CN105628778A - Producing method of molecular imprinted sensor for detecting camptothecin - Google Patents
Producing method of molecular imprinted sensor for detecting camptothecin Download PDFInfo
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- CN105628778A CN105628778A CN201610087750.6A CN201610087750A CN105628778A CN 105628778 A CN105628778 A CN 105628778A CN 201610087750 A CN201610087750 A CN 201610087750A CN 105628778 A CN105628778 A CN 105628778A
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Abstract
The invention discloses a producing method of a molecular imprinted sensor for detecting camptothecin. The producing method is characterized by including modifying glassy carbon electrodes by gamma-methacryloxy propyl trimethoxyl silane, and successfully developing the imprinted electrochemical sensor with specific selectivity on the surfaces of the modified glassy carbon electrodes by combining a sol-gel imprinting technology, gold nanoparticles, a layer-by-layer self-assembly method and a drop casting method. The response of the molecular imprinted sensor for detecting the camptothecin is improved greatly. The imprinted sensor shows high affinity and selectivity for the camptothecin. The molecular imprinted sensor for detecting the camptothecin is connected with an electrochemical workstation to form a molecular recognition sensor with a special template. The imprinted sensor produced by the producing method has the advantages of low cost, high sensitivity, good specificity, rapidity in detection and reusability.
Description
Technical field
The present invention relates to the preparation method of a kind of molecular engram sensor and quickly detect applied technical field, particularly to a kind of preparation method detecting camptothecin molecule trace sensor, specifically based on molecular engram specific recognition effect, for detecting the camptothecine in medicine, biological sample.
Background technology
Camptothecine is a kind of botanical anticancer medicine, extracts and obtain from the Fructus seu radix camptothecae acuminatae (Fructus Camptothecae Acuminatae) of China's distribution Central-South, southwestern. The synthesising racemation camptothecine successes such as the high happy lifes of Chinese chemists in 1976. Intestines and stomach and incidence cancer etc. are had good curative effect by camptothecine, but a few patients has the side effect of hematuria. The active anticancer of 10-hydroxycamptothecine exceedes camptothecine, hepatocarcinoma and incidence cancer is also had obvious curative effects, and side effect is less. Camptothecine generally extracts from the root of Fructus seu radix camptothecae acuminatae (Fructus Camptothecae Acuminatae), stem, skin and seed and obtains. But due in Fructus seu radix camptothecae acuminatae (Fructus Camptothecae Acuminatae) except camptothecine possibly together with other various ingredients, cause that camptothecine extracts the difficulty separating, measuring, therefore, find that a kind of selectivity is good, highly sensitive, the method for the detection camptothecine of use easy and simple to handle is particularly significant. The method of traditional detection camptothecine mainly has high performance liquid chromatography, LC/MS, fluorimetry etc., and chromatographic accuracy is subject to a definite limitation and the somewhat expensive professional of needs of instrument operates, and also limit its application. The factor of fluorescence light method detection interference is relatively more, and accuracy is difficult to ensure that, time-consuming.
Molecular imprinting is one of current exploitation main method of high selectivity material with molecular recognition function, it is by forming a highly cross-linked rigid macromolecule around template molecule, in the network structure of molecularly imprinted polymer, leave the recognition site with binding ability after removing template molecule, template molecule is shown the high a kind of technology selecting recognition performance. This technology increasingly receives the concern of people with its structure effect precordainment and specific recognition, has been used successfully to Solid-Phase Extraction or micro-Solid-Phase Extraction, affinity chromatography or the field such as capillary electrophoresis and sensor.
According to molecular engram sensor prepared by this technology, it is applied to pharmaceutical analysis, environmental conservation and life science play a very important role. Functional molecular is modified on electrode in a suitable manner, prepares that selectivity is good, highly sensitive, have certain service life reproducible electrochemical sensor to become the problem that analysis science worker makes great efforts to explore. But the blotting membrane thickness prepared by traditional immunoblot method is difficult to control to, high-crosslinking-degree makes electron transmission speed and low-response, Monitoring lower-cut is high and regenerates and poorly reversible, affects molecular imprinting application in electrochemical sensor. Therefore, set up a kind of sensitive, quick, easy, specificity is high, the reproducible economic detection method used, to research worker, manufacturing enterprise, Quality Control personnel, import and export commodity inspection, government administration section etc. in the urgent need to, camptothecine content accurate quantitative analysis in food, medicine, Environmental security is measured very necessary, camptothecine is produced and pharmacological research also has great importance.
