CN111057126A - Preparation method and application of metal-organic framework material - Google Patents
Preparation method and application of metal-organic framework material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/04—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing only normal peptide links
- C07K5/06—Dipeptides
- C07K5/06008—Dipeptides with the first amino acid being neutral
- C07K5/06078—Dipeptides with the first amino acid being neutral and aromatic or cycloaliphatic
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses a preparation method and application of a metal-organic framework material. A metal-organic framework material having the chemical formula Cu (L-Phe-L-Phe)2The structural formula of the L-Phe-L-Phe is shown as a formula (1). The preparation process of the metal-organic framework material provided by the invention is simple, the reaction condition is mild, the safety coefficient is high, a high-boiling-point solvent is not adopted in the whole reaction process, and the preparation process is environment-friendly and green.
Description
Technical Field
The invention relates to the technical field of metal-organic framework materials, in particular to a preparation method and application of a metal-organic framework material.
Background
Methylene blue is a dye compound belonging to thiazine class, which was used for the first time in the treatment of bacillary dysentery and subsequently in some clinical medicine for the treatment of certain diseases, such as malaria, methemoglobinemia, cancer chemotherapy and central nervous system diseases. In addition, methylene blue is used as a disinfectant and a bactericide for aquaculture of aquatic products, treating certain fish diseases and the like. Methylene blue has been shown to have a low redox potential and is characterized by efficient cyclic switching of molecules between oxidized and reduced states. For example, methylene blue molecules have antioxidant effects, are capable of efficient electron transport within mitochondria, and reduce the production of superoxide in mitochondria. In addition, methylene blue has high water solubility and lipid solubility, which leads to high permeability in biological membranes and easier entry into intracellular organelles and the like. Therefore, such substances are used in the fields of industry, medicine, skin care, and the like. However, methylene blue itself contains the triphenylmethane structure, and high concentrations of methylene blue can poison animals and lead to death. At present, the United states food supervision and administration (FDA), European Union 6/23/EC directive and Japanese 'affirmation List' set detection standards for the residual quantity of methylene blue in aquatic products, and no relevant regulation for the residual quantity limit of methylene blue is set in China. In addition, studies on the metabolism of methylene blue in animals are relatively rare, and thus intensive studies on the detection of methylene blue and its metabolism in animals are required. In particular, how to rapidly and sufficiently enrich and separate trace/trace methylene blue molecules from a complex matrix and further use the trace/trace methylene blue molecules for qualitative and quantitative analysis and detection is a problem and a challenge to be solved at present.
The metal organic framework material is a porous polymer material formed by assembling metal ions and organic ligands through coordination bonds. Compared with pure inorganic molecular sieves, the metal organic framework has structural diversity and designability, and framework structures with different shapes, sizes, pore diameters and different rigidity and flexibility degrees can be formed by introducing different metal ions and organic bridging ligands. This feature can play an important role in the adsorption/desorption process.
Disclosure of Invention
The invention provides a preparation method and application of a metal-organic framework material, wherein dipeptide molecules with specific action on methylene blue are used as organic ligands, and the metal-organic framework material capable of effectively and selectively adsorbing the methylene blue is developed through coordination of carboxyl and amino of oligopeptide molecules and copper ions, and is further used for electrochemical detection of the metal-organic framework material.
One object of the present invention is to provide a metal-organic framework material, which is composed of phenylalanine dipeptide and copper ion, and whose chemical formula is Cu (L-Phe-L-Phe)2The structural formula of L-Phe-L-Phe is shown as a formula (1),
L-Phe-L-Phe (FF for short) having a linear formula of C6H5CH2CH(NH2)CONHCH(CH2C6H5)COOH。
Another object of the present invention is to provide a method for preparing the metal-organic framework material, comprising the following steps:
(1) adding phenylalanine dipeptide into an alcohol solution, and uniformly mixing, wherein the solid-to-liquid ratio of the phenylalanine dipeptide to the alcohol solution is 0.01-0.02 g/mL, so as to obtain a mixed solution;
(2) dropwise adding a copper ion solution into the mixed solution obtained in the step (1), and stopping dropwise adding the copper ion solution when the mixed solution is changed from white turbid to a dark blue clear transparent solution;
(3) standing the blue clear transparent solution obtained in the step (2) in a dry environment, reacting for 6-48 hours, cooling to room temperature to obtain a mixed solution with blue blocky crystals separated out, centrifugally separating the mixed solution with the blue blocky crystals, washing and drying precipitates to finally obtain the metal organic framework material.
