CN104087572A - Protein and metal organic skeleton compound composite material and preparation method thereof - Google Patents
Protein and metal organic skeleton compound composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a protein and metal organic skeleton compound composite material and a preparation method thereof. The preparation method of the protein and metal organic skeleton compound composite material comprises the step of carrying out reaction on protein, zinc ions and an organic ligand in a solvent, so that the protein and metal organic skeleton compound composite material is obtained, wherein the organic ligand is any one of 2-methylimidazole, benzimidazole and imidazole. The preparation method of the protein and metal organic skeleton compound composite material is simple in operation and mild in conditions, the obtained protein and metal organic skeleton compound composite material product is high in protein embedding rate, and the required drugs are easily available; the biological composite material, namely the protein and metal organic skeleton compound composite material, has the advantages of high porosity, large specific surface area, good stability, good catalytic activity and the like; after protein is compounded with a metal organic skeleton material, the stability of the protein is improved, and the catalytic activity of the protein is improved or maintained in a greater degree.
Description
Technical field
The present invention relates to a kind of protein and metallic organic framework compound composite material and preparation method thereof, belong to hybrid inorganic-organic materials preparing technical field.
Background technology
Metallic organic framework compound (Metal-Organic Frameworks is called for short MOFs) refers to the novel porous nano crystal material with periodic network structure that metal ion and organic ligand form by self-assembly.As the cross products in inorganic materials and coordination chemistry field, this compound has the crystalline structure close with molecular sieve, has the multiple character such as optical, electrical, catalysis simultaneously.Metal-organic framework materials relies on that the porous, specific surface area of self is large, Heat stability is good, the synthetic advantage such as convenient, has been subject to extensive concern in the field such as gas adsorption and chemical catalysis.In the past twenty years year, metallic organic framework compound develops with surprising rapidity, and people have synthesized a large amount of these compounds.The part of constructing this structure has also been extended to even mixed ligand of carboxylic acid, phosphoric acid, sulfonic acid from initial nitrogen ligand.And be also extended to high valence state transition metal ion, rare earth element, alkalies and alkaline earth from common lower valency transition metal with the metal ion of its coordination.From being synthesized out for the first time so far, there are every year about tens kinds of novel MOFs materials to be synthesized out.At present, in chemical catalysis field, the action mode of metal-organic framework materials mainly contains: 1) utilize the metal ion in self-framework to carry out catalysis; 2) utilize porousness to form functionalization structure and carry out catalysis; 3) utilize self nano level cavity to carry out catalysis.In addition, metallic organic framework compound can be used as carrier and has for embedding the material of catalytic activity, as heteropolyacid, metalloporphyrin, metallic nano-particle.
Hybrid inorganic-organic materials, by mix organic molecule practical function in inorganic network, has many high-performances at aspects such as optics, calorifics, electromagnetism and biology.And protein relies on self abundant physiological function, become in recent years the study hotspot in hybrid inorganic-organic materials field, all there is very large application prospect at the aspect such as biocatalysis, life science.Therefore, the hybridization compounding thing of protein molecular and metallic organic framework structure has very high researching value, and the preparation method who finds a kind of albumen-metallic organic framework compound composite material of simple and effective will have very important significance.
Summary of the invention
The object of this invention is to provide a kind of protein and metallic organic framework compound composite material and preparation method thereof, the feature such as that the method has is simple to operate, mild condition, good stability, high, the required medicine of albumen embedding rate are easy to get.
The preparation method of the matrix material of a kind of protein provided by the invention and metallic organic framework compound, comprises the steps:
Protein, zine ion and organic ligand react in solvent, obtain described matrix material;
Described organic ligand be in glyoxal ethyline, benzoglyoxaline and imidazoles any.
In above-mentioned preparation method, the molecular weight of described protein can be 5～300kDa.
In above-mentioned preparation method, described protein can be in cytochrome C, Cytochrome P450, horseradish peroxidase, ethanol dehydrogenase, lipase, acetylcholinesterase, laccase, green fluorescent protein, glucose oxidase, trypsinase, subtilisin, carbonic anhydrase, ethanol dehydrogenase, sucrase, superoxide-dismutase and catalase any.
