CN112362704A - Preparation method of molecularly imprinted composite paste electrode sensor for detecting acyclovir - Google Patents
Preparation method of molecularly imprinted composite paste electrode sensor for detecting acyclovir Download PDFInfo
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Abstract
The invention relates to a preparation method of a molecular imprinting composite paste electrode sensor for detecting acyclovir. The preparation method comprises the following steps: preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode; preparation of acyclovir molecularly imprinted polymer: itaconic acid and 3-aminophenylboronic acid are taken as functional monomers, methylene bisacrylamide is taken as a cross-linking agent, dimethyl azodiisobutyrate is taken as an initiator, and acyclovir is taken as a template to carry out cross-linking polymerization reaction to prepare an acyclovir molecularly imprinted polymer; preparing a molecularly imprinted composite paste electrode sensor: and dropwise adding the acyclovir molecularly imprinted polymer modified liquid to the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, volatilizing the solvent, and removing the template molecules by adopting a dropwise coating method to obtain the nano-composite material. The method combines a molecular imprinting technology, a layer-by-layer self-assembly method and a dripping coating method, and the prepared molecular imprinting composite paste electrode sensor is good in response performance, selectivity and sensitivity.
Description
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a preparation method of a molecular imprinting composite paste electrode sensor for detecting acyclovir.
Background
Acyclovir is a purine nucleoside derivative, has an inhibitory effect on DNA synthesis, and has 160 times stronger anti-herpes virus activity than vidarabine. Acyclovir is clinically used for herpes simplex virus encephalitis, herpes virus keratitis, external genital infection, varicella zoster virus infection and cytomegalovirus infection of AIDS, chronic hepatitis B and the like, is a first choice medicament for treating HSV encephalitis, and is superior to vidarabine in reducing morbidity and mortality. In addition, acyclovir can be used for treating herpes zoster, EB virus and varicella complicated by immunodeficiency. Topical application to the skin only, and less skin absorption of acyclovir. However, animal experiments show that long-term use of acyclovir causes problems of poisoning, immunosuppression, drug residue and the like, and harms human health. Therefore, the development of a rapid and accurate detection method for acyclovir is of great significance.
At present, acyclovir detection methods mainly include high performance liquid chromatography, liquid-mass spectrometry and ultraviolet spectrophotometry, instruments of the methods are expensive, professional personnel are required to operate the methods, and the application of the methods is limited due to long detection period. In addition, because the content of acyclovir in a biological sample is low, and coexisting substances interfere with each other, accurate detection of acyclovir is difficult. Therefore, finding a detection method of acyclovir with good selectivity, high sensitivity and simple operation has important use value.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a molecularly imprinted composite paste electrode sensor for detecting acyclovir, which at least partially solves the problems in the prior art.
The first aspect of the application provides a preparation method of a molecularly imprinted composite paste electrode sensor for detecting acyclovir, which comprises the following steps:
step 1), preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: the composite paste electrode takes nano niobium nitride, nano cesium lead bromide and graphene oxide as conductive materials, 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive, and diethanolamine and ethanol as dispersing agents;
step 2), preparation of acyclovir molecularly imprinted polymer: under the alkaline environment and under the protection of nitrogen, taking itaconic acid and 3-aminophenylboronic acid as functional monomers, methylene bisacrylamide as a cross-linking agent, dimethyl azodiisobutyrate as an initiator and acyclovir as a template to perform cross-linking polymerization reaction to prepare an acyclovir molecularly imprinted polymer;
step 3), preparing the molecularly imprinted composite paste electrode sensor:
mixing N, N-dimethylformamide and the acyclovir molecularly imprinted polymer, and heating for dissolving to prepare acyclovir molecularly imprinted polymer modification liquid;
and dropwise adding the acyclovir molecularly imprinted polymer modified liquid to the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, volatilizing a solvent, and removing template molecules by adopting a dropwise coating method to obtain the molecularly imprinted composite paste electrode sensor.
Further, in the step 1), the nano niobium nitride: nano cesium lead bromide: and (3) graphene oxide: 1-carboxyethyl-3-methylimidazole hydrogensulfate: diethanolamine: the mass ratio of the ethanol is (44-48): (8-12): (10-14): (12-16): (6-10): (8-12).
Further, the step 1) is specifically as follows:
adding nano niobium nitride, nano cesium lead bromide, graphene oxide, 1-carboxyethyl-3-methylimidazole bisulfate, diethanolamine and ethanol into an agate mortar in proportion, and uniformly grinding to obtain a mixture carbon paste; and then the mixture carbon paste is filled into a glass tube connected with a lead, and then the mixture carbon paste is obtained by compacting, drying, polishing by using polishing powder and washing by using deionized water.
