CN111175361B - Preparation method of electrochemical molecular imprinting sensor based on chitosan oligosaccharide derivative as functional monomer - Google Patents
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Abstract
A preparation method of an electrochemical molecular imprinting sensor based on a chitosan oligosaccharide derivative as a functional monomer relates to the technical field of electrochemical sensors, and comprises the steps of taking curcumin as a template molecule, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide as a functional monomer oligomer, ethylene glycol dimethacrylate as a cross-linking agent and azobisisobutyronitrile as an initiator, carrying out thermal polymerization on the surface of a glassy carbon electrode to form a curcumin molecular imprinting film, then carrying out electrolytic secondary polymerization in a solution containing N, N-methylene bisacrylamide and ammonium persulfate, reserving a recognition site on the surface of the electrode after elution of eluent, taking ferrocene methanol as an electroactive probe, and measuring the current change of a charge transfer reaction in the recognition process to realize indirect detection of curcumin.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors.
Background
Curcumin is a chemical substance extracted from rhizomes of some plants in Zingiberaceae and Araceae, and is a phenolic compound with diketone structure rare in plant kingdom. Curcumin is an orange yellow crystalline powder, slightly bitter in taste, insoluble in water, and mainly used as a pigment in the food industry. Modern medical research shows that curcumin not only has the effects of reducing blood fat, resisting tumor, resisting inflammation, benefiting gallbladder, resisting oxidation and the like, but also has certain curative effect and prevention effect on a plurality of diseases, such as diabetes, drug-resistant tuberculosis and the like. Therefore, determination of curcumin content in bioactive health products and food flavors is an important analytical task in pharmacological research and food industry.
The existing detection method for curcumin mainly adopts a High Performance Liquid Chromatography (HPLC) combined Ultraviolet (UV) detection method. However, in these methods, because curcumin analogs have the same chromophoric group, the specificity is often not high, and accurate judgment cannot be given to the metabolic products and the stability of the curcumin analogs in some researches, so that it is necessary to develop some detection methods with good specificity and high sensitivity.
Electrochemical analysis methods are widely studied and applied because of their convenient operation, simple instrumentation, high sensitivity, and high accuracy. The molecular imprinting technology is that template molecules and certain functional monomers form a host-guest compound through the interaction between the molecules, and then a certain amount of cross-linking agent and the functional monomers are added to jointly polymerize into a high molecular polymer. After the template molecules are removed, the configuration of the template molecules is recorded in the holes in the rigid polymer, and the precise arrangement of the functional groups in the holes is complementary with the template molecules, so that the template molecules have high recognition capability. The molecular recognition device is an ideal molecular recognition device in the electrochemical sensor due to simple manufacture, good stability, reusability and low cost. When constructing a sensor, the molecularly imprinted polymer is usually fixed on the surface of an electrode of an electrochemical sensor in a suitable form, wherein the form of the molecularly imprinted membrane is usually constructed.
Chinese patent application 201911326503.7 discloses a preparation method of a chitosan oligosaccharide derivative molecular imprinting functional monomer.
Disclosure of Invention
The invention aims to provide a preparation method of an electrochemical molecular imprinting sensor which can be used for measuring the concentration of curcumin and has specificity, sensitivity and stability, and an electrode based on chitosan oligosaccharide derivatives as functional monomers.
The invention comprises the following steps:
1) adding curcumin and N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide into DMF and H with the volume ratio of 1/2-2/12Dissolving the mixture in a mixed solvent consisting of O by ultrasonic waves at room temperature, then adding ethylene glycol dimethacrylate and azobisisobutyronitrile, standing for 5-24 hours, and removing dissolved oxygen by using nitrogen to obtain a mixed solution;
2) dripping the mixed liquid on the surface of a clean glassy carbon electrode, then covering a clean cover glass, placing the glass in a drying oven at the temperature of 55-75 ℃ for heating for 5-20 h, and removing the cover glass to form a layer of transparent polymer film on the surface of the glassy carbon electrode;
3) dissolving N, N-methylene-bisacrylamide and ammonium persulfate in a NaAc/HAc solution with the pH value of 6.5 and the concentration of 0.1-1.5M to obtain a mixed solution; placing the polymerized membrane electrode in the mixed solution, scanning for 10-40 circles at a sweep rate of 20-150 mV/s under cyclic voltammetry within a range of-1.4V-0.5V, and preparing a glassy carbon electrode modified by a secondarily polymerized curcumin molecularly imprinted membrane;
4) and (3) eluting the imprinted molecular curcumin in the molecularly imprinted membrane by using a methanol solution containing 10-50% of acetic acid in mass percent as an eluent for the secondarily polymerized curcumin molecularly imprinted membrane modified glassy carbon electrode, so as to obtain the electrochemical molecularly imprinted sensor based on the chitosan oligosaccharide derivative as the functional monomer.
