CN110698595A

CN110698595A - Synthesis method of bagasse xylan-g-GMA derivative with anticancer activity

Info

Publication number: CN110698595A
Application number: CN201911007946.XA
Authority: CN
Inventors: 李和平; 李明坤; 葛文旭; 杨锦武; 柴建啟; 武晋雄; 耿恺; 杨莹莹; 郑光绿
Original assignee: Guilin University of Technology
Current assignee: Guilin University of Technology
Priority date: 2019-10-22
Filing date: 2019-10-22
Publication date: 2020-01-17

Abstract

The invention discloses a method for synthesizing an anticancer active derivative bagasse xylan-g-GMA. Bagasse xylan is used as a main raw material, glycidyl methacrylate is used as a functional grafting monomer, potassium persulfate solution is used as an initiator, and the bagasse xylan-g-GMA with the anticancer activity is synthesized through a free radical graft copolymerization reaction under a water phase condition. The bagasse xylan-g-GMA is synthesized in the aqueous solution through graft copolymerization, the process and the reaction condition are easy to control, and the product grafting rate is high. By grafting the functional monomer glycidyl methacrylate, the bioactivity of the bagasse xylan is enhanced, and the water solubility and the application performance of the bagasse xylan are improved.

Description

Synthesis method of bagasse xylan-g-GMA derivative with anticancer activity

Technical Field

The invention relates to the field of fine chemical engineering, in particular to a method for synthesizing an anticancer active bagasse xylan-g-GMA derivative.

Background

Xylan is a common plant polysaccharide in the nature, has better reaction activity due to more hydroxyl groups on the molecules and the surface, and can perform esterification reaction, etherification reaction, graft copolymerization reaction and the like. The number of active sites on the surface of the xylan can be effectively increased through graft copolymerization, and meanwhile, because functional groups are introduced to the side chains of xylan molecules, the graft derivatives of the xylan molecules enhance special performances such as anticancer activity and the like while maintaining the biodegradability and the biological activity of the xylan, and are expected to expand the application range in the fields of medicines, foods, materials and the like.

At present, the research on the anticancer aspect of xylan and derivatives thereof is still in the initial stage, mainly because the anticancer activity and the physicochemical property of xylan are low, and xylan cannot be directly used as a medicament. By introducing a functional monomer Glycidyl Methacrylate (GMA), the number of xylan branched chains can be increased, the spatial structure of the xylan branched chains can be changed, and the bioactivity of the xylan can be improved. Meanwhile, the proper initiator concentration and dosage are used to control the free radical reaction and termination mode of GMA graft polymerization, and the water solubility, thermal stability and biological activity of xylan are improved.

The invention takes bagasse xylan as a main raw material, glycidyl methacrylate as a functional grafting monomer and potassium persulfate solution as an initiator, and synthesizes the bagasse xylan-g-GMA with anticancer activity by free radical graft copolymerization reaction under the condition of a water phase.

Disclosure of Invention

The invention aims to improve the stability and the anticancer activity of bagasse xylan, and provides a synthesis method of bagasse xylan grafted glycidyl methacrylate.

The method comprises the following specific steps:

(1) and (3) drying 5-10 g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 4-8 hours to constant weight to obtain the dry-based bagasse xylan.

(2) And (3) weighing 3-8 g of the dry bagasse xylan obtained in the step (2), adding into a 250mL four-neck flask, and then adding 15-20 mL of deionized water. Stirring for 10-15 minutes at room temperature to obtain the xylan suspension.

(3) Weighing 0.2-0.3 g of potassium persulfate in a 50mL beaker, adding 10-15 mL of deionized water into the beaker, and stirring until the deionized water is dissolved to obtain an initiator solution.

(4) Heating the system obtained in the step (2) to 70-90 ℃, dropwise adding the initiator solution obtained in the step (3), and controlling the total mass of the initiator solution to be 1/4 in 10-20 minutes.

