CN114674770A - Preparation method of colorimetric sensor based on metal organic framework wrapped by molecularly imprinted polymer, product and application thereof - Google Patents

Preparation method of colorimetric sensor based on metal organic framework wrapped by molecularly imprinted polymer, product and application thereof Download PDF

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CN114674770A
CN114674770A CN202210337727.3A CN202210337727A CN114674770A CN 114674770 A CN114674770 A CN 114674770A CN 202210337727 A CN202210337727 A CN 202210337727A CN 114674770 A CN114674770 A CN 114674770A
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tdg
organic framework
metal organic
thiodiglycol
mil
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甄淑君
曾怡萌
叶启超
段苏容
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Southwest University
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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Abstract

The invention relates to a preparation method of a colorimetric sensor based on a molecularly imprinted polymer-coated metal organic framework, a product and application thereof, and belongs to the technical field of colorimetric sensors. The invention synthesizes a molecular stamp coated on the surface of a metal organic framework material by using Thiodiglycol (TDG) as a template molecule, alpha-methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent and azodiisobutyronitrile as an initiatorTrace polymers (MIPs). In the method, template molecules TDG are combined with functional monomers alpha-methacrylic acid through hydrogen bonds to generate non-covalent bond effect, binding sites are left after the template molecules are removed by elution to form MIPs, and the MIPs have specific recognition function on the TDG. When the solution contains TDG, the TDG is specifically identified by MIPs on the surface of the metal organic framework material, so that active sites are closed, and the metal organic framework material catalyzes H2O2The oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB) is inhibited in blue, and visual detection of TDG can be realized by detecting the decrease of absorbance value.

Description

Preparation method of colorimetric sensor based on metal organic framework wrapped by molecularly imprinted polymer, product and application thereof
Technical Field
The invention belongs to the technical field of colorimetric sensors, and relates to a preparation method of a colorimetric sensor based on a molecularly imprinted polymer-coated metal organic framework, and a product and application thereof.
Background
Mustard gas (SM) known under the name 2, 2-dichlorodiethyl sulfide has been widely used during world war ii, known as the war king, because of its erosive and toxic properties. Mustard gas is known to produce toxicity based on the spontaneous formation of unstable sulfonium intermediates by intramolecular cyclization. Such cyclic intermediates are readily reactive with a variety of biomolecules, such as sulfhydryl (-SH) and amino (-NH) groups2) Resulting in chromosomal variation, DNA strand variation mutation, apoptosis, and rapid inactivation of thiol-containing proteins and peptides such as glutathione. Skin is one of the most major target organs of poisoning, after the skin is infected with the toxic gas, erythema, edema, erosion and necrosis can be caused, secondary infection is easily caused, and the mustard gas with larger dose can cause general poisoning after being absorbed through skin, respiratory tract and digestive tract, so the clinical manifestations of mustard gas poisoning are diversified. It is known that in biological and environmental substrates, mustard gas can be hydrolyzed to thiodiglycol, a relatively stable, low toxicity, low volatility metabolite. Therefore, the method can be used for diagnosing the mustard gas poisoning by detecting the thiodiglycol and has important significance for medical protection.
The existing detection methods mainly adopt a liquid chromatography-mass spectrometry combined technology (LC-MS) and a gas chromatography-mass spectrometry combined technology (GC-MS), but the detection methods need to carry out relatively complex pretreatment on a sample, namely, Thiodiglycol (TDG) needs to be separated, enriched and derivatized before detection; however, derivatization also causes background signals and produces certain interfering peaks, which have an effect on both sensitivity and accuracy. In addition, LC-MS and GC-MS are large instruments, are expensive and require professional personnel to perform complex operations, so that the existing TDG detection method has certain defects.
