CN115232327B - Metal organic framework material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a metal organic framework material and a preparation method and application thereof, and belongs to the technical field of biosensors. The invention solves the problems of poor reproducibility, weak anti-interference capability and the like of the existing electrochemical immunosensor. The invention provides a metal organic framework material, and the metal organic framework material is applied to an electrochemical immunosensor. The linear range of the electrochemical immunosensor was found to be 0.005 to 100U/mL, with the lowest detection limit of 0.0029U/mL (S/N = 3). In addition, the relative standard deviation of repeated detection of the sensor is only 0.69%, the response current value after the addition of the interfering substance is basically consistent with the response current of a single cancer embryo antigen, and the relative standard deviation is 0.72%, so that the material is the electrochemical immunosensor material which is the metal organic framework material with highest sensitivity, highest reproducibility and best interference resistance in related reports of cancer embryo antigen detection at present, and has good application prospect.
Description
Technical Field
The invention relates to a metal organic framework material and a preparation method and application thereof, belonging to the technical field of biosensors.
Background
The detection of the cancer embryo antigen is used as an important index for diagnosis and treatment of colorectal cancer, and has important guiding value for diagnosis, treatment, metastasis and recurrence of the colorectal cancer, so that the establishment of a rapid, sensitive and reliable detection method of the cancer embryo antigen is very important. At present, enzyme-linked immunosorbent assay, radioimmunoassay and chemiluminescence immunoassay are mainly used as detection methods for the cancer embryo antigens, but the methods have the problems of long detection time, difficult operation and radioactive pollution, so that the detection of the cancer embryo antigens is greatly restricted. One then combines the robustness and simplicity of immunoassay with the high sensitivity inherent to electrochemical methods, providing a reliable strategy for biosensor development.
The electrochemical immunosensor is taken as a novel biosensor, and the high sensitivity, the specificity and the stability of the identified substances are paid attention by people, in addition, the electrochemical immunosensor integrates the traditional immunoassay and the biosensing technology, so that the analysis time is reduced, the sensitivity and the precision of the assay are improved, the advantages of simple assay process, strong specificity and the like are achieved, and the electrochemical immunosensor is widely applied to the fields of clinical diagnosis, environmental monitoring, food safety and the like. However, the current electrochemical immunosensor still needs to solve the problem of multi-target simultaneous detection capability, and further eliminates the interference caused by the nonspecific adsorption of interfering components in the biological sample on the surface of the electrode. Therefore, focusing on solving the problems of poor reproducibility, poor interference resistance and the like of the electrochemical immunosensor is an important subject facing the research field.
Metal Organic Frameworks (MOFs) are porous ordered nanomaterials formed by highly orderly connecting Metal ions and Organic ligands, and have wide application prospects in the fields of gas storage, biomedicine, catalysis and the like. When the metal-organic composite material is used as an electrode material, the MOFs have very large development potential in sensing application due to the porosity, high specific surface area, excellent conductivity and the like. Therefore, the metal organic framework material is provided and used as a core material of the electrochemical immunosensor, the electrochemical immunosensor can detect the cancer embryo antigen with high sensitivity, excellent reproducibility and interference resistance are shown, and the metal organic framework material is very necessary in clinical diagnosis and bioassay analysis.
Disclosure of Invention
The invention provides a metal organic framework material and a preparation method thereof, which are used for solving the problems of poor reproducibility, weak anti-interference capability and the like of the existing electrochemical immunosensor, and the metal organic framework material is used as a core material of the electrochemical immunosensor, so that the electrochemical immunosensor can detect the cancer embryo antigens with high sensitivity, and the excellent reproducibility and anti-interference capability are shown.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a metal organic framework material, which is abbreviated as MOF-ET4 and has the chemical formula of [ Sm ] 2 (L) 3 ]In the formula, L is C 92 H 58 O 8 。
The invention also aims to provide a preparation method of the metal organic framework material, which comprises the following steps: smCl is added 3 •6H 2 Adding O, ligand and benzoic acid into N, N-dimethylformamide, carrying out ultrasonic treatment for 10min, heating at 120 ℃ for 12h, and sequentially carrying out centrifugation, washing and drying treatment to obtain MOF-ET4.
Further defined, smCl 3 • 6 H 2 O, ligandThe proportion of benzoic acid to N, N-dimethylformamide is 44mg:48mg:500mg:5mL.
To be further limited, smCl 3 •6H 2 The concentration of O was 0.172mmol/L.