Further, in the step 2), an alkaline environment is provided by a 1% NaOH aqueous solution; the weight ratio of the NaOH aqueous solution to the itaconic acid to the 3-aminophenylboronic acid to the acyclovir to the methylene bisacrylamide to the dimethyl azodiisobutyrate is as follows: (58-62): (10-14): (10-14): (3-5): (8-12): (0.5-2.0).
Further, in the step 2), the molar ratio of itaconic acid to 3-aminophenylboronic acid is 1: 1.
further, the step 2) is specifically as follows: adding itaconic acid, 3-aminophenylboronic acid, acyclovir, methylene bisacrylamide and dimethyl azodiisobutyrate into a NaOH solution in proportion in a reactor, stirring for dissolving, introducing nitrogen for removing oxygen, stirring for reacting for 4-6 h at 58-62 ℃ under the protection of nitrogen, then carrying out solid-liquid separation, washing for multiple times, and drying to obtain the acyclovir molecularly imprinted polymer.
Further, in the step 3), the weight ratio of the N, N-dimethylformamide to the acyclovir molecularly imprinted polymer is: (95-98): (2.0-5.0).
Further, in the step 3), removing the template molecules by using a dropping method specifically comprises: and (3) volatilizing the solvent, namely using methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 7-9 hours, washing for multiple times, and removing template molecules to obtain the molecular imprinting paste electrode sensor.
In a second aspect, the present application provides a molecularly imprinted composite paste electrode sensor for detecting acyclovir prepared by the method described in any one of the above.
In a third aspect, the present application provides a method for detecting acyclovir, comprising the following steps:
s1, preparing a standard solution: preparing a group of acyclovir standard solutions with different concentrations including blank standard samples, wherein a base solution is boric acid-potassium chloride-sodium hydroxide buffer solution with the pH value of 8.2;
s2, drawing a working curve: the Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as an auxiliary electrode, the molecular imprinting composite paste electrode sensor is used as a working electrode to form a three-electrode system, the three-electrode system is connected with an electrochemical workstation, and K is3[Fe(CN)6]In the solution, the cyclic voltammetry is adopted to carry out detection in a potential range of-0.6-1.2V, and the response current of a blank standard sample is marked as I0The response current of the standard solution containing acyclovir with different concentrations is IiThe difference of the response current decrease is Δ I ═ I0-IiDrawing a working curve from delta I to c according to the linear relation between the delta I and the mass concentration c of the acyclovir standard solution;
s3, detection of acyclovir: and replacing the standard acyclovir solution in the S1 with the sample to be detected, detecting according to the method of S2, and obtaining the content of the acyclovir in the sample to be detected according to the difference value delta I of the reduction of the response current and the working curve.
Compared with the prior art, the invention combines a molecular imprinting technology with an electrochemical sensor, and provides a molecular imprinting composite paste electrode sensor for detecting acyclovir and a preparation method thereof, wherein the molecular imprinting composite paste electrode sensor mainly takes itaconic acid and 3-aminophenylboronic acid as functional monomers, methylene bisacrylamide as a cross-linking agent, dimethyl azodiisobutyrate as an initiator, and acyclovir as a template to prepare an acyclovir molecularly imprinted polymer; the acyclovir molecularly imprinted polymer is modified on the surface of the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, so that the sensitivity of the sensor is improved, and the acyclovir molecularly imprinted electrochemical sensor is constructed by adopting a drop coating method. Compared with the prior art, the preparation method of the molecularly imprinted composite paste electrode sensor for detecting acyclovir provided by the invention has the following advantages:
(1) the composite paste electrode prepared by the invention takes the nano niobium nitride, the nano cesium lead bromide and the graphene oxide as conductive materials, takes the 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive and takes the diethanolamine as a dispersing agent, has higher conductivity and wide electrochemical window, and also has the advantages of simple preparation method, low cost, easy surface updating, small residual current and the like;
(2) according to the invention, a molecular imprinting technology, a layer-by-layer self-assembly method and a dripping coating method are combined, so that the prepared molecular imprinting composite paste electrode sensor has good response performance, good selectivity and high sensitivity. The molecular imprinting sensor shows higher affinity and selectivity to acyclovir, and the response current and the concentration of the acyclovir are 2.0 multiplied by 10-8～6.0×10-6Has good linear relation in the mol/L range and the detection limit is 5.32 multiplied by 10-8mol/L. The molecularly imprinted composite paste electrode sensor prepared by the method is successfully used for detecting acyclovir in a sample, and the recovery rate is 95.22-104.16%, so that the molecularly imprinted composite paste electrode sensor prepared by the method isThe paste electrode sensor can be widely applied to the related fields of medicine, biology, environmental protection detection and the like.
(3) The molecularly imprinted composite paste electrode sensor provided 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
The following describes embodiments of the present invention in detail with reference to specific examples.