Therefore, it is very necessary to construct a method for simply and rapidly detecting thiodiglycol.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a colorimetric sensor based on a metal-organic framework coated with a molecularly imprinted polymer; the invention also aims to provide a colorimetric sensor based on a metal organic framework wrapped by a molecularly imprinted polymer; the invention also aims to provide an application of the colorimetric sensor based on the molecular imprinting polymer coated metal organic framework in the aspect of detecting TDG.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a colorimetric sensor based on a molecularly imprinted polymer-coated metal organic framework comprises the following steps:
(1) preparation of Metal organic framework Material (Fe-MIL-88 NH)2): dissolving 2-amino-p-xylylene and water-soluble ferric salt in DMF, mixing, adding acetic acid, crystallizing in 120 deg.C oil bath, cooling to room temperature, centrifuging to obtain crystal, washing, and oven drying to obtain metal organic framework material (Fe-MIL-88 NH)2)；
(2) Preparation of colorimetric sensor (Fe-MIL-88 NH)2@ MIPs): TDG, methanol, alpha-methacrylic acid (MAA) and the metal organic framework material (Fe-MIL-88 NH)2) Adding into Ethylene Glycol Dimethacrylate (EGDMA), ultrasonic mixing, adding Azobisisobutyronitrile (AIBN), stirring and heating in oil bath at 70 deg.C for 24 hr to obtain mixture, vacuum filtering, eluting to remove Thiodiglycol (TDG), and oven drying to obtain colorimetric sensor (Fe-MIL-88 NH)2@MIPs)。
Preferably, in step (1), the water-soluble ferric salt is FeCl3·6H2O；
The 2-amino groupPara-xylylene, FeCl3·6H2The molar ratio by volume of O to acetic acid was 0.252: 0.374: 200 mmol, mmol is muL.
Preferably, in step (1), the solvent used for washing is N, N-Dimethylformamide (DMF).
Preferably, in the step (2), the Thiodiglycol (TDG), the methanol, the alpha-methacrylic acid (MAA) and the metal-organic framework material (Fe-MIL-88 NH)2) The mass-to-volume ratio of Ethylene Glycol Dimethacrylate (EGDMA) to Azobisisobutyronitrile (AIBN) was 3:20:80:0.2:3:200, μ g: mL: μ L: g: mL: mg.
Preferably, in the step (2), the method for eluting to remove TDG specifically comprises: the mixture formed with methanol and acetic acid was eluted at 115 ℃ to remove TDG.
More preferably, the volume ratio of methanol to acetic acid in the mixed solution is 9:1.
2. The colorimetric sensor (Fe-MIL-88 NH) based on the metal organic framework coated by the molecularly imprinted polymer prepared by the preparation method2@MIPs)。
3. The colorimetric sensor based on the molecular imprinting polymer-coated metal organic framework is applied to the detection of TDG.
4. A method for detecting TDG specifically comprises the following steps:
mixing the TDG solution to be detected with the colorimetric sensor (Fe-MIL-88 NH)2@ MIPs) in ultrapure water, incubating at 37 deg.C, and adding 3,3',5,5' -Tetramethylbenzidine (TMB) and hydrogen peroxide (H)2O2) Further incubation at 37 ℃ gave a mixed solution, and the absorption spectrum of the mixed solution at 650nm was measured and measured by passing through (. DELTA.A% (. DELTA.A))T-AC)/ACCalculating to obtain the concentration of the TDG to be detected;
wherein Δ a% ═ aT-AC)/AC，ACAbsorbance at 650nm for control group, ATThe absorbance of the resulting mixed solution at 650nm was measured.
Preferably, the control group is distinguished from the mixed solution in that the Thiodiglycol (TDG) solution to be tested is replaced with the same volume of ultrapure water.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of a colorimetric sensor based on a metal organic framework wrapped by a molecularly imprinted polymer, which takes TDG as a template molecule, alpha-methacrylic acid (MAA) as a functional monomer, Ethylene Glycol Dimethacrylate (EGDMA) as a cross-linking agent and Azobisisobutyronitrile (AIBN) as an initiator to synthesize a material (Fe-MIL-88 NH) wrapping the metal organic framework2) The molecularly imprinted polymer (Fe-MIL-88 NH) of (1)2@ MIPs). In the preparation method, a template molecule TDG is combined with a functional monomer alpha-methacrylic acid (MAA) through a hydrogen bond to generate a non-covalent bond effect, then elution is carried out, and binding sites are left after the template molecule is removed to form MIPs with a specific recognition function on the TDG. When TDG is contained in the solution, the target TDG is coated with a metal-organic framework material (Fe-MIL-88 NH)2) Specific recognition of MIPs on the surface, thereby blocking active sites and leading the metal organic framework material (Fe-MIL-88 NH)2) Catalysis H2O2The oxidation of 3,3',5,5' -Tetramethylbenzidine (TMB) is inhibited in blue, and the visual detection of TDG can be carried out by detecting the decrease in absorbance.