The invention relates to a specific application of the functional monomer for detecting curcumin by molecular imprinting, namely curcumin is taken as a template molecule, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide is taken as a functional monomer oligomer, ethylene glycol dimethacrylate is taken as a cross-linking agent, and azobisisobutyronitrile is taken as an initiator, firstly a curcumin molecular imprinting film is formed on the surface of a glassy carbon electrode by thermal polymerization, then the curcumin molecular imprinting film is electrolyzed and secondarily polymerized in a solution containing N, N-methylene-bisacrylamide and ammonium persulfate, an identification site is reserved on the surface of the electrode after elution by eluent, and then ferrocene methanol is taken as an electroactive probe, and the indirect detection of curcumin is realized by measuring the current change of charge transfer reaction in the identification process.
According to the invention, a three-electrode system is formed by using the specific binding effect of the molecularly imprinted membrane on curcumin, taking a molecularly imprinted membrane modified electrode as a working electrode, taking a reference electrode as a saturated calomel electrode and taking an auxiliary electrode as a platinum electrode, so that the high-sensitivity detection on curcumin is realized.
The sensor prepared by the invention can be used for identifying and detecting curcumin, and can be used for indirectly detecting curcumin by using some electroactive substances such as potassium ferricyanide, ferrocenyl methanol and the like as electroactive probes and measuring the current change of charge transfer reaction in the process of identifying curcumin by the molecularly imprinted membrane electrode.
The working principle of the invention is as follows: on the surface of a clean glassy carbon electrode, a layer of molecular imprinting film which takes curcumin as a template molecule, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide as a functional monomer oligomer and ethylene glycol dimethacrylate as a cross-linking agent is covered by thermal polymerization, at the moment, due to the rigid structure of the functional monomer oligomer of the chitosan oligosaccharide derivative, a nano-size structure is formed due to solvent volatilization in the polymerization process (due to the simultaneous occurrence of cross-linking reaction, the precipitated chitosan oligosaccharide structure can not be aggregated), so that a film structure with a very large specific surface area is formed on the surface of the electrode, and the measurement sensitivity is greatly improved. In addition, a larger grid structure is formed in the molecularly imprinted membrane of the chitosan oligosaccharide oligomer, when the molecularly imprinted membrane is used for electrochemical measurement, larger background current is caused, the signal to noise ratio of detection is too small, and the measurement sensitivity is insufficient, so that the thermopolymerization modified electrode is subjected to secondary electrochemical initiation polymerization, and the molecularly imprinted membrane formed by thermopolymerization and template molecules thereof are not conductive and the template molecules are insoluble in electrolyte, so that the electrically initiated polymer is deposited only in gaps in the molecularly imprinted membrane formed by thermopolymerization during secondary polymerization, the background current of the sensor is greatly reduced, and meanwhile, the space where the template molecules and the imprinted membrane are located is further matched, so that after the template molecules are removed from the molecularly imprinted membrane, the molecularly imprinted membrane with good specificity and sensitivity to curcumin molecules can be obtained on the surface of the electrode. During testing, ferrocene methanol is used as an electrochemical probe to test the signal change of differential pulse voltammetry in electrolyte, and the differential pulse voltammetry in electrochemical analysis belongs to a high-sensitivity detection method, so that the molecular imprinting sensor for detecting curcumin with high sensitivity can be obtained.
The invention takes N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide which can form a large grid structure and has strong effect on curcumin molecules as a functional monomer oligomer, and prepares the molecular imprinting sensor on the surface of a glassy carbon electrode by a two-time polymerization method. Due to the strong effect of the functional monomer oligomer on curcumin molecules and the matching property of the spatial structure of molecular imprinting, the signal-to-noise ratio of the sensor during measurement is effectively reduced by secondary polymerization. The results show that the linear range of curcumin measured by the molecular imprinting sensor is 1.0 multiplied by 10-8～2.0×10-6mol/L, detection limit of 0.5X 10-8mol/L. The same glassy carbon electrode is used for preparing the five-time molecular imprinting sensor, the response current of the sensor to the curcumin is measured, the relative standard deviation is 2.9%, and the relative standard deviation of the molecular imprinting sensor prepared by using 3 glassy carbon electrodes in parallel to the curcumin is 3.5%, so that the electrode has good reproducibility. The sensor is placed in an environment of 4 ℃ to examine the stability of the sensor, and after one week, more than 90% of the response current value is still kept, which indicates that the electrode has good stability. Therefore, the invention provides a stable, specific and sensitive molecular imprinting sensor method for detecting curcumin, provides a general preparation method for a molecular imprinting sensor for insoluble compounds similar to curcumin, and has wide application prospects in the fields of organic reactions, organic synthesis, electrochemistry and the like.