It should be noted that, in the case of no conflict, the features in the following embodiments and examples may be combined with each other; moreover, all other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein without making any creative effort fall within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
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 more this technology comes with unique structure-effect preselectivity and specific recognition. The molecular imprinting sensor prepared according to the technology plays an important role in drug analysis and life science research. Therefore, the inventor considers that functional molecules are modified on the electrode in a proper way, establishes a sensitive, rapid, simple, convenient, high-specificity, good-repeatability, economical and applicable detection method, and is necessary for accurately and quantitatively determining the content of acyclovir in drugs and biological samples.
Further, the invention provides a preparation method of the molecularly imprinted composite paste electrode sensor for detecting acyclovir, which comprises the following steps:
step 1), preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: the composite paste electrode takes nano niobium nitride, nano cesium lead bromide and graphene oxide as conductive materials, 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive, and diethanolamine and ethanol as dispersing agents;
step 2), preparation of acyclovir molecularly imprinted polymer: under the alkaline environment and under the protection of nitrogen, taking itaconic acid and 3-aminophenylboronic acid as functional monomers, methylene bisacrylamide as a cross-linking agent, dimethyl azodiisobutyrate as an initiator and acyclovir as a template to perform cross-linking polymerization reaction to prepare an acyclovir molecularly imprinted polymer;
step 3), preparing the molecularly imprinted composite paste electrode sensor:
mixing N, N-dimethylformamide and the acyclovir molecularly imprinted polymer, and heating for dissolving to prepare acyclovir molecularly imprinted polymer modification liquid;
and dropwise adding the acyclovir molecularly imprinted polymer modified liquid to the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, volatilizing a solvent, and removing template molecules by adopting a dropwise coating method to obtain the molecularly imprinted composite paste electrode sensor.
In the above production method, step 1 is a step of producing a carbon paste electrode. Carbon paste electrodes are electrodes of the type that are made by mixing a conductive carbon material (such as graphite powder) with a hydrophobic binder to make a paste, which is then applied to the surface of an electrode rod or filled into an electrode tube. The carbon paste electrode has the advantages of no toxicity, wide electrochemical window, simple preparation method, low cost, easily updated surface, small residual current and the like, and is widely applied to electrochemical analysis, biosensor preparation, environmental detection, food and drug analysis. However, the conventional carbon paste electrode also has some defects, such as poor conductivity, low sensitivity, poor stability and the like. In order to improve the performance of the carbon paste electrode, the composite paste electrode is prepared by adopting nano niobium nitride, nano cesium lead bromide and graphene oxide as conductive materials, matching 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive and using diethanol amine and ethanol as dispersing agents. The prepared composite paste electrode has the advantages of wide electrochemical window, easy surface updating, small residual current and the like; in addition, the conductivity of the carbon paste electrode is improved by 5-6 times compared with that of a common carbon paste electrode, and the preparation method is relatively simple and low in cost.
The reason why the nano niobium nitride, the nano cesium lead bromide and the graphene oxide are selected as the conductive materials in the step 1 is that: niobium nitride is a typical B-1 type compound, and has a sodium chloride crystal structure, a superconducting critical temperature of 17.3K, an upper critical magnetic field of 43T, a critical current density Jc (4.2K, 20T) of 2 x 106A/cm2The material has high thermal stability and chemical stability, and is a super electrode material with excellent performance; cesium lead bromide (CsPbBr)3) The material has a typical perovskite structure, is an electronic functional material with wide application, has the advantages of high dielectric constant, low dielectric loss, good thermal stability and the like, and has attractive prospect in the aspect of photoelectric application. The three conductive materials have good conductivity, and the composite electrode is prepared together, so that the charge transmission is facilitated, and the sensitivity and the selectivity of the electrochemical sensor are improved.
The reason why 1-carboxyethyl-3-methylimidazole hydrogen sulfate is selected as the adhesive in the step 1 is as follows: the ionic liquid has a larger electrochemical window, and can widen the electrochemical window of the obtained electrochemical sensor and improve the capacity. The reason why diethanolamine and ethanol are used as the dispersant is that: the two can be tightly adsorbed on the surface of the solid particle through the interaction of hydrogen bond, Van der Waals force and the like, and a good protective layer is formed on the surface of the particle to play a role in super dispersion.
In the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode prepared in the step, the nano niobium nitride: nano cesium lead bromide: and (3) graphene oxide: 1-carboxyethyl-3-methylimidazole hydrogensulfate: diethanolamine: the mass ratio of ethanol is preferably (44-48): (8-12): (10-14): (12-16): (6-10): (8-12).
Further, the step 1) may specifically be as follows:
adding nano niobium nitride, nano cesium lead bromide, graphene oxide, 1-carboxyethyl-3-methylimidazole bisulfate, diethanolamine and ethanol into an agate mortar in proportion, and uniformly grinding to obtain a mixture carbon paste; and then the mixture carbon paste is filled into a glass tube connected with a lead, and then the mixture carbon paste is obtained by compacting, drying, polishing by using polishing powder and washing by using deionized water. The inner diameter of the glass tube is preferably 4 mm. Furthermore, the content of the nano niobium nitride in the mixture carbon paste is 44-48 wt%, the content of the nano cesium lead bromide is 8-12 wt%, the content of the graphene oxide is 10-14 wt%, the content of the 1-carboxyethyl-3-methylimidazolium hydrogen sulfate is 12-16 wt%, the content of the diethanolamine is 6-10 wt%, and the content of the ethanol is 8-12 wt%.