Further defined, the ligand has the structure:
further defined, the method of preparing the ligand comprises the steps of:
s1, adding 1,3,6, 8-tetra (pinacolato) pyrene, 4' -dibromobiphenyl, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solution, heating and reacting under the protection of argon, after the reaction is finished, spin-drying an organic phase, and performing silica gel column chromatography by using an eluent to obtain a yellow solid which is named as an intermediate 1;
s2, mixing 4-methoxycarbonylphenylboronic acid, the intermediate 1, tetrakis (triphenylphosphine) palladium, tripotassium phosphate and dioxane, sealing under the protection of nitrogen, then placing the mixture in an oil bath, stirring for reaction, separating an organic phase after the reaction is finished, washing the organic phase with water, extracting the organic phase for 3 times with chloroform, then spin-drying the organic phase, heating and boiling the obtained residue in tetrahydrofuran for 2 hours, and filtering the residue while the residue is hot to obtain a yellow solid, wherein the yellow solid is named as an intermediate 2;
and S3, adding the intermediate 2 into a tetrahydrofuran/water mixed solution containing sodium hydroxide, carrying out reflux stirring reaction for 5 hours, carrying out spin-drying on a solvent after the reaction is finished, adding water into the residue, stirring for 2 hours at 25 ℃, then adjusting the pH value to 1, filtering, washing with water, recrystallizing the crude product with N, N-dimethylformamide, filtering, and carrying out vacuum drying to obtain a yellow solid, namely the ligand.
More particularly, the mole ratio of 1,3,6, 8-tetra (pinacolato) pyrene, 4' -dibromobiphenyl, tetrakis (triphenylphosphine) palladium and potassium carbonate in S1 is 0.71:7.05:0.04:14.5.
further limiting, the mixed solution in S1 is prepared by mixing toluene and water according to the volume ratio of 1.
More specifically, the heating reaction temperature in S1 is 105 ℃, and the time is 24h.
To be further limited, the eluent in S1 is prepared by mixing n-hexane and toluene according to a volume ratio of 3.
Further limited, the proportion of 4-methoxycarbonylphenylboronic acid, intermediate 1, tetrakis (triphenylphosphine) palladium, tripotassium phosphate and dioxane in S2 is 5.8mmol:5.8mmol:0.02mmol:10mL of: 2.65mmol.
More specifically, the reaction temperature in the oil bath in S2 is 130 ℃ and the reaction time is 72h.
Further limited, the volume ratio of tetrahydrofuran to water in the tetrahydrofuran/water mixture in S3 is 1.
Further limiting, the ratio of intermediate 2, sodium hydroxide and tetrahydrofuran/water solution in S3 is 0.39mmol:18.75mmol:100mL.
The invention also aims to provide application of the metal organic framework material, in particular to an electrode material for an electrochemical immunosensor.
The invention also provides an electrochemical immunosensor, which comprises an electrode substrate and the metal organic framework material modified on the surface of the electrode substrate, wherein the metal organic framework material is coated with the carcinoembryonic antigen specific monoclonal antibody.
Further defined, the linear range of the electrochemical immunosensor is 0.005 to 100U mL -1 Minimum detection limit of 0.0029U mL −1 (S/N=3)。
The invention has the following beneficial effects:
the invention provides a novel metal organic framework material, which is used as an electrode material of an electrochemical immunosensor for detecting a cancer embryo antigen, wherein the linear range of the electrochemical immunosensor is 0.005-100U mL -1 The lowest detection limit was 0.0029U mL −1 (S/N = 3). The relative standard deviation of repeated detection of the sensor is only 0.69%, the response current value after the addition of the interference substances is basically consistent with the response current of the single cancer embryo antigen, the relative standard deviation is 0.72%, and the method is related report of the current metal organic framework material in the detection of the cancer embryo antigenThe electrochemical immunosensor material with the highest sensitivity, the best reproducibility and the best interference resistance has good application prospect. In addition, the synthesis method of the metal organic framework material provided by the invention also has the advantages of simple process, mild conditions and the like.
Drawings
FIG. 1 is a synthetic route for the preparation of ligands for metal organic framework materials;
FIG. 2 is a result of a responsiveness test of an electrochemical immunosensor;
FIG. 3 is a calibration curve of peak current versus concentration for DPV;
FIG. 4 is a result of a reproducibility test of an electrochemical immunosensor;
FIG. 5 shows the anti-interference test results of the electrochemical immunosensor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The starting materials 1,3,6,8-tetrakis (pinacolato) pyrene (CAS: 1398053-00-3), 4,4' -dibromobiphenyl (CAS: 92-86-4), 4-methoxycarbonylphenylboronic acid (CAS: 99768-12-4) used in the following examples were all purchased directly from Sigma-Aldrich Co.
