CN115508428A - Benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, photoelectrochemical sensor and levodopa detection method - Google Patents

Benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, photoelectrochemical sensor and levodopa detection method Download PDF

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CN115508428A
CN115508428A CN202211147951.2A CN202211147951A CN115508428A CN 115508428 A CN115508428 A CN 115508428A CN 202211147951 A CN202211147951 A CN 202211147951A CN 115508428 A CN115508428 A CN 115508428A
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benzothiadiazole
levodopa
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诸葛文凤
张翠忠
黄唯
彭金云
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Guangxi Normal University for Nationalities
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Abstract

The invention belongs to the technical field of electrochemical sensors, and provides a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, a photoelectrochemical sensor and a levodopa detection method. The benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO is obtained by reacting bromine functionalized reduced graphene oxide with 1,3,5-triacetylbenzene, 4,7-dibromo-2,1,3 benzothiadiazole, tetrakis (triphenylphosphine) palladium and cuprous iodide in a closed environment. The preparation of the photoelectrochemical sensor is to modify the CMP-rGO dispersion liquid on an ITO electrode. The detection of the levodopa is to obtain a linear relation between the photocurrent and the logarithm of the concentration of the levodopa, then to test a sample, and to bring the photocurrent value into the linear relation to obtain the concentration of the levodopa. The detection method has the advantages of simple operation, small device, low cost, quick detection, high-sensitivity identification and the like.

Description

Benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, photoelectrochemical sensor and levodopa detection method
Technical Field
The invention relates to the technical field of detection of levodopa, in particular to a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, a photoelectrochemical sensor, a preparation method of the photoelectrochemical sensor and a detection method of levodopa.
Background
Levodopa (Levodopa, LDA) with chemical name of L-3,4-dihydroxyphenylalanine and molecular formula of C 9 H 11 NO 4 The structural formula is as follows:
Figure BDA0003853695280000011
levodopa is white or off-white crystalline powder, and has no odor. Levodopa is a natural compound, often found in plants. Levodopa has been listed as the gold standard for the treatment of parkinson's disease since the 60's of the 20 th century. Levodopa, unlike dopamine, can cross the blood brain barrier and be converted into dopamine by L-aromatic amino acid decarboxylase, thereby achieving the effect of treating parkinson's disease. However, long-term administration of levodopa also causes side effects such as hypotension, nausea, arrhythmia, etc. Therefore, detection of levodopa is essential for assessing patient condition and preventing side effects.
The conventional methods for detecting levodopa mainly comprise a fluorescence spectrometry method, a high performance liquid chromatography method, a flow injection method and an ultraviolet spectrophotometry method. These methods all allow for the detection of levodopa samples, but they require expensive instrumentation, complex procedures and skilled technicians. For example, the invention patent with publication number CN103364512A discloses a method for detecting the concentration of levodopa methyl ester and levodopa in blood plasma, and discloses a detection method adopting UPLC/MS/MS combination, which needs expensive equipment. The invention patent with publication number CN112179876A discloses a method for detecting levodopa and tyrosinase by in-situ formation of a fluorescent copolymer, which needs to use a fluorescence spectrometer. Thus. The development of a novel method for detecting levodopa is of great significance. The current photoelectrochemical sensor has the advantages of quick response, high sensitivity, simple operation and the like. The novel conjugated microporous polymer coated graphene heterojunction material is synthesized for the first time and used for constructing a photoelectrochemical sensor to realize the rapid detection of levodopa. So far, no report is provided for photoelectrochemical detection of levodopa by a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, a photoelectrochemical sensor, a preparation method of the photoelectrochemical sensor and a detection method of levodopa.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material is provided, and the structural formula of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material is as follows:
Figure BDA0003853695280000021
the preparation method of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps:
adding bromine functionalized reduced graphene oxide rGBr and dry DMF (dimethyl formamide) into a reaction container, mixing, adding triethylamine, converting nitrogen for multiple times in a closed environment, and deoxidizing reactants under the protection of nitrogen; then 1,3,5-triethylenebenzol, 4,7-dibromo-2,1,3 benzothiadiazole, tetrakis (triphenylphosphine) palladium and cuprous iodide are added, and nitrogen is converted for many times in a closed environment; then stirring for a certain time at 90-100 ℃ in the dark under the protection of nitrogen to obtain a crude product; carrying out suction filtration on the crude product, and washing the obtained product for a plurality of times by using trichloromethane, distilled water and acetone in sequence; subsequently, soxhlet extraction was performed with acetone; and drying to obtain the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO.
