CN109806778B - Fixed zirconium silane interface modified polyvinylidene fluoride membrane and preparation and application thereof - Google Patents
Fixed zirconium silane interface modified polyvinylidene fluoride membrane and preparation and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims description 127
- 238000002360 preparation method Methods 0.000 title claims description 13
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- 238000007790 scraping Methods 0.000 claims description 27
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Images
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明涉及一种固定锆硅烷界面改性聚偏氟乙烯膜及其制备和应用。该膜是由乙烯基磷酸/乙烯基三乙氧基硅烷改性的PVDF膜固定金属锆得到。该制备方法包括：PVDF膜制备，PVDF/VPA‑g‑VTES膜制备，固定锆硅烷界面改性聚偏氟乙烯膜制备。该膜不但拥有对特异性蛋白的优异的吸附效果，同时提高了分离效率，降低了生产成本。
The invention relates to a fixed zirconium silane interface modified polyvinylidene fluoride film and its preparation and application. The membrane is obtained by immobilizing metal zirconium on a PVDF membrane modified with vinylphosphoric acid/vinyltriethoxysilane. The preparation method includes: preparation of PVDF membrane, preparation of PVDF/VPA-g-VTES membrane, preparation of fixed zirconium silane interface modified polyvinylidene fluoride membrane. The membrane not only has an excellent adsorption effect on specific proteins, but also improves the separation efficiency and reduces the production cost.
Description
Technical Field
The invention belongs to the field of phosphorus-containing protein separation membranes and preparation and application thereof, and particularly relates to a fixed zirconium silane interface modified polyvinylidene fluoride membrane and a preparation method and application thereof.
Background
PVDF can be used as a base material of an excellent protein separation membrane due to its excellent physical and chemical properties (strength and corrosion resistance), and is combined with a fixed metal chelation affinity chromatography technology, so that the physical properties of the membrane can be improved, and the modification is facilitated, thereby improving the production efficiency and the separation effect. Immobilized Metal-chelating Affinity Chromatography (IMAC) is a new Affinity Chromatography technology appearing in recent years, and is mainly used for separation of biomacromolecules. In 1975, the technique proposed by Paroth, which paid much attention to the fact that some amino acids on the surface of proteins, such as histidine, tryptophan, cysteine, etc., can interact with metal ions specifically, thereby separating the proteins. Compared with the traditional protein separation technology, such as gel filtration chromatography, adsorption chromatography, ion exchange chromatography and the like, the affinity chromatography technology has the advantages that the selectivity and the specificity are realized in the separation and purification process of the protein, and the target protein with high purity can be quickly, simply and pertinently obtained in some complex environments. For this reason, the immobilized metal chelate affinity chromatography has been increasingly regarded as important, and has been applied to not only protein detection and separation and purification, but also directed immobilization of proteins, application of combination techniques, renaturation and purification of proteins, separation and purification of nucleic acids, genetic engineering techniques, and the like.
Chinese patent CN2007100129667 discloses a fixed titanium ion affinity chromatography material and its preparation and application, utilizing the strong interaction between titanium ions and phosphate groups on the phosphoric acid modified solid phase carrier to fix the titanium ions on the carrier, using the fixed titanium ion affinity chromatography material to enrich phosphopeptide, the phosphopeptide is retained on the affinity chromatography material due to the strong chelating action between phosphopeptide and the fixed titanium ions to separate it, but most of the solid phase carriers are microspheres, the production control is difficult, and it is difficult to apply to the actual production.
Chinese patent CN2017101304648 discloses a preparation method of a bifunctional affinity organic polymer matrix capillary monolithic column. The method includes that a monomer containing boric acid groups, a monomer containing phosphoric acid groups, a cross-linking agent, a pore-forming agent and an initiator are subjected to ultrasonic treatment at room temperature until the monomers are completely dissolved, then the mixture is injected into a quartz capillary tube modified by vinyl, and a capillary tube monolithic column is prepared through treatment. However, the separation effect is limited and not significant.
