CN112098492B - Method for photoelectrochemical detection of organophosphorus pesticide by bismuth oxybromide/bismuth sulfide semiconductor heterojunction based on biological induction generation - Google Patents
Method for photoelectrochemical detection of organophosphorus pesticide by bismuth oxybromide/bismuth sulfide semiconductor heterojunction based on biological induction generation Download PDFInfo
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Abstract
The invention discloses a BiOBr/Bi generated based on biological induction 2 S 3 A method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction. The method comprises the steps of mixing malathion with an avidin modified magnetic bead, biotin modified auxiliary DNA and a malathion aptamer for incubation, removing part of the malathion aptamer by using the malathion to enable the auxiliary DNA to recover single strands, triggering by using the auxiliary DNA to form G-rich dsDNA, embedding the dsDNA into Hemin and MnTMPyP for catalyzing Na 2 S 2 O 3 And H 2 O 2 Mixed liquor produces H 2 S, and H 2 S will react with the BiOBr modified on the electrode to generate BiOBr/Bi 2 S 3 The method designs HCR signal amplification based on the specific recognition of malathion and an aptamer thereof, and induces BiOBr/Bi by utilizing biocatalysis 2 S 3 The semiconductor heterojunction amplifies signals so as to realize the photoelectric detection with high sensitivity and high selectivity on the malathion.
Description
Technical Field
The invention relates to a detection method of organophosphorus pesticide, in particular to BiOBr/Bi generated based on biocatalysis induction 2 S 3 A method for detecting organophosphorus pesticide by semiconductor heterojunction photoelectrochemistry belongs to the field of photoelectrochemistry bioanalysis.
Background
The pesticide plays a key role in modern agriculture as a weapon for killing various pests such as weeds, insects, rodents, fungi and the like. Among them, Organophosphorus Pesticides (OPs) are important pesticides, and are widely used as insecticides and nerve agents due to their high efficiency and broad spectrum. However, widespread use of OPs can severely contaminate water resources, soil and agricultural products. And the residue can be transferred to the human body through the food chain. Significantly, OPs will be harmful to the human Central Nervous System (CNS) by inhibiting the activity of acetylcholinesterase (AChE). Therefore, sensitive detection of OPs is becoming more and more important for environmental protection and public health. At present, OPs are mainly determined by gas chromatography-mass spectrometry, liquid chromatography-tandem mass spectrometry, high performance liquid chromatography and other chromatographic methods. However, these methods have the disadvantage of requiring expensive instruments, specialized operators and cumbersome sample handling, making them incapable of low cost and rapid OPs detection. Therefore, there is an urgent need to explore cost-effective, rapid and highly sensitive assay techniques for monitoring OPs.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for detecting malathion through photoelectrochemistry, which skillfully designs HCR signal amplification, generation of a bio-enzyme-like catalyst and biocatalysis induction of BiOBr/Bi based on the specific recognition of the malathion and an aptamer thereof 2 S 3 The signal amplification strategy formed by the semiconductor heterojunction is used for realizing the photoelectric detection with high sensitivity and high selectivity on malathion.
In order to achieve the technical object, the invention is based on biocatalytically induced BiOBr/Bi 2 S 3 Formation of semiconductor heterostructure (BIFBSH) and HCR synthesis of DNA concatemers of horseradish peroxidase mimetics (HSHMDC), a novel PEC sensing platform useful for malathion (Mal) detection is presented. Particularly, the invention provides a BiOBr/Bi generated based on biological induction 2 S 3 A method for photoelectrochemically detecting an organophosphorus pesticide by using semiconductor heterojunction comprises the following steps:
1) modified by avidinMixing and incubating magnetic beads and biotin-modified auxiliary DNA, adding malathion aptamer to hybridize with auxiliary DNA, adding standard malathion solution for incubation, reducing part of auxiliary DNA to generate single strand, and adding hairpin DNA chain H 1 And H 2 Triggering the HCR reaction to form a G-rich helical dsDNA; sequentially and respectively incubating the product obtained by the HCR reaction with Hemin and MnTMPyP to obtain a bioactive enzyme catalyst; reacting a biologically active enzyme catalyst with Na 2 S 2 O 3 And H 2 O 2 Dropwise adding the mixed solution to the surface of the electrode loaded with BiOBr, incubating, and placing in ascorbic acid electrolyte for photoelectric detection to obtain a photocurrent response value;
2) operating a series of standard malathion solutions with different concentrations according to the step 1), obtaining a series of corresponding photocurrent response values, and constructing a standard curve between the concentration of the malathion solution and the photocurrent response values;
3) operating the malathion solution to be detected according to the step 1), obtaining a corresponding photocurrent response value, and calculating the concentration of the malathion solution to be detected according to a standard curve.
