CN112250797A - Synthesis method of active bagasse xylan bromopyruvate-g-AM/MA/BzA - Google Patents
Synthesis method of active bagasse xylan bromopyruvate-g-AM/MA/BzA Download PDFInfo
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Abstract
The invention discloses a method for synthesizing active bagasse xylan bromopyruvate-g-AM/MA/BzA. Bagasse xylan is used as a main raw material, acrylamide, methyl acrylate and benzyl acrylate are used as grafting monomers, and the bagasse xylan-g-AM/MA/BzA is synthesized through a free radical reaction in a water solvent; then, 3-bromopyruvic acid is used as an esterifying agent, p-toluenesulfonic acid and hexadecyltrimethylammonium bromide are used as composite catalysts, and the final product bagasse xylan bromopyruvate-g-AM/MA/BzA is synthesized through an esterification catalytic reaction in an organic solvent. The thermal decomposition rate of the composite modified product is obviously reduced, the thermal stability is improved, the utilization rate of active hydroxyl on a bagasse xylan molecular chain is improved, the functional characteristics and the biological activity of the bagasse xylan molecular chain are optimized, and the composite modified product is expected to be applied to the fields of high polymer materials, drug carriers and the like.
Description
Technical Field
The invention relates to the technical field of biomass functional polymer materials, in particular to a method for synthesizing active bagasse xylan bromopyruvate-g-AM/MA/BzA.
Background
Bagasse xylan, one of natural polysaccharides, has certain effects in resisting tumors and enhancing immunity of the organism. On the basis of the biological activity of bagasse xylan, novel polysaccharide antitumor drugs are developed, and the polysaccharide antitumor drugs have wide application prospects in malignant tumor healing. How to effectively utilize active hydroxyl in the molecular structure of the bagasse xylan to optimize and enhance the biological function of the bagasse xylan has more problems which need to be explored. The common composite modification technology is esterification and grafting, and because the esterifying agent occupies most of active hydroxyl groups on a molecular chain, the grafting efficiency is influenced to a certain degree, particularly multi-element grafting, and the stability of the modified bagasse xylan does not achieve an ideal effect. On the other hand, different types and amounts of the esterification agents lead to different introduced active groups, and thus the activity effect is changed. The more kinds of active groups are introduced into the xylan molecular chain, the greater the influence on the biological activity of xylan is. By a molecular modification method, 3-bromopyruvic acid is used as an esterifying agent to be applied to the modified bagasse xylan polybasic grafted derivative, so that the thermal stability and functionality of the bagasse xylan are improved to a certain extent, and the product has great potential in the application fields of functional polymer materials, drug carriers and the like.
The bagasse xylan is subjected to multi-element grafting modification by using a plurality of monomers such as Acrylamide (AM), Methyl Acrylate (MA), benzyl acrylate (BzA) and the like, so that the utilization rate of hydroxyl groups on a molecular chain can be effectively improved. The bagasse xylan after grafting modification can enhance the thermal stability due to the existence of carbon-oxygen double bonds and benzene rings, so that the biological activity of the bagasse xylan is improved. Meanwhile, 3-bromopyruvate is used as a strong alkylating agent, can inactivate protein or enzyme containing sulfydryl, and has a synergistic anticancer effect. If 3-bromopyruvic acid is used as an esterifying agent, the esterified and modified bagasse xylan polybasic grafted derivative can have a corresponding targeted anticancer effect, so that a reference is provided for the research of the bagasse xylan derivative on a targeted anticancer drug. In addition, the esterified product contains a large amount of carbonyl and acyl, and the thermal stability of the bagasse xylan polybasic graft copolymer can be further improved.