2. The invention discloses a colorimetric sensor based on a metal organic framework wrapped by a molecularly imprinted polymer, which is Fe-MIL-88NH2@ MIPs) Fe-MIL-88NH2As a metal organic framework material, the metal organic framework material has the unique performances of high specific surface area and catalytic efficiency, good thermal stability, easy modification of the outer surface and the like, and has wide application prospect in the field of analysis. The iron-containing metal organic framework material, which is one of the most important transition metal organic materials, also has the advantages of high catalytic efficiency, ultrahigh stability and high biocompatibility in an aqueous medium; and metal organic framework material (Fe-MIL-88 NH)2) The MIPs on the surface are generated by polymerization, and after the template molecule TDG is eluted, a cavity matched with thiodiglycol is left in the high polymer, and the cavities can specifically identify the thiodiglycol, so that a structure similar to a key and a lock is formed, and the selectivity is extremely high. When Fe-MIL-88NH2The MIPs of the surface successfully trap the TDG, which occupies the cavity-enclosed cavity, resulting in Fe-MIL-88NH2Catalysis H2O2The ability to oxidize 3,3',5,5' -Tetramethylbenzidine (TMB) is inhibited, the absorbance at 650nm is reduced, and TDG can be detected by calculating the inhibition rate. Colorimetric sensor of the present invention (Fe-MIL-88 NH)2@ MIPs) has great application prospect, good stability, and can be prepared in advance and stored for a long time.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a process flow of a colorimetric sensor based on a metal organic framework coated with a molecularly imprinted polymer;
FIG. 2 is a metal organic framework material (Fe-MIL-88 NH) prepared in example 12) (A) and colorimetric sensor (Fe-MIL-88 NH) based on metal organic framework wrapped by molecularly imprinted polymer2Scanning electron micrographs of @ MIPs) (B);
FIG. 3 shows the reaction mixture containing Fe-MIL-88NH prepared in example 12@MIPs、H2O2Adding pure water and TDG with the same mass into the mixed solution of TMB to obtain the absorbance of the solution;
FIG. 4 shows H at different concentrations2O2、Fe-MIL-88NH2The influence of @ MIPs, pH, adsorption time and incubation time on the detection of TDG, wherein A is different Fe-MIL-88NH2@ MIPs concentration, B is different H2O2Concentration, C different pH, D different adsorption time, E different incubation time;
FIG. 5 is a colorimetric sensor (Fe-MIL-88 NH) of example 12@ MIPs) to detect the linear test result of the TDG;
FIG. 6 is a colorimetric sensor (Fe-MIL-88 NH) of example 12@ MIPs) to detect the selectivity test result of TDG;
FIG. 7 shows a colorimetric sensor (Fe-MIL-88 NH) according to example 12@ MIPs) to detect the anti-interference capability test result of the TDG.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
In the following examples, TDG, alpha-methacrylic acid (MAA), Ethylene Glycol Dimethacrylate (EGDMA), Azobisisobutyronitrile (AIBN) were all available from adadin Reagents co. Buffer, associated aqueous solution, ultrapure water (18.2 M.OMEGA., Barnstead EASYPure Rodi) was used for the preparation of all samples.