Summary of the invention
It is an object of the invention to combine molecular engram with electrochemical sensor, provide a kind of preparation method detecting camptothecin molecule trace sensor, mainly with camptothecine for template, at the molecular engram sensor that glassy carbon electrode surface is prepared by the electrochemical action between ��-methacryloxypropyl trimethoxy silane, Graphene and nano Au particle.
Instrument and reagent
CHI660B electrochemical workstation (Shanghai Chen Hua instrument company), experiment adopts three-electrode system: platinum electrode is auxiliary electrode, and Ag/AgCl is reference electrode (SCE), and glass-carbon electrode (GCE) is working electrode; KQ-250E type ultrasonic cleaner (Kun Feng ultrasonic instrument company limited).
Graphene; ��-methacryloxypropyl trimethoxy silane, dehydrated alcohol; Trimethylol-propane trimethacrylate, DMF (DMF); Gold chloride; Camptothecine; Acrylic acid; 2,2'-Azobis(2,4-dimethylvaleronitrile), phosphate buffer solution.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method detecting camptothecin molecule trace sensor, it is characterised in that the method has following processing step:
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 10 ~ 15%, temperature rises to 45 �� 2 DEG C, soaks 10 ~ 12h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, adds by following composition mass percentage concentration, concentrated sulphuric acid: 50 ~ 60%, Graphene: 3 ~ 8%, potassium permanganate: 1.0 ~ 5%, ultrasonic disperse 20 ~ 30min, add 32 ~ 42% deionized waters, each constituent content sum is that absolutely temperature rises to 65 �� 2 DEG C of stirring reaction 8 ~ 10h, is cooled to room temperature, filter, it is neutral with deionized water cyclic washing to filtrate, vacuum drying, obtain graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, adds by following composition mass percentage concentration, N, dinethylformamide: 70 ~ 80%, graphene oxide: 2 ~ 5%, acrylic acid: 8 ~ 18%, trimethylol-propane trimethacrylate: 4 ~ 12%, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.5 ~ 2.0%, gold chloride: 0.1 ~ 1.0%, stirs 30 ~ 40min, add camptothecine: 0.1 ~ 1.0%, each constituent content sum is that absolutely temperature rises to 60 �� 2 DEG C of stirring reaction 4 ~ 6h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 6 ~ 8h with acetic acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Advantages of the present invention and effect be:
Sol-gel engram technology, Graphene, nano Au particle, LBL self-assembly method and drop-coating are combined by the present invention, successfully have developed a kind of trace electrochemical sensor with specific selectivity in glassy carbon electrode surface. By comparing with that the response of molecular engram electrode without Graphene and decorated by nano-gold, the response of camptothecin molecule trace sensor prepared by the application is greatly improved. Camptothecine is shown higher affinity and selectivity by this trace sensor, and response current and Fructus seu radix camptothecae acuminatae (Fructus Camptothecae Acuminatae) paper mill wastewater are 1.0 �� 10-7~7.0��10-5In good linear relationship within the scope of mol/L, detection is limited to 1.42 �� 10-8The camptothecin molecule trace sensor that the present invention is prepared by mol/L is used successfully in medicine, biological sample in the detection of camptothecine, the response rate is between 96.12 ~ 104.8%, and the molecular engram sensor that therefore prepared by the present invention can be widely applied to the association areas such as chemical industry, biological medicine, food, environmental protection tests.
