CN111551616B - Preparation method of chloroquine phosphate molecularly imprinted electrochemical sensor - Google Patents
Preparation method of chloroquine phosphate molecularly imprinted electrochemical sensor Download PDFInfo
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- CN111551616B CN111551616B CN202010271984.2A CN202010271984A CN111551616B CN 111551616 B CN111551616 B CN 111551616B CN 202010271984 A CN202010271984 A CN 202010271984A CN 111551616 B CN111551616 B CN 111551616B
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- AEUAEICGCMSYCQ-UHFFFAOYSA-N 4-n-(7-chloroquinolin-1-ium-4-yl)-1-n,1-n-diethylpentane-1,4-diamine;dihydrogen phosphate Chemical compound OP(O)(O)=O.ClC1=CC=C2C(NC(C)CCCN(CC)CC)=CC=NC2=C1 AEUAEICGCMSYCQ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229960002328 chloroquine phosphate Drugs 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 47
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 1-butylsulfonic acid-2-methylimidazolium chloride Chemical compound 0.000 claims abstract description 34
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 11
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960004979 fampridine Drugs 0.000 claims abstract description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract description 8
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 8
- 229940057995 liquid paraffin Drugs 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 238000011049 filling Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000012472 biological sample Substances 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 201000004792 malaria Diseases 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- WHTVZRBIWZFKQO-AWEZNQCLSA-N (S)-chloroquine Chemical compound ClC1=CC=C2C(N[C@@H](C)CCCN(CC)CC)=CC=NC2=C1 WHTVZRBIWZFKQO-AWEZNQCLSA-N 0.000 description 1
- 208000004881 Amebiasis Diseases 0.000 description 1
- 206010001980 Amoebiasis Diseases 0.000 description 1
- 206010035503 Plasmodium vivax infection Diseases 0.000 description 1
- 201000009976 Plasmodium vivax malaria Diseases 0.000 description 1
- 208000005469 Vivax Malaria Diseases 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003356 anti-rheumatic effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001386 capillary affinity electrophoresis Methods 0.000 description 1
- 229960003677 chloroquine Drugs 0.000 description 1
- WHTVZRBIWZFKQO-UHFFFAOYSA-N chloroquine Natural products ClC1=CC=C2C(NC(C)CCCN(CC)CC)=CC=NC2=C1 WHTVZRBIWZFKQO-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- 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
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- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a preparation method of a chloroquine phosphate molecularly imprinted electrochemical sensor, which is characterized in that a gallium nitride paste electrode sensor is prepared by adopting nano gallium nitride, graphene oxide and 1-butylsulfonic acid-2-methylimidazolium chloride; the gallium nitride paste electrode sensor is modified by adopting gamma-aminopropyltrimethoxysilane and carbon quantum dots: taking chloroquine phosphate template molecules, itaconic acid and 4-aminopyridine as monomers to obtain a chloroquine phosphate molecularly imprinted polymer; in a reactor, acetone is added according to the mass percentage concentration of the following components: 94-96%, polyamide: 2-4%, and chloroquine phosphate molecularly imprinted polymer: 1.5-3.0% of a chloroquine phosphate molecularly imprinted polymer modification solution; and then dripping 40-50 mu L of the solution into a carbon quantum dot modified gallium nitride paste electrode to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor. The sensor has high sensitivity and selectivity. Has high sensitivity, good specificity, rapid detection and repeated use.
Description
Technical Field
The invention relates to the technical field of a preparation method and rapid detection application of a molecular imprinting sensor, in particular to a preparation method of a chloroquine phosphate molecular imprinting electrochemical sensor, which is used for detecting chloroquine phosphate in a sample.
Background
Chloroquine phosphate is N ', N' -diethyl-N4- (7-chloro-4-quinolyl) -1, 4-pentanediamine diphosphate, and can be used for treating malaria such as malignant malaria and vivax malaria sensitive to chloroquine. Can also be used for treating extraintestinal amebiasis, and also has antirheumatic effect. The method for measuring chloroquine phosphate with simple research, rapidness, accuracy and high sensitivity is very important for the performance of the drug. At present, methods for detecting chloroquine phosphate mainly comprise high performance liquid chromatography, liquid chromatography-mass spectrometry and the like, the accuracy of the methods is limited to a certain extent, instruments are expensive, professional operation is required, the detection period is long, and the application of the methods is also limited. In addition, the content of chloroquine phosphate in a biological sample is low, and coexisting substances interfere with each other, so that accurate detection of chloroquine phosphate is difficult. Therefore, the method for detecting chloroquine phosphate, which has the advantages of good selectivity, high sensitivity and simple and convenient operation, has important use value.