Preferably, the copper ion solution is a copper acetate solution, and the molar concentration of the copper acetate solution is 0.1-0.2M.
Preferably, the alcohol solution is an ethanol solution, and the volume fraction of ethanol in the ethanol solution is 75-90%.
Preferably, the dark blue clear transparent solution obtained in the step (2) is stood in a drying environment at 80-90 ℃ in the step (3)
Preferably, the step (3) of centrifugally separating the mixture solution of the blue-colored bulk crystals, and washing and drying the precipitate comprises the following specific steps: putting the mixed solution with the blue blocky crystals into a centrifuge tube, and centrifuging by adopting a centrifuge to obtain blue blocky crystal sediment, wherein the rotation speed of the centrifuge is 3000r/min, and the centrifuging time is 3 min; and removing the centrifuged supernatant, adding an alcohol solvent, fully mixing uniformly, performing centrifugal separation again, repeatedly operating for 3-5 times until the centrifuged supernatant is clear, and drying the sapphire blocky crystal precipitate in an oven at the temperature of 60 ℃ for 6 hours.
The invention also provides application of the metal-organic framework material modified electrode in methylene blue detection. The metal-organic framework material is used for selective adsorption separation of methylene blue dye in a complex mixed solution matrix.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the metal-organic framework material provided by the invention is simple, the reaction condition is mild, the safety coefficient is high, a high-boiling-point solvent is not adopted in the whole reaction process, and the preparation process is environment-friendly and green;
(2) the dipeptide L-phenylalanine-L-phenylalanine is used as an organic ligand, and the selectivity of the material to methylene blue is improved by utilizing the interaction of biomolecules to the methylene blue;
(3) the electrode modified by the material can be used for specific electrochemical detection of methylene blue.
Drawings
FIG. 1 shows the phenylalanine dipeptide Phe-Phe and the product Cu (FF) in the form of a blue lump crystal according to example 1 of the present invention2XRD spectrum of (1);
FIG. 2 shows the phenylalanine dipeptide Phe-Phe and the product Cu (FF) in the form of blue lump crystal according to example 1 of the present invention2FTIR spectra of;
FIG. 3 is an XPS spectrum of the phenylalanine dipeptide, copper acetate monohydrate and a dark blue product of example 1 of the present invention;
FIG. 4 is a Cu element XPS spectrum of example 1 of the present invention, wherein a is a Cu element XPS spectrum of copper acetate monohydrate, and b is a Cu element XPS spectrum of a blue-colored bulk crystal material;
FIG. 5 is a C element XPS spectrum of example 1 of the present invention, wherein a is the C element XPS spectrum of phenylalanine dipeptide and b is the C element XPS spectrum of a blue-colored bulk crystal material;
FIG. 6 is an N-element XPS spectrum of example 1 wherein a is an N-element XPS spectrum of phenylalanine dipeptide and b is an N-element XPS spectrum of a blue-colored bulk crystal material;
FIG. 7 is an O element XPS spectrum of example 1 of the present invention, wherein a is the O element XPS spectrum of phenylalanine dipeptide and b is the O element XPS spectrum of a dark blue bulk crystal material;
FIG. 8 is an SEM topography at different scales for a blue bulk crystalline material in example 1 of the present invention;
FIG. 9 is an SEM topography at different scales for the sapphire bulk crystalline material in comparative example 1;
FIG. 10 shows a bare glassy carbon electrode, a glassy carbon electrode modified with a Nafion film, and Nafion/Cu (FF) in example 2 of the present invention2A CV cycle curve diagram of the glassy carbon electrode modified by the mixed membrane after the glassy carbon electrode is stabilized in a 0.1M KCl solution;
FIG. 11 shows Nafion/Cu (FF) in example 2 of the present invention2A CV curve change diagram of the glassy carbon electrode modified by the mixed membrane along with the increase of the methylene blue concentration;
FIG. 12 shows Nafion/Cu (FF) in example 2 of the present invention2Mixed film modified glassy carbon electrode with increasing tetracycline concentrationA CV curve variation graph;
FIG. 13 shows Nafion/Cu (FF) in example 2 of the present invention2A CV curve change diagram of the glassy carbon electrode modified by the mixed membrane along with the rise of the concentration of the bisphenol A;
FIG. 14 shows Nafion/Cu (FF) in example 2 of the present invention2A CV curve change diagram of the mixed membrane modified glassy carbon electrode along with the increase of the concentration of the 2' -bromobiphenyl ether;
FIG. 15 shows Nafion/Cu (FF) in example 2 of the present invention2And (3) a CV curve change diagram of the mixed membrane modified glassy carbon electrode along with the increase of the bromophenol blue concentration.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The raw materials and equipment used in the following examples:
the dipeptide L-Phe-L-Phe was obtained from Shanghai intense Biotech, Inc., copper acetate monohydrate (98%, 500g), absolute ethanol (AR) was obtained from Shanghai national pharmaceutical Chemicals, Inc. The powder X-ray diffraction spectrum is collected by a Rigaku Japan Utima IV full-automatic multifunctional X-ray diffractometer; the Fourier infrared spectrum is collected by a Bruker Vertex 80v type vacuum infrared spectrometer; the X-ray photoelectron spectrum is collected by an ESCALB 250Xi type X-ray photoelectron spectrometer; the scanning electron microscope image is collected by a Hitachi S-3700N scanning electron microscope; the electrochemical detection experiment was collected by Shanghai Chenghua electrochemical workstation CHI 660E.
