CN110591004A - Synthetic method of bioactive bagasse xylan oxalate-g-HEMA - Google Patents
Synthetic method of bioactive bagasse xylan oxalate-g-HEMA Download PDFInfo
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- CN110591004A CN110591004A CN201910868209.2A CN201910868209A CN110591004A CN 110591004 A CN110591004 A CN 110591004A CN 201910868209 A CN201910868209 A CN 201910868209A CN 110591004 A CN110591004 A CN 110591004A
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention discloses a method for synthesizing bioactive bagasse xylan oxalate-g-HEMA. The method comprises the steps of taking bagasse xylan as a main raw material, and firstly, taking vanillic acid as an esterifying agent in an N, N-dimethylformamide solvent to synthesize bagasse xylan oxalate through catalytic esterification; then ammonium persulfate is used as an initiator, and HEMA is used as a grafting monomer to synthesize a target product bagasse xylan aromatic oxalate-g-HEMA with bioactivity. Vanillic acid and HEMA are introduced into the structure of the obtained target product, so that the problem of poor water solubility of the bagasse xylan is solved, the biological activity of the bagasse xylan is greatly improved by the active groups of the bagasse xylan, and the bagasse xylan has high application value in the fields of medicines, foods, functional materials and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for synthesizing bioactive bagasse xylan oxalate-g-HEMA.
Background
The invention utilizes bagasse, which is a large amount of biomass resource in Guangxi province and is not fully utilized, to extract bagasse xylan as a main experimental raw material, improves inherent biological activity of the bagasse xylan by chemical modification, and obtains new functional characteristics to improve the utilization rate and economic benefit of the bagasse. The study proves that the vanillic acid has no obvious difference with hydroquinone in the aspect of inhibiting the tyrosinase, is a good mixed type tyrosinase inhibitor, and can be used for preventing and treating diseases such as melanoma, pigmentation and the like. Meanwhile, the xylan also has various activities related to biological organisms such as anti-tumor, immunoregulation, anti-inflammation and oxidation resistance, and the advantages of the xylan and the xylan are combined if the xylan is esterified by the vanillic acid, so that the application value of the xylan in the fields of health care and pharmacy is improved.
In recent years, researchers at home and abroad have been devoted to xylan single-modified derivatives such as esterified modified derivatives, etherified modified derivatives and grafted modified derivatives, and research and development on xylan complex modified derivatives are still in an initial stage. The monomer containing the vinyl group can obviously improve the bioactivity of the polysaccharide by grafting modification of the polysaccharide, and the monomer containing the vinyl group is introduced into the main chain of the bagasse xylan as a functional substituent, so that the bioactivity of the bagasse xylan monoesterified derivative can be further improved. Hydroxyethyl methacrylate (HEMA) selected by the invention is a polar vinyl monomer containing active hydroxyl, and HEMA is grafted to the esterified bagasse xylan main chain, so that the problem of poor water solubility can be solved, and the original biological activity can be greatly enhanced.
The method takes bagasse xylan as a main raw material, firstly takes vanillic acid as an esterifying agent in an N, N-dimethylformamide solvent, and synthesizes bagasse xylan oxalate through catalytic esterification; then ammonium persulfate is used as an initiator, and HEMA is used as a grafting monomer to synthesize a target product bagasse xylan aromatic oxalate-g-HEMA with bioactivity.
Disclosure of Invention
The invention aims to improve the bioactivity of bagasse xylan, further graft modification is carried out on the basis of bagasse xylan monoesterification reaction, and a synthetic method of bioactive bagasse xylan aromatic oxalate-g-HEMA is provided.
The method comprises the following specific steps:
(1) and (3) placing 15.0-25.0 g of bagasse xylan into a vacuum constant-temperature oven at 60 ℃ to dry for 24 hours to constant weight, so as to obtain dry-based bagasse xylan.
(2) Weighing 12.0-21.0 g of the dry bagasse xylan obtained in the step (1) into a four-neck flask provided with a stirrer, a thermometer and a reflux device, adding 6.0-12.0 g of vanillic acid and 60-90 mL of analytically pure N, N-dimethylformamide, heating to 50-80 ℃ under stirring, and continuing stirring for 10-15 minutes.
(3) And (3) adding 0.6-1.2 g of p-toluenesulfonic acid and 0.03-0.045 g of tetraisopropyl titanate into the material system obtained in the step (2), and stirring and reacting for 5-7 hours at the temperature of 50-80 ℃.