Preferably, the bromine-functionalized reduced graphene oxide rGBr, DMF and triethylamine are in a ratio of g/ml/m1 of 0.1-0.5:72-144:6-12. More preferably, the 1,3,5-triethyleneyne benzene, 4,7-dibromo-2,1,3 benzothiadiazole, tetrakis (triphenylphosphine) palladium, and cuprous iodide are in a molar ratio of 1.5: 1.8.
preferably, the bromine-functionalized reduced graphene oxide rGBr and DMF are mixed by ultrasound.
Preferably, the drying means vacuum drying at 60 ℃.
Preferably, the soxhlet extraction time is 36-48h.
The method for preparing the photoelectrochemical sensor by using the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps: ultrasonically dispersing a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO in N, N-dimethylformamide to form a dispersion liquid; and transferring the dispersed liquid drops to a conductive surface of the ITO electrode to prepare a CMP-rGO modified electrode CMP-rGO/ITO, and airing at room temperature for later use.
Preferably, the concentration of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material dispersed in N, N-dimethylformamide is 2mg/mL.
The method for detecting levodopa by using the photoelectrochemical sensor prepared by the method comprises the following steps:
(1) Establishing a linear relation: preparing levodopa standard solutions with different concentrations; a phosphate buffer solution is used as electrolyte, a CMP-rGO modified electrode CMP-rGO/ITO is used as work, a calomel electrode is used as a reference electrode, and a platinum electrode is used as an auxiliary electrode to form a three-electrode system; adding a levodopa standard solution into the electrolyte, and respectively detecting the levodopa standard solutions with different concentrations by adopting a time-counting current method, so as to obtain a linear relation between photocurrent and logarithm of the levodopa concentration;
(2) And (3) detection: and (3) detecting the concentration of the levodopa in the sample to be detected by adopting a standard addition method in a phosphate buffer solution, and determining the content of the levodopa in the sample according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
Preferably, the phosphate buffer solution used in the steps (1) and (2) has a concentration of 0.2mol/L and a pH value of 6.0.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention discloses a novel benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material (CMP-rGO) and application of the novel benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material to construction of a photoelectrochemical sensor for detecting levodopa, and belongs to the technical field of detection of levodopa. The invention adopts a dropping coating method to drop and coat CMP-rGO on an Indium Tin Oxide (ITO) electrode to prepare a CMP-rGO modified electrode, constructs a three-electrode system with a platinum electrode and a calomel electrode, and adopts a chronoamperometry to detect levodopa. The result shows that in the range of 0.005-40 mu mol/L, the photocurrent of the levodopa and the logarithm of the levodopa concentration have two sections of good linear relations, the correlation coefficients are 0.9974 and 0.9920 respectively, and the detection limit is 0.0027 mu mol/L. The determination method provided by the invention provides a new thought for the detection of levodopa and widens the application field of the conjugated microporous polymer.
2. The CMP-rGO prepared by the method is simple in synthesis method and easy to synthesize.
Drawings
FIG. 1 scanning electron microscope picture of CMP-rGO;
FIG. 2 Transmission Electron microscopy images of CMP-rGO;
FIG. 3 FT-IR plots of CMP-rGO and 1,3,5-triethylenebene;
FIG. 4 solid nuclear magnetic map of CMP-rGO;
FIG. 5 is a graph of photocurrent for different concentrations of levodopa; wherein the concentration of levodopa is 5 × 10 -9 ,1.25×10 -8 ，2.5×10 -8 ,1.0×10 -7 ,3.75×10 -7 ,1.5×10 -6 ,4×10 -6 ,5×10 -6 ,7.5×10 -6 ,1×10 -5 ,1.5×10 -5 ,3×10 -5 ,4×10 -5 mol/L。
Fig. 6 log standard graph of levodopa photocurrent versus levodopa concentration.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
The invention provides a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material which has a general structural formula as follows:
Figure BDA0003853695280000041
1. preparation example of CMP-rGO
The preparation route of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP is as follows:
Figure BDA0003853695280000051
the graphene oxide and the bromine functionalized reduced graphene oxide can be purchased from commercial sources or synthesized by a laboratory, and the following methods can be referred to in the method for synthesizing relevant raw materials in the laboratory.