Further, in the step 1), the mixing mass ratio of curcumin, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide, ethylene glycol dimethacrylate and azobisisobutyronitrile is 3-5: 5-10: 20-50: 1-5. Wherein curcumin is a template molecule, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide is a template molecule, ethylene glycol dimethacrylate is a cross-linking agent, and azodiisobutyronitrile is a reaction initiator. The cross-linking agent is used in the largest proportion, the functional monomer oligomer is used as the main material of the molecular engram film, the proportion of the functional monomer oligomer is slightly smaller to form the optimal molecular engram space, and the proportion of the template molecule is the smallest to enable more entering and exiting into the polymer film. The initiator is only a trace amount.
The mixing mass ratio of the N, N-methylene bisacrylamide and the ammonium persulfate in the step 2) is 5-25: 1-5. Wherein N, N-methylene bisacrylamide is used as a cross-linking agent, and ammonium persulfate is used as an initiator. In this case, a template molecule is not required, and only a polymer having a three-dimensional structure is formed.
Drawings
FIG. 1 is a block diagram of the preparation process of the molecular imprinting sensor of the present invention.
Fig. 2 is a cyclic voltammogram of curcumin molecularly imprinted membrane electrolytic polymerization.
FIG. 3 is a scanning electron microscope image of curcumin molecularly imprinted membrane modified electrode stripper plate.
FIG. 4 is a cyclic voltammogram of a curcumin molecularly imprinted membrane modified electrode in different states.
FIG. 5 is a plot of cyclic voltammograms before and after elution of a non-molecularly imprinted membrane modified electrode.
Fig. 6 is a graph of differential pulse voltammetry peak current response of the molecularly imprinted polymeric membrane modified glassy carbon electrode to curcumin of different concentrations.
Fig. 7 is a calibration curve of current response versus curcumin concentration for a molecularly imprinted sensor.
FIG. 8 is a graph of differential pulse voltammetry peak current response of a molecularly imprinted polymeric membrane modified glassy carbon electrode and a non-molecularly imprinted membrane modified electrode to 2 μ M curcumin and analogues thereof.
Detailed Description
Firstly, preparing a molecular imprinting sensor.
The preparation method of the molecular imprinting sensor of the embodiment is shown in FIG. 1.
1. Thermal polymerization:
3mg curcumin and 6mg N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide were added to 5mL solution of DMF and H at equal volume ratio2Dissolving in mixed solvent of O by ultrasonic wave at room temperature, adding 50mg of cross-linking agent ethylene glycol dimethacrylate(EGDMA), 1.5mg initiator Azobisisobutyronitrile (AIBN). After standing for 12 hours, the mixture was purged with nitrogen gas for at least 10 minutes to remove dissolved oxygen, thereby obtaining a mixed solution. Transfer 5 μ l of the mixture to the clean glassy carbon electrode surface and cover with a clean cover glass. And then placing the glass substrate in a 65 ℃ oven for heating for 12h, removing the cover glass, and forming a layer of transparent polymer film on the surface of the glassy carbon electrode.
2. Preparing a molecular imprinting sensor:
dissolving 20mg of N, N-Methylene Bisacrylamide (MBA) and 1.5mg of Ammonium Persulfate (APS) in 3mL of acetic acid buffer solution with the concentration of 0.5M, pH value of 6.5, placing the polymeric membrane electrode in the solution, and performing cyclic voltammetry scanning for 10 circles within the range of-1.4V to 0.2V at the sweeping speed of 40 mV/s to prepare a secondary polymerized curcumin molecularly imprinted membrane modified glassy carbon electrode.
The cyclic voltammetry line of the glassy carbon electrode modified by the secondarily polymerized curcumin molecularly imprinted membrane is shown in figure 2.
And eluting the imprinted molecular curcumin in the molecularly imprinted membrane by using a methanol solution containing 30% of acetic acid as an eluent to obtain the molecularly imprinted polymeric membrane modified glassy carbon electrode, wherein the modified electrode is the molecularly imprinted sensor for measuring curcumin.