As a preferable scheme, the avidin modified magnetic beads and the biotin modified auxiliary DNA are incubated for 10-30 min at the temperature of 30-40 ℃. Further preferably, biotin-modified helper DNA (S) 1 ) The concentration of the magnetic beads in the reaction system is 0.5-1.0 mu M, and the concentration of the avidin-modified magnetic beads in the reaction system is 4-6 mg mL -1 。
As a preferable scheme, the hybridization process of the malathion aptamer and the auxiliary DNA is incubation for 0.5-1.5 h at the temperature of 30-40 ℃. Further preferably, the concentration of the malathion aptamer in the reaction system is 0.5-1.0 mu M.
As a preferred embodiment, the hairpin DNA strand H 1 And H 2 The following pre-treatments were performed before use: heating to 90-100 ℃, preserving heat for 4-6 minutes, and cooling at room temperature.
As a preferable scheme, the product obtained by HCR reaction is incubated with Hemin at room temperature for 50-70 min, then is magnetically separated, washed and incubated with MnTMPyP at room temperature for 20-30 min.The generation process of the bioactive enzyme catalyst comprises the following steps: adding a Hemin solution into a product obtained by HCR reaction, and incubating for 50-70 min to complex Hemin in double-stranded DNA to form DNAzyme; and after magnetic washing, adding a MnTMPyP solution, and continuously incubating for 20-30 min to enable the MnTMPyP to be embedded into the dsDNA. More preferably, the concentration of the Hemin solution is 0.5-1 mg ml -1 And the concentration of the MnTMPyP solution is 2.5-5 mu M.
As a preferable scheme, the electrode with the surface loaded with the BiOBr is obtained by dripping BiOBr dispersion liquid on the surface of the electrode and drying.
As a preferred embodiment, the BiOBr is obtained by the following preparation method: and (2) carrying out solvothermal reaction on bismuth nitrate and 1-dodecyl-3-methylimidazolium bromide in an ethylene glycol monomethyl ether medium to obtain the catalyst.
Preferably, the temperature of the solvothermal reaction is 150-170 ℃ and the time is 12-36 h.
The BiOBr prepared by the solvothermal reaction has a flower-like structure and has higher specific surface area and activity compared with the general BiOBr, and the specific preparation method comprises the following steps: stirring Bi (NO) 3 ) 3 ·5H 2 O to ethylene glycol monomethyl ether followed by slow addition of 1-dodecyl-3-methylimidazolium bromide ([ C ] 12 Mim]Br) is added into the solution, ultrasonic treatment is carried out for 10-30 min, and clear and transparent mixed solution is formed; transferring the mixed solution into an autoclave, and carrying out hydrothermal reaction for 12-36 h at the temperature of 150-170 ℃; and cooling to room temperature, centrifuging the obtained milky white powder product, washing with water and ethanol for several times respectively, collecting milky white powder, and drying at 40-80 ℃ overnight to obtain the BiOBr powder. More preferably, Bi (NO) is added 3 ) 3 ·5H 2 O (0.3g) was dissolved in 10mL of ethylene glycol monomethyl ether, and then 0.6g of 1-dodecyl-3-methylimidazolium bromide ([ C ] was slowly added under constant stirring 12 Mim]Br), stirring uniformly, and then carrying out ultrasonic treatment for 20 min; transferring the mixture into a stainless steel autoclave lined with Teflon, and heating to 160 ℃ for reaction for 24 hours; after cooling, a milky white product was observed at the bottom of the autoclave, which was washed 3 times with deionized water and ethanol alternately, at 80%Drying at the temperature of the mixture overnight to obtain BiOBr powder.