The invention of Chinese patent CN 20161038454 belongs to the field of analytical chemistry, and relates to a method for enriching phosphate compounds from biological samples by using a titanium immobilized magnetic microsphere extraction technology. The method adopts a functionalized magnetic composite material of titanium immobilized magnetic microspheres, and achieves rapid separation by applying an external magnetic field in the extraction and enrichment process; the method comprises the steps of activating titanium immobilized magnetic microspheres, loading the activated titanium immobilized magnetic microspheres, adopting a certain solvent for cleaning and elution, extracting phosphate compounds in a biological sample, carrying out nitrogen-blowing concentration, redissolving the phosphate compounds by using a certain solvent, and then analyzing the phosphate compounds by using high performance liquid tandem mass spectrometry or gas tandem mass spectrometry to determine the content of the phosphate compounds in the biological sample. The used titanium immobilized magnetic microspheres can be reused after being cleaned by the regeneration solvent. However, the mechanical properties of the microspheres are poor, the reuse rate is not high, and the chemical properties are unstable.
Chinese patent CN2008102117279 relates to a method for off-line and on-line enrichment of phosphopeptide or phosphorylated protein by a functional modified open-tube capillary column: the open-tube capillary column with the inner wall provided with the zirconium phosphate functional group capable of selectively adsorbing phosphopeptide or phosphorylated protein is prepared, the phosphopeptide or phosphorylated protein can be enriched after a sample is loaded, and non-phosphopeptide or non-phosphorylated protein and salt are removed by utilizing a cleaning buffer solution, however, the manufacturing cost of the open-tube capillary column is too high, and the effect is not obvious.
Chinese patent CN2007101575241 relates to high-selectivity enrichment of phosphorylated peptides, in particular to a preparation method of a polymer material for enriching phosphorylated peptide fragments. The method adopts monomers with phosphate groups to carry out polymerization reaction to directly form polymer materials with phosphate groups. The material generates phosphate zirconium group after being acted by solution containing zirconium ion, so that phosphopeptide can be specifically enriched and purified from complex protein enzymolysis liquid. However, the degree of polymerization of the phosphoric acid group-containing monomer polymer is not high enough, and the physicochemical results are unstable, and thus it is difficult to use the polymer in actual production.
Therefore, the development of a preparation method of the phosphorus-containing protein separation membrane which has stable physical and chemical properties, simple process, safety, environmental protection and convenient industrial production has practical significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fixed zirconium silane interface modified polyvinylidene fluoride membrane and preparation and application thereof, so as to overcome the defects that in the prior art, a high-risk medicine is used in the phosphorylation process of the traditional fixed metal chelating affinity microsphere, the mechanical property is poor, repeated adsorption can not be carried out for many times, the cost is high, the efficiency is low, the specific adsorption capacity is not high, and the like.
The invention adopts the thermally induced phase separation and silane interface crosslinking technology, effectively solves the problems of low efficiency and high cost of the fixed metal chelating affinity technology, improves the specific adsorption to the phosphoprotein, improves the safety of the experiment and has wide application prospect.
The interface modified polyvinylidene fluoride membrane for fixing zirconium silane is obtained by fixing metal zirconium on a PVDF membrane modified by vinylphosphoric acid/vinyltriethoxysilane.
The preparation method of the PVDF membrane modified by the vinylphosphoric acid/vinyltriethoxysilane comprises the following steps: dissolving vinyl phosphate VPA and vinyl triethoxysilane VTES in a mixed solution of triethyl phosphate and water, adding an initiator to obtain a prepolymer, and immersing the PVDF film in the prepolymer.