Step 2 is a process for preparing acyclovir molecularly imprinted polymer, wherein the acyclovir molecularly imprinted polymer is prepared by a layer-by-layer self-assembly method, template molecules and functional monomers are arranged in a self-organizing manner, a monomer-template molecule compound with multiple action sites is formed spontaneously by non-covalent bonds, and the action is preserved after cross-linking polymerization. In the step, the reason that itaconic acid and 3-aminophenylboronic acid are used as functional monomers is as follows: the itaconic acid molecule contains two active carboxyl groups and a double bond, and the double bond and the carboxyl group are in a conjugated relation, so the itaconic acid can be polymerized with other monomers with different numbers to form a polymer. The methylene bisacrylamide is taken as a crosslinking agent, and has the following functions: the polymer obtained by polymerizing the itaconic acid and the acrylamide has good plasticity and adhesive force. The function of using azobisisobutyric acid dimethyl ester as an initiator is as follows: the azo diisobutyrate dimethyl ester is used as an initiator, the initiation activity is moderate, and the polymerization reaction is easy to control.
In the cross-linking polymerization reaction, the alkaline environment required for the reaction is preferably provided by a 1% aqueous NaOH solution. Further, the weight ratio of the NaOH aqueous solution to the itaconic acid to the 3-aminophenylboronic acid to the acyclovir to the methylene bisacrylamide to the dimethyl azodiisobutyrate is as follows: (58-62): (10-14): (10-14): (3-5): (8-12): (0.5-2.0). More preferably, the molar ratio of itaconic acid to 3-aminophenylboronic acid is 1: 1.
the step 2 may specifically be as follows: adding itaconic acid, 3-aminophenylboronic acid, acyclovir, methylene bisacrylamide and dimethyl azodiisobutyrate into a NaOH solution in proportion in a reactor, stirring for dissolving, introducing nitrogen for removing oxygen, stirring for reacting for 4-6 h at 58-62 ℃ under the protection of nitrogen, then carrying out solid-liquid separation, washing for multiple times, and drying to obtain the acyclovir molecularly imprinted polymer. Furthermore, in the reactor, the content of NaOH aqueous solution is 58-62 wt%, the content of itaconic acid is 10-14 wt%, the content of 3-aminophenylboronic acid is 10-14 wt%, the content of acyclovir is 3-5 wt%, the content of methylene bisacrylamide is 8-12 wt%, and the content of dimethyl azodiisobutyrate is 0.5-2.0 wt%.
Step 3) is a step of preparing a molecularly imprinted composite paste electrode sensor, wherein N, N-dimethylformamide and the acyclovir molecularly imprinted polymer are mixed to prepare an acyclovir molecularly imprinted polymer modification liquid, and the modification liquid has the function of forming a film on the surface of a paste electrode; and then, dropwise adding the polymer modified liquid to the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode prepared in the step 1) for modification, and finally removing template molecules by adopting a dropwise coating method to obtain the acyclovir molecularly imprinted composite paste electrode sensor.
In the step, the weight ratio of the N, N-dimethylformamide to the acyclovir molecularly imprinted polymer is preferably as follows: (95-98): (2.0-5.0). The step of removing the template molecules by the drop coating method may specifically be as follows: and (3) volatilizing the solvent, namely using methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 7-9 h, washing for multiple times, and removing template molecules to obtain the acyclovir molecularly imprinted paste electrode sensor. Further, in the step of mixing the N, N-dimethylformamide and the acyclovir molecularly imprinted polymer, the N, N-dimethylformamide accounts for 95-98 wt% of the total amount of the N, N-dimethylformamide and the acyclovir molecularly imprinted polymer.
