CN113945619B - Preparation method and application of MPBA@Au-MOF composite material photoelectrochemical sensor - Google Patents

Preparation method and application of MPBA@Au-MOF composite material photoelectrochemical sensor Download PDF

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CN113945619B
CN113945619B CN202111209002.8A CN202111209002A CN113945619B CN 113945619 B CN113945619 B CN 113945619B CN 202111209002 A CN202111209002 A CN 202111209002A CN 113945619 B CN113945619 B CN 113945619B
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CN113945619A (en
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夏莲
程圆圆
田晓霞
张玲东
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Qufu Normal University
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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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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract

The invention belongs to the technical field of metal organic frame composite materials, and particularly relates to a preparation method and application of an MPBA@Au-MOF composite material photoelectrochemical sensor, in particular to a method for determining Sialic Acid (SA) content by adopting a composite material photoelectrochemistry and visualization dual-function of an MPBA/SA/MPBA@Au-MOF sandwich structure. After SA and MPBA are combined, conversion of the photoelectric signal occurs by the administration of incident light, and detection of SA content is performed by observing the change in the electrical signal. Meanwhile, as the MOF-Au@MPBA composite material has catalytic performance, TMB (colorless) in the electrolyte is oxidized into oxidized ox TMB (blue) when incident light is given, and SA content is simply judged by observing the color change of the electrolyte. The method can simply, conveniently and rapidly detect the SA content.

Description

Preparation method and application of MPBA@Au-MOF composite material photoelectrochemical sensor
Technical Field
The invention belongs to the technical field of metal organic frame composite materials, and particularly relates to a preparation method and application of an MPBA@Au-MOF composite material photoelectrochemical sensor. Specifically, a photoelectrochemistry and visualization dual-function MPBA@Au-MOF composite sensor is used for detecting the content of Sialic Acid (SA) in serum.
Background
The metal organic framework material (Metal Organic Frameworks), MOFs for short, is an emerging organic-inorganic hybrid porous solid and has potential application in separation, catalysis, drug delivery and sensing. In addition, the large specific surface area and adjustable pore properties of MOFs have unique advantages over other porous materials because functional groups can be easily incorporated into the scaffold by ligand design or post-synthetic modification. Therefore, the incorporation of different functions in MOFs has been widely studied for various applications. The synthetic methods of MOFs include solvothermal, hydrothermal, microwave, and ultrasonic methods, and are widely used in selective gas adsorption/separation, catalytic reactions, optics, and magnetics. The porphyrin-based metal organic framework nanoparticle adopted by the invention is a crystallization hybridization material composed of metal ions/clusters or organic structural units (porphyrin or metalloporphyrin), and the porphyrin MOF NPs become a powerful platform for photodynamic therapy and thermosensitive agent transmission. 4-mercaptophenyl boronic acid (MPBA) is a thiol-containing boronic acid which can be modified to specifically bind to glycoproteins on the surface of gold nanoparticles, and the borate functional group possessed by MPBA also has the ability to bind sialic acid, which serves as a capture agent for SA. At present, no report of a method for measuring the SA content by using a photoelectrochemistry and visualization dual-function biosensor by adopting a composite material with an MPBA/SA/MPBA@Au-MOF sandwich structure is found at home and abroad.
Disclosure of Invention
The invention aims to provide a preparation method and application of an MPBA@Au-MOF composite photoelectrochemical sensor, which has double functions of photoelectrochemistry and visualization and can realize detection of the SA content of a cancer marker.
The preparation method of the MPBA@Au-MOF composite material photoelectrochemical sensor comprises the following steps:
1) Preparation of MOF-Au@MPBA composite material
Adding MPBA into the MOF-Au composite material aqueous solution, stirring at room temperature, centrifugally collecting a product, washing with water, and drying to obtain the MOF-Au@MPBA composite material;
2) Preparation of the sensor
First, bi was added to a sample bottle 2 S 3 The dispersion liquid, perfluor sulfonic acid-polytetrafluoroethylene copolymer, is treated by ultrasonic, and is added with AuNPs solution and stirred;
then adding MPBA solution, stirring at room temperature, adding SA solution, and continuously stirring for 40 minutes;
finally, adding the MOF-Au@MPBA composite material aqueous solution, and stirring;
and (3) dripping the mixed liquid on ITO conductive glass, and drying at low temperature to obtain the electrode of the MPBA@Au-MOF composite material sensor.
The electrode specifically comprises: ITO/Bi 2 S 3 Au NPs/MPBA/SA/MOF-Au@MPBA composite electrode.
