CN112758943B - Preparation method of macroporous-large mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount - Google Patents
Preparation method of macroporous-large mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount Download PDFInfo
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Abstract
A preparation method of macroporous-big mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount belongs to the technical field of enzyme immobilization. P123 and polystyrene are used as template agents, and a spacing self-assembly method is combined with a hydrothermal method to prepare the macroporous-large mesoporous-small mesoporous three-stage porous silica. Weighing 20g of 10 mass percent P123 aqueous solution, adding 60g of deionized water, 11.9g of 37 mass percent concentrated hydrochloric acid and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing in a 43 ℃ water bath kettle, magnetically stirring, adding the same amount of TEOS again at the interval of 3.5 hours, and continuing to carry out water bath for 24 hours; transferring the obtained solution into a reaction kettle after the water bath is finished, and performing hydrothermal aging for 24 hours; and after the reaction is finished, centrifuging, filtering, washing and calcining the dried sample, wherein the obtained sample has three-stage distributed pore sizes, and the maximum fixed amount of the papain can reach 877 mg/g.
Description
Technical Field
The invention relates to a preparation method of macroporous-big mesoporous-small mesoporous three-stage porous silica with high enzyme immobilization amount, belonging to the technical field of enzyme immobilization.
Background
The natural biocatalyst, enzyme, has the advantages of high efficiency, strong specificity and specificity, and can be applied to various industrial fields such as biofuel production, detergents, food industry and the like. Despite the many attractive properties of enzymes, free enzymes suffer from poor thermostability, pH stability and recycling problems. The invention of the immobilized enzyme technology comes from the beginning, wherein the mesoporous material has strong application prospect as an enzyme immobilized carrier material. When the immobilized enzyme enters the carrier material, no defect is implied, and the immobilized carrier and the immobilized efficiency are low, the stability is poor, the continuous operation equipment is complex, the enzyme leaching rate is high, and the diffusion of enzyme molecules is limited by the network in the porous matrix, so that the immobilized enzyme becomes a main factor for restricting the development of the immobilized enzyme. In recent years, materials having a hierarchical pore structure have attracted a great deal of attention. The composite pore structure combines the advantages of pores in different layers and makes up the defects of single pore. The existence of mesopores can greatly increase the specific surface area of the material, and the large pore volume brought by the mesopores provides convenience for the transfer of the material. The bimodal mesoporous material provides convenience for mass transfer due to high specific surface area and hierarchical pore size, and is widely applied in the field of enzyme immobilization.
The enzyme molecules immobilized by the porous carrier material at present are improved in the aspects of thermal stability, acid-base stability and the like compared with free enzyme, but the problems of low immobilization efficiency and enzyme leaching are still not solved. In order to improve the immobilization efficiency of enzyme molecules and reduce the phenomenon of enzyme leaching, the invention provides a preparation method of macroporous-big mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount. The macroporous-big mesoporous-small mesoporous three-level porous structure greatly increases the fixation efficiency of enzyme molecules, wherein the small mesopores and the large mesopores are used as shell layers and can be used as transport channels of the enzyme molecules and transport channels of the enzyme molecules, the small mesopores are required to be larger than the enzyme molecules, the pore diameter range of the large mesopores can reach about 30nm, the transport speed of the molecules can be greatly increased, the internal hollow macropores are used as a natural enzyme molecule storage warehouse, the enzyme molecules enter the hollow macropores through the large mesopores and the small mesopores of the shell layers, and meanwhile, the hollow macropores can also be used as places where catalytic reaction occurs. The invention prepares the hierarchical porous silicon dioxide enzyme immobilization carrier material by a hydrothermal method and a cooperative self-assembly technology, controls the size of mesoporous of the material by hydrothermal temperature, and controls the range of hollow macropores by the size of a template agent polystyrene microsphere.
Disclosure of Invention
The invention provides a preparation method of macroporous-big mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount, which is used for immobilizing papain molecules, and the carrier material greatly improves the immobilization efficiency of papain and inhibits the enzyme leaching phenomenon.