The structural formula of the vinyl phosphoric acid/vinyl triethoxy silicon is as follows:
the invention discloses a preparation method of a fixed zirconium silane interface modified polyvinylidene fluoride membrane, which comprises the following steps:
(1) dissolving polyvinylidene fluoride (PVDF) in triethyl phosphate, stirring, standing the obtained casting solution, scraping the membrane, quickly putting the glass plate with the casting solution into a mixed coagulation bath of triethyl phosphate and water for coagulation (regulating and controlling the structure of the PVDF membrane by changing the mixing ratio of the triethyl phosphate and the water) after scraping, taking out the glass plate and putting the glass plate into a pure water coagulation bath for continuous coagulation to obtain the PVDF membrane, wherein the mass fraction of the PVDF in the casting solution is 15-18%;
(2) dissolving vinyl phosphoric acid VPA and vinyl triethoxysilane VTES in a mixed solution of triethyl phosphate and water, adding an initiator, and stirring to obtain a vinyl prepolymer solution containing a phosphoric acid group; immersing the PVDF membrane in the step (1) in a vinyl prepolymer solution containing phosphoric acid groups to obtain a PVDF/VPA-g-VTES membrane, wherein the mass ratio of the VPA, VTES, triethyl phosphate and water mixed solution to the initiator is 2-4.5: 1-5: 100: 0.05-0.09;
(3) and (3) immersing the PVDF/VPA-g-VTES membrane in the zirconium oxychloride solution in the step (2) to fix metal zirconium, cleaning the obtained membrane (with deionized water), and drying to obtain the fixed zirconium silane interface modified polyvinylidene fluoride membrane, wherein the concentration of the zirconium oxychloride solution is 50-100 mM.
In the step (1), the stirring temperature is 60-80 ℃, and the stirring time is 8-10 h.
And (2) standing for 10-12 h in the step (1).
The film scraping in the step (1) is as follows: and heating the casting film liquid, the film scraping plate and the glass plate to 50-80 ℃, and scraping the film.
The mass ratio of the triethyl phosphate to the water in the mixed coagulation bath of the triethyl phosphate and the water in the step (1) is 1: 1-4: 1.
The solidification time in the step (1) is 5-60 s; the continuous solidification time is 20-24 h.
The mass ratio of the triethyl phosphate to the water in the mixed solution of the triethyl phosphate and the water in the step (2) is 0.95-1.2: 1.
In the step (2), the initiator is azodiisobutyronitrile.
In the step (2), the stirring temperature is 60-80 ℃, and the stirring time is 12-24 h; the immersion time is 3-8 h.
And (4) immersing for 8-24 h in the step (3).
The invention relates to an application of a fixed zirconium silane interface modified polyvinylidene fluoride membrane.
The preparation process of the invention is as follows: preparing a PVDF solution with a certain concentration, carrying out film scraping at a certain temperature, firstly putting the PVDF solution into a fusion coagulation bath of triethyl phosphate and water, and then putting the PVDF solution into a coagulation bath of pure water; dissolving vinyl phosphoric acid and vinyl triethoxysilane in a mixed solution of triethyl phosphate and water according to a certain content, adding an initiator, and polymerizing at a certain temperature for a period of time to obtain a prepolymer solution; and then putting the prepared PVDF membrane into a prepolymer solution, immersing for a period of time, putting the PVDF membrane into zirconium oxychloride with a certain content for a period of time, and finally cleaning and drying the prepared membrane to obtain the fixed metal zirconium vinyl silane interface modified PVDF membrane.
The PVDF film is prepared by thermally induced phase separation and mixed coagulation bath methods, and is modified by adopting a mode of polymerization of vinyl phosphoric acid and vinyl triethoxysilane and silane interface crosslinking and then fixing metal zirconium through phosphate groups.
Advantageous effects
(1) The invention adopts silane interfacial crosslinking technology to modify the PVDF membrane, effectively improves the affinity of the PVDF membrane and endows the PVDF membrane with phosphate groups.
(2) The invention combines the fixed metal chelating affinity chromatography technology and the membrane separation technology, not only has excellent adsorption effect on specific protein, but also improves the separation efficiency and reduces the production cost.
(3) The invention adopts the method of polymerizing vinyl phosphoric acid and vinyl triethoxysilane to carry out silane interface crosslinking technology to improve the phosphate group, thereby greatly avoiding dangerous phosphorylation process and improving the safety of the experiment.
(4) The affinity membrane prepared by the invention can be used for separating and adsorbing various phosphorus-containing proteins, biological enzymes and other biological products, and has potential application prospect in the field of protein adsorption.