(1) Synthesis of GO
Accurately weighing 1.0010g graphite powder and 0.5010g sodium nitrate, and determining the content of H in 25ml 98% 2 SO 4 The mixture was stirred in an ice bath for 2 hours to obtain a mixed solution. 3.0069g of potassium permanganate were weighed out and 0.1g of the above solution was added in portions every 5 minutes, while keeping the temperature below 20 ℃. The mixed solution was then warmed to 35 ℃ and stirred at 35 ℃ for 2 hours, under vigorous stirring, by addition of 45ml of distilled waterThe resulting solution was diluted. The temperature was raised to 98 ℃ and reacted for 15 minutes, followed by natural cooling. The above solution was poured into 10ml of a mixed solution of 30% hydrogen peroxide and 150ml of distilled water, excess potassium permanganate was removed, and the solution appeared bright yellow. And (3) pickling for three times by using 5% hydrochloric acid, washing to be neutral by using distilled water, and carrying out freeze drying for 48 hours to obtain the Graphene Oxide (GO).
(2) Synthesis of RGO
0.9611g of GO was accurately weighed into 300ml of a 1wt% Sodium Dodecyl Sulfate (SDS) solution, gently stirred for 1 hour, and then the solution was sonicated for 10 minutes. The solution was then centrifuged and the pellet transferred to a 500ml round bottom flask. 0.5ml of NH was added 4 OH and 0.5ml N 2 H 4 :H 2 And (O). The reaction was then heated to 95 ℃ for 1 hour (without stirring) and the product was cooled to room temperature after the reaction was complete.
(3) Synthesis of diazonium salts
Using 4-bromoaniline as a starting material, 4.8186g (0.02801 mol) of 4-bromoaniline was accurately weighed, dissolved in 200ml of distilled water, dissolved by adding a minimum amount of concentrated hydrochloric acid, and then the beaker was placed in a salt ice bath to maintain the solution at 0 ℃, 2.0872g of sodium nitrite (0.03025 mmol, sodium nitrite dissolved in a minimum amount of water beforehand) and 24ml of 20% hydrochloric acid were added dropwise while stirring, and the solution was stirred at 0 ℃ for 45 minutes. The solution changed color from colorless to yellow due to the formation of the diazonium salt.
(4) Synthesis of RGBr
Adding acetone which is not precipitated into the RGO cooled to room temperature, quickly stirring to form RGO dispersion, placing the RGO dispersion into a salt ice bath for precooling, cooling to below 3 ℃, adding the prepared diazonium salt solution into the quickly stirred RGO dispersion by using a suction pipe, keeping the reaction mixture at 0 ℃ in the ice bath, and reacting and stirring for 2 hours. The ice bath was then removed and the reaction stirred at room temperature for 6 hours. The solution was dark green. After the reaction is finished, the mixture is poured into 100ml of acetone, stands for half an hour, is filtered and washed with distilled water, acetone and DMF for three times respectively. And (5) drying the solid at room temperature for 24 hours in vacuum to obtain RGBr.
EXAMPLE 1 preparation of CMP-rGO
The preparation method of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps:
adding 0.1000g of bromine functionalized reduced graphene oxide (rGBr) and 100mL of dry DMF in a round bottom flask and carrying out ultrasonic treatment for 20 minutes; then, 8mL of triethylamine is added, nitrogen is converted for three times in a closed environment, and the reactant is deoxidized for 15 minutes under the protection of the nitrogen; then 0.2722g of 1,3,5-triethylenebenzene, 0.8005g of 4,7-dibromo-2,1,3 benzothiadiazole, 0.0210g of tetrakis (triphenylphosphine) palladium and 0.0084g of cuprous iodide are added, and nitrogen is converted three times in a closed environment; then stirring for 72 hours at 95 ℃ in a dark place under the protection of nitrogen to obtain a crude product; and (3) carrying out suction filtration on the product, and washing the obtained product for several times by using trichloromethane, distilled water and acetone in sequence. Subsequently, soxhlet extraction was performed with acetone for 36 hours, and dried in a vacuum oven at 60 ℃ for 10 hours to obtain CMP-rGO.
Example 2 preparation of CMP-rGO
The preparation method of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps:
0.3000g of bromine functionalized reduced graphene oxide (rGBr) and 72mL of dry DMF were added to a round bottom flask and sonicated for 20 minutes; then, 6mL of triethylamine is added, nitrogen is converted for three times in a closed environment, and the reactant is deoxidized for 15 minutes under the protection of the nitrogen; then 0.2722g 1,3,5-triethylenebenzene, 0.8005g 4,7-dibromo-2,1,3 benzothiadiazole, 0.0210g tetrakis (triphenylphosphine) palladium and 0.0084g cuprous iodide are added, and nitrogen is converted three times in a closed environment; then stirring for 72 hours at 95 ℃ in a dark place under the protection of nitrogen to obtain a crude product; and (3) carrying out suction filtration on the product, and washing the obtained product for several times by using trichloromethane, distilled water and acetone in sequence. Subsequently, soxhlet extraction was performed with acetone for 42 hours, and dried in a vacuum oven at 60 ℃ for 12 hours to obtain CMP-rGO.