Example 1
The metal-organic framework material is prepared by the following steps:
(1) adding 0.312g of phenylalanine dipeptide (L-Phe-L-Phe) into 20mL of ethanol solution, wherein the volume fraction of ethanol in the ethanol solution is 80%, and putting the mixed solution into an ultrasonic device for ultrasonic treatment for 5min to fully and uniformly disperse the mixed solution to obtain milky turbid mixed solution;
(2) placing the obtained mixed solution into a 30mL glass screw sample bottle, dropwise adding about 2.5mL of 0.2M copper acetate aqueous solution into the milky turbid solution, and stopping dropwise adding the copper acetate solution when the white turbid solution is completely changed into a bluish clear transparent solution;
(3) standing the obtained blue clear transparent solution in an oven at 85 ℃, reacting for 10 hours, and cooling to room temperature to obtain a mixed solution with blue blocky crystals separated out; and centrifuging the obtained mixed solution with the blue blocky crystals, cleaning by using an ethanol solution, centrifuging for 3 times, and placing in a 60-DEG C oven for heat preservation for 6 hours to obtain the dried blue blocky crystals, namely the metal-organic framework material. The obtained metal-organic framework material needs to be packaged and stored in a refrigerator at 4 ℃.
Wherein the obtained blue-colored bulk crystal has a chemical formula of Cu (L-Phe-L-Phe)2The product weighed about 0.186g, in which: L-Phe-L-Phe is L-phenylalanine-L-phenylalanine with linear molecular formula of C6H5CH2CH(NH2)CONHCH(CH2C6H5) An organic ligand of COOH, the structural formula of which is as follows:
chemical composition analysis of the product: the PXRD pattern of the obtained dark blue bulk crystal material and the PXRD pattern of the raw material L-Phe-L-Phe dipeptide are compared as shown in FIG. 1. Compared with the PXRD atlas contrast of the raw material dipeptide L-Phe-L-Phe, the dipeptide is known to be used as an organic ligand molecule to be complexed with copper ions to generate a new product, and the reaction product has a better crystal form. The infrared spectra of phenylalanine dipeptide and the reaction product, a blue-colored bulk crystal material, are shown in FIG. 2, comparing the peaks of the carboxyl hydroxyl group and amino group of the dipeptide (3500 to 3100 cm)-1) And C ═ O double bonds of amide bonds (1685 cm)-1) The obvious change is generated, which indicates that the carbon-oxygen double bond in the carboxyl group and the amido bond of the dipeptide is complexed with the copper ion through a coordination bond.
Fig. 3 shows XPS spectra of phenylalanine dipeptide, copper acetate monohydrate, and a sapphire bulk crystal product, respectively, and it can be found that N and Cu elements appear in the product, and the peak intensity of C element is significantly increased. The content ratios of the elements obtained by XPS analysis are shown in Table 1, and compared with the relative atomic content ratio changes of C, N, O and Cu contained in the three samples, the complexation between copper ions and dipeptide is further verified, and a new product is formed.