Secondly, performing scanning electron microscope characterization on the obtained modified glassy carbon electrode:
the characterization of a scanning electron microscope of the modified glassy carbon electrode is shown in figure 3, and from figure 3, the surface of the modified membrane electrode has a plurality of tiny surface depressions, so that the surface area of the membrane is obviously increased, and the adsorption of the molecularly imprinted membrane on template molecule curcumin is facilitated.
And thirdly, the molecularly imprinted sensor obtained in the example 2 is used for electrochemical test.
(1) Cyclic voltammetry tests of different modified molecularly imprinted electrodes:
respectively modifying a bare glassy carbon electrode, a glassy carbon electrode modified by a thermal polymerization molecularly imprinted membrane, a glassy carbon electrode modified by an electrochemically initiated polymerization molecularly imprinted membrane, a glassy carbon electrode modified by a molecularly imprinted membrane after curcumin is eluted, and re-adsorbing the glassy carbon electrode to be a working electrode, wherein the reference electrode is a saturated calomel electrode, and the auxiliary electrode is a platinum electrode; the electrolyte was 0.25M acetate buffer (pH = 6.5) containing 1.0 mmol/L ferrocene methanol; the scanning potential range is-0.1 to 0.5V.
The cyclic voltammogram is shown in FIG. 4.
Cyclic voltammograms of a clean glassy carbon electrode (control), a molecularly imprinted electrode before curcumin elution, a molecularly imprinted electrode after curcumin elution, and a molecularly imprinted electrode after re-adsorption of curcumin were respectively in 10mL of a 0.25M acetic acid buffer solution (ph 6.5) containing 1.0 mM ferrocene methanol.
Wherein curve a is the cyclic voltammogram of a clean glassy carbon electrode in a solution of 10ml of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
Curve b is the cyclic voltammogram of a curcumin molecularly imprinted electrode after thermal polymerization in 10mL of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
Curve c is the cyclic voltammogram of a molecularly imprinted electrode of curcumin after electrochemically initiated polymerization in 10mL of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
Curve d is the cyclic voltammogram of the molecularly imprinted electrode after elution of curcumin in 10mL of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
Curve e is the cyclic voltammogram of the molecularly imprinted electrode after re-adsorption of curcumin in 10mL of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
In addition, the method for obtaining the molecularly imprinted electrode after re-adsorbing curcumin comprises the following steps: soaking the molecular imprinting electrode eluted with curcumin in 0.2M ethanol solution of curcumin to adsorb curcumin until saturation.
As can be seen from fig. 4, the peak current of the bare glassy carbon electrode is the largest (curve a), and after thermal polymerization, a molecularly imprinted film is formed on the surface of the glassy carbon electrode, so that the peak current is obviously reduced, but still larger (curve b), which indicates that more voids in the film on the surface of the electrode are conductive; after the electrochemical initiation polymerization, the peak current of the voltammetry curve becomes very small, the peak shape can not be seen (curve c), when the molecularly imprinted membrane modified electrode removes the template molecule, the peak current of the voltammetry curve is obviously increased (curve d), and when the sensor adsorbs the template molecule again, the peak current of the voltammetry curve is reduced to some extent (curve e).
(2) Cyclic voltammetry testing of non-molecularly imprinted electrodes:
the non-molecular imprinting is that no template molecule is added during the preparation of the molecular imprinting, and other steps are consistent with the preparation of the molecular imprinting.
The cyclic voltammetry test curves for the non-molecularly imprinted membrane modified electrode are shown in FIG. 5.
Curve f is the cyclic voltammogram of a 10mL solution of 0.25M acetate buffer (pH 6.5) containing 1.0 mM ferrocene methanol prior to elution from a non-molecularly imprinted electrode.
Curve g is the cyclic voltammogram after elution from a non-molecularly imprinted electrode in 10mL of a 0.25M solution of acetic acid buffer (pH 6.5) containing 1.0 mM ferrocene methanol.
FIG. 6 is a graph of differential pulse voltammetry peak current response of a molecularly imprinted polymeric membrane modified glassy carbon electrode to curcumin of different concentrations.
