阅读说明：本技术 一种含磷酸锌的海藻酸盐水凝胶抗菌过滤膜的制备方法 (Preparation method of zinc phosphate-containing alginate hydrogel antibacterial filtering membrane ) 是由 赵孔银 程蒙蒙 谢文宾 李子逸 李佳成 杨文栋 林泽 赵慧 高徽徽 于 2019-11-29 设计创作，主要内容包括：本发明公开了一种含磷酸锌的海藻酸盐水凝胶抗菌过滤膜的制备方法。首先将可溶性磷酸盐与海藻酸钠充分混合溶解,得到铸膜液。将该铸膜液刮成膜并浸泡于可溶性锌盐水溶液中充分交联,在海藻酸锌水凝胶生成的同时,在水凝胶中原位生成磷酸锌。随后将得到的含磷酸锌的海藻酸锌水凝胶膜浸泡在可溶性钙盐的水溶液中,钙离子夺取海藻酸锌中的部分锌离子生成海藻酸钙,从而得到含磷酸锌的海藻酸盐水凝胶抗菌过滤膜。水凝胶中原位生成的磷酸盐提高了海藻酸盐水凝胶的机械性能,降低了水凝胶的溶胀性能,磷酸锌赋予海藻酸盐水凝胶良好的抗菌性能。该过滤膜在染料脱盐、印染废水脱色、蛋白质及多肽纯化等领域具有良好的应用前景。(The invention discloses a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate. Firstly, fully mixing and dissolving soluble phosphate and sodium alginate to obtain a membrane casting solution. The casting solution is scraped into a film and is soaked in a soluble zinc salt aqueous solution for full crosslinking, and zinc phosphate is generated in situ in the hydrogel while the zinc alginate hydrogel is generated. And then soaking the obtained zinc alginate hydrogel membrane containing zinc phosphate in an aqueous solution of soluble calcium salt, and capturing partial zinc ions in the zinc alginate by the calcium ions to generate calcium alginate, thereby obtaining the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane. The phosphate generated in situ in the hydrogel improves the mechanical property of the alginate hydrogel, reduces the swelling property of the hydrogel, and the zinc phosphate endows the alginate hydrogel with good antibacterial property. The filter membrane has good application prospect in the fields of dye desalination, printing and dyeing wastewater decolorization, protein and polypeptide purification and the like.)

1. A preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate is characterized by comprising the following steps:

a) preparing a mixture water solution of soluble phosphate with the mass percentage concentration of 0.1-20% and sodium alginate with the mass percentage concentration of 0.2-8%, standing and defoaming to obtain a membrane casting solution;

b) preparing a soluble zinc salt water solution with the mass percentage concentration of 0.2-20% as a first coagulating bath; preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a second coagulating bath;

c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with zinc wires with the diameter of 20-1500 mu m, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 5-240min to obtain a zinc alginate/zinc phosphate hydrogel film; when the soluble zinc salt reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with soluble phosphate, the zinc phosphate salt and the alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 20-80% compared with the tensile strength of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 20-65% of that of the zinc alginate;

d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 5-240min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the alginate hydrogel antibacterial filtering membrane containing zinc phosphate is obtained.

2. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, characterized in that the soluble phosphate is any one or a mixture of two or more of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate and trisodium phosphate.

3. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, wherein the soluble calcium salt is any one or a mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate.

4. The method for preparing zinc phosphate-containing alginate hydrogel antibacterial filtering membrane according to claim 1, characterized in that the soluble zinc salt is any one or a mixture of two or more of zinc chloride, zinc nitrate, zinc sulfate and zinc acetate.

5. The preparation method of the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane is characterized in that zinc ions of zinc phosphate and cross-linked sodium alginate endow the alginate hydrogel with good antibacterial performance, the calcium alginate hydrogel filtering membrane is prevented from being degraded by bacteria in the using process, the filtering membrane has good pollution resistance, and the filtering membrane has good application prospects in dye desalination, emulsion oil separation, printing and dyeing wastewater decolorization and protein and polypeptide purification.