FIG. 4 compares the XPS spectra of the Cu element of the raw material copper acetate monohydrate (FIG. 4a) and the material of the blue-colored bulk crystal (FIG. 4b), and shows that the binding energy of Cu2p of the reaction product is hardly changed significantly, and the valence and chemical environment before and after the reaction are not changed. The relative atomic content ratios obtained by XPS in FIG. 4 for the phenylalanine dipeptide, copper acetate monohydrate, and the product of the royal blue crystal are shown in Table 1, for example.
TABLE 1
Similarly, the binding energy of phenylalanine dipeptide and C1s of the reaction product was also not significantly altered (FIG. 5). The product is subjected to coordination complexation by dipeptide and copper ion, so that the peak positions of nitrogen ion and oxygen ion of the product and the dipeptide are compared, and the result shows that the ion peak binding energy of the two elements is obviously changed, and N1s is changed from the peaks at 398.68eV and 397.38eV (figure 6a) to 397.68eV and 395.88eV (figure 6b), which indicates that the amino-NH of the dipeptide is2The coordination with copper ions causes charge transfer, the electron density of N1s is increased, and the binding energy of N1s is reduced, and the coordination between C ═ O and copper ions causes the electron density of O1s to be reduced, and the binding energy of O1s is increased, while the displacement of O1s from 528.98eV (fig. 7a) to 529.28eV (fig. 7 b). XPS spectrum analysis shows that the amino group and the carboxyl group of dipeptide are coordinated with copper ions. According to elemental analysis, the blue product has C (37.47%), N (3.25%), H (4.09%), O (21.4%), and the molecular ratio of Cu element to FF dipeptide was 1: 2.
and (3) analyzing the appearance of the product: as shown in fig. 8, the morphology of the resulting purplish blue bulk crystalline product existed predominantly as fibers with very little square-shaped product. The diameter of the fiber is mainly between 0.1 and 0.3 μm, and the length is different; the diameter of the block product is mainly above 2 μm.
Example 2
The same as example 1, except that:
the solid-to-liquid ratio of the phenylalanine dipeptide and the ethanol solution in the step (1) is 0.01g/mL, the volume fraction of the ethanol in the ethanol solution is 90%, the molar concentration of the copper acetate solution in the step (2) is 0.1M, and the dark blue clear transparent solution in the step (3) is stood in an oven at 85 ℃ for reaction for 6 hours.
Example 3
The same as example 1, except that:
the solid-to-liquid ratio of the phenylalanine dipeptide and the ethanol solution in the step (1) is 0.02g/mL, the volume fraction of ethanol in the ethanol solution is 75%, the molar concentration of the copper acetate solution in the step (2) is 0.2M, and the dark blue clear transparent solution in the step (3) is stood in an oven at 85 ℃ for reaction for 48 hours.
Comparative example 1
To further illustrate the effect of the preparation conditions on the material properties, the effect of the reaction duration on the morphology of the material was studied as an example. The same as in example 1 except that the reaction time was 48 hours.
0.312g of phenylalanine dipeptide (L-Phe-L-Phe) was added to 20mL of an ethanol solution, and the mixture was put into an ultrasonic device and subjected to ultrasonic treatment for 5min to sufficiently disperse the mixture uniformly, thereby obtaining a milky turbid solution. The obtained mixed solution is placed in a 30mL glass screw sample bottle, about 2.5mL of 0.2M copper acetate aqueous solution is dropwise added into the milky turbid solution, and the dropwise addition of the copper acetate solution is stopped when the white turbid solution is completely changed into a bluish clear transparent solution. Standing the obtained blue clear transparent solution in an oven at 85 ℃, reacting for 48 hours, and cooling to room temperature to obtain a mixed solution with blue blocky crystals separated out; and centrifuging the obtained mixed solution with the blue blocky crystals, cleaning by using an ethanol solution, centrifuging for 3 times, and placing in a 60-DEG C oven for heat preservation for 6 hours to obtain the dried blue blocky crystals, namely the metal-organic framework material. The obtained metal-organic framework material needs to be packaged and stored in a refrigerator at 4 ℃.
Compared with example 1, the influence of the reaction time on the morphology of the product was mainly investigated. The obtained morphology of the sapphire blue crystal material is shown in fig. 9, and compared with fig. 8, it can be known that the morphology of the product can be effectively influenced by changing the parameters of the reaction conditions, so as to obtain a honeycomb-shaped ellipsoidal material, and it can be obviously observed that the honeycomb sphere is formed by assembling and intertwining a plurality of fibrous materials. Wherein the diameter of the fibers participating in the assembly is about 0.2-1 μm.