According to the content, the invention combines the molecular imprinting technology with the electrochemical sensor, and provides the preparation method of the molecular imprinting composite paste electrode sensor for detecting acyclovir, wherein the preparation method mainly takes itaconic acid and 3-aminophenylboronic acid as functional monomers, methylene bisacrylamide as a cross-linking agent, dimethyl azodiisobutyrate as an initiator, and acyclovir as a template to prepare the acyclovir molecularly imprinted polymer; the acyclovir molecularly imprinted polymer is modified on the surface of the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, so that the sensitivity of the sensor is improved, and the acyclovir molecularly imprinted electrochemical sensor is constructed by adopting a drop coating method. Compared with the prior art, the preparation method of the molecularly imprinted composite paste electrode sensor for detecting acyclovir provided by the invention has the following advantages:
(1) the composite paste electrode prepared by the invention takes the nano niobium nitride, the nano cesium lead bromide and the graphene oxide as conductive materials, takes the 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive and takes the diethanolamine as a dispersing agent, has higher conductivity and wide electrochemical window, and also has the advantages of simple preparation method, low cost, easy surface updating, small residual current and the like;
(2) according to the invention, a molecular imprinting technology, a layer-by-layer self-assembly method and a dripping coating method are combined, so that the prepared molecular imprinting composite paste electrode sensor has good response performance, good selectivity and high sensitivity. The molecular imprinting sensor shows higher affinity and selectivity to acyclovir, and the response current and the concentration of the acyclovir are 2.0 multiplied by 10-8～6.0×10-6Has good linear relation in the mol/L range and the detection limit is 5.32 multiplied by 10-8mol/L. The molecularly imprinted composite paste electrode sensor prepared by the invention is successfully used for detecting acyclovir in a sample, and the recovery rate is 95.22-104.16%, so that the molecularly imprinted composite paste electrode sensor prepared by the invention can be widely applied to the related fields of medicine, biology, environmental protection detection and the like.
(3) The molecularly imprinted composite paste electrode sensor provided by the invention does not use toxic reagents in the preparation process, is environment-friendly and green, and has a simple preparation process.
The invention also provides a molecularly imprinted composite paste electrode sensor for detecting acyclovir, which is prepared by the method. The composite paste electrode sensor prepared by the method has the advantages correspondingly.
In addition, the invention also provides a detection method of acyclovir, which comprises the following steps:
s1, preparing a standard solution: preparing a group of acyclovir standard solutions with different concentrations including blank standard samples, wherein a base solution is boric acid-potassium chloride-sodium hydroxide buffer solution with the pH value of 8.2;
s2, drawing a working curve: a three-electrode system is formed by taking Ag/AgCl as a reference electrode, a platinum wire electrode as an auxiliary electrode and the composite paste electrode sensor as the working electrode according to claim 9, is connected with an electrochemical workstation and is arranged at K3[Fe(CN)6]In the solution, the cyclic voltammetry is adopted to carry out detection in a potential range of-0.6-1.2V, and the response current of a blank standard sample is marked as I0The response current of the standard solution containing acyclovir with different concentrations is IiThe difference of the response current decrease is Δ I ═ I0-IiDrawing a working curve from delta I to c according to the linear relation between the delta I and the mass concentration c of the acyclovir standard solution;
s3, detection of acyclovir: and replacing the standard acyclovir solution in the S1 with the sample to be detected, detecting according to the method of S2, and obtaining the content of the acyclovir in the sample to be detected according to the difference value delta I of the reduction of the response current and the working curve.
Preferably, the concentration of the boric acid-potassium chloride-sodium hydroxide buffer solution with pH of 8.2 in S1 is 0.10 mol/L. In S2, K is3[Fe(CN)6]The concentration of the solution was 4.0 mmol/L.
The method for detecting the content of acyclovir has the advantages of good response performance, good selectivity and high sensitivity. Response current and acyclovir concentration are 2.0 x 10-8～6.0×10-6Has good linear relation in the mol/L range and the detection limit is 5.32 multiplied by 10-8mol/L. The molecularly imprinted composite paste electrode sensor prepared by the invention is successfully used for detecting acyclovir in a sample, the recovery rate is 95.22-104.16%, and the molecularly imprinted composite paste electrode sensor can be widely applied to related fields of medicine, biology, environmental protection detection and the like.
The technical solution of the present application is described below with reference to specific embodiments.
Example 1
(1) Preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: in an agate mortar, adding the nano niobium nitride: 23g, 1-carboxyethyl-3-methylimidazolium hydrogen sulfate: 6g, nano cesium lead bromide: 5g, graphene oxide: 6g, diethanolamine: 4g, ethanol: 6g, grinding uniformly to obtain a mixture carbon paste; then the carbon paste is filled into a glass tube which is connected with a lead and has the inner diameter of phi 4mm, and the carbon paste is obtained by compacting, drying, polishing by using polishing powder and washing by using deionized water; through tests, the conductivity of the composite paste electrode is improved by 5-6 times compared with the conductivity of a common carbon paste electrode;
(2) preparation of acyclovir molecularly imprinted polymer: respectively adding 1% NaOH aqueous solution by mass percent into a reactor: 60g, itaconic acid: 12g, 3-aminophenylboronic acid: 12g, acyclovir: 4g, methylene bisacrylamide: 10g, dimethyl azodiisobutyrate: 2.0g, stirring for dissolving, introducing nitrogen to remove oxygen for 15min, stirring for reacting for 5h at 60 +/-2 ℃ in an oxygen-free atmosphere, carrying out solid-liquid separation, washing for multiple times, and drying to obtain an acyclovir molecularly imprinted polymer;
(3) preparation of an acyclovir molecularly imprinted composite paste electrode sensor: in the reactor, N-dimethylformamide: 9.7g, acyclovir molecularly imprinted polymer: 0.3g, heating and dissolving to prepare acyclovir molecularly imprinted polymer modification liquid; then, 20 mu L of the solution is dripped into the composite paste electrode prepared in the step (1), the composite paste electrode is placed under an infrared lamp, and after the solvent is volatilized, the obtained electrode is coated with methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 8 hours, washing for multiple times, and removing template molecules to obtain the acyclovir molecularly imprinted composite paste electrode sensor.