Above-mentioned preparation method, the mass ratio of described protein and described zine ion can be 0.00001～1:1, specifically can be 0.015～0.06:1,0.015～0.05:1,0.025～0.03:1,0.025～0.06:1,0.015:1,0.025:1,0.03:1,0.05:1 or 0.06:1;
The mol ratio of described zine ion and described organic ligand can be 1:0.1～100, specifically can be 1:1～70,1:1 or 1:70.
In above-mentioned preparation method, described zine ion comes from soluble zinc salt, specifically can be nitric hydrate zinc;
Described solvent can be in water, methyl alcohol, dimethyl formamide, ethanol, dimethyl sulfoxide (DMSO), acetonitrile and acetone any.
In above-mentioned preparation method, the temperature of described reaction can be-10～50 DEG C, specifically can be-4～25 DEG C, 25～35 DEG C 25 DEG C, 35 DEG C ,-4 DEG C; Reaction times can be 0.05～72 hour, specifically can be 2～24 hours, 2 hours or 24 hours.
In above-mentioned preparation method, before described reaction, can carry out respectively supersound process to zine ion solution and organic ligand solution;
Described ultrasonic time can be 0～60 minute, but does not comprise zero, specifically can be 10 minutes;
Described zine ion solution is dissolved in described solvent and is obtained by described zine ion;
Described organic ligand solution is dissolved in described solvent and is obtained by described organic ligand.
In above-mentioned preparation method, before described reaction, described method also comprises to the step that adds tensio-active agent in protein soln;
Described tensio-active agent can be in polyvinylpyrrolidone and pluronic any;
The molecular weight of described polyvinylpyrrolidone is 2,000～3,000,000, specifically can be 10000;
In described protein soln, the concentration of described tensio-active agent can be 0.1～100mg/mL, specifically can be 7.5～15mg/mL, 7.5mg/mL or 15mg/mL;
The mass ratio of described tensio-active agent and described protein can be 0～100:1, but the quality of tensio-active agent is non-vanishing, specifically can be 0.03～0.75:1,0.075～0.3:1,0.15～0.5:1,0.03:1,0.075:1,0.15:1,0.3:1,0.5:1 or 0.75:1.
In above-mentioned preparation method, described protein and metallic organic framework compound composite material can obtain after dry air or vacuum-drying, specifically can be 6 hours described time of drying or 48 hours.
The prepared protein of above-mentioned preparation method and metallic organic framework compound composite material are the present invention further provides.
Protein provided by the invention and metallic organic framework compound composite material can be used for detecting hydrogen peroxide, methylethyl ketone peroxide or tertbutyl peroxide.
The present invention has the following advantages:
The preparation method of protein of the present invention and metallic organic framework compound composite material is simple to operate, mild condition, high, the required medicine of products obtained therefrom albumen embedding rate are easy to get; The advantages such as the Biocomposite material making by the present invention has that porosity is high, specific surface area is large, good stability, catalytic activity are good; After albumen and metal-organic framework materials are compound, protein stability improves, catalytic activity improves or retained largely.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 1.
Fig. 2 is the transmission electron microscope picture of the prepared matrix material of embodiment 1.
Fig. 3 is the transmission electron microscope picture of the prepared matrix material of embodiment 2.
Fig. 4 is the transmission electron microscope picture of the prepared matrix material of embodiment 5.
Fig. 5 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 5.
Fig. 6 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 7.
Fig. 7 is the laser co-focusing shooting figure of the prepared matrix material of embodiment 7.
Fig. 8 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 10.
Fig. 9 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 11.
Figure 10 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 12.
Figure 11 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 18.
Figure 12 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 19.
Figure 13 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 20.
Figure 14 is the scanning electron microscope (SEM) photograph of the prepared matrix material of embodiment 21.
Figure 15 is the X ray diffracting data figure of the prepared matrix material of embodiment 1 and ZIF-8 crystal.