The molecular imprinting technique is one of the main methods for developing a highly selective material having a molecular recognition function, and is a technique that exhibits a high selective recognition property for a template molecule by forming a highly cross-linked rigid polymer around the template molecule, and removing the template molecule to leave a recognition site having a binding ability in a network structure of the molecularly imprinted polymer. The technology is more and more concerned with the configuration and effect presetting and specific identification, and has been successfully used in the fields of solid phase extraction or micro-solid phase extraction, affinity chromatography or capillary electrophoresis, sensors and the like.
The molecular imprinting sensor prepared according to the technology plays an important role in drug analysis and life science research. Modifying functional molecules on electrodes in a proper way, and preparing an electrochemical sensor with good selectivity, high sensitivity and reproducible service life becomes a subject of research efforts of analytical scientists. However, the thickness of the imprinting film prepared by the traditional imprinting method is difficult to control, the high crosslinking degree enables the electron transfer speed and response to be slow, the detection lower limit to be high, and the application of the molecular imprinting technology in the electrochemical sensor is influenced. Therefore, the method is sensitive, rapid, simple, convenient, high in specificity, good in repeatability and economical, and is necessary for accurately and quantitatively measuring the content of chloroquine phosphate in food, medicines and biological samples.
The invention aims to combine molecular imprinting with an electrochemical sensor and provides a preparation method of a chloroquine phosphate molecular imprinting electrochemical sensor, which mainly takes itaconic acid and 4-aminopyridine as functional monomers, 1, 4-butanediol dimethacrylate as a cross-linking agent, azodiisoheptanonitrile as an initiator and chloroquine phosphate as a template, and improves the sensitivity of the sensor by modifying carbon quantum dots on the surface of a gallium nitride paste electrode, and the chloroquine phosphate molecular imprinting electrochemical sensor is constructed by adopting a drop coating method.
Disclosure of Invention
Instruments and reagents
CHI660B electrochemical workstation (shanghai chenhua instruments), the experiment was carried out using a three-electrode system: the platinum wire electrode is an auxiliary electrode, the Ag/AgCl electrode is a reference electrode (SCE), and the Glassy Carbon Electrode (GCE) is a working electrode; KQ-250E model ultrasonic cleaner (Kunfeng ultrasonic Instrument Co., Ltd.).
Graphene oxide; itaconic acid, 4-aminopyridine, 1, 4-butanediol dimethacrylate, azobisheptanonitrile, chloroquine phosphate, carbon quantum dots, nano gallium nitride, 1-butylsulfonic acid-2-methylimidazolium chloride, gamma-aminopropyltrimethoxysilane, liquid paraffin, heptane, ethanol, polyamide, phosphoric acid buffer solution; all reagents used were analytical grade.
A preparation method of a chloroquine phosphate molecularly imprinted electrochemical sensor is characterized by comprising the following process steps:
(1) preparing a gallium nitride paste electrode sensor: adding the following nano gallium nitride into an agate mortar according to the mass percentage: 50-54%, graphene oxide: 18-22%, 1-butylsulfonic acid-2-methylimidazolium chloride salt: 10-14%, liquid paraffin: 6-10%, heptane: 6-10%, wherein the sum of the mass percentages of the components is one hundred percent, and the mixture is uniformly ground to obtain a mixture carbon paste; then the carbon paste is put into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, and the carbon paste is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain the gallium nitride paste electrode sensor;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: adding ethanol into a reactor according to the mass percentage concentration of the following components: 66-70%, gamma-aminopropyltrimethoxysilane: 24-28%, carbon quantum dots: 4-8%, stirring and dissolving, putting the polished gallium nitride paste electrode, soaking at room temperature for 4 hours, heating to 50 +/-2 ℃, reacting at constant temperature for 2 hours, taking out the electrode, washing with absolute ethyl alcohol, and drying to obtain the carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: adding ethanol into a reactor according to the following composition mass percentage: 62-68% of itaconic acid: 6-10%, 4-aminopyridine: 10-14%, chloroquine phosphate: 6-10%, 1, 4-butylene glycol dimethacrylate: 4-8%, azobisisoheptonitrile: 1.0-3.0%, the sum of the contents of all the components is one hundred percent, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, carrying out stirring reaction for 4-6 h at 60 +/-2 ℃, carrying out solid-liquid separation, and adding alcohol into the obtained product: soaking the mixed solution with the hydrochloric acid volume ratio of 6:1 for 8 hours, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in a reactor, acetone is added according to the mass percentage concentration of the following components: 94-96%, polyamide: 2-4%, and chloroquine phosphate molecularly imprinted polymer: 1.5-3.0%, wherein the sum of the contents of the components is one hundred percent, and the chloroquine phosphate molecularly imprinted polymer modification solution is prepared; and (3) dropwise adding 40-50 mu L of the solution to the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
The carbon quantum dots in the step (2) are oil-soluble carbon quantum dots.
