CN113552199B - FeS-based 2 Molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode and preparation method thereof - Google Patents
FeS-based 2 Molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode and preparation method thereof Download PDFInfo
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- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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Abstract
The invention provides a FeS-based method 2 Molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode, preparation method thereof and FeS 2 The preparation method of the/C/MQDs/GCE modified electrode sequentially comprises the following steps: MQDs and FeS 2 Respectively dispersing/C in chitosan-acetic acid solution; dripping the MQDs solution onto the GCE, and drying to obtain MQDs/GCE; feS is carried out 2 Dripping the solution/C onto MQDs/GCE, and drying to obtain FeS 2 The electrode is modified by/C/MQDs/GCE. The invention also discloses a modified electrode prepared by the method, a molecular imprinting electrochemical sensor based on the modified electrode, and a preparation method and application thereof. The invention has good reproducibility, acceptable stability and high selectivity, effectively realizes the simultaneous determination of dipyridamole and quinine sulfate, and solves the problems of complex and expensive detection modes of two substances, and the like.
Description
Technical Field
The invention belongs to the technical field of dual-template molecular imprinting electrochemical sensors, and particularly relates to a dual-template molecular imprinting electrochemical sensor based on FeS 2 Molecularly imprinted electrochemical sensor of/C/MQDs/GCE modified electrode, and preparation method and application thereof.
Background
Dipyridamole (DIP) is a drug that dilates coronary arteries and is antithrombotic, widely used in the treatment of cardiovascular diseases, and also in the control of proliferation of cancer cells. However, uncontrolled use of DIP may lead to mental illness and serious secondary effects, and serious health hazards. Meanwhile, the DIP can also be used as an exciting agent in sports, and can cause deceptive results in sports occasions. Therefore, the canonical use of DIP is of great importance in medical and sporting events. Quinine Sulfate (QS) is a quinoline derivative that binds to DNA of plasmodium to form a complex, inhibits DNA replication and RNA transcription, and thus inhibits protein synthesis by protozoans. Can be used for treating various malaria, leg cramp, pain relieving, and fever preventing. Quinine, however, is potentially toxic and can cause cinchona reaction, acute hemolysis (heat of the black urine), death, rash, itching, and asthma. Therefore, there is a need to develop a simple and inexpensive detection method to achieve high-selectivity and high-sensitivity detection of two substances. In recent years, many analytical methods have been reported to enable high sensitivity detection of DIP and QS, including High Performance Liquid Chromatography (HPLC), spectrophotometry, chemiluminescence, fluorescence, and the like. However, the use of such techniques in rapid low cost detection is limited due to the complexity of the instrument, the lengthy pretreatment process, or the expensive cost of the instrument. In contrast, the electrochemical method has the characteristics of quick response, low cost, high analysis sensitivity and the like. Recently, different electrochemical methods, such as differential pulse voltammetry, cyclic voltammetry, etc., have been used to determine DIP and QS. In addition, the selectivity and sensitivity of these voltammetric techniques can be further enhanced by modifying the electrode surface with various materials. Thus, chemically modified electrodes are widely used in voltammetry to determine the sensitivity and selectivity of various analytes. DIP and QS concentration abnormalities may lead to a range of diseases associated with human health management and treatment. It is therefore interesting to construct a simple and sensitive electrochemical sensing platform to detect these substances simultaneously.
Molecular Imprinting (MIT) is a polymerization method that mimics antigen-antibody effect construction. Due to their specific recognition ability for template molecules, attention has been paid in recent years. Thus, MIT-based Molecularly Imprinted Polymers (MIPs) have higher selectivity for a predetermined target molecule than other structurally similar compounds, and thus become a hotspot for the preparation of novel sensors in recent years. The mechanism of MIP fabrication is based on the principle of lock and key matching, including designing a polymer matrix containing cavities (locks) that are complementary to the target molecule (key) in different ways, e.g., size, shape, or other chemical interactions. In the synthesis of MIP, first, the template molecule (key) and the functional monomer form an interactive polymer; the template is then removed by polar or acid-base solvents or electrolytic techniques to form a three-dimensional microporous structure with specific binding sites of matching size and shape. Therefore, MIP has excellent selectivity and can specifically recognize and bind to substances having similar structures and properties to the imprinted wells.
MIPs have high efficiency in analyte selection and retention and thus have great potential for use in the field of biosensors. However, binding of MIPs and electrochemical methods can enhance the sensitivity and specific recognition ability of template molecules by enhancing the surface adsorption and binding ability and electrocatalytic effect. In addition, the dual-template molecular imprinting technology can realize simultaneous determination of two target analytes, so that the utilization rate of the sensor is greatly improved, the determination time is saved, and the determination efficiency is improved. Recently, mirzajani et al reported an electrochemical sensor based on graphene oxide functionalized aminopropyl triethoxysilane surface MIP for DIP determination. However, there is currently no report on detection of QS by electrochemical molecularly imprinted sensors. Thus, measuring multiple target molecules simultaneously by molecularly imprinted electrochemical biosensors is a challenge.
Although specific binding of MIPs can effectively improve the selectivity of the sensor, its poor conductivity as a polymer membrane material tends to limit its application in electrochemical sensing. In order to overcome these drawbacks, the conductivity of the sensor is improved, and therefore the selection of a conductive substrate having a high specific surface area structure as an integral part of a functional device has attracted a great deal of attention in the manufacture of the sensor. Furthermore, the sensitivity of the MIP sensor depends on the number of recognition sites on the electrode surface. Thus, the preparation of MIPs on a material surface having a high specific surface area can generate a large number of recognition sites, thereby enhancing the accumulation of analytes on the electrode surface. The metal-based nano material has a mixing and compounding function and a high specific surface area, so that the conductivity and the electron transfer rate can be effectively improved. In addition, modification of the electrode surface with nanomaterials can amplify the electrochemical response signal. Ti (Ti) 3 C 2 MXene Quantum Dots (MQDs) have high chemical inertness and excellent greenCompatibility and excellent photoluminescence properties. The amino and hydroxyl groups on the surface are more favorable for the combination of materials and the full play of conductivity. Metal Organic Frameworks (MOFs) are a type of porous coordination polymer formed by self-assembly of metal ions and organic ligands. Iron-based metal organic frameworks (Fe-MOFs) are an important branch of MOFs, with high specific surface area, high porosity, multiple active sites and excellent electrocatalytic activity. In order to further improve the conductivity of Fe-MOFs, the Fe-MOFs can be vulcanized at a high temperature to form FeS with larger specific surface area, high electrochemical activity and good biocompatibility 2 C nanocomposite. Finally, feS is modified on the surface of the electrode 2 the/C can amplify the electrochemical signal and increase the MIP recognition site.