Example 2
(1) Preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: in an agate mortar, adding the nano niobium nitride: 22g, 1-carboxyethyl-3-methylimidazolium hydrogen sulfate: 7g, nano cesium lead bromide: 5g, graphene oxide: 7g, diethanolamine: 5g, ethanol: 4g, grinding uniformly to obtain a mixture carbon paste; then the carbon paste is filled into a glass tube which is connected with a lead and has the inner diameter of phi 4mm, and the glass tube is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain a composite paste electrode; through tests, the conductivity of the composite paste electrode is improved by 5-6 times compared with the conductivity of a common carbon paste electrode;
(2) preparation of acyclovir molecularly imprinted polymer: respectively adding 1% NaOH aqueous solution by mass percent into a reactor: 58g, itaconic acid: 13g, 3-aminophenylboronic acid: 14g, acyclovir: 3g, methylene bisacrylamide: 11g, dimethyl azodiisobutyrate: 0.5g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 4h at 60 +/-2 ℃ in an oxygen-free atmosphere, carrying out solid-liquid separation, washing for multiple times, and drying to obtain an acyclovir molecularly imprinted polymer;
(3) preparation of an acyclovir molecularly imprinted composite paste electrode sensor: in the reactor, N-dimethylformamide: 9.5g, acyclovir molecularly imprinted polymer: 0.5g, heating and dissolving to prepare acyclovir molecularly imprinted polymer modification liquid; then, 16 μ L of the above solution was added dropwise to the composite paste electrode prepared in step (1), and after the dry solvent was evaporated under an infrared lamp, the obtained electrode was treated with methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 8 hours, washing for multiple times, and removing template molecules to obtain the acyclovir molecularly imprinted paste composite electrode sensor.
Example 3
(1) Preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: in an agate mortar, adding the nano niobium nitride: 24g, 1-carboxyethyl-3-methylimidazolium hydrogen sulfate: 6g, nano cesium lead bromide: 6g, graphene oxide: 5g, diethanolamine: 3g, ethanol: 6g, grinding uniformly to obtain a mixture carbon paste; then the carbon paste is filled into a glass tube which is connected with a lead and has the inner diameter of phi 4mm, and the glass tube is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain a composite paste electrode; through tests, the conductivity of the composite paste electrode is improved by 5-6 times compared with the conductivity of a common carbon paste electrode;
(2) preparation of acyclovir molecularly imprinted polymer: respectively adding 1% NaOH aqueous solution by mass percent into a reactor: 62g, itaconic acid: 10g, 3-aminophenylboronic acid: 10g, acyclovir: 5g, methylene bisacrylamide: 12g, dimethyl azodiisobutyrate: 1.0g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 6h at 60 +/-2 ℃ in an oxygen-free atmosphere, carrying out solid-liquid separation, washing for multiple times, and drying to obtain an acyclovir molecularly imprinted polymer;
(3) preparation of an acyclovir molecularly imprinted composite paste electrode sensor: in the reactor, N-dimethylformamide: 9.8g, acyclovir molecularly imprinted polymer: 0.2g, heating and dissolving to prepare acyclovir molecularly imprinted polymer modification liquid; then, 24 mu L of the solution is dripped into the composite paste electrode prepared in the step (1), the composite paste electrode is placed under an infrared lamp, and after the solvent is volatilized, the obtained electrode is coated with methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 8 hours, washing for multiple times, and removing template molecules to obtain the acyclovir molecularly imprinted composite paste electrode sensor.