The molar ratio of itaconic acid to 4-aminopyridine in step (3) is 1: 2.
and (3) introducing nitrogen gas into the polymerization reaction process in the oxygen-free atmosphere.
The invention has the advantages and effects that:
according to the invention, the imprinting technology, the layer-by-layer self-assembly method and the drop coating method are combined, a chloroquine phosphate molecularly imprinted electrochemical sensor is successfully developed on the surface of the carbon quantum dot modified gallium nitride paste electrode, and compared with the response of a molecularly imprinted electrode which is not modified by carbon quantum dots, the chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the method is greatly improved in response, good in selectivity and high in sensitivity. The imprinted sensor has high affinity and selectivity to chloroquine phosphate, and the response current and the concentration of the chloroquine phosphate are 1.0 multiplied by 10-8～6.0×10-6Has good linear relation in the mol/L range and the detection limit of 8.32 multiplied by 10-8mol/L of the chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the invention is successfully used for detecting the chloroquine phosphate in a sample, and the recovery rate is 95.52-104.08%, so that the chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the invention can be widely applied to the related fields of medicine, biology, environmental protection detection and the like.
The chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the invention does not use toxic reagents in the preparation process, is environment-friendly and green, and has a simple preparation process.
Detailed Description
Example 1
(1) Preparing a gallium nitride paste electrode sensor: in an agate mortar, nano gallium nitride: 52g, graphene oxide: 20g, 1-butylsulfonic acid-2-methylimidazolium chloride salt: 12g, liquid paraffin: 8g, heptane: 11mL, and grinding uniformly to obtain a mixture carbon paste; then the carbon paste is put into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, and the carbon paste is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain the gallium nitride paste electrode sensor;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: in the reactor, ethanol: 86mL, γ -aminopropyltrimethoxysilane: 26g, carbon quantum dot: stirring and dissolving 6g, placing the polished gallium nitride paste electrode, soaking at room temperature for 4h, heating to 50 +/-2 ℃, reacting at constant temperature for 2h, taking out the electrode, washing with absolute ethyl alcohol, and drying to obtain a carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: in the reactor, ethanol: 81mL, itaconic acid: 8g, 4-aminopyridine: 12g, chloroquine phosphate: 8g, 1, 4-butanediol dimethacrylate: 6g, azobisisoheptonitrile: 2g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 4-6 h at 60 +/-2 ℃, performing solid-liquid separation, and adding alcohol into the obtained product: soaking the mixed solution with the hydrochloric acid volume ratio of 6:1 for 8 hours, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in the reactor, acetone: 12mL, polyamide: 0.3g, chloroquine phosphate molecularly imprinted polymer: 0.2g, preparing chloroquine phosphate molecularly imprinted polymer modification liquid; and (3) dropwise adding 45 mu L of the solution into the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the carbon quantum dot modified gallium nitride paste electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
Example 2
(1) Preparing a gallium nitride paste electrode sensor: in an agate mortar, nano gallium nitride: 25g, graphene oxide: 11g, 1-Butylsulfonic acid-2-methylimidazolium chloride salt: 5g, liquid paraffin: 5g, heptane: 5mL, and grinding uniformly to obtain a mixture carbon paste; then the carbon paste is put into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, and the carbon paste is compacted, dried, polished by polishing powder, polished and washed by deionized water, thus obtaining the gallium nitride paste electrode sensor;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: in the reactor, ethanol: 83mL, γ -aminopropyltrimethoxysilane: 27g, carbon quantum dot: 7g, stirring and dissolving, putting the polished gallium nitride paste electrode into the container, soaking the gallium nitride paste electrode at room temperature for 4 hours, heating the gallium nitride paste electrode to 50 +/-2 ℃, reacting the gallium nitride paste electrode at a constant temperature for 2 hours, taking out the gallium nitride paste electrode, washing the gallium nitride paste electrode with absolute ethyl alcohol, and drying the gallium nitride paste electrode to obtain a carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: in the reactor, ethanol: 78mL, itaconic acid: 6g, 4-aminopyridine: 10g, chloroquine phosphate: 6g, 1, 4-butanediol dimethacrylate: 8g, azobisisoheptonitrile: 2g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 4-6 h at 60 +/-2 ℃, performing solid-liquid separation, and adding alcohol into the obtained product: soaking the mixed solution with the hydrochloric acid volume ratio of 6:1 for 8 hours, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in the reactor, acetone: 12mL, polyamide: 0.3g, chloroquine phosphate molecularly imprinted polymer: 0.3g, preparing chloroquine phosphate molecularly imprinted polymer modification liquid; and (3) dropwise adding 40 mu L of the solution into the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the carbon quantum dot modified gallium nitride paste electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
Example 3