Disclosure of Invention
The present invention provides a FeS-based solution to the above problems in the prior art 2 Molecularly imprinted electrochemical sensor of/C/MQDs/GCE modified electrode and preparation method thereof, and Ti-based sensor 3 C 2 Mxene Quantum Dots (MQD) and FeS 2 Carbon nano material modified glass electrode (FeS) 2 The method is used for preparing a molecular imprinting dual-template electrochemical sensor, is used for simultaneously detecting Dipyridamole (DIP) and Quinine Sulfate (QS), has good reproducibility, acceptable stability and high selectivity, simultaneously effectively realizes simultaneous determination of dipyridamole and quinine sulfate, and solves the problems of complex and expensive detection modes of two substances and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: providing a FeS 2 The preparation method of the/C/MQDs/GCE modified electrode sequentially comprises the following steps:
(1) MQDs and FeS 2 dispersing/C in 0.1-0.3wt% chitosan-acetic acid solution to obtain MQDs solution and FeS 2 a/C solution;
(2) Dripping 1-2 mu L of MQDs solution onto GCE, and drying at 50-70 ℃ to obtain MQDs/GCE;
(3) 7-8 mu L FeS 2 Dripping the solution/C onto MQDs/GCE, and drying at 50-70deg.C to obtain FeS 2 The electrode is modified by/C/MQDs/GCE.
Further, after the MQDs material is coated on the surface of the electrode, feS is added dropwise 2 C; MQDs solution and FeS 2 The concentration of the solution/C was 2mg/mL.
FeS described above 2 FeS prepared by preparation method of/C/MQDs/GCE modified electrode 2 The electrode is modified by/C/MQDs/GCE.
FeS described above 2 The application of the/C/MQDs/GCE modified electrode in the preparation of a molecularly imprinted electrochemical sensor.
FeS-based 2 The preparation method of the molecularly imprinted electrochemical sensor with the/C/MQDs/GCE modified electrode comprises the following steps:
the FeS is prepared by 2 Immersing the/C/MQDs/GCE modified electrode into a 0.01-0.02M phosphate buffer solution containing dipyridamole, quinine sulfate and beta-cyclodextrin, performing CV electropolymerization by a three-electrode system, immersing into a mixed solution formed by mixing methanol and acetic acid according to a volume ratio of 7-9:2, and stirring for 6-10min to remove template molecules to obtain the FeS-based electrode 2 Molecularly imprinted electrochemical sensor of/C/MQDs/GCE modified electrode, which is marked as FeS 2 /C/MQDs/MIP/GCE。
Further, the molar ratio of dipyridamole, quinine sulfate and beta-cyclodextrin is 1:1:3.
Further, methanol and acetic acid were mixed in a volume ratio of 8:2.
Further, the electropolymerization potential was in the range of-0.1 to 0.9V, the number of polymerization cycles was 20, and the scanning speed was 90mV/s.
The FeS-based 2 FeS-based preparation method of molecular imprinting electrochemical sensor with/C/MQDs/GCE modified electrode 2 A molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode.
The FeS-based 2 The application of the molecularly imprinted electrochemical sensor of the/C/MQDs/GCE modified electrode in dipyridamole and quinine sulfate detection is provided.
In summary, the invention has the following advantages:
1. the invention is based on titanium carbide Mxene Quantum Dots (MQD) and FeS 2 Carbon nano material modified glass electrode (FeS) 2 /C/MQDs/GCE), and willThe method is used for preparing a molecular imprinting dual-template electrochemical sensor, is used for simultaneously detecting Dipyridamole (DIP) and Quinine Sulfate (QS), has good reproducibility, acceptable stability and high selectivity, simultaneously effectively realizes the simultaneous determination of dipyridamole and quinine sulfate, and solves the problems of complex and expensive detection modes of two substances and the like.
2. FeS-based obtained by the invention 2 The molecularly imprinted electrochemical sensor of the/C/MQDs/GCE modified electrode showed excellent analytical performance with detection limits of DIP and QS of 8.68 nM (S/n=3) and 0.072 μm (S/n=3), respectively, with linear ranges of 0.05-1000 μm,0.4-1000 μm, respectively. Furthermore, dual-template MIP electrochemical sensors have good reproducibility, acceptable stability and high selectivity. In addition, the sensor is also used for measuring DIP and QS in biological samples (human serum and urine) and DIP in tablets, has satisfactory recovery rate (90.12% -107.89%) and relative standard deviation (RSD, 0.38% -6.36%), and has wide practical application prospect in electroanalysis.
3. MQDs with rich amino functional groups are synthesized by a hydrothermal method; feS (FeS) 2 the/C composite material is prepared by adopting Fe-MOFs in-situ high-temperature vulcanization technology. MQDs and FeS then 2 The composition of the/C layer by layer is combined on the surface of the GCE to form FeS 2 the/C/MQDs/GCE to enhance the conductivity and activity specific surface area of the sensor. Then, functional monomer selection is carried out through Density Functional Theory (DFT) calculation, and a proper monomer is predicted to be beta-cyclodextrin (beta-CD), so that a basis is provided for reasonably designing the dual-template MIPs. Double template molecular imprinting electrochemical sensor (FeS) 2 the/C/MQDs/MIP/GCE) is prepared by electropolymerization in the presence of the functional monomer beta-cyclodextrin and the template molecules DIP and QS. Differential Pulse Voltammetry (DPV), cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were used to characterize the electrochemical properties of the fabricated sensors; feS with high affinity for DIP and QS 2 the/C/MQDs/MIP/GCE sensor shows excellent pre-concentration capability. In addition, the prepared sensor has good stability, reproducibility, repeatability and specificity. And, the biosensor has also been successfully applied to the measurement of DIP and QS in biological samples, and has also been successfully applied to the measurement of DIP in tablets.
