example 2
(1) Preparing a black phosphorus/hemin composite material: introducing nitrogen into 4mL of isopropanol solution of hemin for 5min, adding 1mL of isopropanol dispersion liquid (0.2mg/mL) of black phosphorus nanosheet, and stirring for 48h under the nitrogen protection atmosphere. After the reaction, the sample is treated by ultrasonic treatment through an ultrasonic cleaning machine, is centrifuged through a centrifuge (the rotating speed: 10000rpm, the time: 10min), and finally the centrifuged sample is sealed in an isopropanol solution, so that the black phosphorus/hemin composite material with the ratio of 1:4 is obtained.
(2) Preparing an electrochemical sensor: and modifying the prepared black phosphorus/hemin composite material on the surface of the electrode, and carrying out electrochemical test.
Example 3
(1) Preparing a black phosphorus/hemin composite material: introducing nitrogen into 6mL of isopropanol solution of hemin for 5min, adding 1mL of isopropanol dispersion liquid (0.2mg/mL) of black phosphorus nanosheet, and stirring for 48h under the nitrogen protection atmosphere. After the reaction, the sample is treated by ultrasonic treatment through an ultrasonic cleaning machine, is centrifuged through a centrifuge (the rotating speed: 10000rpm, the time: 10min), and finally the centrifuged sample is sealed in isopropanol solution, so that the black phosphorus/hemin composite material with the ratio of 1:6 is obtained.
(2) Preparing an electrochemical sensor: and modifying the prepared black phosphorus/hemin composite material on the surface of the electrode, and carrying out electrochemical test.
Example 4
(1) Preparing a black phosphorus/hemin composite material: introducing nitrogen into 8mL of isopropanol solution of hemin for 5min, adding 1mL of isopropanol dispersion liquid (0.2mg/mL) of black phosphorus nanosheet, and stirring for 48h under the nitrogen protection atmosphere. After the reaction, the sample is treated by ultrasonic treatment through an ultrasonic cleaning machine, is centrifuged through a centrifuge (the rotating speed: 10000rpm, the time: 10min), and finally the centrifuged sample is sealed in isopropanol solution, so that the black phosphorus/hemin composite material with the ratio of 1:8 is obtained.
(2) Preparing an electrochemical sensor: and modifying the prepared black phosphorus/hemin composite material on the surface of the electrode, and carrying out electrochemical test.
FIG. 1 is a transmission electron micrograph of different samples (from left to right, black phosphorus/hemin composite material). It can be observed from the figure that the surface of the black phosphorus alone is very porous, which indicates that the black phosphorus is easily corroded; and after the black phosphorus and the hemin are compounded, pores on the surface disappear, which shows that the black phosphorus/hemin composite material is not easy to be oxidized and is more stable.
FIG. 2 is a graph comparing the black phosphorus and the black phosphorus/hemin composite from top to bottom, respectively) at room temperature over different periods of time (2019.10.15 and 2019.10.28). It can be observed from the figure that the black phosphorus sheet becomes transparent and the black phosphorus/hemin composite material does not change obviously after the same standing time, which indicates that the black phosphorus/hemin composite material is not easy to be oxidized at room temperature and is more stable.
FIG. 3 is a CV diagram of the response of different ratios of the Hemiphos/Hemiphene composite material to NO. As can be seen from the figure, the ratio is 1: the black phosphorus/hemin composite material of 6 shows the highest NO oxidation current, namely the optimal ratio of the black phosphorus to the hemin in the composite material is 1: 6.
the optimal ratio (example 4) of the black phosphorus/hemin composite was used for electrochemical detection of nitric oxide produced by drug-stimulated cells.
Fig. 4 shows a scale of 1: 6A comparison graph of the time-lapse current response curves of the black phosphorus/hemin composite material under different drug stimuli. As can be seen from the figure, the composite material of the black phosphorus/hemin produces a significant current signal on the cells stimulated by acetylcholine, but does not produce a significant current signal after hemoglobin is added. The black phosphorus/hemin composite material can detect NO generated by cells in situ, and therefore, can be used for preparing electrochemical biosensors.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a black phosphorus/hemin composite material is characterized by comprising the following steps:
and mixing the black phosphorus nanosheet dispersion liquid and the hemin dispersion liquid under the protection of inert gas atmosphere, stirring, and then carrying out centrifugal separation to obtain the black phosphorus/hemin composite material.
2. The preparation method of the black phosphorus/hemin composite material according to claim 1, wherein the black phosphorus nanosheet dispersion liquid is an isopropanol solution or an N-methylpyrrolidone solution of black phosphorus nanosheets, and the concentration is 0.1-0.5 mg/mL.
3. The method of claim 1, wherein the heme dispersion is an isopropanol solution or an N-methylpyrrolidone solution of heme chloride, and the concentration of heme chloride is 3-7 mg/mL.
4. The method for preparing a black phosphorus/hemin composite material according to claim 3, wherein the hemin dispersion is prepared by: dispersing hemin in isopropanol, ultrasonic treating, centrifuging, and collecting supernatant.
5. The preparation method of the black phosphorus/hemin composite material according to claim 1, wherein the volume ratio of the black phosphorus nanosheet dispersion liquid to the hemin dispersion liquid is 1: 2-1: 8.
6. The method for preparing the black phosphorus/hemin composite material according to claim 1, wherein the stirring time is 48-72h, the centrifugal rotation speed is 10000-15000rpm, and the centrifugal time is 10-15min when the black phosphorus nanosheet dispersion liquid and the hemin dispersion liquid are mixed.
7. A black phosphorus/hemin composite prepared according to the method of any one of claims 1 to 6.
8. An electrochemical biosensor, comprising an electrode and the black phosphorus/hemin composite material of claim 7 modified on the electrode.
9. The electrochemical biosensor according to claim 8, wherein the electrochemical biosensor is prepared by: dispersing the black phosphorus/hemin composite material in a mixed solution of isopropanol and Nafion, wherein the volume ratio of the isopropanol to the Nafion in the mixed solution is 6:1-7:1, and then dispersing the obtained dispersion material on a modified electrode to obtain the black phosphorus/hemin composite material.
10. Use of an electrochemical biosensor according to claim 8 or 9 for the in situ detection of NO in drug-stimulated cancer cells.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113433189A (en) * | 2021-05-14 | 2021-09-24 | 苏州科技大学 | Graphite alkyne/heme composite material and preparation method and application thereof |
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| CN108445065A (en) * | 2018-03-06 | 2018-08-24 | 海南师范大学 | A kind of preparation method and its electrocatalysis characteristic research of black phosphorus alkene hemin modified electrode |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN111167488A (en) * | 2020-01-10 | 2020-05-19 | 苏州科技大学 | Visible light response type platinum/black phosphorus/oxygen defect bismuth tungstate composite material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108445065A (en) * | 2018-03-06 | 2018-08-24 | 海南师范大学 | A kind of preparation method and its electrocatalysis characteristic research of black phosphorus alkene hemin modified electrode |
| CN108772079A (en) * | 2018-04-26 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of nanometer of black phosphorus/graphene composite material |
| CN111167488A (en) * | 2020-01-10 | 2020-05-19 | 苏州科技大学 | Visible light response type platinum/black phosphorus/oxygen defect bismuth tungstate composite material and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113433189A (en) * | 2021-05-14 | 2021-09-24 | 苏州科技大学 | Graphite alkyne/heme composite material and preparation method and application thereof |
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