EXAMPLE 3 preparation of CMP-rGO
The preparation method of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps:
0.5000g of bromine functionalized reduced graphene oxide (rGBr) and 144mL of dry DMF are added into a round bottom flask and subjected to ultrasonic treatment for 30 minutes; then, adding 12mL of triethylamine, converting nitrogen for three times in a closed environment, and deoxidizing reactants for 15 minutes under the protection of nitrogen; then 0.2722g of 1,3,5-triethylenebenzene, 0.8005g of 4,7-dibromo-2,1,3 benzothiadiazole, 0.0210g of tetrakis (triphenylphosphine) palladium and 0.0084g of cuprous iodide are added, and nitrogen is converted three times in a closed environment; then stirring for 72 hours at 100 ℃ in a dark place under the protection of nitrogen to obtain a crude product; and (3) carrying out suction filtration on the product, and washing the obtained product for several times by using trichloromethane, distilled water and acetone in sequence. Subsequently, soxhlet extraction was performed with acetone for 48 hours, and dried in a vacuum oven at 60 ℃ for 12 hours to obtain CMP-rGO.
2. Characterization of CMP-rGO
The morphology of the synthesized CMP-rGO is characterized by a Scanning Electron Microscope (SEM), as shown in FIG. 1, and the CMP-rGO is a stacked sheet structure and has a rough surface as can be seen from the SEM image. The synthesized CMP-rGO is further confirmed to be a sheet-like structure by transmission electron microscopy, as shown in FIG. 2. CMP-rGO and 1,3,5-triacetoxybenzene were structurally characterized by a spectrum 65 Fourier transform infrared spectrometer, as shown in FIG. 3. 1382-1626cm -1 The absorption peak of (2) is the vibration of the skeleton of the benzene ring. Compared with 1,3,5-triethylenebenzol, CMP-rGO is 1382-1626cm -1 The absorption peak is weakened. At 3472cm -1 The absorption peak is the stretching vibration of-OH, which is probably due to the sample absorbing moisture. CMP-rGO is 2200cm -1 There is a weak absorption peak, which is assigned to C.ident.C. The formation of the expected bond indicates that the coupling reaction was successfully performed. In addition, CMP-rGO was also characterized by solid nuclear magnetic resonance, as shown in FIG. 4. There are two low intensity peaks at 88.34 and 95.36ppm, which are assigned to C ≡ C; the peaks at 116.68-154.79ppm are assigned to carbon atoms on the benzene ring.
3. Preparation of photoelectrochemical sensor
EXAMPLE 4 preparation of photoelectric chemical sensor
The method for preparing the photoelectrochemical sensor by using the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material comprises the following steps: ultrasonically dispersing 2mg of benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material in 1mLN, N-dimethylformamide to form 2mg/mL of CMP-rGO dispersion liquid; and transferring 15 mu L of dispersion liquid to be coated on the conductive surface of the ITO electrode to prepare a CMP-rGO modified electrode CMP-rGO/ITO, and airing at room temperature for later use.
4. Detection method of levodopa
Example 5 detection method of Levodopa
The photoelectrochemical sensor prepared in example 4 was used to detect levodopa, and the method included the following steps:
(1) Establishing a linear relation: preparing standard levodopa solution with different concentrations of 5 × 10 -9 ,1.25×10 -8 ，2.5×10 -8 ,1.0×10 -7 ,3.75×10 -7 ,1.5×10 -6 ,4×10 -6 ,5×10 -6 ,7.5×10 -6 ,1×10 -5 ,1.5×10 -5 ,3×10 -5 ,4×10 -5 mol/L. A three-electrode system is formed by taking CMP-rGO/ITO as a working electrode, a calomel electrode as a reference electrode and a platinum electrode as an auxiliary electrode; and (3) taking 0.2mol/L PBS buffer solution with pH of 6.0 as electrolyte, adding the levodopa standard solution into the electrolyte, and detecting the levodopa standard solution with different concentrations by adopting a chronoamperometry. The relationship between the logarithm of the levodopa and the photocurrent is shown in fig. 6, the photocurrent increases with the increase of the levodopa concentration, the photocurrent of the levodopa and the logarithm of the levodopa concentration present two good linear relationships, and the linear equations are I respectively 1 ＝0.1194lgC+0.5788(R 2 ＝0.9974),I 2 ＝0.5535lgC+0.2898(R 2 = 0.9920) detection limit 0.0027 μmol/L.