Technical Field

The invention relates to a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, belonging to the field of functional materials and membrane separation.

The invention relates to the technical fields of filtering membranes, hydrogels, antibacterium and the like. In particular to a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate.

Background

The membrane separation technology is an environment-friendly new technology, does not produce secondary pollution, has low energy consumption and simple operation compared with the traditional wastewater treatment method, and is one of the most promising water treatment technologies at present. The traditional membrane is usually made of inorganic materials, organic high molecular materials or inorganic-organic composite materials, and the structure of the traditional membrane is divided into a plurality of types; different materials and structures determine the direction of application and the degree of separation of the membrane, and thus correspond to different applications. The polymer membrane has the advantages of small size, low energy consumption, simple preparation, low price and the like, but has certain disadvantages, such as poor organic solvent resistance, easy membrane pollution generation, easy bacteria breeding and the like.

The polymer gel is a multi-element system consisting of a polymer three-dimensional network and a solvent, and the hydrogel has good hydrophilicity because the hydrogel contains more than 80% of water. Sodium alginate is a natural high molecular substance which can be extracted from kelp or brown algae, has wide sources and low price, and is widely applied to the fields of food, biological medicine, wastewater treatment and the like at present. Sodium alginate and calcium ions can form hydrogel through ionic crosslinking. Zhao Kong Yin, etc. have prepared a series of calcium alginate-based hydrogel filtration membranes [ patent of invention ZL201310424398.7, ZL201310424399.1, ZL201310424397.2 ], these calcium alginate-based filtration membranes have good anti-pollution performance, but have the disadvantages of poor mechanical properties, low mechanical strength and easy degradation by bacteria.

Malaguerski I, et al prepared a metallic Zn sodium alginate based nanocomposite by a simple process, impregnating carbonate and phosphate mineral phases [ mater.Lett, 2018, 212, 32-36 ]. The mineralized samples exhibited different morphology and properties compared to the unmineralized samples. Bacteriostatic tests on escherichia coli, staphylococcus aureus and candida albicans show that the mineralized sample has higher removal efficiency on microorganisms than an unmineralized sample. The metal zinc mineralized alginate can be used as an antibacterial material with low price and easy production. Meanwhile, Malagurski I et al also studied the synthesis and antibacterial properties of zinc mineralized sodium alginate nanocomposites. The novel bioactive antibacterial material is prepared by adopting sodium alginate-mediated zinc mineral phase biomineralization. The synthesis process is simple and low in cost, and prepares two different zinc alginate mineralized nanometer composite materials of zinc carbonate/zinc alginate and zinc phosphate/zinc alginate. Aiming at the antibacterial property research of sodium alginate containing zinc ions, turlybekulya et al researches the biocompatibility and antibacterial property of a composite material by using analytically pure sodium alginate-hydroxyapatite-sodium alginate dual-phase zinc oxide and hydroxyapatite-zinc oxide as main raw materials and adopting orthogonal experimental design [ mater.sci.eng, 2019, 104, 109965 ]. The antibacterial activity evaluation is carried out on gram-negative bacteria (escherichia coli and pseudomonas aeruginosa) and gram-positive bacteria (staphylococcus aureus and staphylococcus epidermidis) by adopting a co-culture method and an improved agar diffusion method. Biocompatibility experiments and cytotoxicity evaluations were performed with mouse fibroblasts. The embedding process of zinc ions in hydroxyapatite and sodium alginate matrixes is illustrated, and the influence of the zinc ions on the performance of the bionic composite material is discussed in detail. Multiple studies show that zinc can effectively inhibit the growth and development of bacteria and yeasts. Zinc plays an important role in the development of novel antibacterial agents, and zinc-doped hydroxyapatite is further applied to biomedicine. In this respect, the phase of zinc oxide, as well as the calcium replacement process of zinc in calcium apatites and alginates, should be well explored.