The method takes bagasse xylan as a main raw material, acrylamide, methyl acrylate and benzyl acrylate as grafting monomers, firstly, a redox initiator is dripped by a semi-continuous starvation method, and the bagasse xylan-g-AM/MA/BzA is synthesized by a free radical reaction in a water solvent; then, bagasse xylan-g-AM/MA/BzA is used as a main reactant, 3-bromopyruvic acid is used as an esterifying agent, p-toluenesulfonic acid and hexadecyltrimethylammonium bromide are used as composite catalysts, and the final product, namely bagasse xylan bromopyruvate-g-AM/MA/BzA, is synthesized through an esterification catalytic reaction in an organic solvent.
Disclosure of Invention
The invention aims to improve the utilization rate of active hydroxyl on a bagasse xylan molecular chain and enhance the thermal stability of the bagasse xylan, thereby enhancing the biological activity of the bagasse xylan, expanding the application of the bagasse xylan in the fields of high polymer materials, drug carriers and the like, and providing a synthetic method of active bagasse xylan bromopyruvate-g-AM/MA/BzA.
The method comprises the following specific steps:
(1) and (3) placing 15-20 g of bagasse xylan into a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to obtain the dry-based bagasse xylan.
(2) Weighing 0.80-1.60 g of ammonium persulfate and 0.40-0.80 g of sodium bisulfite in a 50mL beaker according to the mass ratio of ammonium persulfate to sodium bisulfite being 2:1, adding 20-25 mL of distilled water, stirring and dissolving uniformly to prepare a redox system initiator solution, and pouring the redox system initiator solution into a 100mL constant-pressure dropping funnel for later use.
(3) Weighing 1.0-3.0 g of acrylamide, respectively weighing 1.0-3.0 mL of analytically pure methyl acrylate and 1.0-3.0 mL of analytically pure benzyl acrylate, and mixing with 10-30 mL of analytically pure benzyl acrylate according to a volume ratio VAcetone (II):VWater (W)The aqueous solution of analytically pure acetone prepared at a ratio of 1:3 was placed in a 50mL beaker together, and after uniform dissolution by stirring, a monomer mixture was obtained and poured into another 100mL constant pressure dropping funnel for further use.
(4) Weighing 12.0-18.0 g of the dry bagasse xylan obtained in the step (1), placing the dry bagasse xylan into a 250mL four-neck flask, adding 60-120 mL of distilled water, heating to 50-55 ℃, and stirring for 20-30 minutes to obtain the bagasse xylan activation solution.
(5) Adding about one third of the mixed initiator solution obtained in the step (2) to the bagasse xylan activation solution obtained in the step (4), stirring for 10-20 minutes, then synchronously dropwise adding the monomer mixed solution obtained in the step (3) and the rest two thirds of the initiator solution obtained in the step (2), controlling the temperature at 50-65 ℃ and the dropwise adding time at 3-4 hours, continuing to react for 3-5 hours after the dropwise adding is finished, and cooling the obtained material to room temperature.
(6) And (3) precipitating the material obtained in the step (5) for 25-35 minutes by using 50-70 mL of analytically pure acetone, and after suction filtration, washing and suction filtration the precipitate for 2-3 times by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol in sequence. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a bagasse xylan-g-AM/MA/BzA crude product.
(7) Placing the bagasse xylan-g-AM/MA/BzA crude product obtained in the step (6) into a Soxhlet extractor, and adding 150-200 mL of analytically pure acetone for extraction for 18-24 hours; and (3) taking out the materials after extraction, putting the materials into a watch glass, and drying the materials in a vacuum constant-temperature drying oven at the temperature of 60 ℃ for 16-24 hours until the weight is constant to obtain the pure graft copolymer bagasse xylan-g-AM/MA/BzA.