Drawings
FIG. 1 is a TEM image (inset: HRTEM image) of MQDs (A) and FTIR analysis of MQDs powder (B), feS 2 C (inset: TEM image) (C), feS 2 /C/MQDs/GCE（D），FeS 2 /C/MQDs/MIP/GCE（E），FeS 2 SEM of/C/MQDs/NIP/GCE (F) and FeS 2 EDS-element spectra (G) of O, N, C, ti, fe, S and F in/C/MQDs;
FIG. 2 is a UV-Vis absorption spectrum (Abs) and photoluminescence spectrum (ultrapure water (a) and aqueous MQDs (b) under 365 nm UV lamp irradiation, aqueous MQDs (c)) of MQDs;
FIG. 3 is FeS 2 XRD pattern of/C;
FIG. 4 shows XPS full spectrum (A) of MQDs, C1 s XPS spectrum (B) of MQDs, N1 s XPS spectrum (C) of MQDs, ti 2p XPS spectrum (D) of MQDs, feS 2 XPS full spectrum (E), feS of/C 2 C1 s XPS spectrum (F), feS of C 2 Fe 2p XPS spectrum (G), feS of C 2 S2 p XPS spectrum (H) of/C;
FIG. 5 is a diagram of (A) bare GCE (a), MQDs/GCE (b), feS 2 /C/MQDs/GCE（c）、FeS 2 Before elution of (d), feS of/C/MQDs/MIP/GCE 2 After elution of (e) and FeS of/C/MQDs/MIP/GCE 2 Modified electrode of/C/MQDs/NIP/GCE (f) etc. containing 5.0. 5.0 mM [ Fe (CN) 6 ] 3-/4- CV response in 0.5M KCl solution; (B) Bare GCE (a), MQDs/GCE (b), feS 2 /C/MQDs/GCE（c）、FeS 2 /C/MQDs/MIP/GCE（d）、FeS 2 DPV reaction (40 [ mu ] M DIP and QS containing) in 0.01M PBS buffer (pH 3.5)/C/MQDs/NIP/GCE (e); (C) Bare GCE (a), MQDs/GCE (b), feS 2 /C/MQDs/GCE（c）、FeS 2 Modified electrodes containing 5.0. 5.0 mM [ Fe (CN) before elution (d), feS2/C/MQDs/MIP/GCE after elution (e) and the like 6 ] 3-/4- EIS response in 0.5M KCl solution; (D) FeS (FeS) 2 EIS response of/C/MQDs/NIP/GCE (f) (a-e and C-oneCausing;
FIG. 6 shows the sensor FeS under different experimental conditions 2 DPV amperometric response of/C/MQDs/MIP/GCE in 0.01M in PBS containing 40 μM DIP and QS (in the case of background subtraction): template 1: template 2: molar ratio of functional monomer (a), number of electropolymerization cycles (B), pH (C), elution time (D), incubation time (E) and scan rate (F);
FIG. 7 is the effect of eluent type: methanol: acetic acid=8:2 (v/v) (a), methanol: water=1:1 (v/v) (b), methanol: modified electrode FeS eluted with 5 eluents dimethyl sulfoxide=1:1 (v/v) (c), hydrochloric acid (d), sodium hydroxide (e) and ethanol (f) 2 DPV current response of/C/MQDs/MIP/GCE to 40 [ mu ] M DIP and QS;
FIG. 8 is FeS 2 DPV reaction of/C/MQDs/MIP/GCE in 0.01M PBS (pH 3.5), wherein the concentration of DIP and QS are different: 0-500. Mu.M DIP in the presence of 250. Mu.M QS (A); a calibration curve (B) between DIP concentration and peak current; in the presence of a 100 [ mu ] M DIP (C), QS is 0-500 [ mu ] M; a calibration curve between QS concentration and peak current (D); sensor FeS 2 DPV response curves of/C/MQDs/MIP/GCE in the presence of only DIP (E) and only QS (G) and corresponding linear regression equations (F) and (H);
FIG. 9 shows the passage of FeS in PBS buffer (pH 3.5) containing different concentrations of DIP and QS 2 DPV response curves (A) in concentration ranges of 0.05-1000 mu M and 0.4-1000 mu M and peak current calibration curves (B) of DIP and QS in corresponding concentration change ranges are obtained by a/C/MQDs/MIP/GCE test;
FIG. 10 shows that 50. Mu.M DIP (red) and QS (black) were contained in PBS solution (A), human urine sample (B) and human serum sample (C). In the absence of other interferents (a) and in the presence of the following interferents: glucose (b), KCl (c), mgSO 4 （d），NaCl（e），CaCl 2 (f) DPV response of DIP and QS in case of sucrose (g), citric acid (h), urea (i), uric acid (j), oxalic acid (k), VC (l), DA (m), aspirin (n);
figure 11 is a graph of glucose at 500 μm,KCl，MgSO 4 ，NaNO 3 ，CaCl 2 DPV response (with background subtracted) of 50 μm DIP and QS in the presence of sucrose, citric acid, urea, uric acid, oxalic acid, VC, DA, aspirin;
FIG. 12 is FeS 2 CMQDs/MIP/GCE and FeS 2 DPV current response to Ascorbic Acid (AA), azithromycin (AZI), ceftazidime active ester (BPTA), phenol (Ph), fast urine (INN)) for 50 [ mu ] M DIP (A) and QS (B) and corresponding 50 [ mu ] M structural analogues (hypoxanthine (Hx), DPV;
FIG. 13 is a FeS in the presence of 500 [ mu ] M DIP and QS 2 (A) repeatability and (B) repeatability of/C/MQDs/MIP/GCE.