Drawings
FIG. 1 is an infrared spectrum of a PVDF film (a) and a PVDF/VPA-g-VTES film (b) in example 7;
FIG. 2 is an SEM image of the top (A1, B1, C1) and bottom (A2, B2, C2) surfaces of PVDF membranes at different stages in example 7, where A1 and A2 are PVDF membranes, B1 and B2 are PVDF/VPA-g-VTES membranes, and C1 and C2 are Zr + PVDF/VPA-g-VTES membranes;
FIG. 3 is an XRD spectrum of PVDF membrane (a), PVDF/VPA-g-VTES membrane (b) and Zr + PVDF/VPA-g-VTES membrane (c) in example 7.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Sources of experimental materials are shown in table 1:
TABLE 1
| Name of Material | Specification of | Manufacturer of the product |
| Polyvinylidene fluoride (PVDF) | 6020 | Suwei (Shanghai) Co., Ltd |
| Vinyl Phosphonic Acid (VPA) | Analytical purity | Aladdin Chemicals Ltd |
| Vinyl Triethoxysilane (VTES) | (High purity) | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Triethyl phosphate (TEP) | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Azobisisobutyronitrile (AIBN) | Chemical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Polyvinylpyrrolidone (PVP) | Chemical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Ovalbumin | Biochemical reagent | Aladdin Chemicals Ltd |
Example 1
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 18%, dissolving for 8h at 60 ℃, standing the casting solution for 10h, pouring the casting solution on a 50 ℃ membrane scraping plate, scraping the membrane by using a 300 mu m scraper, then putting the membrane into a mixed solution of TEP and water with the mass ratio of 1:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 20h, and then peeling off the membrane to obtain the PVDF membrane.
(2) 2g of Vinyl Phosphoric Acid (VPA), 1g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.05g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and water in a mass ratio of 1:1 at 60 ℃, polymerization is carried out for 12h, then the PVDF membrane in the step (1) is immersed in the solution for 3h, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 50mM ZrOCl2Chelating metal ion Zr for 8h, putting ZrOCl2And carrying out dehydration condensation on the silane coupling agent in pure water to form a network structure, and drying the obtained membrane in a drying oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The mass fraction of zirconium metal contained in the prepared membrane is 0.06%, and the adsorption quantity of the zirconium metal to ovalbumin is 8.3 mg/g.
Example 2
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 18%, dissolving for 8h at 65 ℃, standing the casting solution for 10h, pouring the casting solution on a 60 ℃ membrane scraping plate, scraping the membrane by using a 300 mu m scraper, then putting the membrane into a mixed solution of TEP and water with the mass ratio of 1:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling off the membrane to obtain the PVDF membrane.
(2) 2.5g of Vinyl Phosphoric Acid (VPA), 1.5g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.06g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and 1:1 (mass ratio) of water at 65 ℃ for polymerization for 16h, then the PVDF membrane in the step (1) is immersed in the solution for 3h, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 50mM ZrOCl2Chelating metal ion Zr for 12h, putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The obtained film contained 1.529% of zirconium metal by mass, and the adsorption amount of the zirconium metal to ovalbumin was 10.5 mg/g.
Example 3
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 70 ℃ for 9h, standing the casting solution for 10h, pouring the casting solution on a 60 ℃ film scraping plate, scraping the film by using a 500-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 2:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 2.5g of Vinyl Phosphoric Acid (VPA), 1.5g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.06g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and 1:1 (mass ratio) of water at 70 ℃ for polymerization for 24 hours, then the PVDF membrane in the step (1) is immersed in the solution for 3 hours, and the prepolymer diffuses into the membrane during immersion in the solution, thus obtaining the PVDF/VPA-g-VTES membrane.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 75mM ZrOCl2The solution is added with ZrOCl after 16h of chelating metal ion Zr2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The obtained film contained 2.34% of zirconium metal by mass, and the adsorption amount of the zirconium metal to ovalbumin was 21.1 mg/g.