Example 4
(1) Preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: in an agate mortar, adding the nano niobium nitride: 12g, 1-carboxyethyl-3-methylimidazolium hydrogen sulfate: 4g, nano cesium lead bromide: 2.5g, graphene oxide: 3g, diethanolamine: 2g, ethanol: 3g, grinding uniformly to obtain a mixture carbon paste; then the carbon paste is filled into a glass tube which is connected with a lead and has the inner diameter of phi 4mm, and the glass tube is compacted, dried, polished by polishing powder, polished and washed by deionized water to obtain a composite paste electrode; through tests, the conductivity of the composite paste electrode is improved by 5-6 times compared with the conductivity of a common carbon paste electrode;
(2) preparation of acyclovir molecularly imprinted polymer: respectively adding 1% NaOH aqueous solution by mass percent into a reactor: 58g, itaconic acid: 14g, 3-aminophenylboronic acid: 13g, acyclovir: 5g, methylene bisacrylamide: 8g, dimethyl azodiisobutyrate: 1.5g, stirring and dissolving, introducing nitrogen to remove oxygen for 15min, stirring and reacting for 5.5h at 60 +/-2 ℃ in an oxygen-free atmosphere, carrying out solid-liquid separation, washing for multiple times, and drying to obtain an acyclovir molecularly imprinted polymer;
(3) preparation of an acyclovir molecularly imprinted composite paste electrode sensor: in the reactor, N-dimethylformamide: 9.6g, acyclovir molecularly imprinted polymer: 0.4g, heating and dissolving to prepare acyclovir molecularly imprinted polymer modification liquid; then, 18 μ L of the solution is added dropwise to the composite paste electrode prepared in the step (1), the composite paste electrode is placed under an infrared lamp, and after the solvent is evaporated, the obtained electrode is treated with methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 8 hours, washing for multiple times, and removing template molecules to obtain the acyclovir molecularly imprinted composite paste electrode sensor.
Example 5
The acyclovir molecularly imprinted niobium nitride composite paste electrode sensor prepared in the embodiment 1-4 is used for detecting acyclovir, and comprises the following steps:
(1) preparing a standard solution: preparing a group of acyclovir standard solutions with different concentrations including blank standard samples, wherein a base solution is boric acid-potassium chloride-sodium hydroxide buffer solution with the pH value of 8.2;
(2) drawing a working curve: Ag/AgCl is used as a reference electrode, a platinum wire electrode is used as an auxiliary electrode, the acyclovir molecularly imprinted niobium nitride composite paste electrode 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 carry out detection in a potential range of-0.6-1.2V, and the response current of a blank standard sample is marked as I0The response current of the standard solution containing acyclovir with different concentrations is IiThe difference of the response current decrease is Δ I ═ I0-IiThe mass concentration c of the standard acyclovir solution and the delta I form a linear relation, and a working curve from the delta I to the delta c is drawn;
(3) detection of acyclovir: by usingReplacing the standard acyclovir solution in the step (1) with the actual sample to be detected, detecting according to the method in the step (2), and obtaining the content of acyclovir in the sample to be detected according to the difference value delta I and the working curve of the reduction of the response current; the detection limit is 5.32 multiplied by 10-8mol/L, and the recovery rate is 95.22-104.16%.
Said K3[Fe(CN)6]The concentration of the solution is 4.0 mmol/L;
the concentration of the boric acid-potassium chloride-sodium hydroxide buffer solution with the pH of 8.2 is 0.10 mol/L.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a molecular imprinting composite paste electrode sensor for detecting acyclovir is characterized by comprising the following steps:
step 1), preparing a nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode: the composite paste electrode takes nano niobium nitride, nano cesium lead bromide and graphene oxide as conductive materials, 1-carboxyethyl-3-methylimidazole hydrogen sulfate as an adhesive, and diethanolamine and ethanol as dispersing agents;
step 2), preparation of acyclovir molecularly imprinted polymer: under the alkaline environment and under the protection of nitrogen, taking itaconic acid and 3-aminophenylboronic acid as functional monomers, methylene bisacrylamide as a cross-linking agent, dimethyl azodiisobutyrate as an initiator and acyclovir as a template to perform cross-linking polymerization reaction to prepare an acyclovir molecularly imprinted polymer;
step 3), preparing the molecularly imprinted composite paste electrode sensor:
mixing N, N-dimethylformamide and the acyclovir molecularly imprinted polymer, and heating for dissolving to prepare acyclovir molecularly imprinted polymer modification liquid;
and dropwise adding the acyclovir molecularly imprinted polymer modified liquid to the nano niobium nitride/nano cesium lead bromide/graphene oxide composite paste electrode, volatilizing a solvent, and removing template molecules by adopting a dropwise coating method to obtain the molecularly imprinted composite paste electrode sensor.
2. The method according to claim 1, wherein in the step 1), the ratio of nano niobium nitride: nano cesium lead bromide: and (3) graphene oxide: 1-carboxyethyl-3-methylimidazole hydrogensulfate: diethanolamine: the mass ratio of the ethanol is (44-48): (8-12): (10-14): (12-16): (6-10): (8-12).
3. The preparation method according to claim 2, wherein the step 1) is specifically:
adding nano niobium nitride, nano cesium lead bromide, graphene oxide, 1-carboxyethyl-3-methylimidazole bisulfate, diethanolamine and ethanol into an agate mortar in proportion, and uniformly grinding to obtain a mixture carbon paste; and then the mixture carbon paste is filled into a glass tube connected with a lead, and then the mixture carbon paste is obtained by compacting, drying, polishing by using polishing powder and washing by using deionized water.