Figure 16 is Fourier's infrared analysis data plot of the prepared matrix material of ZIF-8 crystal, embodiment 1 and cytochrome C.
Figure 17 is the fluorescence spectrum figure of the prepared cytochrome C/ZIF-8 matrix material of embodiment 1 and cytopigment.
Figure 18 is the thermogravimetric curve of the prepared cytochrome C/ZIF-8 matrix material of embodiment 1 and ZIF-8 crystal.
Figure 19 is that the enzyme of the prepared matrix material of embodiment 1 is lived and comparison diagram.
Figure 20 is the enzyme kinetics curve of the prepared matrix material of embodiment 1.
Figure 21 is the detection curve of the prepared matrix material of embodiment 1 to hydrogen peroxide.
Figure 22 is the detection curve of the prepared matrix material of embodiment 1 to methylethyl ketone peroxide (MEKP).
Figure 23 is the detection curve of the prepared matrix material of embodiment 1 to tertbutyl peroxide (TBHP).
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
In following embodiment, in gained matrix material, albumen embedding rate can obtain by following formula:
Total protein concentration × 100% adding in protein content/system in embedding rate=matrix material.
In following embodiment, protein content is to obtain by thermogravimetric analysis data, the first paragraph of matrix material thermogravimetric curve drops to albumen (or albumen and pluronic) and decomposes generation, calculates the content of albumen in matrix material according to the shared proportion of this Quality Down section.
Synthesizing of the matrix material of embodiment 1, protein and metallic organic framework compound
1, preparation is containing the aqueous solution of cytochrome C 50mg/mL, polyvinylpyrrolidone (PVP, molecular weight is 10,000) 15mg/mL.
The aqueous solution of the nitric hydrate zinc that 2, compound concentration is 25mmol/L respectively, the methanol solution of the glyoxal ethyline that concentration is 25mmol/L, carries out respectively supersound process 10 minutes to gained solution.
3, get the solution 50 μ L of step 1 gained and mix with zine ion solution, the each 50mL of glyoxal ethyline solution in step 2, at 25 DEG C, leave standstill 24 hours.
4, step 3 products therefrom is gone out by centrifugation, with methyl alcohol repeated washing 3 times, the product after washing is placed at 25 DEG C to air drying 6 hours, obtain albumen embedding rate 82% in product.
Respectively as depicted in figs. 1 and 2, from Fig. 1 and Fig. 2, the body shape of gained matrix material is rhombus regular dodecahedron for the stereoscan photograph of matrix material prepared by the present embodiment and transmission electron microscope photo, and grain diameter is between the μ m of 100nm～1.
As shown in figure 15, as shown in Figure 15, matrix material has retained the crystal face in metallic organic framework compound (ZIF-8) to the X-ray diffractogram of matrix material prepared by the present embodiment.
Fourier's infrared analysis of matrix material prepared by the present embodiment as shown in figure 16, as shown in Figure 16, infrared peak, matrix material fingerprint region and metallic organic framework compound (ZIF-8) are similar, consistent with the amido linkage peak position in albumen at the infrared peak at 1664cm-1 place.
As shown in figure 17, as shown in Figure 17, before and after Guanidinium hydrochloride is processed, the photoluminescent property of matrix material is consistent with natural enzyme in the fluorescent spectroscopy of matrix material prepared by the present embodiment.
Cytochrome C/ZIF-8 matrix material prepared by the present embodiment and the thermogravimetric analysis of ZIF-8 crystal are as shown in figure 18, as shown in Figure 18, matrix material starts 250 DEG C of left and right to decompose, and 250～350 DEG C occur that first paragraph declines, and the decomposition temperature of ZIF-8 crystal is 450 DEG C of left and right.
The enzyme of matrix material prepared by the present embodiment is lived as shown in figure 19, as shown in Figure 19, in matrix material, the enzyme work of cytochrome C exceeds 10 times of left and right than natural enzyme, PVP in preparation system and zine ion are lived and are had respectively 79% and 57% raising cytochrome C enzyme, and glyoxal ethyline, ZIF-8 etc. all have no significant effect catalytic activity.