Detailed Description
The experimental reagents used in the invention are as follows: 2-methylimidazole (C) 4 H 6 N 2 More than or equal to 98.0 percent), ferrous chloride, tetrahydrate (FeCl) 2 ·4H 2 O, 99.0% or more), acetone (C) 3 H 6 O is more than or equal to 99.5 percent); sublimed sulfur (S, > 99.9%); titanium aluminum carbide (Ti) 3 AlC 2 More than or equal to 98.0 percent); hydrofluoric acid (HF, more than or equal to 99.5%); chitosan (C) 6 H 11 NO 4 ) N, the deacetylation degree is more than or equal to 95.0 percent); uric acid (C) 5 H 4 N 4 O3, > 99.0%) was purchased from Shanghai Michelin reagent Co., ltd. Potassium ferricyanide (K) 3 [Fe(CN) 6 ]More than or equal to 99.5 percent), potassium chloride (KCl more than or equal to 99.5 percent), potassium ferrocyanide (K) 4 [Fe(CN)]·3H 2 O, 99.5% or more), glucose (C) 6 H 12 O 6 99.0% or more), ethanol (CH) 3 CH 2 OH, 99.5% or more), methanol (CH) 3 OH, 99.5% or more), acetic acid (CH 3 COOH, 99.5% or more), ascorbic acid (C) 6 H 8 O 6 99.7% or more) ethanol (CH) 3 CH 2 OH, 99.5% or more), ammonia (NH) 3 ·H 2 O,25.0% -28.0%), nitric acid (HNO 3 65.0% -68.0%), ceftazidime active ester (C) 20 H 22 N 4 O 4 S 3 Dipyridamole (C),. Gtoreq.97%) 24 H 40 N 8 O 4 More than or equal to 98.0 percent); quinine sulfate (C) 40 H 48 N 4 O 4 ·H 2 SO 4 ·2H 2 O); beta-cyclodextrin (C) 42 H 7 0O 35 Not less than 99.0 percent); ultrapure water (18.25 M.OMEGA.cm) -1 ）。
The experimental equipment used in the invention is as follows: electrochemical testing was performed at room temperature using a three-electrode system. The modified glassy carbon electrode is a working electrode (diameter 5. 5 mm), the platinum column electrode is an auxiliary electrode, and the Ag/AgCl electrode is a reference electrode. All electrodes were purchased from the Sijin Yingkole combination technology limited public (Sijin, china). The instrument for performing the electrochemical test is purchased from Shanghai Chenhua at the Chenhua workstation CHI 660E. The constant temperature water bath and the ultrasonic cleaner are purchased from Shanghai Ningbo new Zhi Biotech Co., ltd, and the high-speed refrigerated centrifuge is purchased from Anhui Zhongjia scientific instrument Co., ltd. Vacuum freeze-dryer was purchased from Huaxing. The blast drying box is purchased from Shanghai-Heng scientific instruments Co., ltd; the high temperature tube furnace was purchased from Henan Cheng Instrument laboratory Equipment Co., ltd, and the constant temperature heating stirrer was purchased from Henan Cheng instruments Co., ltd. Scanning (SEM) and Transmission Electron Microscopy (TEM) were performed using Zeiss Supra 55 (Carl Zeiss AG) and JEOL2100f (JEOL), respectively. The X-ray powder diffraction (XRD) pattern was recorded using a DX-2700 XRD instrument (Dendong, china). X-ray photoelectron spectroscopy (XPS) was recorded using Escalab250Xi (AMICUS, shimadzu). FTIR spectra were collected by a Fourier transform infrared spectrometer (FTIR-8400S, shimadzu, japan). Energy dispersive X-ray spectroscopy (EDS) and elemental mapping were characterized using JEOL2100f (JEOL).
Example 1
FeS 2 Preparation of/C/MQDs/GCE modified electrode
FeS 2 The synthesis of/C and MQDs is according to the reported literature. Thereafter, 2mg MQDs and 2mg FeS were added 2 C was dispersed in 0.2% chitosan-acetic acid solution (CS) of 1 mL, respectively. 1.5 mu.L of MQDs solution was dropped onto GCE and dried at 60 ℃. Then 7.5. Mu.L FeS was added 2 dropping/C solution onto the obtained MQDs/GCE, and drying at 60deg.C to obtain FeS 2 The electrode is modified by/C/MQDs/GCE.
FeS-based 2 Preparation of molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode
Modified electrode (FeS) 2 C/MQDs/GCE) was immersed in 0.01M phosphate buffer (PBS, pH 3.5) containing 1 mM DIP, 1 mM QS and 3 mM. Beta. -CD as functional monomers, and then the modified electrode was immersed therein, and FeS was obtained by CV electropolymerization of a three-electrode system 2 /C/MQDs/MIP/GCE. The electropolymerization potential is in the range of-0.1 to 0.9V, the polymerization cycle number is 20, and the scanning speed is 90mV/s. After electropolymerization to form a MIP film, it was immersed in methanol: acetic acid (v/v=8/2) solution, slowly stirred for 8 min to remove template molecules and form blotting cavities for DIP and QS specific recognition. The preparation method of the non-molecularly imprinted polymer (NIP) is the same as MIP, but the polyelectrolyte solution does not contain DIP and QS.
Example 2
2.4 Characterization of nanomaterials
During the preparation of the modified electrode, SEM and TEM were used to characterize the morphology of the composite nanomaterial. As can be seen from the TEM in FIG. 1A, the MQDs are uniformly dispersed, with an average size of about 3 nm. HRTEM images (inset in fig. 1A) show the lattice properties of MQD particles. The lattice spacing is 0.23 nm, corresponding to the 008 lattice plane of MQD. Meanwhile, fourier transform infrared spectroscopy (FTIR) is used to characterize the type of functional groups on MQDs surfaces. As shown in figure 1B of the drawings, respectively observe-OH, -NH, -C=O-C-F and Ti-O, etc. MQD at 3105 cm -1 The vibration at this point was due to-NH groups, which suggests that the surface of MQD was passivated by-NH groups. It is due to the presence of these functional groups that the subsequent substance binding and the increase of active sites is more favored.