As a preferred embodiment, the biologically active enzyme catalyst is reacted with Na 2 S 2 O 3 And H 2 O 2 And dropwise adding the mixed solution to the surface of the electrode with the BiOBr loaded on the surface, and incubating for 10-15 min.
As a preferred embodiment, the hairpin DNA strand H 1 And H 2 Added at equal volume and equal concentration. DNA chain H 1 The sequence of (A) is: 5'-AGG GCG GGT GGT TTA GTC AAG ATG GAG AAT TGC TTC TTG ACT GCT GGT GTT TGG GT-3', respectively; DNA chain H 2 The sequence of (A) is: 5'-TGG GTC AAT TCT CCA TCT TGA CTA ATC ACC AGC AGT CAA GAA TGG GTA GGG CGG G-3' are provided.
The process of the present invention for forming G-rich helical dsDNA by hybrid chain reaction: firstly, utilizing the specific recognition of malathion and its aptamer to remove partial aptamer on the magnetic bead, only retaining auxiliary DNA, dripping hairpin DNA chain H into the reaction system containing auxiliary DNA 1 And H 2 Triggering the HCR reaction, magnetically washing with Tris buffer after incubation, releasing the helper DNA (S) 1 ) Can be mixed with H 1 Partial hybridization pairing, and H 1 The remaining part may be reacted with H 2 Partial hybridization pairs are repeated continuously, and finally a long double-helix DNA chain is formed on the magnetic beads.
The invention relates to the reaction of a biologically active enzyme catalyst with Na 2 S 2 O 3 And H 2 O 2 The mixed solution is dripped to the surface of an ITO electrode with BiOBr loaded on the surface, and incubation is carried out to generate BiOBr/Bi 2 S 3 A semiconductor heterojunction, and more particularly a method comprising the steps of: (a) ultrasonically dispersing BiOBr, then dropwise adding the BiOBr onto the surface of an ITO electrode, and drying at room temperature to obtain the ITO electrode with BiOBr loaded on the surface; (b) reacting a biologically active enzyme catalyst with Na 2 S 2 O 3 And H 2 O 2 The mixture was dropped on BiOBr/ITO and incubated for several minutes. More preferably, the concentration of the BiOBr dispersion is 4mg mL -1 . Dropwise addition of a biologically active enzyme catalyst with Na 2 S 2 O 3 And H 2 O 2 The volume of the mixture was 20. mu.L. Step (b) organismsActive enzyme catalyst and Na 2 S 2 O 3 And H 2 O 2 The reaction time of the mixed solution and the BiOBr/ITO is 12 min. Most preferred flower-like BiOBr/Bi 2 S 3 The synthesis method of the semiconductor heterojunction comprises the following steps: (a) ultrasonically dispersing 4mg of BiOBr powder in 1mL of ultrapure water, dropwise adding 10 mu L of BiOBr powder on the surface of an ITO electrode, and drying at room temperature; (b) taking 20 mu L of bioactive enzyme catalyst and Na 2 S 2 O 3 And H 2 O 2 The mixture was added dropwise to BiOBr/ITO and incubated at room temperature for 12min to produce BiOBr/Bi 2 S 3 A semiconductor heterojunction.
In the photoelectric detection process, ascorbic acid solution (AA) is used as electrolyte, visible light is used as exciting light, and a three-electrode system is used for detecting photocurrent, namely: ITO is a working electrode; the platinum wire is used as a counter electrode; Ag/AgCl is used as a reference electrode. The concentration of AA is 0.1M. The power of the light source is 500W.