4. The preparation method according to claim 1, wherein in the step 2), the alkaline environment is provided by a 1% NaOH aqueous solution; the weight ratio of the NaOH aqueous solution to the itaconic acid to the 3-aminophenylboronic acid to the acyclovir to the methylene bisacrylamide to the dimethyl azodiisobutyrate is as follows: (58-62): (10-14): (10-14): (3-5): (8-12): (0.5-2.0).
5. The preparation method according to claim 4, wherein the molar ratio of itaconic acid to 3-aminophenylboronic acid in the step 2) is 1: 1.
6. the preparation method according to claim 1, wherein the step 2) is specifically: adding itaconic acid, 3-aminophenylboronic acid, acyclovir, methylene bisacrylamide and dimethyl azodiisobutyrate into a NaOH solution in proportion in a reactor, stirring for dissolving, introducing nitrogen for removing oxygen, stirring for reacting for 4-6 h at 58-62 ℃ under the protection of nitrogen, then carrying out solid-liquid separation, washing for multiple times, and drying to obtain the acyclovir molecularly imprinted polymer.
7. The preparation method of claim 1, wherein in the step 3), the weight ratio of the N, N-dimethylformamide to the acyclovir molecularly imprinted polymer is as follows: (95-98): (2.0-5.0).
8. The preparation method according to claim 1, wherein in the step 3), the removing of the template molecule by the droplet coating method specifically comprises: and (3) volatilizing the solvent, namely using methanol: the volume ratio of acetic acid is 8: 1, soaking the mixed solution for 7-9 hours, washing for multiple times, and removing template molecules to obtain the molecular imprinting paste electrode sensor.
9. A molecularly imprinted composite paste electrode sensor for detecting acyclovir prepared according to the method of any one of claims 1 to 8.
10. The detection method of acyclovir is characterized by comprising the following steps:
s1, preparing a standard solution: preparing a group of acyclovir standard solutions with different concentrations including blank standard samples, wherein a base solution is boric acid-potassium chloride-sodium hydroxide buffer solution with the pH value of 8.2;
s2, drawing a working curve: a three-electrode system is formed by taking Ag/AgCl as a reference electrode, a platinum wire electrode as an auxiliary electrode and the molecularly imprinted composite paste electrode sensor as the working electrode according to claim 9, is connected with an electrochemical workstation and is arranged at K3[Fe(CN)6]In the solution, the cyclic voltammetry is adopted to carry out detection in a potential range of-0.6-1.2V, and the response current of a blank standard sample is marked as I0The response current of the standard solution containing acyclovir with different concentrations is IiThe difference of the response current decrease is Δ I ═ I0-IiDrawing a working curve from delta I to c according to the linear relation between the delta I and the mass concentration c of the acyclovir standard solution;
s3, detection of acyclovir: and replacing the standard acyclovir solution in the S1 with the sample to be detected, detecting according to the method of S2, and obtaining the content of the acyclovir in the sample to be detected according to the difference value delta I of the reduction of the response current and the working curve.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100172993A1 (en) * | 2006-08-11 | 2010-07-08 | Amarjit Singh | Particles for delivery of active ingredients, process of making and compositions thereof |
| CN101812158A (en) * | 2010-03-02 | 2010-08-25 | 苏州凯达生物医药技术有限公司 | Acyclovir molecularly imprinted polymer, preparation method and application thereof |
| CN103690970A (en) * | 2013-12-27 | 2014-04-02 | 云南联合药业有限责任公司 | Method for preparing targeting predrug from peat, targeting predrug and application |
| CN105131181A (en) * | 2015-08-26 | 2015-12-09 | 河北大学 | Preparation method for ionic liquid hybrid imprinted material |
| CN109985025A (en) * | 2017-12-29 | 2019-07-09 | 沈阳药科大学 | Eye Atrigel with pH triggering drug release characteristic |
-
2020
- 2020-10-29 CN CN202011180935.4A patent/CN112362704B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100172993A1 (en) * | 2006-08-11 | 2010-07-08 | Amarjit Singh | Particles for delivery of active ingredients, process of making and compositions thereof |
| CN101812158A (en) * | 2010-03-02 | 2010-08-25 | 苏州凯达生物医药技术有限公司 | Acyclovir molecularly imprinted polymer, preparation method and application thereof |
| CN103690970A (en) * | 2013-12-27 | 2014-04-02 | 云南联合药业有限责任公司 | Method for preparing targeting predrug from peat, targeting predrug and application |
| CN105131181A (en) * | 2015-08-26 | 2015-12-09 | 河北大学 | Preparation method for ionic liquid hybrid imprinted material |
| CN109985025A (en) * | 2017-12-29 | 2019-07-09 | 沈阳药科大学 | Eye Atrigel with pH triggering drug release characteristic |
Non-Patent Citations (1)
| Title |
|---|
| NESRINE ABDELREHIM EL GOHARY ET AL: "Voltammetric Determination of Valaciclovir Using a Molecularly Imprinted Polymer Modified Carbon Paste Electrode", 《ELECTROANALYSIS》 * |
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