Example 1:
this example illustrates the preparation of a metal-organic framework material COF-ET4 as follows:
(1) As shown in fig. 1, ligand 1:
(1) synthesis of intermediate 1:
to a mixed solution of 20 ml of toluene and 20 ml of water were added 1,3,6, 8-tetrakis (pinacolato) pyrene (starting material, 1,0.5 g, 0.71 mmol), 4' -dibromobiphenyl (starting material, 2,2.2 g, 7.05 mmol), tetrakis (triphenylphosphine) palladium (46 mg, 0.04 mmol), and potassium carbonate (0.2 g, 14.5 mmol) in this order, and the mixture was heated at 105 ℃ for 24 hours under argon atmosphere. The organic phase was then spin dried and subjected to silica gel column chromatography with n-hexane: toluene (v/v = 3) as eluent to give 0.69 g of a yellow solid, intermediate 1, in 86% yield.
The intermediate 1 obtained was subjected to structural characterization:
<1> nuclear magnetic characterization identification result:
hydrogen spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 8.03 (m, 10 H), 7.72 (d, 8 H), 7.55 (d, 4 H), 7.45 (m, 16 H)。
carbon spectrum: 13 C NMR (100 MHz, CDCl 3 ): δ 140.55, 139.63, 137.80, 137.79, 136.82, 135.98, 133.17, 131.94, 131.85, 131.50, 129.63, 128.62, 128.46, 128.03, 126.92, 125.13, 124.99, 124.78, 122.04。
<2> results of mass spectrometry:
ESI(m/z): [M+H] + Calcd. for C 64 H 38 Br 4 , 1126.62; Found, 1127.14。
<3> results of elemental analysis test:
Calcd. for C 64 H 38 Br 4 , C, 68.23, H, 3.4; Found, C, 69.15, H, 4.1。
as can be seen from the above, the structure of the obtained intermediate 1 is as follows:
(2) synthesis of intermediate 2:
to a 30 ml sealed tube were added 4-methoxycarbonylphenylboronic acid (1.04 g, 5.8 mmol), intermediate 1 (0.55 g, 0.485 mmol), tetrakis (triphenylphosphine) palladium (starting material 3,0.02 g, 0.02 mmol) and tripotassium phosphate (0.55 g, 10 ml), dioxane (15 ml, 2.65 mmol) in that order, and sealed under nitrogen. Then the mixture is placed in an oil bath, stirring reaction is carried out for 72 hours at 130 ℃, after the reaction is finished, the organic phase is washed by water, chloroform is used for extracting for 3 times, 50 milliliters each time, the residue obtained after the organic phase is dried in a spinning mode is heated and boiled in tetrahydrofuran for 2 hours and is filtered while the residue is hot, 0.53 gram of yellow solid is obtained, namely the intermediate 2, and the yield is 82%.
The intermediate 2 obtained was structurally characterized:
<1> nuclear magnetic characterization and identification results:
hydrogen spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 8.12 (m, 16 H), 7.88 (d, 8 H), 7.74 (d, 8 H), 7.5 (d, 2 H), 7.33 (d, 8 H), 7.22 (m, 12 H)。
carbon spectrum: 13 C NMR (100 MHz, CDCl 3 ): δ 166.66, 144.41, 140.93, 137.80, 137.79, 136.82, 135.98, 133.17, 131.85, 131.50, 130.39, 130.13, 129.83, 129.63, 128.62, 128.03, 126.92, 125.13, 124.99, 124.78, 52.07。
<2> results of mass spectrometric characterization:
ESI(m/z): [M+H] + Calcd. for C 96 H 66 O 8 , 1347.58; Found, 1348.14。
<3> results of elemental analysis test:
Calcd. for C 96 H 66 O 8 , C, 85.57, H, 4.94, O, 9.5; Found, C, 85.12, H, 5.3, O, 9.1。
as can be seen from the above, the structure of the obtained intermediate 2 is as follows:
(3) synthesis of ligand 1:
to a 250 ml round bottom flask were added in sequence intermediate 2 (0.5 g, 0.39 mmol), followed by 100ml of a tetrahydrofuran/water (v/v = 1) mixed solution containing sodium hydroxide (0.75 g, 18.75 mmol), and stirred under reflux for 5 hours. After the solvent was dried by spinning, 50 ml of water was added to the residue, and the mixture was stirred at 25 ℃ for 2 hours, and then the pH was adjusted to 1 with 1 mol/l hydrochloric acid. Filtered and washed with water. The crude product was then recrystallized from N, N-dimethylformamide, filtered and dried under vacuum to give 0.46 g of a yellow solid, the desired ligand, in 91% yield.