Wherein:
the preparation method of the MOF-Au@MPBA composite material specifically comprises the following steps:
2mg of MPBA was added to MOF-Au solution (1 mL,1 mg/mL) and the resulting mixture was stirred overnight (8-12 hours) at room temperature. The product was collected by centrifugation at 8000rpm for 5min, repeatedly washed 3 times with purified water, and dried in an oven at 60 ℃.
The sensor was prepared as follows:
first 3mL 2mg/mL Bi 2 S 3 The dispersion (30. Mu.L Nafion added) was added to the sample bottle, 1.5mL of the NPs solution was added, and the mixture was stirred for 2 hours; then 1mL MPBA solution (0.1 mM) was added and stirred overnight (8-12 hours) at room temperature; adding 1mL of SA solution with different concentrations, stirring for 40min, and fully reacting; finally, 1mL of MPBA@Au-MOF solution (1 mg/mL) is added, stirring is carried out for 30-40min, and finally 150 mu L of the mixture is dripped on ITO conductive glass (pretreated by acetone, ethanol and pure water) and is dried at low temperature.
The preparation method of the MOF-Au composite material comprises the following steps:
MOF and HAuCl 4 Sequentially adding into water, stirring, adding newly prepared NaBH 4 And (3) the solution is used for obtaining a MOF-Au crude product, and the MOF-Au composite material is obtained after washing the MOF-Au crude product with water, acetone and water in sequence.
Preferably, 600. Mu.L of MOF (40 mg/mL) and 1mL of HAuCl 4 (10 mg/mL) was added sequentially to 250mL of purified water. The mixture was magnetically stirred for 10s and 800. Mu.L of freshly prepared NaBH was rapidly added 4 Solution (3.8 mg/mL). The synthesized MOF-Au product was washed once by centrifugation with purified water at 10000rpm for 15min to remove unreacted free Au NPs. Then washing with acetone twice repeatedly, washing with purified water once to remove excessive DMF, and finally dispersing the product into purified water again.
The preparation method of the MOF comprises the following steps:
adding zirconium oxychloride, tetra (4-carboxyphenyl) porphyrin and benzoic acid into N, N-dimethylformamide, stirring for reaction, centrifuging to collect a product after the reaction is finished, washing the product with N, N-dimethylformamide and acetone in sequence, and drying to obtain the MOF.
Preferably, 60mg of zirconium oxychloride, 20mg of tetra (4-carboxyphenyl) porphyrin (H 2 TCPP) and 580mg benzoic acid were added to 20ml n, n-Dimethylformamide (DMF). Stirring the above mixture at 95deg.C for 5 hr, centrifuging at 10000rpm for 15min to collect product, repeatedly washing with DMF for 2 times, washing with acetone once, and collecting the product in the presence of acetoneDrying in an oven at 60 ℃.
The MPBA@Au-MOF composite material photoelectrochemical sensor disclosed by the invention is prepared by adopting the preparation method.
The application of the MPBA@Au-MOF composite photoelectrochemical sensor is used for detecting the SA content in serum.
The application comprises the following steps:
an electrode of an MPBA@Au-MOF composite material photoelectrochemical sensor is used as a working electrode, a detection mode of three electrodes is utilized, a xenon lamp is used as a light source, an electrochemical workstation is used for collecting electric signals, and the electric signals contain 0.8mM TMB and 1.0mM Ce 3+ The pH of the acetic acid-sodium acetate buffer solution is 6.5, a linear relation between an electric signal and SA concentration is established, and the SA content in serum is detected by a standard adding method, wherein the electrolyte is changed from colorless to blue in the detection process.
The MPBA@Au-MOF composite material has catalytic performance, incident light is given, active oxygen substances are generated through conversion between Ce (III) and Ce (IV), TMB (colorless) in electrolyte is oxidized into oxidized TMB (blue), and SA detection is easily realized through visualization.
The MPBA@Au-MOF composite material photoelectrochemical sensor (ITO/Bi) 2 S 3 Au NPs/MPBA/SA/MOF-Au@MPBA composite electrode biosensor) for detecting SA with linear range of 0.1-2 mmol L -1 The lower detection limit reaches 87 mu mol L -1 Correlation coefficient R 2 Up to 0.993.
ITO/Bi prepared by the invention 2 S 3 The application principle of the AuNPs/MPBA/SA/MOF-Au@MPBA composite electrode biosensor is as follows: when SA and the vicinal diol of MPBA are combined in a secondary mode, under the condition that incident light is given, photoelectric signals have a corresponding conversion phenomenon, and the change of the electric signals is measured. Meanwhile, the MPBA@Au-MOF composite material has certain catalytic performance, TMB (colorless) in the electrolyte can be oxidized into ox TMB (oxidized state, blue) and the SA content can be simply judged through color change.