(5) Measuring 5-10 mL of analytically pure monomer Glycidyl Methacrylate (GMA), placing the monomer Glycidyl Methacrylate (GMA) in a 50mL constant-pressure dropping funnel, beginning to drop the analytically pure monomer GMA when the total mass of the initiator solution is 1/4 after the system in the step (4) is dropped, and controlling the dropping to be completed within 3-4 hours; and continuously stirring and reacting for 1-2 hours, and cooling the materials to room temperature.

(6) And (5) carrying out suction filtration on the material obtained in the step (5), and sequentially washing and carrying out suction filtration for 3-4 times by using 25-30 mL of analytically pure absolute ethyl alcohol and 25-30 mL of analytically pure acetone respectively. And (3) putting the filter cake into a watch glass, and drying the watch glass in a vacuum constant-temperature drying oven at the temperature of 60 ℃ for 24 hours until the weight is constant, thus obtaining the bagasse xylan-g-GMA crude product.

(7) And (3) placing the crude product obtained in the step (6) into a Soxhlet extractor, extracting with 30-50 mL of analytically pure acetone for 24 hours, taking out the extracted sample, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the pure bagasse xylan-g-GMA graft copolymer.

(8) Calculating the monomer conversion rate (C) and the grafting rate (G) of the product by adopting a mass method, wherein the calculation formula is as follows:

in the formula:

W₀-the mass of raw bagasse xylan in g;

W₁bagasse xylan-g-GMA crude productMass, in g;

W₂-pure bagasse xylan-g-GMA mass in g;

W_m-mass of monomer in g;

c-monomer conversion,%;

g-graft ratio,%.

The bagasse xylan-g-GMA is synthesized in the aqueous solution through graft copolymerization, the process and the reaction condition are easy to control, and the product grafting rate is high. By grafting the functional monomer glycidyl methacrylate, the bioactivity of the bagasse xylan is enhanced, the water solubility and the application performance of the bagasse xylan are improved, and the application range of the bagasse xylan is wider.

Drawings

FIG. 1 is an IR chart of raw bagasse xylan.

FIG. 2 is an IR chart of bagasse xylan-g-GMA.

FIG. 3 XRD pattern of protopanaxase xylan.

FIG. 4 is an XRD pattern of bagasse xylan-g-GMA.

FIG. 5 is a TG-DTG graph of raw bagasse xylan.

FIG. 6 is a TG-DTG graph of bagasse xylan-g-GMA.

FIG. 7 is an SEM image of raw bagasse xylan.

FIG. 8 is an SEM image of bagasse xylan-g-GMA.

Detailed Description

Example (b):

(1) and (3) drying 10g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 8 hours to constant weight to obtain the dry-based bagasse xylan.

(2) Weighing 8g of the dry bagasse xylan obtained in the step (2), adding the dry bagasse xylan into a 250mL four-neck flask, and adding 20mL of deionized water. Stirring at room temperature for 15 minutes gave a xylan suspension.

(3) 0.3g of potassium persulfate was weighed into a 50mL beaker, 15mL of deionized water was added to the beaker, and the mixture was stirred until dissolved to obtain an initiator solution.

(4) Heating the system obtained in the step (2) to 70 ℃, starting to dropwise add the initiator solution obtained in the step (3), and controlling the time for dropwise adding 1/4 of the total mass of the initiator solution within 10-15 minutes.

(5) Measuring 6mL of analytically pure monomer Glycidyl Methacrylate (GMA), placing the analytically pure monomer GMA into a 50mL constant-pressure dropping funnel, beginning to drop the analytically pure monomer GMA when the total mass of the initiator solution is 1/4 after the system in the step (4) is dropped, and controlling the dropping to be finished within 4 hours; the reaction was stirred for an additional 2 hours and the batch was cooled to room temperature.

