CN-122011228-A - Polysaccharide hydroformylation modification method based on plasma technology

Abstract

A polysaccharide hydroformylation modification method based on a plasma technology relates to the technical field of biological material modification and is used for solving the problems of environmental pollution, harsh reaction conditions and complex product purification existing in the existing chemical oxidation method. Comprises the following steps of S1 preparing polysaccharide solution. Dissolving polysaccharide in solvent, stirring to dissolve completely to obtain homogeneous polysaccharide solution. S2, performing in-situ oxidation treatment on the plasma. In an inert gas atmosphere, a coaxial dielectric barrier discharge device is used for generating plasma, and active substances of the plasma directly act on the polysaccharide solution, so that aldehyde groups are introduced into a polysaccharide molecular chain, and an aldehyde polysaccharide solution is obtained. S3, freeze drying and molding. And freeze-drying the obtained aldehyde polysaccharide solution to obtain the aldehyde polysaccharide solid material with the three-dimensional porous network structure. The method is simple and convenient to operate, easy to popularize, simple in equipment, short in flow, free of complex purification steps, and beneficial to laboratory and large-scale production and application.

Inventors

• WANG XIAOLONG
• SUN RUIRUI
• ZHAO TONG
• ZHANG YUANTAO
• SUN YING
• LIU YADI
• WANG WENYU

Assignees

• 山东大学

Dates

Publication Date

20260512

Application Date

20260318

Claims (9)

1. 1. The polysaccharide hydroformylation modification method based on the plasma technology is characterized by comprising the following steps of: S1, preparing polysaccharide solution Dissolving polysaccharide in solvent, stirring to dissolve completely to obtain homogeneous polysaccharide solution; S2, plasma in-situ oxidation treatment In an inert gas atmosphere, generating plasma by using a coaxial dielectric barrier discharge device, wherein active substances of the plasma directly act on the polysaccharide solution, so that aldehyde groups are introduced into a polysaccharide molecular chain to obtain an aldehyde polysaccharide solution; S3, freeze drying and forming And freeze-drying the obtained aldehyde polysaccharide solution to obtain the aldehyde polysaccharide solid material with the three-dimensional porous network structure.
2. 2. The method of claim 1, wherein in step S1, the polysaccharide is at least one selected from the group consisting of hyaluronic acid and salts thereof, alginic acid and salts thereof, chondroitin sulfate, dextran, and chitosan.
3. 3. The method for modifying polysaccharide aldehyde group according to claim 2, wherein in step S1, the weight average molecular weight of the polysaccharide is 10kDa to 500kDa, and the concentration of the polysaccharide solution is 1mg/mL to 10mg/mL.
4. 4. The method for modifying polysaccharide formylation according to claim 3, wherein in step S1, the solvent is deionized water, and the stirring speed is 500r/min-1000r/min.
5. 5. The method of modifying polysaccharide aldehyde groups according to claim 4, wherein in step S2, the discharge power of the plasma treatment is 10W to 50W, and the duration of the plasma treatment is 0.5 hours to 4 hours.
6. 6. The method according to claim 5, wherein in the step S2, the inert gas atmosphere is pure argon, pure helium, a mixed gas of argon and oxygen, or a mixed gas of helium and oxygen.
7. 7. The method of modifying polysaccharide aldehyde groups according to claim 6, wherein in step S2, when an oxygen-containing mixed gas is used, the volume ratio of oxygen is 1% to 5%, and the flow rate of the gas is 0.2SLM to 1.0SLM.
8. 8. The method for modifying polysaccharide formylation as claimed in claim 7, wherein the step S3 comprises the steps of S3.1, pre-freezing and solidifying the formylated polysaccharide solution at-80 ℃ and below, and S3.2, and then performing sublimation drying under the condition that the vacuum degree is lower than 10 Pa.
9. 9. The method of modifying polysaccharide formylation as claimed in claim 8, wherein the sublimation drying time is from 24 hours to 72 hours.