According to elemental analysis, the blue product has C (38.03%), N (3.27%), H (4.35%), O (22.98%), and the molecular ratio of Cu element to FF dipeptide was 1: 2. the result shows that the reaction time is prolonged, the morphology of the product is only changed, and the molecular composition of the product is not obviously influenced.
Comparative example 2
To further investigate the effect of the volume fraction of ethanol in the ethanol-water mixed solution on the yield during the reaction, the effect of the volume fraction of ethanol on the yield of the product was compared at about 75% and 90%, respectively.
Two portions of 0.312g phenylalanine dipeptide (L-Phe-L-Phe) are respectively weighed and added into 16.85mL ethanol solution (the volume fraction of ethanol in the ethanol solution is about 75%) and 20.25mL ethanol solution (the volume fraction of ethanol in the ethanol solution is about 90%), and the mixed solution is put into an ultrasonic device for ultrasonic treatment for 5min to be fully dispersed uniformly, so that milky turbid solution is obtained. The obtained mixed solution was placed in 30mL of glass screw sample bottle A and sample bottle B, and about 5.5mL of 0.1M aqueous solution of copper acetate and 2.5mL of 0.2M aqueous solution of copper acetate were added dropwise to the milky turbid solutions in bottle A and bottle B, respectively. Standing the obtained blue clear transparent solution in an oven at 85 ℃, reacting for 6 hours, and cooling to room temperature to obtain a mixed solution with blue blocky crystals separated out; and centrifuging the obtained mixed solution with the blue blocky crystals, cleaning by using an ethanol solution, centrifuging for 3 times, placing in a 60-DEG C oven, preserving the temperature for 6 hours to obtain dried blue blocky crystals, namely the metal-organic framework material, and weighing. Under the above two ethanol volume fractions, the mass of the metal-organic framework material obtained under the condition of sample bottle A was 0.087g, and the mass of the product obtained under the condition of sample bottle B was 0.102 g.
The above experimental results show that the volume fraction of ethanol affects the yield of the product.
Example 4
The electrode modified by the blue-colored crystal product prepared in the embodiment 1 is used for detecting different types of aromatic ring organic pollutant models by cyclic voltammetry by adopting an electrochemical analysis station, and the influence of the concentration of the organic pollutant on an electrochemical signal is judged by observing and comparing the characteristics and changes of CV curves. Methylene blue, bromophenol blue, 2' -bromobiphenyl ether, bisphenol A and tetracycline are adopted as organic pollutant molecular models.
Preparing an electrode: in the embodiment, a three-electrode system is adopted, wherein a glassy carbon electrode with the diameter of 3mm is used as a working electrode, a platinum wire electrode is used as an auxiliary electrode, and an Ag/AgCl electrode is used as a reference electrode. The glassy carbon electrode is firstly polished to a mirror surface by using W0.3 mu M aluminum oxide polishing powder, then surface dirt is washed off by using ultrapure water and ethanol, the electrode is dried, and then the electrode is activated in a sulfuric acid solution with the concentration of 0.5-1.0M. 5mg of the blue crystal product obtained in the example 1 is dissolved in 100 mu L of Nafion ethanol solution (mass fraction is 0.5 percent), and the mixture is fully and uniformly dispersed by ultrasonic treatment for 5-15 min. And dripping 10 mu L of a blue crystal product/Nafion mixed solution on the surface of a glassy carbon electrode, and measuring a CV curve of the modified electrode to different types of organic pollutant molecules between-0.4V and 0.8V along with the change of the analyte concentration after drying.