Examples
Colorimetric sensor (Fe-MIL-88 NH) based on metal organic framework wrapped by molecularly imprinted polymer2@ MIPs), the specific preparation method comprises the following steps:
(1) preparation of Metal organic framework Material (Fe-MIL-88 NH)2): dissolving 0.252g of 2-amino-p-xylylene and 0.374g of water-soluble ferric iron salt in 15mL of DMF, mixing, adding 200 mu L of acetic acid, crystallizing in an oil bath at 120 ℃ for 4h, cooling to room temperature after crystallization, performing centrifugal separation to obtain crystals, washing off excessive reactants on the crystals by using DMF, and drying to obtain the metal organic framework material (Fe-MIL-88 NH)2)；
(2) Preparation of colorimetric sensor (Fe-MIL-88NH2@ MIPs): mu.L of TDG solution (concentration 100. mu.g/mL), 20mL of methanol, 80. mu.L of alpha-methacrylic acid (MAA) and 0.2g of metal-organic framework material (Fe-MIL-88 NH) prepared in the above step2) Adding into 3mL EGDMA, ultrasonic mixing, adding 200mg AIBN, stirring and heating in oil bath at 70 deg.C for 24 hr to obtain mixture, vacuum filtering to obtain brown powder, eluting with mixed solution (methanol and acetic acid at first ratio of 9:1) at 115 deg.C for 24 hr to remove TDG, and oven drying to obtain colorimetric sensor (Fe-MIL-88 NH)2@MIPs)。
Fig. 1 is a preparation process of a colorimetric sensor based on a molecularly imprinted polymer-coated metal organic framework, and the working principle is as follows: firstly, a metal organic framework material (Fe-MIL-88 NH) is synthesized2) Then, TDG is used as template molecule, MAA is used as functional monomer, EGDMA is used as cross-linking agent, AIBN is used as initiator to synthesize the coating metal organic framework material (Fe-MIL-88 NH)2) The molecularly imprinted polymer (Fe-MIL-88 NH) of (1)2@ MIPs), wherein a template molecule TDG is combined with a functional monomer MAA through hydrogen bonds to generate non-covalent bond action, then elution is carried out by using a special solvent (mixed solution formed by methanol and acetic acid in a volume ratio of 9:1), the template molecule is removed to leave a binding site, so as to form the MIPs, holes matched with the size, the space structure and the binding site of the template molecule are left in the skeleton of the polymer, so that the MIPs have a memory function, and therefore the MIPs have a specific recognition function on the TDG. When the target solution contains TDG, the target TDG can be recognized by MIPs, and the TDG blocks the binding sites on the MIPs, so that the metal-organic framework material (Fe-MIL-88 NH)2) Catalysis H2O2The capacity of oxidizing 3,3',5,5' -Tetramethylbenzidine (TMB) is inhibited, and visual detection of TDG can be realized by detecting the inhibition rate of an absorbance value.
FIG. 2 shows Fe-MIL-88NH prepared in example 12Electron micrograph (A) of (A) and Fe-MIL-88NH prepared in example 12Electron microscopy of @ MIPs (B). As can be seen from A in FIG. 2, Fe-MIL-88NH prepared in example 12The crystal is octahedral, has uniform particle size and is 100-200 nm in size; as can be seen from B in FIG. 2, Fe-MIL-88NH prepared in example 12@ MIPs gaugeThe particle size of the spherical structure is between 0.5 and 1 mu m, which indicates that the MIPs are successfully coated on the Fe-MIL-88NH2Of (2) is provided.
Performance testing
1. Feasibility verification for detecting TDG (time domain gradient) by colorimetric sensor based on molecular imprinting polymer-coated metal organic framework
To the solution containing Fe-MIL-88NH prepared in example 12@MIPs、H2O2The mixed solution with TMB was added with pure water and Thiodiglycol (TDG) of equal mass, and the absorbance of the added solution was measured, and the result is shown in fig. 3, where the absorbance after TDG addition is significantly lower than that of the solution with pure water of equal mass. As can be seen from FIG. 3, Fe-MIL-88NH2@ MIPs can catalyze H2O2And TMB, which is a blue color, and generates a characteristic absorption peak at 650 nm. When in H2O2、TMB、Fe-MIL-88NH2After the @ MIPs mixed solution is added with TDG, the absorbance is greatly reduced, which indicates that the TDG is Fe-MIL-88NH2@ MIPs successfully capture, TDG occupies the cavity and blocks the sites, so that TMB color development is inhibited, thereby reducing the absorbance of the solution.
And (3) calculating: the solution to be tested containing 10 mug/mL TDG target is tested, and three groups are tested in parallel, and the absorption values are respectively 0.389, 0.385 and 0.385. The absorbance of the blank control group was measured at the same time and was 0.969, 0.857, 0.859, 0.864, 0.894, 0.961, 0.944, and 0.881, respectively, and the average value of the absorbance of the blank control group was calculated to be 0.913. The calculated average value (delta A%) of the inhibition rate is 57.67%, and the log delta A% is substituted into 0.16log c +1.12, so that the concentration of the solution to be detected is calculated to be 10137.65ng/mL, and compared with 10 mu g/mL, the calculation error is 1.38%, which indicates that the colorimetric sensor based on the metal-organic framework wrapped by the molecular imprinting polymer, prepared by the invention, can be used for detecting the content of TDG.