(1) Preparing a gallium nitride paste electrode sensor: in an agate mortar, nano gallium nitride: 27g, graphene oxide: 9g, 1-Butylsulfonic acid-2-methylimidazolium chloride salt: 5g, liquid paraffin: 4g, heptane: grinding the mixture to be uniform by 12mL to obtain a mixture carbon paste; then the carbon paste is put into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, and the carbon paste is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain the gallium nitride paste electrode sensor;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: in the reactor, ethanol: 44mL, γ -aminopropyltrimethoxysilane: 12g, carbon quantum dot: 3g, stirring and dissolving, putting the polished gallium nitride paste electrode into the container, soaking the gallium nitride paste electrode at room temperature for 4 hours, heating the gallium nitride paste electrode to 50 +/-2 ℃, reacting the gallium nitride paste electrode at a constant temperature for 2 hours, taking out the gallium nitride paste electrode, washing the gallium nitride paste electrode with absolute ethyl alcohol, and drying the gallium nitride paste electrode to obtain a carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: in the reactor, ethanol: 78mL, itaconic acid: 10g, 4-aminopyridine: 14g, chloroquine phosphate: 9g, 1, 4-butanediol dimethacrylate: 4g, azobisisoheptonitrile: 1g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, reacting for 4-6 h at 60 +/-2 ℃, performing solid-liquid separation, and adding alcohol into the obtained product: soaking the mixed solution with the hydrochloric acid volume ratio of 6:1 for 8 hours, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in the reactor, acetone: 12.5mL, polyamide: 0.2g, chloroquine phosphate molecularly imprinted polymer: 0.2g, preparing chloroquine phosphate molecularly imprinted polymer modification liquid; and (3) dropwise adding 50 mu L of the solution into the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the carbon quantum dot modified gallium nitride paste electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
Example 4
(1) Preparing a gallium nitride paste electrode sensor: in an agate mortar, nano gallium nitride: 51g, graphene oxide: 19g, 1-butylsulfonic acid-2-methylimidazolium chloride salt: 14g, liquid paraffin: 6g, heptane: 15mL, and grinding uniformly to obtain a mixture carbon paste; then the carbon paste is put into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, and the carbon paste is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain the gallium nitride paste electrode sensor;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: in the reactor, ethanol: 86mL, γ -aminopropyltrimethoxysilane: 28g, carbon quantum dot: 4g, stirring and dissolving, putting the polished gallium nitride paste electrode into the container, soaking the gallium nitride paste electrode at room temperature for 4 hours, heating the gallium nitride paste electrode to 50 +/-2 ℃, reacting the gallium nitride paste electrode at a constant temperature for 2 hours, taking out the gallium nitride paste electrode, washing the gallium nitride paste electrode with absolute ethyl alcohol, and drying the gallium nitride paste electrode to obtain a carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: in the reactor, ethanol: 81mL, itaconic acid: 7g, 4-aminopyridine: 11g, chloroquine phosphate: 10g, 1, 4-butanediol dimethacrylate: 5g, azobisisoheptonitrile: 3g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 4-6 h at 60 +/-2 ℃, performing solid-liquid separation, and adding alcohol into the obtained product: soaking the mixed solution with the hydrochloric acid volume ratio of 6:1 for 8 hours, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in the reactor, acetone: 12mL, polyamide: 0.4g, chloroquine phosphate molecularly imprinted polymer: 0.15g, preparing chloroquine phosphate molecularly imprinted polymer modification liquid; and (3) dropwise adding 48 mu L of the solution into the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the carbon quantum dot modified gallium nitride paste electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
Example 5
The chloroquine phosphate molecularly imprinted electrochemical sensor prepared in the embodiment 1-4 is used for detecting chloroquine phosphate, and comprises the following steps:
(1) preparing a standard solution: preparing a group of chloroquine phosphate standard solutions with different concentrations including blank standard samples, wherein the base solution is phosphate buffer solution with pH7.2;
(2) drawing a working curve: Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as an auxiliary electrode, the chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the method is used as a working electrode to form a three-electrode system, and the three-electrode system is connected with a CHI660B electrochemical workstation at K3[Fe(CN)6]In the solution, the cyclic voltammetry is adopted to detect within the potential range of-1.2-0.8V, and the response current of the blank standard sample is marked as I0The response current of the chloroquine phosphate standard solution with different concentrations is IiThe difference of the response current decrease is Δ I ═ I0-IiThe mass concentration c of the delta I and the chloroquine phosphate standard solution is linearDrawing a delta I-c working curve according to the sexual relation;
(3) detection of chloroquine phosphate: replacing the chloroquine phosphate standard solution in the step (1) with a sample to be detected, detecting according to the method in the step (2), and obtaining the content of the chloroquine phosphate in the sample to be detected according to the difference value delta I and the working curve of the reduction of the response current;
said K3[Fe(CN)6]The concentration of the solution is 5.0 mmol/L;
the concentration of the phosphate buffer solution with the pH value of 7.2 is 80 mmol/L.