Description

Polysaccharide hydroformylation modification method based on plasma technology Technical Field The invention relates to the technical field of biological material modification, in particular to a polysaccharide hydroformylation modification method based on a plasma technology. Background The natural polysaccharide is taken as an important biological macromolecule, and has wide application prospect in the fields of tissue engineering, drug delivery and regenerative medicine biomedicine by virtue of excellent biocompatibility, hydrophilicity and degradability. However, such materials generally have problems of too high water solubility, insufficient structural stability and mechanical properties, and limit their direct application as structural scaffold materials. The vicinal diol structure on the molecular chain is converted into aldehyde group through oxidation reaction, and then the hydrogel is constructed through Schiff base reaction and amino compound crosslinking, so that the method is one of effective strategies for overcoming the limitations and expanding the functions and the application of the hydrogel. Currently, the hydroformylation of such polysaccharides relies primarily on chemical oxidation, with sodium periodate oxidation being the most common. However, conventional chemical oxidation processes suffer from several non-negligible drawbacks. For example, sodium periodate oxidizing agents are highly toxic and environmentally hazardous, requiring complex and time-consuming purification procedures to remove residues after reaction, not only increasing process costs, but also introducing biosafety risks. Chemical residues may interfere with the activity of aldehyde groups and affect the biocompatibility of the final material. These drawbacks fundamentally limit the application of chemical oxidation in high-end, sensitive biomedical settings. In recent years, atmospheric pressure cold plasma has shown great potential in the field of material modification due to its unique physicochemical properties. As a non-thermal equilibrium plasma, the atmospheric pressure cold plasma is rich in high-energy electrons, active nitrogen-oxygen species and excited molecules, and can realize oxidation treatment under mild conditions. Compared with the traditional chemical oxidation method, the atmospheric pressure cold plasma technology has the remarkable advantages of no reagent addition, no solvent residue and low energy consumption, and is regarded as an environment-friendly material modification technology. However, as a green and controllable tool, a technology for directly utilizing low-temperature atmospheric pressure plasma to treat and modify polysaccharide has not been reported at present. Disclosure of Invention The invention aims to provide a polysaccharide hydroformylation modification method based on a plasma technology, which is used for solving the problems of environmental pollution, harsh reaction conditions and complex product purification existing in the existing chemical oxidation method. The technical scheme adopted for solving the technical problems is that the polysaccharide hydroformylation modification method based on the plasma technology comprises the following steps of. S1, preparing a polysaccharide solution. Dissolving polysaccharide in solvent, stirring to dissolve completely to obtain homogeneous polysaccharide solution. S2, performing plasma in-situ oxidation treatment. In an inert gas atmosphere, a coaxial dielectric barrier discharge device is used for generating plasma, and active substances of the plasma directly act on the polysaccharide solution, so that aldehyde groups are introduced into a polysaccharide molecular chain, and an aldehyde polysaccharide solution is obtained. S3, freeze drying and molding. And freeze-drying the obtained aldehyde polysaccharide solution to obtain the aldehyde polysaccharide solid material with the three-dimensional porous network structure. Further, the polysaccharide is at least one selected from hyaluronic acid and its salt, alginic acid and its salt, chondroitin sulfate, dextran or chitosan. Further, the polysaccharide has a weight average molecular weight of 10kDa to 500kDa, and the polysaccharide solution has a concentration of 1mg/mL to 10mg/mL. Further, the solvent is deionized water, and the rotating speed during stirring is 500r/min-1000r/min. Further, the discharge power of the plasma treatment is 10 to 50W, and the duration of the plasma treatment is 0.5 to 4 hours. Further, the inert gas atmosphere is pure argon, pure helium, a mixed gas composed of argon and oxygen or a mixed gas composed of helium and oxygen. Further, when an oxygen-containing mixed gas is used, the volume ratio of oxygen is 1% to 5%, and the flow rate of the gas is 0.2SLM to 1.0SLM. Further, the step S3 of freeze drying comprises S3.1 of pre-freezing and solidifying the formylated polysaccharide solution at a temperature of-80 ℃ and below, and S3.2 of sublimation d