Furthermore, the optical properties of the MQD in fig. 2 indicate that the ultraviolet absorption peak of the MQD is about 280 nm. Meanwhile, MQDs have a fluorescence emission peak at 425 nm at 320 nm excitation wavelength. The inset of fig. 5 shows that upon irradiation with 365 nm uv lamps, blue fluorescence occurs, which becomes transparent in sunlight. After high temperature sulfidation, the early Fe-MOF formation is converted to carbon dopingHybrid FeS 2 . It can be seen that after high temperature thiosulfate, part of the MOF morphology is preserved and part of the structure collapses (fig. 1C). FeS (FeS) 2 Peaks at equal positions at 2θ=28.51 °, 33.08 °, 37.11 °, 40.78 °, 47.71 ° and 50.49 °, respectively, correspond to FeS 2 Diffraction at the (1-1-1), (2-0-0), (2-1-1), (2-2-0), (2-2-1)) crystal planes (FIG. 3) (PDF # 42-1340).
In addition, X-ray photoelectron spectroscopy (XPS) tests were performed to further analyze the elemental composition and chemical bond status of the different samples. Fig. 4A shows three peaks of MQD at 284.82 eV, 402.60 eV and 459.64 eV, which are attributed to C1 s, N1 s and Ti 2p, respectively. It can also be seen from the total spectrum (fig. 4A) that the Ti content is relatively small. This is due to the high temperature and hydrothermal etching of part of the Ti during the material synthesis. The C1 s spectrum of MQDs (fig. 4B) consists of C-C (284.80 eV), C-N (286.28 eV), c=o (288.54 eV), and C-F (288.54 eV) peaks, where C-C is from the MQDs and carbon impurities in the test strip. In the N1 s spectrum (fig. 4C), 401.46 eV, 401.90 eV and 407.14 eV correspond to N-H, =nh, respectively 2 + and-NO 3 . Wherein the N-H band is obtained from the reaction between ammonia and carboxyl groups. However, the Ti 2p spectrum (fig. 4D) shows two major 2p spectra at 452.05 eV and 459.33 eV 3/2 Peaks, which are mainly attributed to Ti-C and Ti-O, respectively. 2p shown at 463.98 eV 1/2 The peak is due to Ti-O, whereas O comes from dissolved oxygen. FIG. 4E shows FeS 2 The three peaks of/C at 284.50 eV, 163.04 eV and 709.20 eV are attributed to C1S, S2 p and Fe 2p, respectively. The C1 s spectrum (fig. 4F) consists of peaks of C-C (284.80 eV), C-O (286.39 eV) and O-c=o (288.94 eV). Notably, O-c=o is related to the Fe-MOF precursor. The binding energies of 707.60 eV, 711.12 eV, 720.35 eV and 724.35 eV in the Fe 2p spectrum (FIG. 4G) correspond to (Fe-S) 2p, respectively 3/2 、Fe 2p 3/2 、(Fe-S) 2p 1/2 And Fe 2p 1/2 . In the S2 p spectrum (FIG. 4H), 162.87 eV and 164.05 eV are attributed to S 2- 2p of (2) 3/2 And 2p 1/2 .168.95 The peaks at eV and 170.12 eV are represented by SO 4 2- Caused by the formation of (a) in the mold. The above resultsIndicating MQDs and FeS 2 Successful synthesis of/C. However, in MQDs and FeS 2 Uniformly dispersing/C, and coating on the surface of GCE to obtain MQDs/FeS 2 The uniform distribution of/C (FIG. 1D) shows that the film forming stability of the composite material is better than that of FeS 2 and/C due to the rational use of chitosan. Furthermore, feS shown in FIG. 1G 2 EDS spectra of/C/MQDs/GCE indicated that GCE was successfully modified. Furthermore, feS in FIG. 1G 2 The element map of/C/MQDs/GCE shows a uniform distribution of O, N, C, ti, fe, S and F elements. The results show that the prepared nano material is successfully modified on the surface of the electrode. Subsequently, feS 2 CMQDs/MIP/GCE and FeS 2 SEM of/C/MQDs/NIP/GCE (post elution) is shown in FIGS. 1E and 1F, respectively. It can be seen that after MIP formation, the electrode surface is more uniform and smoother than that of fig. 1D. The resulting MIP has some cavity structure and is coarser than NIP because the template molecules in the MIP are eluted to form the imprint cavity. Morphological and elemental analysis showed FeS 2 the/C/MQDs/MIP/GCE biosensor has been successfully prepared.
2.5 Electrochemical characterization of modified electrodes
Containing 5.0. 5.0 mM [ Fe (CN) 6 ] 3-/4- In a 0.5M KCl solution, GCE and other modified electrodes were scanned over a range of-0.2-0.6V (scan rate 100 mV/s) to analyze the conductivity of the different modified electrodes. As shown in FIG. 5, when MQDs are modified on the electrode (curve b), the peak current intensity of MQD/GCE is increased compared to GCE (curve a). Furthermore, feS 2 After dropping the/C material into the MQDs/GCE modified electrode, the peak current again increases (curve C). The above results further demonstrate that the two nano materials prepared have good conductivity and strong electron transfer capability. Curves d and e show the intensity of the current response before and after MIP elution. After electropolymerization, the peak current is significantly reduced due to poor conductivity of the resulting MIP film. However, the elution process of the template molecules results in the formation of imprint cavities to expose the built-in material, thereby enhancing the electron transfer capability of the modified electrode surface. Thus, a significant increase in peak current of curve d relative to the peak current of curve e can be observed. Electrokinetic compared to before and after molecular imprinting elutionThe peak current of the modified electrode after polymerization to form the NIP film is reduced (curve f). This is because the polymer film is not a conductive film, which prevents electrons from entering the electrode surface.