The mensuration that above-mentioned cytochrome C enzyme is lived specifically joins nitrogen-bis-(3-ethyl-benzothiazole-6-sulfonic acid) di-ammonium salts (ABTS) as substrate taking hydrogen peroxide and 22-.8 μ M cytochrome C, 2mM hydrogen peroxide and 532 μ M ABTS are added in 1mL phosphate buffer solution (50mM, pH7.0), measure the ultraviolet absorptivity at 415nm place, live according to the change calculations enzyme of ultraviolet absorptivity.Cytochrome C is replaced with respectively to the matrix material prepared in above-described embodiment, is added with the cytochrome C of PVP or is added with the cytochrome C of zine ion, other operation is consistent, the enzyme work of measuring taking cytochrome C is as 100%, and the relative enzyme that calculates respectively matrix material, is added with the cytochrome C of PVP or is added with the cytochrome C of zine ion is lived.
The enzyme kinetics curve of matrix material prepared by the present embodiment as shown in figure 20, as shown in Figure 20, the V of cytochrome C in matrix material
maxraise and K
mreduce.
Matrix material prepared by the present embodiment detects as shown in figure 21 hydrogen peroxide, as shown in Figure 21, taking cytochrome C/ZIF-8 matrix material during as catalyzer, to concentration at 5nM to the hydrogen peroxide liquid to be measured between 1 μ M, concentration of hydrogen peroxide and fluorescence intensity have good linear relationship.While selecting natural fine Cytochrome C to make catalyzer, cannot effectively detect hydrogen peroxide.
Matrix material prepared by the present embodiment detects as shown in figure 22 methylethyl ketone peroxide, as shown in Figure 22, taking cytochrome C/ZIF-8 matrix material during as catalyzer, to concentration at 100nM to the methylethyl ketone peroxide liquid to be measured between 1 μ M, methylethyl ketone peroxide concentration and fluorescence intensity have good linear relationship.While selecting natural fine Cytochrome C to make catalyzer, cannot effectively detect methylethyl ketone peroxide.
Matrix material prepared by the present embodiment detects as shown in figure 23 tertbutyl peroxide, as shown in Figure 23, taking cytochrome C/ZIF-8 matrix material during as catalyzer, to concentration at 2 μ M to the tertbutyl peroxide liquid to be measured between 20 μ M, tertbutyl peroxide concentration and fluorescence intensity have good linear relationship.While selecting natural fine Cytochrome C to make catalyzer, cannot effectively detect tertbutyl peroxide.
Synthesizing of embodiment 2-7, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, difference is, cytochrome C is replaced with successively to horseradish peroxidase, ethanol dehydrogenase, dredges the thermophilic hyphomycete lipase of cotton shape, acetylcholinesterase, laccase and green fluorescent protein, obtain albumen embedding rate in product and be all greater than 70%.
The transmission electron microscope picture of the matrix material of compound horseradish peroxidase as shown in Figure 3.
As shown in Figure 4, scanning electron microscope (SEM) photograph as shown in Figure 5 for the transmission electron microscope picture of the matrix material of compound acetylcholinesterase.
As shown in Figure 6, laser co-focusing is taken figure as shown in Figure 7 to the scanning electron microscope (SEM) photograph of the matrix material of composite green fluorescin.
Can be learnt by above-mentioned each figure, the composite body shape that embodiment 2-7 prepares is rhombus regular dodecahedron.As seen from Figure 7 embedding the matrix material shows green fluorescence of green fluorescent protein.
Synthesizing of embodiment 8-9, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, the temperature of reaction of step 3 is replaced with respectively to-4 DEG C and 35 DEG C by 25 DEG C, obtains albumen embedding rate in product and is all greater than 80%.
Synthesizing of embodiment 10, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, the protein concentration of step 1 is replaced with to 100mg/mL, obtains albumen embedding rate approximately 78% in product.