(8) Weighing 2.0-6.0 g of pure bagasse xylan-g-AM/MA/BzA obtained in the step (7) and placing the pure bagasse xylan-g-AM/MA/BzA into a 250mL four-neck flask according to the mass ratio mP-toluenesulfonic acid:mBagasse xylan-g-AM/MA/BzA0.1:1 and m3-Bromopyruvic acid:mBagasse xylan-g-AM/MA/BzA1.0-3.0 g of esterifying agent 3-bromopyruvic acid, 0.1-0.15 g of catalyst hexadecyltrimethylammonium bromide and 0.05-0.15 g of catalyst p-toluenesulfonic acid are sequentially added according to the proportion of 1:1, and then 50-70 mL of analytically pure dichloroethane is added as a solvent. Heating to 50-75 ℃ while stirring, continuously stirring for reaction for 5-8 hours, and cooling the obtained material to room temperature.
(9) And (3) precipitating the material obtained in the step (8) for 25-35 minutes by using 50-70 mL of analytically pure acetone, and after suction filtration, washing and suction filtration the precipitate for 2-3 times by using 50-70 mL of analytically pure acetone and 20-50 mL of absolute ethyl alcohol in sequence. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 18-24 hours to constant weight to obtain the bagasse xylan bromopyruvate-g-AM/MA/BzA product.
(10) And (3) measuring the esterification substitution degree of the bagasse xylan bromopyruvate-g-AM/MA/BzA product obtained in the step (9) by using an acid-base titration method, which comprises the following specific steps: accurately weighing about 0.5g of a product sample into a 50mL conical flask, adding 20mL of deionized water into the conical flask, fully shaking, adding 3 drops of phenolphthalein indicator, titrating the sample solution to light red by using a 0.5mol/L NaOH standard solution, and maintaining the red color within 30 seconds without removing the indicator. Adding 2.5mL of 0.5mol/L sodium hydroxide solution, shaking up, sealing, placing in an electric oscillator at room temperature, shaking for saponification for 4 hours, titrating with 0.5mol/L hydrochloric acid standard solution until the solution system is colorless, and recording the volume of the hydrochloric acid standard solution consumed by titration as V1(ii) a Under the same conditions, a blank titration was carried out with the pure bagasse xylan graft product, and the volume V of the hydrochloric acid-depleted standard solution was recorded0. Mass fraction (w) of carboxylic acid acyl groups in the target productc) Bagasse xylan bromopyruvate-g-AM/MA/BzA esterification substitution Degree (DS)C) The calculation formula of (a) is as follows:
in the formula:
wc-the target product contains the mass fraction of carboxylic acid acyl groups,%;
V0blank titration of the bagasse xylan graft product consumes the volume of a hydrochloric acid standard solution in unit mL;
V1titrating the volume of the hydrochloric acid standard solution consumed by the target product in mL;
CHCl-hydrochloric acid standard solution concentration, in moL/L;
m is the mass of the target product sample in g;
DSc-degree of esterification substitution of bagasse xylan bromopyruvate-g-AM/MA/BzA;
m and 132-acyl group of Carboxylic acid esterifying agent and relative molecular mass of the bagasse xylan anhydroxylose unit.
Compared with the original bagasse xylan, the bagasse xylan bromopyruvate-g-AM/MA/BzA obtained by the invention has the advantages that the thermal decomposition rate is obviously reduced, and the thermal stability is improved. The compound modification product not only improves the utilization rate of active hydroxyl on the bagasse xylan molecular chain, but also optimizes the functional characteristics and the biological activity of the bagasse xylan molecular chain, and widens the application range of the bagasse xylan molecular chain in the fields of high polymer materials, drug carriers and the like.
Drawings
FIG. 1 is an SEM photograph of raw bagasse xylan.
FIG. 2 is an SEM photograph of bagasse xylan bromopyruvate-g-AM/MA/BzA prepared in accordance with an embodiment of the present invention.
FIG. 3 is an IR chart of raw bagasse xylan and bagasse xylan bromopyruvate-g-AM/MA/BzA prepared according to an example of the present invention; wherein: a is an IR chart of original bagasse xylan, and b is an IR chart of bagasse xylan bromopyruvate-g-AM/MA/BzA prepared in the examples of the present invention.