The technical scheme of the invention synthesizes BiOBr/Bi 2 S 3 The semiconductor heterojunction, BiOBr has typical layered microsphere structure, large specific surface area and flaky Bi 2 S 3 Provides a sufficiently large load area. BiOBr/Bi compared to the photoelectric signal of BiOBr alone 2 S 3 The photoelectric signal of the semiconductor heterojunction is obviously enhanced. This is because BiOBr and Bi 2 S 3 The energy levels are mutually matched to form a cascade energy band structure, so that the separation of photo-generated electron hole pairs is effectively promoted, the photocurrent intensity is obviously improved, and the detection sensitivity is improved.
The detection principle of the technical scheme of the invention is as follows: in the absence of malathion, the photoelectrochemical response of the BiOBr was detected; in the presence of malathion, aptamers on Magnetic Beads (MB) compete for the retention of the helper DNA (S) only due to the specific recognition of malathion with its aptamers 1 ). When H is present 1 And H 2 In the presence of this, HCR is triggered, eventually forming a long G-rich double stranded DNA (dsDNA). When Hemin is added, it will combine with double-stranded DNA to generate G-quadruplex/heme, i.e. having horseradish peroxidase activityThe DNAzyme can obviously improve Na 2 S 2 O 3 Reduction to H 2 S and formation of Bi 2 S 3 Thus increasing photocurrent after introducing Hemin. Meanwhile, when MnTMPyP is continuously added, the photocurrent is observed to be obviously enhanced, the synergistic effect of the two catalysts is proved, and the response value of the photoelectric signal and the concentration of the malathion form a linear correlation relationship in a certain range. Therefore, the PEC adaptation platform with excellent detection performance and excellent feasibility provides a new approach for the detection of malathion.
The invention provides BiOBr/Bi based on biocatalytic induced synthesis 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction comprises the following steps:
(1) construction of photoelectrochemical biosensor: add 10. mu.L of biotin-modified helper DNA (S) to a 1.5mL centrifuge tube 1 1.0. mu.M) and 10. mu.L of avidin-modified magnetic beads (Strep-MB, 5mg mL) -1 ) After incubation for 20min at 37 ℃, 10 mu L malathion aptamer (1.0 mu M) is added for continuous incubation for 1 h; after magnetic washing, 10. mu.L of 0.001-1000ng mL solution was added -1 Of malathion competes for the aptamer sequence, resulting in S 1 Reducing to single strand, and respectively collecting 10 μ L of H 1 (1.0. mu.M) and H 2 (1.0. mu.M) was added to the centrifuge tube to trigger the HCR reaction, and a very long duplex DNA strand was formed after incubation with mixing at 37 ℃ for 75 min; the HCR product was then mixed with 15. mu.L of Hemin (1mg mL) -1 ) Incubating for about 60min, complexing Hemin in double-stranded DNA to form DNAzyme, magnetically separating, washing, adding 10 μ L MnTMPyP with concentration of 5.0 μ M, and incubating for 25min to embed MnTMPyP into dsDNA to form enzyme with catalytic effect; to the resulting product was added 20. mu.L of Na 2 S 2 O 3 (7mM) and H 2 O 2 (5mM) to obtain a mixture of the biologically active enzyme catalyst and Na 2 S 2 O 3 And H 2 O 2 Mixing the solution; the bioactive enzyme catalyst in the mixed solution can catalyze Na 2 S 2 O 3 By reduction of (2) to produce H 2 S, and H 2 S can react with BiOBr to generate BiOBr/Bi 2 S 3 The compound increases the photocurrent to obtain the photoelectrochemical biosensor;
(2) photoelectric chemical detection of malathion: 10 μ L of BiOBr dispersion (4mg mL) -1 ) Drop-wise onto a clean indium tin oxide electrode (ITO) surface. After drying at room temperature, 20. mu.L of the extract containing H was taken 2 And dropwise adding the product solution of the S on BiOBr/ITO, incubating for 12min, and detecting photocurrent response by using a three-electrode system and 0.1M ascorbic acid aqueous solution as electrolyte and visible light as exciting light. Because the concentration of the malathion added in the step (1) is different, the number of the malathion aptamers which are competitively dropped is also different, so that S triggering HCR reaction 1 Also varied in the amount of Hemin and MnTMPyP combined as catalyst, resulting in BiOBr/Bi formation 2 S 3 The amount of the photo-electrochemical response increases, and therefore the magnitude of the increase in the photo-electrochemical response also varies. Repeating the above operations, and drawing a standard curve according to the photocurrent response value and the standard sample concentration; and replacing the malathion standard solution with the solution to be detected to carry out the detection, and obtaining a concentration result through a standard curve.