According to previous reports, DIP and QS are both electrochemically active substances. FeS (FeS) 2 The sensing mechanism of the/C/MQDs/MIP/GCE electrode pair DIP and QS follows two steps: first, the imprinted cavity formed on the MIP membrane specifically binds to the template molecule. Next, in FeS 2 The electrochemical reduction process of DIP and QS is realized on the surface of the/C/MQDs/MIP/GCE electrode. Since this process involves electron transfer between DIP and QS, the electrochemical behavior of DIP and QS was evaluated by DPV (fig. 5B). The template molecule has a reduction peak (very weak QS, relatively stronger DIP) on the exposed GCE surface with a lower current response than the nanomaterial-modified GCE (curve a). This property can be attributed to the good catalytic ability of the nanomaterial to the DIP and QS electro-reduction processes. After elution of the MIP, a blotting cavity is formed, which matches the template size, shape and functional group. Thus, DIP and QS can be specifically recognized and bound to functional groups within the blotting cavity through hydrogen bonds. Thus, peak currents of DIP and QS were significantly enhanced after incubation (curve d). In contrast, the NIP films prepared do not have template cavities and therefore do not promote the reduction of the electrode surfaces DIP and QS (curve e). Thus, it can be observed that the current response of the NIP to the test subject is minimal.
EIS was used to evaluate the presence of different modified electrodes at 5.0. 5.0 mM [ Fe (CN) with 0.5M KCl 6 ] 3-/4- Resistance in solution. As shown in fig. 5C, the semicircle diameter of the Nyquist spectrum of GCE (curve a) is significantly larger than MQDs modified electrode (curve b). The results show that GCE has a large charge transfer resistance (Rct). Modification of FeS on MQDs/GCE electrode 2 after/C, the Rct value decreases significantly (curve C). This is due to FeS 2 and/C has good conductivity, and the high adsorption capacity can enhance the electron transfer capacity of the composite material. Rct after MIP elution (curve e) is smaller than before elution (curve e) because the blotting cavity formed after elution is K 4 [Fe(CN) 6 ]/ K 3 [Fe(CN) 6 ]Provides a pathway for the redox reaction. FIG. 5D shows FeS 2 the/C/MQDs/NIP/GCE has the largest Rct value (curve f) since NIP consists of poly beta-CD and has no blotting cavity. The results are consistent with CV characterization conclusions.
Example 3
In order to improve the measurement performance of the imprinting nanocomposite, a series of experimental factors such as the molar ratio of the template to the monomer, the polymerization circle number, the pH value, the elution and incubation time, the scanning rate and the like are respectively researched. By making FeS under single factor parameters 2 The electrochemical responses of DIP and QS were measured by DPV in PBS (pH 3.5) buffer containing a mixture of 40. Mu.M DIP and QS. The results of the optimization section are shown below.
The number and strength of molecularly imprinted cavities formed by CV electropolymerization is related to the ratio of template molecules to functional monomers. As shown in FIG. 6A, the peak current response is strongest when the ratio of template to functional monomer is 1:1:3, between 1:1:0.5 and 1:1:7. Thus, the optimal molar ratio of template molecules DIP and QS to functional monomer is 1:1:3. In addition, the number of electropolymerization cycles is an important factor directly affecting the thickness and stability of the MIP film. As shown in FIG. 6B, the number of turns is between 5 and 30, and the peak current is found to be strongest when the number of turns is 20. Thus, the optimal number of polymerization cycles is 20.
The pH of the test environment will influence the degree of dissociation of the MIP from the DIP and QS functionalities, and thus the interaction of the MIP with the template molecule functionalities. As shown in fig. 6C, in 0.01M PBS, the DPV peak current of DIP and QS both increased and decreased as the pH changed from 2 to 7. The peak current of DIP is at pH 3.0. But QS has the strongest peak current response at pH 4.0, which may be related to the strength of hydrogen bonds formed by specific recognition of the template molecule and the molecular imprinting chamber under different pH environments. Thus, a PBS solution of 0.01M, pH 3.5 was determined to be the optimal condition for electrochemical molecular imprinting detection of DIP and QS.
The elution time has a great influence on the number and structure of the imprint cavities formed. As shown in fig. 6D, the DPV peak current gradually decreases as the elution time increases. When the elution time reached 8 min, there was almost no DPV response, indicating that the template molecule was almost removed. Thus, the optimal elution time for the template molecules in the molecularly imprinted membrane is 8 min.
The length of incubation determines the number of template molecules bound to the blotting chamber. As shown in fig. 6E, the DPV response of DIP and QS increases gradually over the adsorption time-between 15 min and 40min, and at 35min the DPV response of DIP and QS has reached steady state because the cavity at the electrode surface is already in saturation. Therefore, the optimal incubation time was set to 35min.
The choice of scanning rate is an important factor in preparing molecularly imprinted membranes. As shown in FIG. 6F, between 30-130 mV/s and 90mV/s, the DPV response is strongest for DIP and QS. Thus, the optimal scanning speed for forming the molecularly imprinted membrane was 90mV/s.
3.7 Selection of eluent
The eluent can affect the elution degree of the template molecules and cause a certain damage to the molecular imprinting membrane. As shown in fig. 7, 6 eluents commonly used in the molecular imprinting direction were selected for comparison study in this study. The peak response of DIP and QS was highest when the eluent was methanol: acetic acid=8:2 (v/v). This is because other eluents cause certain damage to the modified electrode due to their own characteristics during the elution process, resulting in a decrease in the specific recognition sites of the molecularly imprinted membrane of the detection substance. Thus, the eluent selected in the present invention is methanol: acetic acid = 8:2 (v/v).