Detailed description of the invention
Embodiment 1
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 12%, temperature rises to 45 �� 2 DEG C, soaks 11h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, be separately added into, concentrated sulphuric acid: 30mL, Graphene: 5g, potassium permanganate: 3g, ultrasonic disperse 25min, add deionized water: 37mL, temperature rises to 65 �� 2 DEG C of stirring reaction 9h, it is cooled to room temperature, filters, be neutral with deionized water cyclic washing to filtrate, vacuum drying, obtains graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, be separately added into, N, dinethylformamide: 7.9mL, graphene oxide: 0.3g, acrylic acid: 1.0g, trimethylol-propane trimethacrylate: 1.0g, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.1g, gold chloride: 0.05g, stirs 35min, adds camptothecine: 0.05g, temperature rises to 60 �� 2 DEG C of stirring reaction 5h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 7h with hydrochloric acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Embodiment 2
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 10%, temperature rises to 45 �� 2 DEG C, soaks 10h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, be separately added into, concentrated sulphuric acid: 27mL, Graphene: 8g, potassium permanganate: 2g, ultrasonic disperse 20min, add deionized water: 40mL, temperature rises to 65 �� 2 DEG C of stirring reaction 8h, it is cooled to room temperature, filters, be neutral with deionized water cyclic washing to filtrate, vacuum drying, obtains graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, be separately added into, N, dinethylformamide: 7.4mL, graphene oxide: 0.5g, acrylic acid: 1.8g, trimethylol-propane trimethacrylate: 0.5g, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.05g, gold chloride: 0.07g, stirs 30min, adds camptothecine: 0.08g, temperature rises to 60 �� 2 DEG C of stirring reaction 4h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 6h with hydrochloric acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Embodiment 3
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 15%, temperature rises to 45 �� 2 DEG C, soaks 12h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, be separately added into, concentrated sulphuric acid: 32mL, Graphene: 3g, potassium permanganate: 5g, ultrasonic disperse 30min, add deionized water: 32mL, temperature rises to 65 �� 2 DEG C of stirring reaction 10h, it is cooled to room temperature, filters, be neutral with deionized water cyclic washing to filtrate, vacuum drying, obtains graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, be separately added into, N, dinethylformamide: 8.5mL, graphene oxide: 0.2g, acrylic acid: 0.8g, trimethylol-propane trimethacrylate: 0.6g, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.2g, gold chloride: 0.1g, stirs 40min, adds camptothecine: 0.1g, temperature rises to 60 �� 2 DEG C of stirring reaction 6h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 8h with hydrochloric acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Embodiment 4
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 13%, temperature rises to 45 �� 2 DEG C, soaks 11.5h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, be separately added into, concentrated sulphuric acid: 29mL, Graphene: 4g, potassium permanganate: 1g, ultrasonic disperse 22min, add deionized water: 42mL, temperature rises to 65 �� 2 DEG C of stirring reaction 8.5h, it is cooled to room temperature, filters, be neutral with deionized water cyclic washing to filtrate, vacuum drying, obtains graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, be separately added into, N, dinethylformamide: 7.6mL, graphene oxide: 0.4g, acrylic acid: 1.2g, trimethylol-propane trimethacrylate: 1.1g, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.1g, gold chloride: 0.04g, stirs 32min, adds camptothecine: 0.06g, temperature rises to 60 �� 2 DEG C of stirring reaction 5.5h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 6.5h with hydrochloric acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Embodiment 5
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 14%, temperature rises to 45 �� 2 DEG C, soaks 10.5h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, be separately added into, concentrated sulphuric acid: 30mL, Graphene: 6g, potassium permanganate: 3g, ultrasonic disperse 28min, add deionized water: 35mL, temperature rises to 65 �� 2 DEG C of stirring reaction 9.5h, it is cooled to room temperature, filters, be neutral with deionized water cyclic washing to filtrate, vacuum drying, obtains graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, be separately added into, N, dinethylformamide: 7.6mL, graphene oxide: 0.3g, acrylic acid: 1.5g, trimethylol-propane trimethacrylate: 0.4g, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.15g, gold chloride: 0.02g, stirs 38min, adds camptothecine: 0.03g, temperature rises to 60 �� 2 DEG C of stirring reaction 4.5h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 7.5h with hydrochloric acid (volume ratio is ethanol: acetic acid is 8:1) mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
Embodiment 6
By the camptothecin molecule trace sensor prepared by above-described embodiment 1 ~ 5, for the detection of camptothecine, step is as follows:
(1) standard solution preparation: preparing one group of camptothecin standard solution including the variable concentrations of blank standard specimen, end liquid is the phosphate buffered solution of pH7.0;
(2) working curve is drawn: be reference electrode by Ag/AgCl, and platinum electrode is auxiliary electrode, and the camptothecin molecule trace sensor electrode prepared by the embodiment of the present application 1 ~ 5 is working electrode composition three-electrode system, connects CHI660B electrochemical workstation, at K3[Fe(CN)6] in solution, adopt cyclic voltammetry to detect in-0.30 ~ 0.3V potential range, the response current of blank standard specimen is designated asI 0 , the response current of the camptothecin standard solution containing variable concentrations isI i , the difference that response current reduces is��I=I 0 -I i ,��IMass concentration with camptothecin standard solutioncBetween linear, draw��I~cWorking curve;
(3) detection of camptothecine: replace the camptothecin standard solution in step (1) with testing sample, detects according to the method for step (2), according to the difference that response current reduces��IAnd working curve, obtain the content of camptothecine in testing sample;
Described K3[Fe(CN)6] concentration of solution is 5mmol/L;
The concentration of the phosphate buffered solution of described pH7.0 is at 80mmol/L.