The preparation method of the BiOBr specifically comprises the following steps: 0.3g of Bi (NO) 3 ) 3 ·5H 2 O is dissolved in 10mL of ethylene glycol monomethyl ether, and then 0.6g of 1-dodecyl-3-methylimidazolium bromide ([ C ] is slowly added with constant stirring 12 Mim]Br), stirring uniformly, and then carrying out ultrasonic treatment for 20 min; transferring the mixture into a stainless steel autoclave lined with teflon, and heating to 160 ℃ for reaction for 24 hours; after cooling, a milky white product was observed at the bottom of the autoclave, washed alternately with deionized water and ethanol 3 times, and dried overnight at 80 ℃ to obtain the BiOBr powder.
The preparation method of the BiOBr dispersion liquid comprises the following steps: 4mg of BiOBr powder was ultrasonically dispersed in 1mL of ultrapure water.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) the invention adopts a green in-situ generation method to synthesize flower-shaped BiOBr/Bi 2 S 3 Semiconductor heterojunctions, the energy bands of which can be matched to form a cascadeThe energy band structure effectively promotes the separation of photo-generated electron hole pairs and obviously improves the photocurrent intensity;
2) the invention improves the detection sensitivity by a non-enzymatic amplification method and assists the DNA (S) under the isothermal condition 1 ) And H 1 Partial complementary pairing, with two H in a metastable state 1 And H 2 Partial complementary pairing can also be performed to complete the assembly process of the duplex DNA strands. The double helix DNA chain can combine a large amount of Hemin and MnTMPyP to catalyze BiOBr/Bi 2 S 3 The formation of a semiconductor heterojunction, thereby improving the photocurrent intensity;
3) the invention adopts specific recognition of malathion and an aptamer thereof, and adopts an HCR signal amplification strategy to generate BiOBr/Bi by biocatalysis 2 S 3 The semiconductor heterojunction improves the light current intensity so as to realize the high-sensitivity and high-selectivity photoelectric detection of malathion;
4) the signal amplification type photoelectrochemical sensing strategy for detecting malathion, which is constructed by the invention, is 0.001-1000ng mL -1 In the concentration range, the photocurrent has a good linear relation with the logarithm of the concentration of the target, and the method has the advantages of wide linear range and low detection line.
Drawings
FIG. 1 shows a biocatalytic induction based BiOBr/Bi 2 S 3 The principle schematic diagram of the method for detecting the organophosphorus pesticide by semiconductor heterojunction photoelectrochemistry.
FIG. 2(A) is a scanning electron microscope image of BiOBr material; FIG. 2(B) shows flower-like BiOBr/Bi 2 S 3 Scanning electron microscopy of semiconductor heterojunctions.
FIG. 3 shows BiOBr and BiOBr/Bi 2 S 3 Energy spectra of semiconductor heterojunctions.
FIG. 4 shows the results of the detection of the standard sample in example 1, A: example 1 a graph of target concentration versus corresponding photocurrent response was measured; b: example 1 photocurrent response value and detection target concentration log-linear graph; c: results of the selectivity examination of example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific implementation examples, but the scope of the present invention is not limited thereby.
Example 1
(1) 0.3g of Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 10mL of ethylene glycol monomethyl ether, and then 0.6g of 1-dodecyl-3-methylimidazolium bromide ([ C ] was slowly added under uniform stirring 12 Mim]Br), stirring uniformly, and then carrying out ultrasonic treatment for 20 min; transferring the mixture into a stainless steel autoclave lined with Teflon, and heating to 160 ℃ for reaction for 24 hours; after cooling, a milky white product was observed at the bottom of the autoclave, washed alternately with deionized water and ethanol 3 times, and dried overnight at 80 ℃ to obtain BiOBr powder.