Compared with the prior art, the invention has the following beneficial effects:
1) The preparation process is simple and is carried out at room temperature without using highly toxic reagents.
2) The highly uniform nanoscale cavity and large specific surface area of the porphyrin MOF play an important role in the specific recognition of the target, and promote the enrichment of the target in the hole, so that a lower detection limit and higher sensitivity are obtained.
3) MPBA@Au-MOF possesses higher catalytic performance than other MOFs.
4) The response is rapid, and the detection can be carried out after 40s stabilization.
Drawings
FIG. 1 is a scanning electron microscope image of a MOF (A) and a MOF-Au composite (B) of the present invention;
FIG. 2 is an XRD diffraction pattern of the MOF and MOF-Au composites of the invention;
FIG. 3 is an ultraviolet view of the MOF and MOF-Au composites of the invention;
FIG. 4 is an infrared plot of the MOF and MOF-Au composites of the present invention;
FIG. 5 is an XPS diagram of a MOF-Au composite of the present invention;
FIG. 6 shows that the component (A) of the present invention is Bi 2 S 3 Is embedded with Bi 2 S 3 Is a transmission electron microscope image; (B) Is Bi 2 S 3 Transmission electron microscope images of/Au NPs, and embedded transmission electron microscope images of the Au NPs; C-F is Bi 2 S 3 Mapping diagram of/Au NPs;
FIG. 7 is a graph of electrical signals (A) and impedance (B) measured by different electrodes of the present invention; in the figure: a: ITO, b: ITO/Bi 2 S 3 ，c：ITO/Bi 2 S 3 /Au，d：ITO/Bi 2 S 3 /Au/MPBA，e：ITO/Bi 2 S 3 /Au/MPBA/SA，f：ITO/Bi 2 S 3 /Au/MPBA/SA/MOF@Au@MPBA。
FIG. 8 is a graph of time variation of the incubation SA of the present invention;
FIG. 9 is a graph (A) showing the variation of the electrical signal caused by SA at different concentrations and a graph (B) showing the linear relationship between 0.1 and 2mmol/L according to the present invention, wherein (C) is a graph showing the stability of the composite electrode, and (D) is a graph showing the selectivity of the composite electrode; (A) And (B), a-l represent SA concentrations of 0,0.1,0.12,0.14,0.16,0.18,0.2,0.4,0.6,0.8,1,2mM, respectively; (D) Wherein a-h are respectively visual corresponding graphs of blank groups and added target detection objects of Cys, phe, BSA, cys+SA, phe+SA, BSA+SA, cys+Phe+BSA+SA;
FIG. 10 shows the corresponding color changes of SA at different concentrations according to the present invention, wherein the SA concentrations added in sequence from left to right are 0.2,0.5 and 1mM, respectively.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation process of the MOF-Au composite material comprises the following steps:
preparation of MOF-Au composite
mu.L MOF (40 mg/mL) and 1mL HAuCl 4 (10 mg/mL) was added sequentially to 250mL of purified water. The mixture was magnetically stirred for 10s and 800. Mu.L of freshly prepared NaBH was rapidly added 4 Solution (3.8 mg/mL). The synthesized MOF-Au product was washed once by centrifugation with purified water at 10000rpm for 15min to remove unreacted free Au NPs. The washing was then repeated twice with acetone and once with purified water to remove excess DMF (the MOF described above was formulated with DMF) and finally the product was dispersed in purified water.
To prepare the MOF, 60mg of zirconium oxychloride, 20mg of tetra-ortho- (4-carboxyphenyl) porphyrin (H 2 TCPP) and 580mg benzoic acid were added to 20ml n, n-Dimethylformamide (DMF). The mixture was stirred at 95℃for 5 hours, centrifuged at 10000rpm for 15 minutes to collect the product, and the product was repeatedly washed with DMF for 2 times and acetone once more, and dried in an oven at 60 ℃.
Preparation of ITO/Bi 2 S 3 Au NPs/MPBA/SA/MOF-Au@MPBA electrode
First 3mL 2mg/mL Bi 2 S 3 Adding the dispersion liquid into a sample bottle1.5mL of Au NPs solution is added and stirred for 2 hours; then 1mL MPBA solution (0.1 mM) was added and stirred overnight at room temperature; adding 1mL of SA solution with different concentrations, stirring for 40min, and fully reacting; finally adding 1mM PBA@Au-MOF solution (1 mg/mL), stirring for 40min, finally dripping 150 μl of the mixture onto ITO conductive glass (pretreated with acetone, ethanol, and pure water), drying at low temperature to obtain electrode, and adding the electrode into acetic acid-sodium acetate (pH 6.5) electrolyte (containing 0.8mM TMB and 1.0mM Ce) 3+ ) SA detection can be realized by utilizing one detection mode of three electrodes through the change of an electric signal.