Figure 4 is an XRD pattern of raw bagasse xylan.
FIG. 5 is an XRD pattern of bagasse xylan bromopyruvate-g-AM/MA/BzA prepared in accordance with an example of the present invention.
FIG. 6 is a graph showing TG and DTG curves of raw bagasse xylan.
FIG. 7 is a TG and DTG curve of bagasse xylan bromopyruvate-g-AM/MA/BzA prepared in accordance with an example of the present invention.
Detailed Description
Example (b):
(1) and (3) drying 20g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to obtain the dry-based bagasse xylan.
(2) Weighing 1.60g of ammonium persulfate and 0.80g of sodium bisulfite in a 50mL beaker according to the mass ratio of ammonium persulfate to sodium bisulfite of 2:1, adding 25mL of distilled water, stirring and dissolving uniformly to prepare redox system initiator solution, and pouring the redox system initiator solution into a 100mL constant-pressure dropping funnel for later use.
(3) 2.0g of acrylamide are weighed, 2.0mL of analytically pure methyl acrylate and 2.0mL of analytically pure benzyl acrylate are weighed respectively, and the volume ratio of the weighed quantity to the volume ratio of 20mL of analytically pure benzyl acrylate is VAcetone (II):VWater (W)The aqueous solution of analytically pure acetone prepared at a ratio of 1:3 was placed in a 50mL beaker together, and after uniform dissolution by stirring, a monomer mixture was obtained and poured into another 100mL constant pressure dropping funnel for further use.
(4) Weighing 12.0g of the dry bagasse xylan obtained in the step (1), placing the dry bagasse xylan into a 250mL four-neck flask, adding 120mL of distilled water, heating to 50 ℃, and stirring for 20-30 minutes to obtain the bagasse xylan activation solution.
(5) Adding about one third of the mixed initiator solution obtained in the step (2) to the bagasse xylan activation solution obtained in the step (4), stirring for 10-20 minutes, then synchronously dropwise adding the monomer mixed solution obtained in the step (3) and the rest two thirds of the initiator solution obtained in the step (2), controlling the temperature at 60 ℃ and the dropwise adding time at 3-4 hours, continuing to react for 3-5 hours after the dropwise adding is finished, and cooling the obtained material to room temperature.
(6) And (3) precipitating the material obtained in the step (5) by using 60mL of analytically pure acetone for 30 minutes, and after suction filtration, washing and suction filtration the precipitate by using 80mL of analytically pure acetone and 60mL of analytically pure absolute ethyl alcohol sequentially for 3 times. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a bagasse xylan-g-AM/MA/BzA crude product.
(7) Placing the bagasse xylan-g-AM/MA/BzA crude product obtained in the step (6) into a Soxhlet extractor, and adding 200mL of analytically pure acetone for extraction for 24 hours; and (3) taking out the materials after extraction, putting the materials into a watch glass, and placing the watch glass in a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours until the weight is constant to obtain the pure graft copolymer bagasse xylan-g-AM/MA/BzA.
(8) Weighing 5.0g of the pure bagasse xylan-g-AM/MA/BzA obtained in the step (7) and placing the pure bagasse xylan-g-AM/MA/BzA into a 250mL four-neck flask according to the mass ratio mP-toluenesulfonic acid:mBagasse xylan-g-AM/MA/BzA0.1:1 and m3-Bromopyruvic acid:mBagasse xylan-g-AM/MA/BzA2.5g of esterifying agent 3-bromopyruvic acid, 0.15g of catalyst cetyltrimethylammonium bromide and 0.10g of catalyst p-toluenesulfonic acid were added in this order in a ratio of 1:1, and 70mL of analytically pure dichloroethane was added as a solvent. Heating to 65 ℃ under stirring, continuously stirring for reacting for 6 hours, and cooling the obtained material to room temperature.