3.7 MIP response characteristics and calibration curves
Under optimal detection conditions, different concentrations of DIP and QS in 0.01M PBS buffer (pH 3.5) were evaluated and measured simultaneously using the DPV method. And subtracting the background value obtained by the blank concentration test to construct a standard curve. Simultaneous DIP and QS determination is the primary goal of this task. First, the effect of DIP and QS on electrochemical response is performed with the concentration of one species fixed and the concentration of the other species increasing. Fig. 8A and 8B show a DPV curve and a fitted linear curve (after background subtraction) with DIP concentration in PBS buffer (pH 3.5) in the presence of 250 μm QS, respectively, in the interval 1-500 μm. The linear regression equation for DIP is: ip (μa) = -0.0664C (μΜ) -1.27967 (R) 2 =0.99008)。Fig. 8C and 8D are DPV plots (after background subtraction) of different concentrations QS (1-500 μm) in 100 μm DIP in PBS buffer (pH 3.5), the linear regression equation for QS is Ip (ua) = -0.07176C (μm) -0.45664 (R 2 = 0.99876). The results show that one of the test substances shows a linear corresponding relationship with the concentration change in the gradient range, while the other test substance has no obvious change in signal. This illustrates that DIP and QS are utilizing FeS 2 There was no interference with the electrochemical measurements performed by the/C/MQDs/MIP/GCE. Subsequently, simultaneous sensing capability is achieved by varying the concentration of DIP and QS. Fig. 8E to 8H depict DPV curves and corresponding linear regression equations for the presence of two detectors alone on a biosensor. The linear regression equations corresponding to DIP and QS are: ip (μa) = -0.06966C (μΜ) -1.18037 (R) 2 =0.99032)，Ip(μA)=-0.07206C(μM)-0.7109(R 2 = 0.99489). The feasibility of simultaneous detection of two detection objects is further verified by comparing the slopes of the linear regression equations.
The results show that the reduced signal peaks of DIP and QS occur at-0.79V and-1.02V, with corresponding DPV response concentrations of DIP and QS being 0.05-1000 μm and 0.4-1000 μm, respectively. As expected, the current response signals of DIP and QS are positively correlated with their concentrations (fig. 9B). The concentration of DIP and QS versus the current change for the range of concentration gradients is expressed as a regression linear relationship: ip (μa) = -0.07138C (μΜ) -0.62353 (R) 2 = 0.9919) and Ip (μa) = -0.06248C (μm) -1.27574 (R) 2 = 0.9910). The detection Limits (LOD) for DIP and QS were calculated based on 3σ/S to be 8.68 nM and 0.072 μM, respectively, in combination with the linear regression curve. Wherein sigma is FeS 2 The standard deviation of the peak current at the corresponding species detection lower limit (n=3) for/C/MQDs/MIP/GCE, S being the slope of the species detection calibration curve. The above results indicate FeS 2 The simultaneous detection of DIP and QS by/C/MQDs/MIP/GCE is feasible and reliable. Table 1 shows a comparison of the performance characteristics of the sensors in this study with other reported methods or other methods in the literature. It can be seen that the sensitivity and wide linear range of DIP and QS in this work is almost higher than other methods. Notably, there are few methods for electrochemical molecular imprinting to determine QS as opposed to itIn addition, the sensitivity of electrochemical measurement methods is lower than this work. In summary, the method has a broader linear operating range and a lower LOD, and is more suitable for simultaneous determination of DIP and QS, which can be attributed to the molecular imprinting method used in the method.
Table 1 comparison of the preparation process of the invention with other processes
Example 4
Biosensor selectivity, repeatability, reproducibility and stability
To evaluate FeS 2 Selectivity of the/C/MQDs/MIP/GCE sensor 13 potential interferents were added to 0.01M PBS (pH 3.5) solution at fixed concentrations of DIP and QS, respectively, and the sensor was manufactured in a solution containing only 50. Mu.M of the analyte (a) and a solution containing 50. Mu.M of the analyte and 500. Mu.M of glucose (b) or KCl (C), mgSO, respectively, as shown in FIG. 10 4 （d），NaNO 3 （e），CaCl 2 (f) Incubation was performed in different solutions of sucrose (g), citric acid (h), urea (i), uric acid (j), oxalic acid (k), VC (l) DA (m), aspirin (n). There is a slight change in the current response of DIP and QS compared to the blank solution (a)<5%). In the presence of 13 potential interfering factors simultaneously, the DPV response of DIP and QS was reduced by 9.7% and 2.2%, respectively (FIG. 11). The above results show that the prepared imprinted polymer nanocomposite has significant selectivity for DIP and QS, while the effect of interferents is almost negligible. Furthermore, the blotting factor (IF) was used to further evaluate the selectivity of the proposed sensor. Based on previous reports, IF is calculated by the following formula:
wherein,,I MIP and I NIP Representing the electrode electricity modified by imprinting and non-imprinting nanometer composite respectivelyThe current response of each analogue was chemically detected. As shown in FIG. 12, the IF values of 50. Mu.M of the detection objects DIP and QS were calculated to be 2.917 and 2.646, respectively, demonstrating FeS 2 the/C/MQDs/MIP/GCE can specifically recognize DIP and QS. The imprinting factors (Hx: 1.186, AA:1.330, AZI:1.270; BPTA:1.276, ph:1.280, INN: 0.937) calculated for the corresponding analogues of the two detection substances at a concentration of 50. Mu.M were each estimated to be 1, indicating that the sensor has a non-specific recognition capacity for them. Taken together, the results indicate that the sensor system has good selectivity, which may be due to the presence of FeS 2 The imprinted cavity formed by the surface of the/C/MQDs/MIP/GCE can be better matched with the spatial structures of DIP and QS molecules.
Based on the optimized conditions, 5 batches of molecularly imprinted biosensors were prepared to study FeS 2 Reproducibility of/C/MQDs/MIP/GCE. After incubation in a solution containing 50 μm DIP and QS, these modified electrodes were tested by the DPV method. The Relative Standard Deviation (RSD) values of the two test objects among the five test results were found to be 3.9% and 2.54%, respectively (fig. 13A), indicating that the prepared sensor had good reproducibility. By using the same FeS 2 the/C/MQDs/MIP/GCE sensor performs 5 tests on the solution containing 50 μm DIP and QS to determine the reproducibility of the sensing system, and each test procedure followed the elution-adsorption step. RSD values for DIP and QS were calculated to be 3.3% and 3.0%, respectively (fig. 13B), showing good reproducibility. Thereafter, the prepared FeS 2 the/C/MQDs/MIP/GCE was stored in an environment at 4deg.C for 20 days and then the stability of the sensor system was evaluated. From the change in peak DPV current, the DIP and QS responses decreased by 5.4% and 5.3% after 20 days of storage, respectively. The above results indicate that the sensing system is reliable for DIP and QS detection applications.