1. A preparation method of macroporous-big mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount comprises the following steps:
(1) dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use;
(2) weighing 20g of the solution obtained in the step (1), adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing in a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃;
(3) after the TEOS is added for the first time, adding the same amount of TEOS into the solution obtained in the step (2) again at the interval of 3.5 hours, and continuing water bath for 24 hours;
(4) after the water bath is finished, transferring the solution obtained in the step (3) into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature to be adjusted between 100 ℃ and 140 ℃;
(5) centrifuging the product obtained in the step (4) after the reaction is finished, removing supernatant, repeatedly performing suction filtration, washing and centrifugation on the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven;
(6) and (4) calcining the dried sample obtained in the step (5), keeping the temperature at 550 ℃ for 4h, and increasing the temperature at the rate of 1 ℃/min to obtain the final sample of the macroporous-big mesoporous-small mesoporous three-level porous silica.
And (4) carrying out enzyme immobilization performance experiments on the papain molecules of the final sample obtained in the step (6).
2. In the step (2), ultrasonically dispersing the polystyrene microsphere emulsion; concentrated hydrochloric acid with a mass fraction of 37% is a volatile and pungent drug substance and rapidly proceeds in a fume hood while being dropped.
Drawings
FIG. 1. Nitrogen adsorption and desorption curves of macroporous, large mesoporous and small mesoporous three-stage porous silica of examples 1-5
FIG. 2 is a graph showing the pore size distribution of the three-stage porous silica of examples 1 to 5, i.e., large mesopore-small mesopore
FIG. 3 Transmission Electron micrograph of macroporous, Large mesoporous, Small mesoporous Tertiary porous silica of examples 1-5
FIG. 4 example 1-5 immobilization of papain by macroporous-Large meso-Small meso-porous Tertiary silica
Detailed Description
Example 1
Dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use; weighing 20g of the obtained solution, adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃; after the TEOS is added for the first time, adding the same amount of TEOS again at the interval of 3.5 hours, and continuing the water bath for 24 hours; after the water bath is finished, transferring the obtained solution into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature at 100 ℃; centrifuging the obtained product after the reaction is finished, removing supernatant, repeatedly filtering, washing and centrifuging the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven; calcining the dried sample, keeping the temperature at 550 ℃ for 4h, and increasing the temperature at the rate of 1 ℃/min to obtain the final sample of the macroporous-large mesoporous-small mesoporous three-level porous silica; enzyme immobilization performance experiments were performed on the papain molecules in the final samples obtained.
Example 2
Dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use; weighing 20g of the obtained solution, adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃; after the TEOS is added for the first time, adding the same amount of TEOS again at an interval of 3.5 hours, and continuing the water bath for 24 hours; after the water bath is finished, transferring the obtained solution into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature at 110 ℃; centrifuging the obtained product after the reaction is finished, removing supernatant, repeatedly filtering, washing and centrifuging the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven; calcining the dried sample, keeping the temperature at 550 ℃ for 4h, and increasing the temperature at the rate of 1 ℃/min to obtain the final sample of the macroporous-large mesoporous-small mesoporous three-level porous silica; the resulting final samples were subjected to enzyme immobilization performance experiments on papain molecules.
Example 3
Dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use; weighing 20g of the obtained solution, adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃; after the TEOS is added for the first time, adding the same amount of TEOS again at the interval of 3.5 hours, and continuing the water bath for 24 hours; after the water bath is finished, transferring the obtained solution into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature at 120 ℃; centrifuging the obtained product after the reaction is finished, removing supernatant, repeatedly filtering, washing and centrifuging the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven; calcining the dried sample, keeping the temperature at 550 ℃ for 4h, and increasing the temperature at the rate of 1 ℃/min to obtain the final sample of the macroporous-large mesoporous-small mesoporous three-level porous silica; the resulting final samples were subjected to enzyme immobilization performance experiments on papain molecules.
Example 4
Dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use; weighing 20g of the obtained solution, adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃; after the TEOS is added for the first time, adding the same amount of TEOS again at the interval of 3.5 hours, and continuing the water bath for 24 hours; after the water bath is finished, transferring the obtained solution into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature at 130 ℃; centrifuging the obtained product after the reaction is finished, removing supernatant, repeatedly filtering, washing and centrifuging the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven; calcining the dried sample, keeping the temperature at 550 ℃ for 4h, and increasing the temperature at the rate of 1 ℃/min to obtain the final sample of the macroporous-large mesoporous-small mesoporous three-level porous silica; the resulting final samples were subjected to enzyme immobilization performance experiments on papain molecules.