(2) Ultrasonically dispersing 4mg of BiOBr powder prepared in the step (1) in 1mL of ultrapure water, and dropwise adding 10 mu L of BiOBr powder on the surface of an ITO electrode. And drying at room temperature to obtain the BiOBr/ITO electrode.
(3) Add 10. mu.L of biotin-modified helper DNA (S) to a 1.5mL centrifuge tube 1 1.0. mu.M) and 10. mu.L of avidin-modified magnetic beads (Strep-MB, 5mg mL) -1 ) After incubation for 20min at 37 ℃, 10 mu L malathion aptamer (1.0 mu M) is added for continuous incubation for 1 h; after magnetic washing, 10. mu.L of 80ng mL was added -1 Of malathion competes for the aptamer sequence, resulting in S 1 Reducing to single strand, and respectively collecting 10 μ L of H 1 (1.0. mu.M) and H 2 (1.0. mu.M) was added to the centrifuge tube to trigger the HCR reaction, and a very long duplex DNA strand was formed after incubation with mixing at 37 ℃ for 75 min;
(4) mixing the HCR product obtained in step (3) with 15. mu.L of Hemin (1mg mL) -1 ) Incubating for 60min, magnetically separating, washing, adding 10 μ L MnTMPyP with concentration of 5.0 μ M, and incubating for 25min to obtain enzyme with catalytic effect; to the magnetic product was added 20. mu.L of Na 2 S 2 O 3 (7mM) and H 2 O 2 (5mM) mixture to catalyze Na 2 S 2 O 3 By reduction of (2) to produce H 2 And S, magnetically separating the obtained solution for subsequent use.
(5) Dripping 20 μ L of the product solution obtained in step (4) on the electrode in step (2), and incubating at room temperatureGrowing for 12min to form Bi on the surface of the electrode by catalysis 2 S 3 The composite deposit of (1). After washing with ultrapure water, photocurrent response was measured using a 0.1M ascorbic acid aqueous solution as an electrolyte and a 500W Xe lamp as a light source. Due to DNAzyme and MnTMPyP to Na 2 S 2 O 3 And H 2 O 2 The mixed solution has a synergistic catalysis effect, so that the photocurrent response value is increased, and the photocurrent response value has a determined relation with the concentration of the malathion, thereby realizing the sensitive detection of the malathion; and replacing the malathion standard solution with the solution to be detected to perform the detection, and obtaining a concentration result through a standard curve.
Under the same conditions, Chlorpyrifos (Chlorpyrifos) and Dichlorvos (Dichlorvos) are respectively used as target objects, and the selectivity of the method is examined.
The DNA sequence used in example 1 is as follows: (these sequences were designed by the Applicant and synthesized by the firm of the Applicant company, Biotechnology engineering (Shanghai)
FIG. 1 shows a biocatalytic induction based BiOBr/Bi method according to the present invention 2 S 3 The principle and the process schematic diagram of the method for detecting the photoelectrochemical organophosphorus pesticide generated by the semiconductor heterojunction.
FIG. 2 shows BiOBr material and flower-like BiOBr/Bi 2 S 3 Scanning electron microscopy of semiconductor heterojunctions. The scanning electron microscope picture shows that the BiOBr is in a typical layered microsphere structure, has larger specific surface area and is flaky Bi 2 S 3 Provides enough large load area, thereby successfully synthesizing the BiOBr/Bi 2 S 3 A composite material that enhances photocurrent response.
The EDS spectrum results of FIG. 3 show that BiOBr is mainly composed of Bi, oxygen and bromine, while Bi is 2 S 3 After being generated, the material mainly comprises bismuth, oxygen, bromine and sulfur elements.