(4) And (4) carrying out suction filtration on the material obtained in the step (3), washing with 45-90 mL of analytically pure absolute ethyl alcohol, and carrying out suction filtration for 3 times respectively to obtain a filter cake.
(5) And (5) putting the filter cake obtained in the step (4) into a watch glass, and putting the watch glass in a vacuum constant-temperature oven at 60 ℃ for drying for 24 hours until the weight is constant, so as to obtain the bagasse xylan oxalate.
(6) And (3.0-7.5 g of the bagasse xylan vanillic acid ester obtained in the step (5) is added into another four-neck flask provided with a stirrer, a thermometer and a reflux condenser, 45-75 mL of distilled water is added, and the mixture is stirred for 5-10 minutes at room temperature.
(7) 0.30-0.75 g of ammonium persulfate is dissolved in 15-30 mL of distilled water, the mixture is stirred uniformly at room temperature to obtain an initiator solution, and the initiator solution is poured into a constant-pressure dropping funnel with the volume of 100 mL.
(8) 3.0-7.5 g of hydroxyethyl methacrylate monomer and 30-45 mL of distilled water are added into a 100mL small beaker, stirred uniformly at room temperature to obtain a monomer solution, and the monomer solution is poured into another constant-pressure dropping funnel with the volume of 100 mL.
(9) And (3) heating the system obtained in the step (6) to 50-65 ℃, starting to dropwise add the initiator solution obtained in the step (7), starting to dropwise add the monomer solution obtained in the step (8) synchronously after one third of the total mass of the initiator is dropwise added, controlling the dropwise addition to be finished within 4-6 hours, and continuing to react for 2-3 hours.
(10) And (3) after the reaction is finished, filtering the product obtained in the step (9) to obtain a filter cake, precipitating for 15-25 minutes by using 75-105 mL of analytically pure acetone, filtering after precipitation, washing the precipitate by using 30-45 mL of analytically pure absolute ethyl alcohol, filtering for 3 times, putting the filter cake into a glass vessel, and drying in a vacuum constant-temperature oven at 60 ℃ for 24 hours to constant weight to obtain the final product, namely the bagasse xylan aromatic oxalate-g-HEMA.
(11) The grafting rate and grafting efficiency of the xylan derivative were determined by the following method: wrapping the bagasse xylan vanillic acid-g-HEMA obtained in the step (10) by using filter paper, putting the wrapped bagasse xylan vanillic acid-g-HEMA into a Soxhlet extractor, adding 100-150 mL of acetone serving as an extracting agent into a flask, heating the flask in a constant-temperature water bath at 80-85 ℃, continuously extracting a sample in the Soxhlet extractor for 24 hours, taking out the extracted sample, and drying the sample in a drying oven at 60 ℃ for 24 hours to reach constant weight. The calculation formula of the grafting rate and the grafting efficiency is as follows:
in the formula:
g-grafting ratio,%;
GE — grafting efficiency,%;
W0-mass of raw bagasse xylan in g;
W1-mass of extracted pure bagasse xylan vanillic acid-g-HEMA, in g;
W2-mass of crude bagasse xylan vanillic acid-g-HEMA, in g.
The target product structure obtained by the invention is introduced with vanillic acid and HEMA, so that the problem of poor water solubility of the bagasse xylan is solved, the biological activity of the bagasse xylan is greatly improved by the active groups of the two, and the bagasse xylan has high application value in the fields of medicines, foods, functional materials and the like.
Drawings
FIG. 1 is an infrared spectrum of xylan from bagasse.
FIG. 2 is an infrared spectrum of bagasse xylan oxalate-g-HEMA synthesized by the present invention.
FIG. 3 is an SEM image of raw bagasse xylan.
FIG. 4 is an SEM image of bagasse xylan ester-g-HEMA synthesized in accordance with the present invention.
FIG. 5 is a graph showing TG and DTG curves of raw bagasse xylan.
FIG. 6 is a graph showing TG and DTG profiles of bagasse xylan ester oxalate-g-HEMA synthesized by the present invention.
The specific implementation mode is as follows:
example (b):
(1) and (3) placing 18.0g of bagasse xylan into a vacuum constant-temperature oven at 60 ℃ to dry for 24 hours to constant weight, thereby obtaining the dry-based bagasse xylan.
(2) Weighing 12.0 of the dry bagasse xylan obtained in the step (1) into a four-neck flask provided with a stirrer, a thermometer and a reflux device, adding 6.0g of vanillic acid and 60mL of analytically pure N, N-dimethylformamide, heating to 50 ℃ under stirring, and continuing stirring for 10 minutes.