As shown in Figure 8, as shown in Figure 8, surface imperfection degree increases the stereoscan photograph of matrix material prepared by the present embodiment compared with the matrix material that the matrix material that the present embodiment prepares makes with embodiment 1.
Synthesizing of embodiment 11, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, the polyvinylpyrrolidone concentration of step 1 is replaced with to 7.5mg/mL, obtains albumen embedding rate approximately 75% in product.
As shown in Figure 9, as shown in Figure 9, surface imperfection degree increases the stereoscan photograph of matrix material prepared by the present embodiment compared with the matrix material that the matrix material that the present embodiment prepares makes with embodiment 1.
Synthesizing of embodiment 12, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, the protein concentration of step 1 is replaced with to 100mg/mL, and the polyvinylpyrrolidone concentration of step 1 is replaced with to 7.5mg/mL, obtains albumen embedding rate approximately 67% in product.
As shown in figure 10, as shown in Figure 10, surface imperfection degree increases the stereoscan photograph of matrix material prepared by the present embodiment compared with the matrix material that the matrix material that the present embodiment prepares makes with embodiment 1.
Synthesizing of embodiment 13, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, nitric hydrate zinc solution and glyoxal ethyline strength of solution replace with 50mmol/L, obtain albumen embedding rate approximately 84% in product.
Synthesizing of embodiment 14, protein and metallic organic framework compound composite material
Operation steps is with embodiment 1, and difference is, glyoxal ethyline is replaced with to benzoglyoxaline, obtains albumen embedding rate approximately 80% in product.
Synthesizing of embodiment 15, protein and metallic organic framework compound composite material
Operation steps is with embodiment 14, and difference is, cytochrome C is replaced with and dredges the thermophilic hyphomycete lipase of cotton shape, obtains albumen embedding rate approximately 78% in product.
Synthesizing of embodiment 16, protein and metallic organic framework compound composite material
Operation steps is with embodiment 14, and difference is, methyl alcohol is replaced with to DMF, obtains albumen embedding rate approximately 73% in product.
Synthesizing of embodiment 17, protein and metallic organic framework compound composite material
Operation steps is with embodiment 14, and difference is, nitric hydrate zinc solution and glyoxal ethyline strength of solution are replaced with to 30mmol/L by 25mmol/L, obtains albumen embedding rate approximately 82% in product.
Synthesizing of embodiment 18, protein and metallic organic framework compound composite material
1, the nitric hydrate zinc aqueous solution that compound concentration is 0.49mol/L respectively, the glyoxal ethyline aqueous solution that concentration is 3.47mol/L, carries out respectively supersound process 10 minutes to gained solution.In glyoxal ethyline solution, add cytochrome C, making cytochrome C concentration is 0.1mg/mL.
2, get the zine ion solution 0.5mL of step 1 gained and mix with glyoxal ethyline in step 1 and the mixing solutions 5mL of cytochrome C, at 25 DEG C, leave standstill 2 hours.
3, step 2 products therefrom is gone out by centrifugation, water repeated washing 3 times, is placed in lower 25 DEG C of vacuum by the product after washing and is dried 48 hours, obtains albumen embedding rate approximately 82% in product.
As shown in figure 11, as shown in Figure 11, the matrix material particle size distribution range of this example gained is larger for the stereoscan photograph of matrix material prepared by the present embodiment, and the corner angle of rhombic dodecahedron are less obvious.
Synthesizing of embodiment 19, albumen/metallic organic framework compound composite material
Operation steps is with embodiment 18, and difference is, the cytochrome C concentration of step 1 is replaced with to 0.15mg/mL, obtains albumen embedding rate approximately 75% in product.
As shown in figure 12, as shown in Figure 12, the matrix material particle size distribution range of this example gained is larger for the stereoscan photograph of matrix material prepared by the present embodiment, and the corner angle of rhombic dodecahedron are less obvious.
Synthesizing of embodiment 20, albumen/metallic organic framework compound composite material
1, prepare the aqueous solution that contains cytochromeC2 0mg/mL, contains polyvinylpyrrolidone (PVP, molecular weight is 10,000) 15mg/mL.