The invention discloses a preparation method of an alginate hydrogel antibacterial filtering membrane containing zinc phosphate. Firstly, fully mixing and dissolving soluble phosphate and sodium alginate to obtain a membrane casting solution. The casting solution is scraped into a film and is soaked in a soluble zinc salt aqueous solution for full crosslinking, and zinc phosphate is generated in situ in the hydrogel while the zinc alginate hydrogel is generated. And then soaking the obtained zinc alginate hydrogel membrane containing zinc phosphate in an aqueous solution of soluble calcium salt, and capturing partial zinc ions in the zinc alginate by the calcium ions to generate calcium alginate, thereby obtaining the zinc phosphate-containing alginate hydrogel antibacterial filtering membrane. The phosphate generated in situ in the hydrogel improves the mechanical property of the alginate hydrogel, reduces the swelling property of the hydrogel, and the zinc phosphate endows the alginate hydrogel with good antibacterial property. The filter membrane has good application prospect in the fields of dye desalination, printing and dyeing wastewater decolorization, protein and polypeptide purification and the like.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to solve the technical problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, and the calcium alginate hydrogel filtering membrane has low strength and is easy to degrade by bacteria.

The invention provides a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, and solves the problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, is low in strength of a calcium alginate hydrogel filtering membrane, is easy to degrade by bacteria and the like.

The invention provides a preparation method of a zinc phosphate-containing alginate hydrogel antibacterial filtering membrane, which is characterized by comprising the following steps:

a) preparing a mixture water solution of soluble phosphate with the mass percentage concentration of 0.1-20% and sodium alginate with the mass percentage concentration of 0.2-8%, standing and defoaming to obtain a membrane casting solution;

b) preparing a soluble zinc salt water solution with the mass percentage concentration of 0.2-20% as a first coagulating bath; preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a second coagulating bath;

c) pouring the casting solution obtained in the step a) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20-1500 mu m, and immediately putting the glass plate and the scraped film into the first coagulation bath obtained in the step b) for soaking for 5-240min to obtain a zinc alginate/zinc phosphate hydrogel film; when the soluble zinc salt reacts with sodium alginate to generate zinc alginate hydrogel, zinc phosphate is generated in the zinc alginate hydrogel with soluble phosphate, the zinc phosphate salt and the alginate are crosslinked through zinc ions to generate an organic-inorganic hybrid structure, and the physical enhancement effect is added, so that the tensile strength of the zinc alginate/zinc phosphate hydrogel is improved by 20-80% compared with the tensile strength of the zinc alginate hydrogel, and the swelling rate of the zinc alginate/zinc phosphate hydrogel in physiological saline is reduced to 20-65% of that of the zinc alginate;

d) soaking the zinc alginate/zinc phosphate hydrogel membrane obtained in the step c) in the second coagulation bath obtained in the step b) for 5-240min, wherein the binding capacity of calcium ions and alginate is stronger compared with that of zinc ions, so that calcium ions can capture part of zinc ions in zinc alginate to generate calcium alginate, and the alginate hydrogel antibacterial filtering membrane containing zinc phosphate is obtained.

The soluble phosphate is any one or a mixture of two or more of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate and trisodium phosphate; the soluble calcium salt is any one or mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate; the soluble zinc salt is any one or a mixture of two or more of zinc chloride, zinc nitrate, zinc sulfate and zinc acetate.

In the invention, zinc phosphate and zinc ions of cross-linked sodium alginate endow alginate hydrogel with good antibacterial performance, so that the calcium alginate hydrogel filtering membrane is prevented from being degraded by bacteria in the using process, has good pollution resistance, and has good application prospect in dye desalination, emulsion oil separation, printing and dyeing wastewater decolorization and protein and polypeptide purification.

Detailed Description

Specific examples of the present invention will be described below, but the present invention is not limited to the examples.