(3) And (3) adding 0.6 g of p-toluenesulfonic acid and 0.03g of tetraisopropyl titanate into the material system obtained in the step (2), and stirring and reacting for 6 hours at the temperature of 80 ℃.
(4) And (4) carrying out suction filtration on the material obtained in the step (3), washing with 50mL of analytically pure absolute ethyl alcohol, and carrying out suction filtration 3 times respectively to obtain filter cakes.
(5) And (5) putting the filter cake obtained in the step (4) into a watch glass, and putting the watch glass in a vacuum constant-temperature oven at 60 ℃ for drying for 24 hours until the weight is constant, so as to obtain the bagasse xylan oxalate.
(6) And (3) adding 6.0g of the bagasse xylan vanillic acid ester obtained in the step (5) into another four-neck flask provided with a stirrer, a thermometer and a reflux condenser, adding 60mL of distilled water, and stirring at room temperature for 10 minutes.
(7) 0.60g of ammonium persulfate was dissolved in 30mL of distilled water, and stirred at room temperature to obtain an initiator solution, which was poured into a constant pressure dropping funnel having a volume of 100 mL.
(8) 4.5g of hydroxyethyl methacrylate monomer and 35mL of distilled water are added into a 100mL small beaker, stirred uniformly at room temperature to obtain a monomer solution, and the monomer solution is poured into another constant-pressure dropping funnel with the volume of 100 mL.
(9) And (3) heating the system obtained in the step (6) to 60 ℃, starting to dropwise add the initiator solution obtained in the step (7), starting to dropwise add the monomer solution obtained in the step (8) synchronously after one third of the total mass of the initiator is dropwise added, controlling the dropwise addition to be finished within 4-6 hours, and continuing to react for 2 hours.
(10) And (3) after the reaction is finished, filtering the product obtained in the step (9) to obtain a filter cake, precipitating for 15 minutes by using 75mL of analytically pure acetone, filtering after precipitation, washing the precipitate by using 45mL of analytically pure absolute ethyl alcohol, filtering for 3 times, putting the filter cake into a glass vessel, and drying in a vacuum constant-temperature oven at 60 ℃ for 24 hours to constant weight to obtain the final product, namely the bagasse xylan aromatic oxalate-g-HEMA.
The product was analyzed by IR at 1744.62cm-1The position is a stretching vibration peak of ester carbonyl, which shows that ester bonds formed after the esterification reaction of xylan are superposed with ester bonds of hydroxyethyl methacrylate; at 1467.37cm-1A skeleton vibration absorption peak with a vanillic acid benzene ring structure shows that the xylan and the vanillic acid have esterification reaction; at 3220.13cm-1The peaks appearing on the left and right are double peaks appearing in the phenolic hydroxyl group of vanillic acid and the hydroxyl group of the polysaccharide compound. By SEM analysis, the surface appearance of the particles is contrasted, so that the original bagasse xylan is round or approximately round, the particles are complete, and the surface is smooth; the bagasse xylan-g-HEMA particles have rough surfaces, greatly changed surface shapes and surfacesA large amount of wrinkles and gullies exist, the roughness is uneven, the roughness is obviously increased, and a plurality of hole-shaped structures exist. The results prove that the structure of the bagasse xylan is changed to a great extent after modification, the molecular surface structure of the original bagasse xylan is damaged, and two active groups of VA and HEMA are introduced.
The analysis of the product by TG-DTG shows that the thermal decomposition of the product can be divided into 3 stages. In the first stage, the mass loss is about 20 percent at 0-240 ℃, and mainly the moisture loss; at the second stage, the mass loss rate is obviously accelerated at 240-400 ℃, and about 50% of mass is lost, namely the breakage of chemical bonds connected with the xylan main chain after esterification or grafting modification; in the third stage, the mass loss is about 26 percent at 400-600 ℃, and the main chain of the bagasse xylan aromatic oxalate-g-HEMA is broken; the mass does not change much after 600 ℃. Obviously, the bagasse xylan obtained after modification has improved thermal stability.