2. Optimization of experimental conditions
To obtain optimum sensitivity of the developed sensor, for H2O2Concentration, Fe-MIL-88NH2The @ MIPs concentration, pH, adsorption time and incubation time are optimizedAnd (4) transforming. FIG. 4 is H2O2Concentration, Fe-MIL-88NH2The influence of @ MIPs concentration, pH, adsorption time and incubation time on the detection of TDG. As can be seen from A in FIG. 4, Fe-MIL-88NH2The detection effect is best when the concentration of @ MIPs is 0.1 mg/mL. As can be seen in B of FIG. 4, H2O2When the concentration of (A) is 200. mu.M, when H is added2O2The concentration is more than 200 mu M, the inhibition rate is slightly reduced, which indicates that H2O2Too high concentration of (B) will be on Fe-MIL-88NH2Has an inhibitory activity. Fe-MIL-88NH2The amount of holes in @ MIPs determines the amount of adsorbed TDG and catalytic H2O2Degree of bluish coloration of the oxidized TMB. Similar to peroxidase, Fe-MIL-88NH2The catalytic activity of (A) is closely related to pH, and pH also has an influence on the color development reaction of TMB, as can be seen from C in FIG. 4, at pH 5, Fe-MIL-88NH2The catalytic activity of (a) is optimal. Fe-MIL-88NH2Full adsorption time of @ MIPs for TDG, Fe-MIL-88NH2Catalysis H2O2The incubation time of the oxidized TMB is particularly critical to the experiment, as can be seen in D in FIG. 4 and E in FIG. 4, Fe-MIL-88NH2The adsorption time plateaued at 30min, indicating that TDG has been completely adsorbed and entered the cavity, Fe-MIL-88NH2Catalysis H2O2The optimal incubation time for oxidation of TMB was 40 min.
3. Linear test to detect TDG
As the TDG concentration increases, the absorbance value at 650nm continues to decrease and the inhibition increases. Under optimized experimental conditions, the inhibition rate and the TDG concentration are between 1ng/mL and 100 mu g/mL (R)20.9855) and the linear equation is log Δ a% ═ 0.16log c +1.12, with a detection limit of 3.79ng/mL (S/N = 3).
4. Selective test for detecting TDG
To further examine the selectivity of this protocol for detecting TDG, a series of TDG analogs were tested, including glutamic acid (Glutamate), Phenylalanine (Phenylalanine), Methionine (Methionine), gamma-Aminobutyric acid (gamma-Aminobutyric acid), Valine (Valine), Proline (Proline). As a result, compared with Thiodiglycol (TDG), the inhibition rate of the analogues is very low (as shown in FIG. 6), which indicates that the colorimetric sensor based on the molecularly imprinted polymer coated metal organic framework has good selectivity for detecting TDG.
5. Test for detecting anti-interference capability of TDG
To further examine the anti-interference ability of this protocol, 100. mu.g/mL of various inorganic ions, saccharides, urea, uric acid, and amino acids were added in the presence of 10. mu.g/mL of TDG. As a result, the influence of the interfering substances on the inhibition rate is small (as shown in FIG. 7), which indicates that the colorimetric sensor based on the metal organic framework wrapped by the molecularly imprinted polymer has extremely strong anti-interference capability in detecting TDG.
In summary, the invention discloses a preparation method of a colorimetric sensor based on a metal organic framework wrapped by a molecularly imprinted polymer, which takes TDG as a template molecule, MAA as a functional monomer, EGDMA as a cross-linking agent and AIBN as an initiator to synthesize a material (Fe-MIL-88 NH) wrapping the metal organic framework2) The molecularly imprinted polymer (Fe-MIL-88 NH) of (1)2@ MIPs). In the preparation method, a template molecule TDG is combined with a functional monomer MAA through a hydrogen bond, then elution is carried out, and binding Sites (MIPs) are left after the template molecule is removed, wherein the binding Sites (MIPs) have a specific recognition function on the TDG. When TDG is contained in the solution, the target TDG is replaced by Fe-MIL-88NH2Specific recognition of MIPs on the surface, thereby blocking active sites, and leading Fe-MIL-88NH2Catalysis H2O2The oxidized TMB is inhibited from being blue, and the TDG can be visually detected by detecting the reduction of the absorbance value. The invention discloses a colorimetric sensor based on a metal organic framework wrapped by a molecularly imprinted polymer, which is Fe-MIL-88NH2@ MIPs) metal organic framework material (Fe-MIL-88 NH)2) As a metal organic framework material, the metal organic framework material has unique performances of high specific surface area, high catalytic efficiency, good thermal stability, good external