The ligand 1 obtained was subjected to structural characterization:
<1> nuclear magnetic characterization identification result:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO): δ 8.23 (d, 8 H), 8.13 (d, 8 H), 7.88 (d, 8 H), 7.72 (d, 8 H), 7.5 (d, 2 H), 7.32 (d, 8 H), 7.21 (m, 12 H)。
carbon spectrum: 13 C NMR (100 MHz, DMSO): δ 167.69, 144.13, 140.93, 137.68, 137.60, 136.38, 135.32, 132.44, 131.07, 130.86, 130.23, 129.63, 129.61, 128.55, 127.91, 126.71, 126.66, 125.08, 124.99, 124.95。
<2> results of mass spectrometric characterization:
ESI(m/z): [M+H] + Calcd. for C 92 H 58 O 8 , 1291.47; Found, 1292.03。
<3> results of elemental analysis test:
Calcd. for C 92 H 58 O 8 , C, 85.56, H, 4.53, O, 9.91; Found, C, 85.12, H, 4.9, O, 9.1。
in conclusion, the structure of the ligand 1 obtained is as follows:
(2) Synthesis of metal-organic framework material MOF-ET4:
adding SmCl 3 •6H 2 O (44 mg, 0.172 mmol/l), a ligand (48 mg, 0.037 mmol) and 500mg of benzoic acid were added to 5ml of N, N-dimethylformamide, and then the mixture was sonicated for 10 minutes, and further subjected to solvothermal treatment at 120 ℃ for 12 hours in an autoclave, the reaction system was centrifuged at 10000 rpm for 20 minutes using a centrifuge, the solid was filtered, soaked in 30 ml of ethanol for 12 hours, and then washed 3 times with 10ml of acetone. Finally, vacuum drying is carried out at 100 ℃ to obtain the MOF-ET4.
Carrying out structural characterization on the obtained MOF-ET4:
<1> the synthesized MOF-ET4 crystal is stored in a glass capillary, and the crystal structure is tested by adopting single crystal X-ray, the instrument is a Bruker-Apex II type CCD detector, and a Cu K alpha (lambda = 1.54178A) X-ray source is used for collection. The data was corrected for absorbance by the SADABS program, and not for extinction or decay. The solution was performed directly using the SHELXTL software package and the results are shown in Table 1.
TABLE 1
(3) Preparing an electrochemical immunosensor by adopting the metal organic framework material MOF-ET4 obtained by the preparation method:
bare Glassy Carbon Electrodes (GCEs) were polished with 0.3 micron particle size alumina powder and sonicated in water for 5 minutes, then 10 microliters of 5 mg/ml MOF-ET4 was dispersed in 5% chitosan solution, dropped on the cleaned bare glassy carbon electrodes, and dried. Another 10 microliters (0.1U mL) −1 ) The carcinoembryonic antigen-specific monoclonal antibody (anti-CEA) of (2) is coated on the MOF-ET4/GCE electrode surface, incubated at 4 ℃ for 25 minutes, and washed with phosphate buffer (pH = 7). To block non-specific binding sites on the sensor, 5 μ l of 1% Bovine Serum Albumin (BSA) was added, incubated at 4 ℃ for 30 minutes, and washed with phosphate buffer (pH = 7), to prepare an electrochemical immunosensor.
The performance of the obtained electrochemical immunosensor is characterized:
<1> test of responsiveness of electrochemical immunosensor:
the response of the electrochemical immunosensor to the Cancer Embryonic Antigen (CEA) is researched by adopting a differential pulse voltammetry, wherein the potential range is-0.2V to 0.6V, the potential increment is 0.004V, the pulse amplitude is 0.05V, the pulse width is 0.2 s, the sample width is 0.0167 s, and the pulse period is 0.5 s.
The electrochemical immunosensor is inserted into the cancer embryo antigens with different concentrations to be detected, and after the antibody in the electrode is combined with the Cancer Embryo Antigens (CEA) to be detected, the change of the charge density of the interface between the surface membrane of the electrode and the solution can be caused, so that the change of the membrane potential can be generated.
The results of the responsiveness test are shown in fig. 2, and it can be seen from fig. 2 that the peak current is decreased when the antigen concentration is increased, because the additional protein molecules block the transfer of electrons.