Claims (5)
1. A preparation method of a chloroquine phosphate molecularly imprinted electrochemical sensor is characterized by comprising the following process steps:
(1) preparing a gallium nitride paste electrode: adding the following nano gallium nitride into an agate mortar according to the mass percentage: 50-54%, graphene oxide: 18-22%, 1-butylsulfonic acid-2-methylimidazolium chloride salt: 10-14%, liquid paraffin: 6-10%, heptane: 6-10%, wherein the sum of the mass percentages of the components is one hundred percent, and the mixture is uniformly ground to obtain a mixture carbon paste; then, filling the carbon paste into a glass tube which is connected with a lead and has the inner diameter of phi 4.5mm, compacting, drying, polishing by using polishing powder, and washing by using deionized water to obtain a gallium nitride paste electrode;
(2) preparing a carbon quantum dot modified gallium nitride paste electrode: adding ethanol into a reactor according to the mass percentage concentration of the following components: 66-70%, gamma-aminopropyltrimethoxysilane: 24-28%, carbon quantum dots: 4-8%, stirring and dissolving, putting the polished gallium nitride paste electrode, soaking at room temperature for 4 hours, heating to 50 +/-2 ℃, reacting at constant temperature for 2 hours, taking out the electrode, washing with absolute ethyl alcohol, and drying to obtain the carbon quantum dot modified gallium nitride paste electrode;
(3) preparation of chloroquine phosphate molecularly imprinted polymer: adding ethanol into a reactor according to the following composition mass percentage: 62-68%, itaconic acid: 6-10%, 4-aminopyridine: 10-14%, chloroquine phosphate: 6-10%, 1, 4-butylene glycol dimethacrylate: 4-8%, azobisisoheptonitrile: 1.0-3.0%, wherein the sum of the content of each component is one hundred percent, stirring for dissolving, introducing nitrogen for deoxidizing for 15min, carrying out stirring reaction for 4-6 h at 60 +/-2 ℃, carrying out solid-liquid separation, soaking the obtained product in a mixed solution of methanol and hydrochloric acid with the volume ratio of 6:1 for 8h, washing for multiple times, removing template molecules, and drying to obtain the chloroquine phosphate molecularly imprinted polymer;
(4) preparing a chloroquine phosphate molecularly imprinted electrochemical sensor: in a reactor, acetone is added according to the mass percentage concentration of the following components: 94-96%, polyamide: 2-4%, and chloroquine phosphate molecularly imprinted polymer: 1.5-3.0%, wherein the sum of the contents of all the components is one hundred percent, and the chloroquine phosphate molecularly imprinted polymer modification liquid is prepared; and (3) dropwise adding 40-50 mu L of the modification solution into the carbon quantum dot modified gallium nitride paste electrode prepared in the step (2), placing the electrode under an infrared lamp, and volatilizing the dry solvent to obtain the chloroquine phosphate molecularly imprinted electrochemical sensor.
2. The method for preparing a chloroquine phosphate molecularly imprinted electrochemical sensor as claimed in claim 1, wherein the carbon quantum dots in step (2) are oil-soluble carbon quantum dots.
3. The method for preparing a chloroquine phosphate molecularly imprinted electrochemical sensor according to claim 1, wherein the molar ratio of itaconic acid to 4-aminopyridine in the step (3) is 1: 2.
4. the method for preparing a chloroquine phosphate molecularly imprinted electrochemical sensor as claimed in claim 1, wherein the oxygen-free atmosphere in step (3) is nitrogen gas introduced into the polymerization reaction process.
5. The chloroquine phosphate molecularly imprinted electrochemical sensor prepared by the method for preparing the chloroquine phosphate molecularly imprinted electrochemical sensor according to claim 1.
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