2, compound concentration is the aqueous solution of 0.49mol/L nitric hydrate zinc respectively, and the aqueous solution of the glyoxal ethyline that concentration is 3.47mol/L carries out respectively supersound process 10 minutes to gained solution.
3, get the glyoxal ethyline solution of 5mL step 2 gained, add the solution 25 μ L of step 1 gained, gained solution is mixed with the nitric hydrate zinc solution of 0.5mL step 2 gained, at 25 DEG C, leave standstill 2 hours.
4, step 3 products therefrom is gone out by centrifugation, water repeated washing 3 times, is placed in lower 25 DEG C of vacuum by the product after washing and is dried 48 hours, obtains albumen embedding rate approximately 84% in product.
As shown in figure 13, as shown in Figure 13, the matrix material particle size distribution range of this example gained is larger for the stereoscan photograph of matrix material prepared by the present embodiment, and the corner angle of rhombic dodecahedron are less obvious.
Synthesizing of embodiment 21, albumen/metallic organic framework compound composite material
Operation steps is with embodiment 20, and difference is, the cytochrome C concentration of step 1 is replaced with to 30mg/mL, obtains albumen embedding rate approximately 78% in product.
As shown in figure 14, as shown in Figure 14, the matrix material particle size distribution range of this example gained is larger for the stereoscan photograph of matrix material prepared by the present embodiment, and the corner angle of rhombic dodecahedron are less obvious.
The foregoing is only preferred embodiment of the present invention, all variations of doing according to the present patent application the scope of the claims and modification, all should belong to covering scope of the present invention.
Claims (9)
1. a preparation method for the matrix material of protein and metallic organic framework compound, comprises the steps:
Protein, zine ion and organic ligand react in solvent, obtain described matrix material;
Described organic ligand be in glyoxal ethyline, benzoglyoxaline and imidazoles any.
2. preparation method according to claim 1, is characterized in that: the molecular weight of described protein is 5～300kDa.
3. preparation method according to claim 1 and 2, is characterized in that: described protein be in cytochrome C, Cytochrome P450, horseradish peroxidase, ethanol dehydrogenase, lipase, acetylcholinesterase, laccase, green fluorescent protein, glucose oxidase, trypsinase, subtilisin, carbonic anhydrase, ethanol dehydrogenase, sucrase, superoxide-dismutase and catalase any.
4. according to the preparation method described in any one in claim 1-3, it is characterized in that: the mass ratio of described protein and described zine ion is 0.00001～1:1;
The mol ratio of described zine ion and described organic ligand is 1:0.1～100.
5. according to the preparation method described in any one in claim 1-4, it is characterized in that:
Described zine ion comes from soluble zinc salt;
Described solvent be in water, methyl alcohol, dimethyl formamide, ethanol, dimethyl sulfoxide (DMSO), acetonitrile and acetone any.
6. according to the preparation method described in any one in claim 1-5, it is characterized in that: the temperature of described reaction is-10～50 DEG C, the time is 0.05～72 hour.
7. according to the preparation method described in any one in claim 1-6, it is characterized in that: before described reaction, described method also comprises the step of zine ion solution and organic ligand solution being carried out respectively to supersound process;
Described zine ion solution is dissolved in described solvent and is obtained by described zine ion;
Described organic ligand solution is dissolved in described solvent and is obtained by described organic ligand.
8. according to the preparation method described in any one in claim 1-7, it is characterized in that: before described reaction, described method also comprises to the step that adds tensio-active agent in protein soln;
Described tensio-active agent be in polyvinylpyrrolidone and pluronic any;
The molecular weight of described polyvinylpyrrolidone is 2,000～3,000,000;
In described protein soln, the concentration of described tensio-active agent is 0.1～100mg/mL;
The mass ratio of described tensio-active agent and described protein is 0～100:1, but the quality of described tensio-active agent is non-vanishing.
9. prepared protein and the metallic organic framework compound composite material of preparation method described in any one in a claim 1-8.
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