surface modification property and the like, and has wide application prospects in the field of analysis. The iron-containing metal organic framework material is one of the most important transition metal organic materials, and also shows high catalytic efficiency and super high catalytic efficiency in an aqueous mediumHigh stability and high biocompatibility; and metal organic framework material (Fe-MIL-88 NH)2) Surface MIPs are produced by polymerization, after the template molecule TDG is eluted, a cavity matching TDG is left in the polymer, and these cavities can specifically recognize thiodiglycol, forming a structure similar to a "key and lock" with very high selectivity. When MIPs successfully capture TDG, the TDG occupies the cavity closed cavity, so that the metal-organic framework material (Fe-MIL-88 NH)2) Catalysis H2O2The ability to oxidize TMB is inhibited, the absorbance at 650nm is reduced, and TDG can be detected by calculating the inhibition rate. Colorimetric sensor of the present invention (Fe-MIL-88 NH)2@ MIPs) has great application prospect, good stability, and can be prepared in advance and stored for a long time.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (10)

1. A preparation method of a colorimetric sensor based on a molecularly imprinted polymer-coated metal organic framework is characterized by comprising the following steps:
(1) preparing a metal organic framework material: dissolving 2-amino-p-xylylene and water-soluble ferric salt in DMF, mixing, adding acetic acid, crystallizing in 120 deg.C oil bath, cooling to room temperature, centrifuging to obtain crystal, washing, and oven drying to obtain metal organic framework material Fe-MIL-88NH2；
(2) Preparing a colorimetric sensor: thiodiglycol, methanol, alpha-methacrylic acid and the Fe-MIL-88NH2Adding into ethylene glycol dimethacrylate, ultrasonic mixing, adding azobisisobutyronitrile, stirring and heating in oil bath at 70 deg.C for 24 hr to obtain mixture, pumpingAnd (4) eluting after filtering to remove the thiodiglycol, and drying to obtain the colorimetric sensor.
2. The method according to claim 1, wherein in the step (1), the water-soluble ferric salt is FeCl3·6H2O；
The molar ratio of iron to acetic acid in the 2-amino-p-xylylene and water-soluble ferric iron salt is 0.252: 0.374: 200 mmol, mmol is muL.
3. The method according to claim 1, wherein in the step (1), the solvent used for the washing is N, N-dimethylformamide.
4. The method according to claim 1, wherein in the step (2), the thiodiglycol, methanol, α -methacrylic acid, Fe-MIL-88NH2The mass-volume ratio of the ethylene glycol dimethacrylate to the azobisisobutyronitrile is 3:20:80:0.2:3:200, and the weight-volume ratio of the microgram to the microliter to the gram to the mg.
5. The method for preparing the composite material according to claim 1, wherein in the step (2), the method for eluting to remove the thiodiglycol is specifically as follows: the mixture of methanol and acetic acid was eluted at 115 ℃ to remove thiodiglycol.
6. The method according to claim 5, wherein the volume ratio of methanol to acetic acid in the mixed solution is 9:1.
7. The colorimetric sensor based on the metal organic framework coated by the molecularly imprinted polymer prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the colorimetric sensor based on the molecularly imprinted polymer-coated metal-organic framework of claim 7 for detecting thiodiglycol.
9. A method for detecting thiodiglycol is characterized by comprising the following steps:
adding a thiodiglycol solution to be detected and the colorimetric sensor of claim 7 into ultrapure water, incubating at 37 ℃, adding 3,3',5,5' -tetramethylbenzidine and hydrogen peroxide, further incubating at 37 ℃ to obtain a mixed solution, measuring the absorption spectrum of the mixed solution at 650nm, and passing through a.DELTA.A% (A) (-)T-AC)/ACCalculating to obtain the concentration of the thiodiglycol to be detected;
wherein Δ a% ═ aT-AC)/AC，ACAbsorbance at 650nm for control group, ATThe absorbance of the resulting mixed solution at 650nm was measured.
10. The method for detecting thiodiglycol according to claim 9, wherein the control group is different from the mixed solution in that the thiodiglycol solution to be detected is replaced with the same volume of ultrapure water.
CN202210337727.3A 2022-03-31 2022-03-31 Preparation method of colorimetric sensor based on metal organic framework wrapped by molecularly imprinted polymer, product and application thereof Pending CN114674770A (en)

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