The other two electrodes respectively adopt Ag/AgCl as a reference electrode and a platinum wire as an auxiliary electrode.
The invention uses ITO/Bi 2 S 3 The Au NPs/MPBA/SA/MOF-Au@MPBA composite electrode is successfully applied to sensitive detection of SA standard solution.
The method comprises the following specific steps:
1) The MOF-Au@MPBA composite material prepared by the invention is dispersed into an aqueous solution to prepare the MOF-Au@MPBA composite material with the concentration of 1mg mL -1 Is a dispersion of (a).
2) Adding Bi to a sample bottle 2 S 3 Dispersion, perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion), ultrasonic treatment, au NPs solution, stirring at room temperature for 2 hours, adding MPBA solution, and adding from 0.1mmol L -1 To 2mmol L -1 Stirring at room temperature for 40min, adding the prepared MOF-Au@MPBA composite material, dripping 150 mu L of the mixed solution onto ITO conductive glass, drying, detecting a photocurrent signal by a chemical workstation, observing the color change of the electrolyte, drawing a working curve according to the relation between the photocurrent signal intensity and the SA concentration, and recording the color change of the electrolyte by a photo.
FIG. 7A is a graph of electrical signals measured for different composite electrodes in example 1 of the present invention, bi was compounded on ITO conductive glass 2 S 3 The electric signal is obviously increased after the material is prepared; in ITO/Bi 2 S 3 After the Au NPs are combined on the electrode, the electric signal is further increased due to good conductivity of the Au; in ITO/Bi 2 S 3 After MPBA, SA and MOF-Au@MPPBA are sequentially compounded on the/Au NPs electrode, the electric signal is gradually reduced due to the gradual increase of steric hindrance.
FIG. 7B is a graph showing the impedance measured for electrodes made of different composite materials in example 1 of the present invention, bi was compounded on ITO conductive glass 2 S 3 The impedance increases after the material; in ITO/Bi 2 S 3 After the Au NPs are compounded on the electrode, the impedance is reduced; in ITO/Bi 2 S 3 After MPBA, SA and MOF-Au@MPPBA are sequentially compounded on the/Au NPs electrode, the steric hindrance is gradually increased.
FIG. 8 is a diagram of ITO/Bi corresponding to 0.4mM SA of example 1 of the present invention 2 S 3 Electrical signal plot of/AuNPs/MPBA/SA/MOF-au@mpba composite electrode as a function of incubation time. With the increase of the incubation time, the electric signal gradually increases, and when the time increases to 40min, the electric signal reaches the maximum value, and the incubation time is continuously increased, so that the electric signal is obviously reduced. Therefore, in this example, an incubation time of 40min was chosen as the optimal condition for detection of SA.
FIG. 9B shows SA concentration of 0.1 to 2mmol L -1 In the range, the detection SA shown by the embodiment of the invention has a good linear range. Linear result Δi (μa) =0.964lgc+1.338, r 2 =0.993, the lowest detection limit is 87 μmol L -1 。
FIG. 9D is a selective control of an embodiment of the invention, in order to demonstrate the selectivity of the composite of the invention for SA, 2 control groups were designed to measure the change in electrical signal of the composite in the presence of a blank and interfering substances. The result shows that the electric signal of the composite material can be changed only in the presence of the object to be detected, and other various interfering substances basically do not influence the change of the electric signal intensity.
Example 2
ITO/Bi prepared in example 1 2 S 3 The Au NPs/MPBA/SA/MOF-Au@MPBA composite electrode is successfully applied to the standard addition method and the simple visual method detection of SA in human serum.
The method comprises the following specific steps of;
1) By adding three different concentrations (0.2, 0.5 and 1.0mmol L) -1 ) S of (2)A recovery experiment was performed. In the test solution, human serum was finally diluted 20-fold;
2) By adding three different concentrations (0.2, 0.5 and 1.0mmol L) -1 ) And (3) visually inspecting the SA. In the test solution, human serum was finally diluted 20-fold;
3) The remainder were as in example 1.
As can be seen from table 1, the recovery rate is in the range of 98.0% -100.8%, and the relative standard deviation (n=3) is less than 3%, indicating that the sensor has higher accuracy and precision in detecting the SA concentration in the human serum biological sample.
TABLE 1
As can be seen from fig. 10, the corresponding color changes of SA at different concentrations can be used to easily determine the SA content in human serum biological samples.