Example 5
Analysis and use of sensors in real samples
Each sample was tested 3 times using standard addition methods to calculate recovery and RSD. As shown in Table 2, the recovery rates of DIP and QS were 95.22% -107.89% and the RSD was 0.38% -6.36%. Table 3 compares the two methods of HPLC and DPV for determining DIP in the tablets. The recovery rate is 96.50% -106.97%, and the RSD is 0.94% -4.38%. The accuracy of this method was compared in conjunction with HPLC performed on biological samples (table 4). By the end result, a comparison of the two methods can be found to show acceptable differences. These results indicate that the biosensor can be reliably used for simultaneous measurement of DIP and QS.
Table 2 results of DIP and QS measurements in actual samples (n=3)
Table 3 DPV and HPLC results of determination of DIP in dipyridamole tablets (n=3)
Table 4 HPLC method determination of DIP and QS results in actual samples (n=3)
The invention constructs a novel electrochemical molecular imprinting dual-detection system and realizes simultaneous determination of DIP and QS in an actual sample based on a dual-template MIP sensor. By modifying MQDs and FeS on the surface of GCE 2 and/C, the amplification effect of the electric signal is realized. Thereafter, in FeS 2 MIP film (FeS) is formed on the surface of/C/MQDs/GCE 2 /C/MQDs/MIP/GCE) to increase the selectivity and sensitivity of the biosensor and to increase the number of recognition sites for the template molecule. The FeS produced was studied by CV, DPV and EIS techniques 2 Electrochemical behavior of/C/MQDs/MIP/GCE. In fact, MIP sensors have a higher recognition capability for DIP and QS than non-imprinted sensors. Double imprinting method of MIP electrode and FeS 2 The electrocatalytic effect of the/C/MQDs enhances the preconcentration effect and improves FeS 2 The sensitivity of DIP and QS was determined by/C/MQDs/MIP/GCE. The electrochemical current signal response of DIP and QS sensors was 0.05-1000 μm (R 2 = 0.99008) and0.4-1000 μM（R 2 = 0.99876) and has been successfully applied to simultaneous determination of DIP and QS in serum and urine. The developed MIP sensing system has good reproducibility and repeatability, acceptable stability and high selectivity. In addition, the recovery rate of the sample and the tablet is between 95.22% and 107.89%, and the RSD value is between 0.38% and 6.36%, which shows that the method has good biomedical application prospect.
Although specific embodiments of the invention have been described in detail with reference to the accompanying drawings, it should not be construed as limiting the scope of protection of the present patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (10)
1. FeS (FeS) 2 The preparation method of the/C/MQDs/GCE modified electrode is characterized by comprising the following steps in sequence:
(1) MQDs and FeS 2 dispersing/C in 0.1-0.3wt% chitosan-acetic acid solution to obtain MQDs solution and FeS 2 a/C solution; the MQDs is Ti 3 C 2 Mxene quantum dots;
(2) Dripping 1-2 mu L of MQDs solution onto GCE, and drying at 50-70 ℃ to obtain MQDs/GCE;
(3) 7-8 mu L FeS 2 Dripping the solution/C onto MQDs/GCE, and drying at 50-70deg.C to obtain FeS 2 The electrode is modified by/C/MQDs/GCE.
2. FeS according to claim 1 2 The preparation method of the/C/MQDs/GCE modified electrode is characterized in that after MQDs materials are coated on the surface of the electrode, feS is added dropwise 2 C; MQDs solution and FeS 2 The concentration of the solution/C was 2mg/mL.
3. The FeS of any of claims 1-2 2 FeS prepared by preparation method of/C/MQDs/GCE modified electrode 2 The electrode is modified by/C/MQDs/GCE.
4. The FeS of claim 3 2 The application of the/C/MQDs/GCE modified electrode in the preparation of a molecularly imprinted electrochemical sensor.
5. FeS-based 2 The preparation method of the molecularly imprinted electrochemical sensor with the/C/MQDs/GCE modified electrode is characterized by comprising the following steps of:
the FeS of claim 3 2 Immersing the/C/MQDs/GCE modified electrode into a 0.01-0.02M phosphate buffer solution containing dipyridamole, quinine sulfate and beta-cyclodextrin, performing CV electropolymerization by a three-electrode system, immersing into a mixed solution formed by mixing methanol and acetic acid according to a volume ratio of 7-9:2, and stirring for 6-10min to remove template molecules to obtain the FeS-based electrode 2 Molecularly imprinted electrochemical sensor of/C/MQDs/GCE modified electrode, which is marked as FeS 2 /C/MQDs/MIP/GCE。
6. The FeS-based system of claim 5 2 The preparation method of the molecularly imprinted electrochemical sensor with the/C/MQDs/GCE modified electrode is characterized in that the mol ratio of dipyridamole to quinine sulfate to beta-cyclodextrin is 1:1:3.
7. The FeS-based system of claim 5 2 The preparation method of the molecularly imprinted electrochemical sensor with the/C/MQDs/GCE modified electrode is characterized in that methanol and acetic acid are mixed according to a volume ratio of 8:2.
8. The FeS-based system of claim 5 2 The preparation method of the molecularly imprinted electrochemical sensor with the/C/MQDs/GCE modified electrode is characterized in that the electropolymerization potential range is-0.1-0.9V, the polymerization cycle number is 20, and the scanning speed is 90mV/s.
9. FeS-based according to any of claims 5-8 2 FeS-based preparation method of molecular imprinting electrochemical sensor with/C/MQDs/GCE modified electrode 2 A molecularly imprinted electrochemical sensor with/C/MQDs/GCE modified electrode.
10. Claim(s)FeS-based as described in claim 9 2 The application of the molecularly imprinted electrochemical sensor of the/C/MQDs/GCE modified electrode in dipyridamole and quinine sulfate detection is provided.
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