Example 5
Dissolving a certain amount of P123 (triblock copolymer template) in deionized water to prepare a 10% mass fraction P123 aqueous solution for later use; weighing 20g of the obtained solution, adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37% and 0.1g of polystyrene microspheres (PS), adding 2.55g of Tetraethoxysilane (TEOS), placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃; after the TEOS is added for the first time, adding the same amount of TEOS again at the interval of 3.5 hours, and continuing the water bath for 24 hours; after the water bath is finished, transferring the obtained solution into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature at 140 ℃; centrifuging the obtained product after the reaction is finished, removing supernatant, repeatedly filtering, washing and centrifuging the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven; calcining the dried sample, keeping the temperature at 550 ℃ for 4h, and raising the temperature at the rate of 1 ℃/min to obtain the final sample macroporous-large mesoporous-small mesoporous three-stage porous silica; the resulting final samples were subjected to enzyme immobilization performance experiments on papain molecules.
Fig. 1 is a nitrogen adsorption and desorption curve of macroporous-large mesoporous-small mesoporous three-level porous silica, from which it can be seen that samples are in an obvious class iv nitrogen adsorption and desorption curve at different temperatures, fig. 2 is a pore size distribution diagram of macroporous-large mesoporous-small mesoporous three-level porous silica, from which the most probable pore size distribution of large mesoporous-small mesoporous porous silica can be seen: the small mesoporous range is 6.4 nm-10.5 nm, and the large mesoporous range is 17.5 nm-29.6 nm. FIG. 3 is a transmission electron micrograph of the macroporous-large mesoporous-small mesoporous three-level porous silica, in which the existence of the outer hierarchical pore and the large hollow core can be clearly seen, and the size of the large hollow pore is between 200 and 1000 nm. FIG. 4 shows the papain immobilization amount of macroporous, large mesoporous and small mesoporous three-level porous silica, and it can be seen from the figure that enzyme carrier materials prepared by carrier materials under different hydrothermal temperature conditions all have an oversized papain immobilization amount; the fixing amount of the sample to the papain reaches 682-877 mg/g. Wherein the minimum is material prepared at 100 deg.C, the fixed amount is 682mg/g, the maximum is material prepared at 140 deg.C, and the fixed amount is 877 mg/g.
Claims (2)
1. A preparation method of macroporous-big mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount comprises the following steps:
(1) dissolving a triblock copolymer template agent P123 into deionized water to prepare a P123 aqueous solution with the mass fraction of 10% for later use;
(2) weighing 20g of the solution obtained in the step (1), adding 60g of deionized water, 11.9g of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.1g of polystyrene microspheres, adding 2.55g of tetraethoxysilane TEOS, placing the mixture into a water bath kettle, magnetically stirring, and keeping the temperature at 43 ℃;
(3) after the TEOS is added for the first time, adding 2.55g of the same amount of TEOS into the solution obtained in the step (2) again at intervals of 3.5 hours, and continuing the water bath for 24 hours;
(4) after the water bath is finished, transferring the solution obtained in the step (3) into a reaction kettle, performing hydrothermal aging for 24 hours, and keeping the hydrothermal temperature to be adjusted between 100 ℃ and 140 ℃;
(5) centrifuging the product obtained in the step (4) after the reaction is finished, removing supernatant, repeatedly performing suction filtration, washing and centrifugation on the precipitate until the pH of the supernatant is neutral, and drying the centrifuged sample in a 50 ℃ drying oven;
(6) and (4) calcining the dried sample obtained in the step (5), and keeping the temperature at 390 ℃ and 550 ℃ for 4h respectively, wherein the heating rate is 1 ℃/min, so as to obtain the final sample of the macroporous-large mesoporous-small mesoporous three-level porous silica.
2. The method for preparing macroporous-large mesoporous-small mesoporous three-level porous silica with high enzyme immobilization amount according to claim 1, wherein in the step (2), the polystyrene microspheres are dispersed by ultrasound.
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| CN102398907A (en) * | 2010-09-08 | 2012-04-04 | 清华大学 | Method for preparing mesoporous silicon oxide microballoons |
| BR102014028798A2 (en) * | 2014-10-14 | 2016-05-24 | Univ Fed De Alagoas | zsm-22 zeolite synthesis with reduced crystallization time and no use of organic structure |
| CN105480984A (en) * | 2015-12-22 | 2016-04-13 | 东北大学 | Spherical ordered graded mesoporous silicon dioxide and preparation method thereof |
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