Claims (10)

1. A preparation method of a 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor is characterized by comprising the following steps of: the method comprises the following steps:
1) Preparation of MOF-Au@4-mercaptophenylboronic acid composite material
Adding 4-mercaptophenyl boric acid into the MOF-Au composite material water solution, stirring at room temperature, centrifugally collecting a product, washing with water, and drying to obtain the MOF-Au@4-mercaptophenyl boric acid composite material;
2) Preparation of the sensor
First, bi was added to a sample bottle 2 S 3 The dispersion liquid, perfluor sulfonic acid-polytetrafluoroethylene copolymer, is treated by ultrasonic, and is added with AuNPs solution and stirred;
then adding 4-mercaptophenylboronic acid solution, stirring at room temperature, adding sialic acid solution, and continuing stirring for 40 minutes;
finally, adding the MOF-Au@4-mercaptophenyl boric acid composite material aqueous solution, and stirring to obtain a mixed solution;
and (3) dripping the mixed liquid on ITO conductive glass, and drying at low temperature to obtain the electrode of the 4-mercaptophenylboronic acid@Au-MOF composite material sensor.
2. The method for preparing the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor according to claim 1, which is characterized in that: the preparation method of the MOF-Au@4-mercaptophenyl boric acid composite material specifically comprises the following steps:
2mg of 4-mercaptophenylboronic acid is added to a 1mL concentration of 1mg/mL aqueous solution of the MOF-Au composite material, and the resulting mixture is stirred at room temperature for 8-12 hours; the product was collected by centrifugation at 8000rpm for 5min, washed 3 times with purified water and dried in an oven at 60 ℃.
3. The method for preparing the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor according to claim 1, which is characterized in that: the sensor was prepared as follows:
first, 3mL Bi was added at a concentration of 2mg/mL 2 S 3 Adding the dispersion liquid and 30 mu L of perfluorosulfonic acid-polytetrafluoroethylene copolymer into a sample bottle, and carrying out ultrasonic treatment; 1.5mL of AuNPs solution was added and stirred for 2 hours;
then, 1mL of a 0.1mM solution of 4-mercaptophenylboronic acid was added and stirred at room temperature for 8-12 hours; adding 1mL sialic acid solution, and stirring for 40 min;
finally, adding 1mL concentration of 1mg/mL 4-mercaptophenylboronic acid@Au-MOF solution, stirring for 30-40 minutes, finally taking 150 mu L of the obtained mixed liquid to drop on ITO conductive glass, and drying at low temperature;
wherein, the ITO conductive glass is pretreated by acetone, ethanol and pure water.
4. The method for preparing the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor according to claim 1, which is characterized in that: the preparation method of the MOF-Au composite material comprises the following steps:
MOF and HAuCl 4 Sequentially adding into water, stirring, adding newly prepared NaBH 4 The solution is used to obtain MOF-Au crude product, which is washed by water, acetone and water in turnAnd then obtaining the MOF-Au composite material.
5. The method for preparing the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor according to claim 4, which is characterized in that: the preparation method of the MOF comprises the following steps:
adding zirconium oxychloride, tetra (4-carboxyphenyl) porphyrin and benzoic acid into N, N-dimethylformamide, stirring for reaction, centrifuging to collect a product after the reaction is finished, washing the product with N, N-dimethylformamide and acetone in sequence, and drying to obtain the MOF.
6. A4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor is characterized in that: prepared by the preparation method of any one of claims 1 to 5.
7. Use of a 4-mercaptophenylboronic acid @ Au-MOF composite material photoelectrochemical sensor according to claim 6, characterized in that: for detecting sialic acid content in serum.
8. The use according to claim 7, characterized in that: the electrode of the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor is used as a working electrode, a detection mode of three electrodes is utilized, a xenon lamp is used as a light source, an electrochemical workstation is used for collecting electric signals, and the electric signals comprise 0.8mM TMB and 1.0mM Ce 3+ The acetic acid-sodium acetate buffer solution is taken as electrolyte, the pH value of the acetic acid-sodium acetate buffer solution is 6.5, a linear relation between an electric signal and sialic acid concentration is established, and the sialic acid content in serum is detected by a standard adding method, and the electrolyte is changed from colorless to blue in the detection process.
9. The use according to claim 7, characterized in that: the linear range of sialic acid detected by the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor is 0.1-2 mmol L -1 Correlation coefficient R 2 Up to 0.993.
10. The use according to claim 7, characterized in that: the detection lower limit of sialic acid detected by the 4-mercaptophenylboronic acid@Au-MOF composite material photoelectrochemical sensor reaches 87 mu mol L -1 。
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