FIG. 3 is a linear relationship between the electrochemical immunosensor and CEA concentration, ranging from 0.005 to 100U mL -1 The corresponding linear equations are respectively I = -3.8033 XC CEA +98.895（R 2 = 0.9932) and I = -0.5941 xc CEA +96.542（R 2 = 0.9913), the lowest limit of detection (LOD) value was 0.0029U mL −1 (S/N = 3), it can be demonstrated that the electrochemical immunosensor has a wider detection range and a lower detection limit, because the MOF-ET4 material has good conductivity, providing more binding sites for antigens, and thus has excellent sensitivity.
<2> reproducibility test of electrochemical immunosensor:
reproducibility is an important performance index of the electrochemical immunosensor, 5 electrochemical immunosensors are prepared by the same method as the method (3), and the electrochemical immunosensors are inserted into 0.1U mL -1 And 5 replicate tests were performed for each sensor.
The test result is shown in FIG. 4, the relative standard deviation of which is 0.69% by calculation, and the electrochemical immunosensor prepared by using the metal organic framework material MOF-ET4 can be proved to have good reproducibility.
<3> anti-interference test of electrochemical immunosensor:
cancer antigen-125 (CA-125), cancer antigen 19-9 (CA 19-9), immunoglobulin (lgG), alpha-fetoprotein (AFP) are used as interfering substances, and 1U mL is added −1 CEA of (2) was added to 100U mL of each −1 The interfering substance is inserted into an electrochemical immunosensor for detection.
The test result is shown in fig. 5, and it can be seen that the response current value of the added interfering substance is substantially consistent with the response current of a single CEA, and the relative standard deviation is 0.72%, which indicates that the interference of other analytes is negligible, and this proves that the electrochemical immunosensor has good anti-interference capability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (9)
1. The metal organic framework material is characterized in that the material is MOF-ET4 for short, and the chemical formula is [ Sm [ ([ Sm ]) 2 (L) 3 ]In which L is C 92 H 58 O 8 ；
The structure of L is as follows:
2. a process for the preparation of a metal organic framework material as claimed in claim 1, characterized in that SmCl is added 3 ·6H 2 O, ligand and benzoic acid toN, NIn dimethylformamide, ultraPerforming sound treatment for 10min, heating at 120 ℃ for 12h, and sequentially performing centrifugation, washing and drying to obtain MOF-ET4.
3. A method for preparing a ligand used in the method for preparing a metal organic framework material according to claim 2, characterized by comprising the steps of:
s1, adding 1,3,6, 8-tetra (pinacolato) pyrene, 4' -dibromobiphenyl, tetra (triphenylphosphine) palladium and potassium carbonate into a mixed solution, heating and reacting under the protection of argon, after the reaction is finished, spin-drying an organic phase, and performing silica gel column chromatography by using an eluent to obtain a yellow solid which is named as an intermediate 1;
s2, mixing 4-methoxycarbonylphenylboronic acid, the intermediate 1, tetrakis (triphenylphosphine) palladium, tripotassium phosphate and dioxane, sealing under the protection of nitrogen, then placing the mixture in an oil bath, stirring for reaction, separating an organic phase after the reaction is finished, washing the organic phase with water, extracting the organic phase for 3 times with chloroform, then spin-drying the organic phase, heating and boiling the obtained residue in tetrahydrofuran for 2 hours, and filtering the residue while the residue is hot to obtain a yellow solid, wherein the yellow solid is named as an intermediate 2;
s3, adding the intermediate 2 into a tetrahydrofuran/water mixed solution containing sodium hydroxide, refluxing and stirring for reaction for 5 hours, drying the solvent after the reaction is finished, adding water into the residue, stirring for 2 hours at 25 ℃, then adjusting the pH to 1, filtering, washing the crude product with water, and then adding the crude product into a reactor for reactionN, NRecrystallizing with dimethylformamide, filtering, and vacuum drying to obtain yellow solid as ligand.
4. The method for preparing a ligand according to claim 3, wherein the heating reaction in S1 is carried out at 105 ℃ for 24 hours.
5. The method for preparing the ligand according to claim 3, wherein the eluent in S1 is prepared by mixing n-hexane and toluene according to a volume ratio of 3.
6. The process for the preparation of the ligand according to claim 3, wherein the reaction temperature in S2 in an oil bath is 130 ℃ and the reaction time is 72 hours.
7. The method according to claim 3, wherein the volume ratio of tetrahydrofuran to water in the tetrahydrofuran/water mixture in S3 is 1.
8. Use of the metal-organic framework material according to claim 1 for the preparation of an electrode material for electrochemical immunosensors.
9. An electrochemical immunosensor comprising an electrode substrate and the metal-organic framework material of claim 1 modified on the surface of the electrode substrate, wherein the metal-organic framework material is coated with carcinoembryonic antigen-specific monoclonal antibodies.
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