FIG. 4 shows the results of the standard assays of example 1, as shown in FIG. 4B, at 0.001-1000ng mL -1 Within the malathion concentration range, a good linear relation exists between the photocurrent response value and the logarithm of the concentration of the target substance. In addition, in order to prove the practical application of the invention in life, the specificity and the selectivity of the method to malathion are also examined, and dichlorvos and chlorpyrifos are selected as interferents. The experimental result shows that the photocurrent response of the high-concentration interferent and the photocurrent response of the blank sample have no obvious difference, and the photocurrent of the mixture of the target and the interferent is similar to the photocurrent of the single target. Therefore, this method for malathion detection has good selectivity and specificity (fig. 4C).
The above description is only for the best mode of the invention, and all equivalent changes and modifications made in accordance with the claims of the invention should be covered by the present invention.
Claims (9)
1. BiOBr/Bi based on biological induction generation 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: comprises the following steps:
1) mixing and incubating avidin modified magnetic beads and biotin modified auxiliary DNA, firstly adding malathion aptamer and auxiliary DNA for hybridization, then adding standard malathion solution for incubation, reducing part of auxiliary DNA to generate single strand, and then adding hairpin DNA strand H 1 And H 2 Triggering the HCR reaction to form a G-rich helical dsDNA; sequentially and respectively incubating the product obtained by the HCR reaction with Hemin and MnTMPyP to obtain a bioactive enzyme catalyst; reacting a biologically active enzyme catalyst with Na 2 S 2 O 3 And H 2 O 2 Dropwise adding the mixed solution to the surface of the electrode loaded with BiOBr, incubating, and placing in ascorbic acid electrolyte for photoelectric detection to obtain a photocurrent response value;
2) operating a series of standard malathion solutions with different concentrations according to the step 1), obtaining a series of corresponding photocurrent response values, and constructing a standard curve between the concentration of the malathion solution and the photocurrent response values;
3) operating the malathion solution to be detected according to the step 1), obtaining a corresponding photocurrent response value, and calculating the concentration of the malathion solution to be detected according to a standard curve.
2. The BIOBr/Bi based on bio-induced production of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: and incubating the avidin-modified magnetic beads and the biotin-modified auxiliary DNA at the temperature of 30-40 ℃ for 10-30 min.
3. The BIOBr/Bi based on bio-induced production of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: the hybridization process of the malathion aptamer and the auxiliary DNA is as follows: incubating for 0.5-1.5 h at 30-40 ℃.
4. The BIOBr/Bi based on biological induction generation of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: hairpin DNA chain H 1 And H 2 The following pre-treatments were performed before use: heating to 90-100 ℃, preserving the heat for 4-6 minutes, and cooling at room temperature.
5. The BIOBr/Bi based on bio-induced production of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: and incubating the product obtained by the HCR reaction with Hemin at room temperature for 50-70 min, magnetically separating, washing, and incubating with MnTMPyP at room temperature for 20-30 min.
6. The BIOBr/Bi based on bio-induced production of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: the electrode with the surface loaded with the BiOBr is obtained by dripping BiOBr dispersion liquid on the surface of the electrode and drying.
7. The BIOBr/Bi based on bio-induced production of claim 6 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: the BiOBr is obtained by the following preparation method: and (2) carrying out solvothermal reaction on bismuth nitrate and 1-dodecyl-3-methylimidazolium bromide in an ethylene glycol monomethyl ether medium to obtain the catalyst.
8. The BIOBr/Bi based on bio-induced production of claim 7 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: the temperature of the solvothermal reaction is 150-170 ℃, and the time is 12-36 h.
9. The BIOBr/Bi based on biological induction generation of claim 1 2 S 3 The method for photoelectrochemical detection of organophosphorus pesticide by semiconductor heterojunction is characterized by comprising the following steps: biologically active enzyme catalyst and Na 2 S 2 O 3 And H 2 O 2 And dropwise adding the mixed solution to the surface of the electrode loaded with BiOBr on the surface, and incubating for 10-15 min.
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| CN202010953873.XA CN112098492B (en) | 2020-09-11 | 2020-09-11 | Method for photoelectrochemical detection of organophosphorus pesticide by bismuth oxybromide/bismuth sulfide semiconductor heterojunction based on biological induction generation |
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