Example 4
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 80 ℃ for 10h, standing the casting solution for 12h, pouring the casting solution on a 70 ℃ film scraping plate, scraping the film by using a 500-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 2:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 3g of Vinyl Phosphoric Acid (VPA), 2g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.07g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and water in a mass ratio of 1:1 at 70 ℃, polymerization is carried out for 24 hours, then the PVDF membrane in the step (1) is immersed in the solution for 3 hours, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 75mM ZrOCl2Chelating metal ion Zr in the solution for 20h, and putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The mass fraction of zirconium metal contained in the prepared membrane was 4.32%, and the adsorption amount of zirconium metal to ovalbumin was 34.5 mg/g.
Example 5
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 80 ℃ for 10h, standing the casting solution for 12h, pouring the casting solution on a 70 ℃ film scraping plate, scraping the film by using a 500-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 3:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 3g of Vinyl Phosphoric Acid (VPA), 3g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.06g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and water in a mass ratio of 1:1 at 70 ℃, polymerization is carried out for 24 hours, then the PVDF membrane in the step (1) is immersed in the solution for 3 hours, and the prepolymer diffuses into the membrane in the process of immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Adding P in step (2)VDF/VPA-g-VTES membranes immersed in 100mM ZrOCl2Chelating metal ion Zr in the solution for 20h, and putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The obtained film contained 4.462% of zirconium metal by mass, and the adsorption amount of the zirconium metal to ovalbumin was 38.8 mg/g.
Example 6
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 80 ℃ for 10h, standing the casting solution for 10h, pouring the casting solution on a 60 ℃ film scraping plate, scraping the film by using a 500-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 3:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 3.5g of Vinyl Phosphoric Acid (VPA), 4g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.08g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and 1:1 (mass ratio) of water at 70 ℃ for polymerization for 24 hours, and then the PVDF membrane in the step (1) is immersed in the solution for 3 hours, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 100mM ZrOCl2Chelating metal ion Zr in the solution for 20h, and putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The mass fraction of zirconium metal contained in the obtained membrane was 6.750%, and the adsorption amount of zirconium metal to ovalbumin was 53.8 mg/g.
Example 7
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 80 ℃ for 10h, standing the casting solution for 12h, pouring the casting solution on a film scraping plate at 80 ℃, scraping the film by using a 300-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 3:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 4g of Vinyl Phosphoric Acid (VPA), 4.5g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.09g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and 1:1 (mass ratio) of water at 80 ℃, polymerization is carried out for 24 hours, then the PVDF membrane in the step (1) is immersed in the solution for 8 hours, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 100mM ZrOCl2Chelating metal ion Zr in the solution for 20h, and putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The obtained film contains 8.740% of zirconium metal by mass, and the adsorption amount of the zirconium metal to ovalbumin is 161.7 mg/g.
FIG. 1 shows that: in the reaction process, a silane interface cross-linked structure is formed inside the PVDF membrane, so that phosphate groups and Si-O-Si are formed inside the membrane, and a curve b is 1260cm-1Corresponds to P ═ O, while the peaks of the P-O and P OH groups are at 830cm-1About, and the characteristic peak of Si is 1260cm-1The left and right positions show that the modified PVDF membrane contains silicon and phosphorus groups, and the PVDF/VPA-G-VTES hybrid membrane is proved to be successfully added with the phosphate groups.
FIG. 2 shows that: as can be seen from the figure, the PVDF membrane using thermally induced phase separation has more porous and uniform membrane pores than the conventional PVDF membrane, so the water flux of the PVDF membrane prepared by this method is also extremely high, and the lower surface has a more dense surface than the upper surface due to the close adhesion to the glass plate during the membrane scraping process. B1 and B2 are the upper and lower surface images of PVDF membrane modified by VPA and VTES silane interfacial crosslinking, and it can be seen from the images that the modified PVDF membrane has a plurality of mutually crosslinked structures on the surface, namely, the net structure formed by the prepolymer of VPA and VTES in the membrane is denser than that of pure PVDF membrane. C1 and C2 are top and bottom surface views of PVDF/VPA-g-VTES membranes after chelating metallic zirconium, and it is clear from the views that the amount of chelated metallic zirconium is very large. Comparing the three films before and after the reaction, it was found that significant changes were produced in the surface of the film as the modification proceeded.