Response current and Fructus seu radix camptothecae acuminatae (Fructus Camptothecae Acuminatae) paper mill wastewater are 1.0 �� 10-7~7.0��10-5In good linear relationship within the scope of mol/L, detection is limited to 1.42 �� 10-8The camptothecin molecule trace sensor that the present invention is prepared by mol/L is used successfully in medicine, biological sample in the detection of camptothecine, the response rate is between 96.12 ~ 104.8%, and the molecular engram sensor that therefore prepared by the present invention can be widely applied to the association areas such as chemical industry, biological medicine, food, environmental protection tests.
Claims (4)
1. the preparation method detecting camptothecin molecule trace sensor, it is characterised in that the method has following processing step:
(1) pretreatment of glassy carbon electrode: by glass-carbon electrode successively with 0.1 ��m of Al2O3Powder carries out surface finish, then high purity water ultrasonic cleaning is used, dry up with nitrogen, glass-carbon electrode is put into containing in the alcoholic solution that ��-methacryloxypropyl trimethoxy silane mass percentage concentration is 10 ~ 15%, temperature rises to 45 �� 2 DEG C, soaks 10 ~ 12h, and taking-up dehydrated alcohol fully washs, dry up with nitrogen, obtain pretreatment glass-carbon electrode;
(2) preparation of graphite oxide: in the reactor, adds by following composition mass percentage concentration, concentrated sulphuric acid: 50 ~ 60%, Graphene: 3 ~ 8%, potassium permanganate: 1.0 ~ 5%, ultrasonic disperse 20 ~ 30min, add 32 ~ 42% deionized waters, each constituent content sum is that absolutely temperature rises to 65 �� 2 DEG C of stirring reaction 8 ~ 10h, is cooled to room temperature, filter, it is neutral with deionized water cyclic washing to filtrate, vacuum drying, obtain graphene oxide;
(3) preparation of trace colloidal sol: in the reactor, adds by following composition mass percentage concentration, N, dinethylformamide: 70 ~ 80%, graphene oxide: 2 ~ 5%, acrylic acid: 8 ~ 18%, trimethylol-propane trimethacrylate: 4 ~ 12%, 2,2'-Azobis(2,4-dimethylvaleronitrile): 0.5 ~ 2.0%, gold chloride: 0.1 ~ 1.0%, stirs 30 ~ 40min, add camptothecine: 0.1 ~ 1.0%, each constituent content sum is that absolutely temperature rises to 60 �� 2 DEG C of stirring reaction 4 ~ 6h, obtains trace colloidal sol;
(4) preparation method of camptothecin molecule trace sensor: the trace colloidal sol taking step (3) is added drop-wise on pretreatment glass-carbon electrode prepared by step (1) in 10 �� L, it is placed under infrared lamp, volatilize after dry solvent, used ethanol to soak 6 ~ 8h with acetic acid mixed solution, removed the template molecule on electrode,Obtain camptothecin molecule trace sensor.
2. a kind of preparation method detecting camptothecin molecule trace sensor according to claim 1, it is characterised in that the camptothecine described in step (3) and the mol ratio of gold chloride are that 1:1 is optimum.
3. a kind of preparation method detecting camptothecin molecule trace sensor according to claim 1, it is characterised in that the volume ratio of ethanol described in step (4) and hydrochloric acid mixed solution is ethanol: acetic acid=8:1.
4. the detection camptothecin molecule trace sensor prepared by a kind of preparation method detecting camptothecin molecule trace sensor according to claim 1.
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| CN107179346A (en) * | 2017-05-25 | 2017-09-19 | 济南大学 | A kind of preparation method for being used to detect the molecular engram sensor of anthocyanidin |
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