Cyclic voltammetry CV curves: fig. 10 shows CV curves of a bare glassy carbon electrode, a glassy carbon electrode modified by a Nafion membrane, and a product/glassy carbon electrode modified by a Nafion membrane after stabilization by cyclic voltammetry in an aqueous solution of 0.1M KCl. From the figure, the above three electrodes show different characteristic CV curves in 0.1M KCl solution, and the product/Nafion film is successfully modified to the surface of the glassy carbon electrode and shows different interface properties. The electrode was inserted into 10mL of KCl solution, CV curves of organic molecule solutions at different concentrations were measured, 5 μ L of the sample to be measured was added after each measurement, and the CV curves were measured after waiting for 30 seconds. FIG. 11 shows the product/Nafion membrane modified glassy carbon electrodes at different concentrationsCV curves in the methylene blue solution, measured as methylene blue at a concentration of 5mM was added to the KCl solution, gradually disappeared the peak near-0.04V and formed a new peak near-0.29V, respectively. Fig. 12 is a graph showing the variation of CV curves of the glassy carbon electrode modified by the product/Nafion membrane in tetracycline solutions with different concentrations, and as the concentration of tetracycline in the electrolyte increases, the peak of the CV curve near 0.025V gradually disappears, and no new peak is generated. In order to show the selectivity of the material to methylene blue, three molecules of bisphenol A, 2' -bromobiphenyl ether and bromophenol blue are additionally adopted as reference comparisons. FIGS. 13 to 15 are CV-concentration change curves of 10mM bisphenol A, 5mM 2' -bromobiphenyl ether and 2mM bromophenol blue which are sequentially added dropwise into the electrolyte of the modified electrode, respectively, and experimental results show that no obvious relationship is generated along with the concentration change. The CV-analyte concentration change diagram shows that the modified electrode has the capability of selectively identifying methylene blue, the CV curve characteristic change is obvious, the modified electrode can be used as an identification means, the aim of analyzing whether the methylene blue exists or not can be achieved through the change of the CV curve characteristic peak value, and the lowest limit value of the detection range is 5 multiplied by 10-4mM。
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. A metal-organic framework material, characterized in that the chemical formula of the metal-organic framework material is Cu (L-Phe-L-Phe)2The structural formula of L-Phe-L-Phe is shown as a formula (1),
2. the method of preparing a metal-organic framework material according to claim 1, comprising the steps of:
(1) adding phenylalanine dipeptide into an alcohol solution, and uniformly mixing, wherein the solid-to-liquid ratio of the phenylalanine dipeptide to the alcohol solution is 0.01-0.02 g/mL, so as to obtain a mixed solution;
(2) dropwise adding a copper ion solution into the mixed solution obtained in the step (1), and stopping dropwise adding the copper ion solution when the mixed solution is changed from white turbid to a dark blue clear transparent solution;
(3) standing the blue clear transparent solution obtained in the step (2) in a dry environment, reacting for 6-48 hours, cooling to room temperature to obtain a mixed solution with blue blocky crystals separated out, centrifugally separating the mixed solution with the blue blocky crystals, washing and drying precipitates to finally obtain the metal organic framework material.
3. The method for preparing a metal-organic framework material according to claim 2, wherein the copper ion solution is a copper acetate solution, and the molar concentration of the copper acetate solution is 0.1-0.2M.
4. The method for preparing a metal-organic framework material according to claim 2, wherein the alcohol solution is an ethanol solution, and the volume fraction of ethanol in the ethanol solution is 75-90%.
5. The method for preparing a metal-organic framework material according to claim 2, wherein the step (3) is to leave the dark blue clear transparent solution obtained in the step (2) standing in a dry environment at 80-90 ℃.
6. The method for preparing a metal-organic framework material according to claim 2, wherein the step (3) of centrifuging the mixture solution of the blue-colored bulk crystals, washing the precipitate and drying comprises the following specific steps: putting the mixed solution with the blue blocky crystals into a centrifuge tube, and centrifuging by adopting a centrifuge to obtain blue blocky crystal sediment, wherein the rotation speed of the centrifuge is 3000r/min, and the centrifuging time is 3 min; and removing the centrifuged supernatant, adding an alcohol solvent, fully mixing uniformly, performing centrifugal separation again, repeatedly operating for 3-5 times until the centrifuged supernatant is clear, and drying the sapphire blocky crystal precipitate in an oven at the temperature of 60 ℃ for 6 hours.
7. Use of the metal-organic framework material modified electrode of claim 1 in methylene blue detection.
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| CN114470150A (en) * | 2021-12-13 | 2022-05-13 | 完美（广东）日用品有限公司 | Application of chicken-derived small molecular peptide in preparation of product for preventing and improving liver injury and secondary symptoms of liver injury and product |
| CN114470150B (en) * | 2021-12-13 | 2022-12-27 | 完美（广东）日用品有限公司 | Application of chicken-derived small molecular peptide in preparation of product for preventing and improving liver injury and secondary symptoms thereof and product |
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