(6) And (5) carrying out suction filtration on the material obtained in the step, and sequentially washing and carrying out suction filtration for 3 times by using 25mL of analytically pure absolute ethyl alcohol and 25mL of analytically pure acetone respectively. And (3) putting the filter cake into a watch glass, and drying the watch glass in a vacuum constant-temperature drying oven at the temperature of 60 ℃ for 24 hours until the weight is constant, thus obtaining the bagasse xylan-g-GMA crude product.

(7) And (3) placing the crude product obtained in the step (6) into a Soxhlet extractor, extracting with 50mL of analytically pure acetone for 24 hours, taking out the extracted sample, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the pure bagasse xylan-g-GMA graft copolymer.

(8) The grafting rate of the bagasse xylan-g-GMA as a product is determined to be 56.0%, and the monomer conversion rate is determined to be 89.7%.

Product bagasse xylan-g-GMA by FTIR analysis, 1723.61cm^-1Is the C ═ O stretching vibration peak in glycidyl methacrylate, 1250.43cm^-1The peak position is strengthened and is the stretching vibration peak of the three-membered ring in the glycidyl methacrylate, which shows that the glycidyl methacrylate is grafted to the xylan main chain. Changes in the XRD pattern indicate changes in the crystalline regions and extent of the grafted product. TG-DTG analysis shows that the main phase of the weight loss of bagasse xylan-g-GMA is 200-420 ℃, the phase is the phase with the fastest xylan mass reduction rate, but the cooling rate of 200-280 ℃ is smaller than that of 280-420 ℃, and the total mass loss of the phase accounts for about 60% of the total mass. By SEM analysis, the surface appearance of the particles before and after modification is compared, and the surface bulges are increased after the glycidyl methacrylate graft copolymerization, but the surface bulges are still smooth, and the shape of the surface is similar to that of the litchi rind.

Claims

1. A method for synthesizing an anticancer active derivative bagasse xylan-g-GMA is characterized by comprising the following specific steps:

(1) drying 5 ~ 10g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 4 ~ 8 hours to constant weight to obtain dry-based bagasse xylan;

(2) weighing 3 ~ 8g of the dry bagasse xylan obtained in the step (2), adding the dry bagasse xylan into a 250mL four-neck flask, adding 15 ~ 20mL deionized water, and stirring at room temperature for 10 ~ 15 minutes to obtain a xylan suspension;

(3) weighing 0.2 ~ 0.3.3 g of potassium persulfate in a 50mL beaker, adding 10 ~ 15mL of deionized water into the beaker, stirring until the deionized water is dissolved to obtain an initiator solution, and pouring the initiator solution into a 50mL constant-pressure dropping funnel for later use;

(4) heating the system obtained in the step (2) to 70 ~ 90 ℃, starting to dropwise add the initiator solution obtained in the step (3), and controlling the time to be 10 ~ 20 minutes and dropwise adding 1/4 of the total mass of the initiator solution;

(5) weighing 5 ~ 10mL of analytically pure monomer Glycidyl Methacrylate (GMA), placing the GMA in a 50mL constant-pressure dropping funnel, beginning to drop the analytically pure monomer GMA when the total mass of the initiator solution is 1/4 after the system in the step (4) is dropped, controlling the dropping time to be 3 ~ 4 hours and finishing the dropping at the same time, continuously stirring and reacting for 1 ~ 2 hours, and cooling the material to room temperature;

(6) carrying out suction filtration on the material obtained in the step (5), sequentially washing with 25 ~ 30mL of analytically pure absolute ethyl alcohol and 25 ~ 30mL of analytically pure acetone, and carrying out suction filtration for 3 ~ 4 times, putting the filter cake into a watch glass, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours until the weight is constant, thus obtaining a bagasse xylan-g-GMA crude product;

(7) and (3) placing the crude product obtained in the step (6) into a Soxhlet extractor, extracting with 30 ~ 50mL of analytically pure acetone for 24 hours, taking out the extracted sample, and drying in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the pure bagasse xylan-g-GMA graft copolymer.