Claims (1)
1. A preparation method of bioactive bagasse xylan oxalate-g-HEMA is characterized by comprising the following specific steps:
(1) placing 15.0 ~ 25.0.0 g of bagasse xylan into a vacuum constant-temperature oven at 60 ℃ to dry for 24 hours to constant weight, so as to obtain dry-based bagasse xylan;
(2) weighing 12.0 ~ 21.0.0 g of the dry bagasse xylan obtained in the step (1) into a four-neck flask provided with a stirrer, a thermometer and a reflux device, adding 6.0 ~ 12.0.0 g of vanillic acid and 60 ~ 90mL of analytically pure N, N-dimethylformamide, heating to 50 ~ 80 ℃ under stirring, and continuing stirring for 10 ~ 15 minutes;
(3) adding 0.6 ~ 1.2.2 g of p-toluenesulfonic acid and 0.03 ~ 0.045.045 g of tetraisopropyl titanate into the material system obtained in the step (2), and stirring and reacting at 50 ~ 80 ℃ for 5 ~ 7 hours;
(4) carrying out suction filtration on the material obtained in the step (3), washing with 45 ~ 90mL of analytically pure absolute ethyl alcohol, and carrying out suction filtration for 3 times respectively to obtain filter cakes;
(5) putting the filter cake obtained in the step (4) into a watch glass, and putting the watch glass in a vacuum constant-temperature oven at 60 ℃ for drying for 24 hours until the weight is constant, so as to obtain bagasse xylan oxalate;
(6) adding 3.0 ~ 7.5.5 g of bagasse xylan vanillic acid ester obtained in the step (5) into another four-neck flask provided with a stirrer, a thermometer and a reflux condenser, adding 45 ~ 75mL of distilled water, and stirring at room temperature for 5 ~ 10 minutes;
(7) 0.30 ~ 0.75.75 g of ammonium persulfate is dissolved in 15 ~ 30mL of distilled water, the mixture is stirred uniformly at room temperature to obtain an initiator solution, and the initiator solution is poured into a constant-pressure dropping funnel with the volume of 100 mL;
(8) 3.0 g of 3.0 ~ 7.5.5 g of hydroxyethyl methacrylate monomer and 30 ~ 45mL of distilled water are added into a 100mL small beaker, stirred uniformly at room temperature to obtain a monomer solution, and the monomer solution is poured into another constant-pressure dropping funnel with the volume of 100 mL;
(9) heating the system obtained in the step (6) to 50 ~ 65 ℃, starting to dropwise add the initiator solution obtained in the step (7), starting to dropwise add the monomer solution obtained in the step (8) synchronously after one third of the total mass of the initiator is dropwise added, controlling the dropwise addition to be finished within 4 ~ 6 hours, and continuing to react for 2 ~ 3 hours;
(10) and (3) after the reaction is finished, filtering the product obtained in the step (9) to obtain a filter cake, precipitating for 15 ~ 25 minutes by using 75 ~ 105mL of analytically pure acetone, filtering after precipitation, washing the precipitate by using 30 ~ 45mL of analytically pure absolute ethyl alcohol, filtering for 3 times, putting the filter cake into a glass dish, and drying in a vacuum constant-temperature oven at 60 ℃ for 24 hours to constant weight to obtain the final product, namely the bagasse xylan aromatic oxalate-g-HEMA.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094377A (en) * | 2020-09-06 | 2020-12-18 | 桂林理工大学 | Method for synthesizing bagasse xylan protocatechuate-g-HEMA in ionic liquid |
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| US3872067A (en) * | 1973-09-17 | 1975-03-18 | Morton Norwich Products Inc | Process for preparing chloromethylated polystyrene-divinylbenzene copolymer |
| CN106632856A (en) * | 2016-10-26 | 2017-05-10 | 桂林理工大学 | Preparation method of active bagasse xylan ferulate-g-LME/AA/AM |
| CN110194817A (en) * | 2019-05-28 | 2019-09-03 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan vanilla acid esters-g-HEMA/MAA/EA |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3872067A (en) * | 1973-09-17 | 1975-03-18 | Morton Norwich Products Inc | Process for preparing chloromethylated polystyrene-divinylbenzene copolymer |
| CN106632856A (en) * | 2016-10-26 | 2017-05-10 | 桂林理工大学 | Preparation method of active bagasse xylan ferulate-g-LME/AA/AM |
| CN110194817A (en) * | 2019-05-28 | 2019-09-03 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan vanilla acid esters-g-HEMA/MAA/EA |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112094377A (en) * | 2020-09-06 | 2020-12-18 | 桂林理工大学 | Method for synthesizing bagasse xylan protocatechuate-g-HEMA in ionic liquid |
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Application publication date: 20191220 |