FIG. 3 shows: the PVDF film contains many fluorine (-F) groups on the molecular chain structure, so hydrogen bonds can be formed between molecular chains, and the prepared pure PVDF film has relatively high crystallinity. In the experiment, a VPA and VTES silane interface crosslinking modified PVDF hybrid membrane is adopted, so that a new functional group-phosphate group is formed inside the membrane. The XRD test results of pure PVDF membrane, PVDF membrane after silane interfacial crosslinking modification, and hybrid membrane after chelating metal zirconium are shown in fig. 3. As a crystalline polymer, a PVDF film (a) has an obvious diffraction peak at about 20 degrees, after the PVDF film (b) is blended and modified by VPA and VTES, a new diffraction peak is generated at a 17-degree position, the peak is the diffraction peak of a phosphate group, and the PVDF film (c) after chelating metal zirconium is added with the metal zirconium, so that the film crystallinity is improved, and the diffraction peak is sharper.
Repeated adsorption effect of the hybrid membrane: the desorption rate of more than 85 percent can be still maintained after the process is repeated for 4 times. Meanwhile, a mixed adsorption experiment of the phosphoprotein and the non-phosphoprotein is carried out, and the gel electrophoresis shows that the modified hybrid membrane has excellent specific separation effect on the phosphoprotein.
Example 8
(1) Completely dissolving PVDF in triethyl phosphate (TEP) to prepare a PVDF solution with the mass fraction of 15%, dissolving the PVDF solution at 80 ℃ for 10h, standing the casting solution for 12h, pouring the casting solution on a film scraping plate at 80 ℃, scraping the film by using a 300-micron scraper, then putting the film into a mixed solution of TEP and water with the mass ratio of 4:1 and the temperature of 25 ℃ for solidification for 5s, then putting pure water for solidification for 24h, and then peeling the film to obtain the PVDF film.
(2) 4.5g of Vinyl Phosphoric Acid (VPA), 5g of silane coupling agent Vinyl Triethoxysilane (VTES) and 0.09g of initiator Azobisisobutyronitrile (AIBN) are dissolved in a fusion solution of 100g of triethyl phosphate and water in a mass ratio of 1:1 at 80 ℃, polymerization is carried out for 24 hours, then the PVDF membrane in the step (1) is immersed in the solution for 8 hours, and the prepolymer diffuses into the membrane during immersion in the solution, so that the PVDF/VPA-g-VTES membrane is obtained.
(3) Immersing the PVDF/VPA-g-VTES membrane in the step (2) in 100mM ZrOCl2Chelating metal ion Zr for 24h, putting ZrOCl2And dehydrating and condensing the silane coupling agent in pure water to form a network structure. And (3) drying the obtained membrane in an oven at 100 ℃ for 1h to obtain the PVDF/VPA-g-VTES metal chelating affinity membrane. The obtained film contains 9.456% of zirconium metal by mass, and the adsorption amount of the zirconium metal to ovalbumin is 221.0 mg/g.
Comparative example 1
In micro-column liquid chromatography (μ HPLC) mode, using 10mmol/L, pH6.0 3-morpholine propanesulfonic acid (MOPS) as mobile phase A, and running time is 7 min; taking 10% ammonia water as mobile phase B, and the running time is started from 7 min; the pump flow rate is 0.05 mL/min; the detection wavelength was 280 nm. Taking non-phosphorylated proteins BSA and Hb and phosphorylated protein beta-casein as examples, the protein concentration is 1000 mug/mL, under the condition of mobile phase A, the non-phosphorylated proteins BSA and Hb are not retained on the monolithic column and are directly eluted, while the phosphorylated protein beta-casein is Zr in the monolithic column under the acidic condition4+Chelation is formed; when the mobile phase is switched to the condition B, the beta-casein is eluted, the patent shows the experimental effect by comparing two kinds of elution, and a clear adsorption effect is not given at the same time, so that the experiment can not be quantitatively characterized.
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