(2) And (3) detection: and (3) detecting the concentration of the levodopa in the sample to be detected by adopting a standard addition method in a phosphate buffer solution, and determining the content of the levodopa in the sample according to the linear relation between the photocurrent obtained in the step (1) and the concentration. The sample may be a human serum or urine sample.
5. Reproducibility, stability, selectivity
The reproducibility of the CMP-rGO/ITO sensor is continuously considered, 5 CMP-rGO/ITO sensors are modified under the same experimental conditions, levodopa with the same concentration is detected, and the relative standard deviation of the obtained peak current value is 1.55%, so that the sensor has good reproducibility. Meanwhile, 1 prepared CMP-rGO/ITO is stored at room temperature, and the peak current values are respectively 98.22% of the first detection current and 0.92% of the relative standard deviation after 10 days of detection under the same condition, which indicates that the sensor has better stability.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims (10)

1. The benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material is characterized in that the structural general formula of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO is as follows:
Figure FDA0003853695270000011
2. the preparation method of the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material according to claim 1, which is characterized by comprising the following steps:
adding bromine functionalized reduced graphene oxide rGBr and dry DMF (dimethyl formamide) into a reaction container, mixing, adding triethylamine, converting nitrogen for multiple times in a closed environment, and deoxidizing reactants under the protection of nitrogen; then 1,3,5-triethylenebenzol, 4,7-dibromo-2,1,3 benzothiadiazole, tetrakis (triphenylphosphine) palladium and cuprous iodide are added, and nitrogen is converted for many times in a closed environment; then stirring for a certain time at 90-100 ℃ in the dark under the protection of nitrogen to obtain a crude product; filtering the crude product, and washing the obtained product with chloroform, distilled water and acetone for several times; subsequently, soxhlet extraction was performed with acetone; and drying to obtain the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO.
3. The production method according to claim 2, characterized in that: the bromine functionalized reduced graphene oxide rGBr, DMF and triethylamine in a g/ml/m1 ratio of 0.1-0.5:72-144:6-12.
4. The production method according to claim 3, characterized in that: the 1,3,5-triethylenebenzene, 4,7-dibromo-2,1,3 benzothiadiazole, tetrakis (triphenylphosphine) palladium and cuprous iodide in a molar ratio of 1.5: 1.8.
5. the method of claim 2, wherein: the soxhlet extraction time is 36-48h.
6. A photoelectrochemical sensor, comprising: the benzothiadiazole-based conjugated microporous polymer coating graphene heterojunction material as claimed in claim 1 is modified on a conductive surface of an ITO electrode.
7. The method for preparing the photoelectrochemical sensor by using the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material as claimed in claim 1, is characterized by comprising the following steps of: ultrasonically dispersing a benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material CMP-rGO in N, N-dimethylformamide to form a dispersion liquid; and transferring the dispersed liquid drops to a conductive surface of the ITO electrode to prepare a CMP-rGO modified electrode CMP-rGO/ITO, and airing at room temperature for later use.
8. The method of claim 7, wherein: the benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material is dispersed in N, N-dimethylformamide, and the concentration of the material is 2mg/mL.
9. The method for detecting levodopa by using the photoelectrochemical sensor prepared by the method of claim 7, which is characterized by comprising the following steps:
(1) Establishing a linear relation: preparing levodopa standard solutions with different concentrations; a phosphate buffer solution is used as electrolyte, a CMP-rGO modified electrode CMP-rGO/ITO is used as work, a calomel electrode is used as a reference electrode, and a platinum electrode is used as an auxiliary electrode to form a three-electrode system; adding a levodopa standard solution into the electrolyte, and respectively detecting the levodopa standard solutions with different concentrations by adopting a chronoamperometry so as to obtain a linear relation between the photocurrent and the logarithm of the levodopa concentration;
(2) And (3) detection: and (3) detecting the concentration of the levodopa in the sample to be detected by adopting a standard addition method in a phosphate buffer solution, and determining the content of the levodopa in the sample according to the linear relation between the photocurrent obtained in the step (1) and the concentration.
10. The method as set forth in claim 9, wherein: the concentration of the phosphate buffer solution used in the steps (1) and (2) is 0.2mol/L, and the pH value is 6.0.
CN202211147951.2A 2022-09-20 2022-09-20 Benzothiadiazole-based conjugated microporous polymer coated graphene heterojunction material, photoelectrochemical sensor and levodopa detection method Pending CN115508428A (en)

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