As can be seen from FIG. 5, the cyclic voltammetry curve of the non-molecularly imprinted membrane modified electrode after secondary polymerization is similar to that of the molecularly imprinted membrane modified electrode, but after elution treatment, the difference between the cyclic voltammetry curve and the cyclic voltammetry curve of the non-molecularly imprinted membrane is larger, and the increase of the peak current of the non-molecularly imprinted membrane is not too large, which indicates that the removal of the template molecules has a larger influence on the performance of the molecularly imprinted membrane, while the elution treatment has a smaller influence because the non-molecularly imprinted membrane does not contain the template molecules.
And fourthly, carrying out differential pulse voltammetry test on curcumin by using the molecular imprinting sensor:
taking the molecular imprinting sensor as a working electrode, taking a reference electrode as a saturated calomel electrode, and taking an auxiliary electrode as a platinum electrode; electrolyte was 1.0 mmol/L ferrocene methanol in 0.25M acetate buffer (pH = 6.5); scanning the potential range from-0.5V to 0.4V; the molecularly imprinted sensor was placed in an electrolyte for Differential Pulsed Voltammetry (DPV) scanning, and the results are shown in fig. 6. As can be seen from fig. 5, the sensor has different DPV responses to different concentrations of sudan red-I.
Blank electrolyte Scan Peak Current I of DPVp0Then placing the molecular imprinting sensor in Sudan red-I solution with a certain concentration for incubation, and scanning to obtain peak current IpThen the response current of the sensor is Δ Ip = I p0- IpThe results are shown in FIG. 7.
As can be seen from FIG. 7, Δ I in the measurement rangepThe values are linear with concentration response of sudan red-I. The linear range of curcumin was determined to be 1.0X 10-7～2.0×10-6mol/L. The sensor is placed in an environment at 4 ℃, and after two weeks, more than 90% of the response current value is still kept.
As can be seen from fig. 8, the peak current drop value of the electrochemical molecular imprinting sensor for curcumin is much higher than that of other analogues (tetrahydrocurcumin, ferulic acid, carotene, quercetin), so that the curcumin molecular imprinting sensor prepared by the method has higher selectivity.
The differential pulse voltammetry peak current responses of the non-molecularly imprinted membrane electrode to curcumin and analogues thereof are much smaller than those of the molecularly imprinted membrane modified electrode, but obviously, the non-molecularly imprinted membrane has larger response to the curcumin, which indicates that the functional monomer oligomer has higher binding capacity to curcumin molecules.
Claims (3)
1. The preparation method of the electrochemical molecular imprinting sensor based on the chitosan oligosaccharide derivative as the functional monomer is characterized by comprising the following steps:
1) adding curcumin and N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide into DMF and H with the volume ratio of 1/2-2/12Dissolving the mixture in a mixed solvent consisting of O by ultrasonic waves at room temperature, then adding ethylene glycol dimethacrylate and azobisisobutyronitrile, standing for 5-24 hours, and removing dissolved oxygen by using nitrogen to obtain a mixed solution;
2) dripping the mixed liquid on the surface of a clean glassy carbon electrode, then covering a clean cover glass, placing the glass in a drying oven at the temperature of 55-75 ℃ for heating for 5-20 h, and removing the cover glass to form a layer of transparent polymer film on the surface of the glassy carbon electrode;
3) dissolving N, N-methylene-bisacrylamide and ammonium persulfate in a NaAc/HAc solution with the pH value of 6.5 and the concentration of 0.1-1.5M to obtain a mixed solution; placing the polymerized membrane electrode in the mixed solution, scanning for 10-40 circles at a sweep rate of 20-150 mV/s under cyclic voltammetry within a range of-1.4V-0.5V, and preparing a glassy carbon electrode modified by a secondarily polymerized curcumin molecularly imprinted membrane;
4) and (3) eluting the imprinted molecular curcumin in the molecularly imprinted membrane by using a methanol solution containing 10-50% of acetic acid in mass percent as an eluent for the secondarily polymerized curcumin molecularly imprinted membrane modified glassy carbon electrode, so as to obtain the electrochemical molecularly imprinted sensor based on the chitosan oligosaccharide derivative as the functional monomer.
2. The method for preparing an electrochemical molecular imprinting sensor based on a chitosan oligosaccharide derivative as a functional monomer according to claim 1, wherein the mixing mass ratio of curcumin, N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide, ethylene glycol dimethacrylate and azobisisobutyronitrile in the step 1) is 3-5: 5-10: 20-50: 1-5.
3. The method for preparing an electrochemical molecular imprinting sensor based on a chitosan oligosaccharide derivative as a functional monomer according to claim 1, wherein the mixing mass ratio of N, N-methylenebisacrylamide to ammonium persulfate in the step 2) is 5-25: 1-5.
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