(9) And (3) precipitating the material obtained in the step (8) by using 60mL of analytically pure acetone for 30 minutes, and after suction filtration, washing and suction filtration the precipitate by using 60mL of analytically pure acetone and 40mL of absolute ethyl alcohol sequentially for 3 times. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain the product bagasse xylan bromopyruvate-g-AM/MA/BzA.
(10) Measuring the esterification substitution degree of the product bagasse xylan bromopyruvate-g-AM/MA/BzA obtained in the step (9) by adopting an acid-base titration method, and measuring the DScIs 0.30.
SEM analysis of the product bagasse xylan bromopyruvate-g-AM/MA/BzA shows that the bagasse xylan bromopyruvate-g-AM/MA/BzA particles are irregular in appearance, rough and uneven in surface, a plurality of branches are mutually crosslinked, the parts are of net structures, the internal structures are complex, and the appearance of the bagasse xylan surface is greatly changed due to the branched chain introduced by esterification grafting. By IR analysis, the bagasse xylan bromopyruvate-g-AM/MA/BzA showed 2921.05cm-1Methylene antisymmetric absorption ofPeak 1662.86cm-1Characteristic absorption peak of amide bond in acrylamide (1728.99 cm)-1The peak of coincidence between the ester group of (A) and the C ═ O stretching vibration absorption peak of the carbonyl group in 3-bromopyruvic acid, and the peak of coincidence between the C ═ O stretching vibration absorption peaks of methyl acrylate and benzyl acrylate, 650.01cm-1And the characteristic peaks show that the grafting monomers of acrylamide, methyl acrylate, benzyl acrylate and 3-bromopyruvic acid successfully react with hydroxyl on bagasse xylan, and the molecular chain of the bagasse xylan is introduced with the characteristic groups of acrylamide, methyl acrylate, benzyl acrylate and 3-bromopyruvic acid. XRD analysis shows that the bagasse xylan bromopyruvate ester-g-AM/MA/BzA has obvious diffraction peaks at 11.2 degrees, 12.5 degrees, 19.4 degrees, 23.1 degrees, 25.5 degrees and 31.7 degrees; the contrast finds that compared with the original bagasse xylan, the modified bagasse xylan derivative has small change of diffraction peaks within an angle of 10-30 degrees, a new and obvious diffraction peak of 31.7 degrees appears after 30 degrees, and some fine diffraction peaks appear later, which indicates that the modified bagasse xylan forms a new crystallization area, the crystallinity is increased, and the crystal area is enlarged. The TG-DTG curve of the analyzed product can be divided into five stages along with the change process of the product quality along with the temperature, the loss amount of the sample is 10 percent in the temperature range of 0-100 ℃, and the reduction of the part of the quality can be caused by the evaporation of part of residual water in the sample; the mass loss of the sample in the temperature range of 100 ℃ to 200 ℃ is about 20%, probably caused by the removal of crystal water in the sample and the cleavage of the bonds of some of the unreacted hydroxyl groups in the xylan; the mass loss of the sample is about 35% in the temperature range of 200-400 ℃, and the mass loss of the whole sample is the most at the stage, mainly caused by the breakage of xylan molecular chains; approximately 30% of the sample mass loss in the 400 ℃ to 530 ℃ range, probably due to branch scission after graft esterification; the sample quality is basically unchanged at 530-800 ℃. By thermogravimetric comparison analysis with the original bagasse xylan, it can be shown that the thermal stability of the bagasse xylan is improved by esterification graft modification.
Claims (1)
1. A method for synthesizing active bagasse xylan bromopyruvate-g-AM/MA/BzA is characterized by comprising the following specific steps:
(1) placing 15-20 g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours to obtain dry-based bagasse xylan;
(2) weighing 0.80-1.60 g of ammonium persulfate and 0.40-0.80 g of sodium bisulfite in a 50mL beaker according to the mass ratio of ammonium persulfate to sodium bisulfite =2:1, adding 20-25 mL of distilled water, stirring and dissolving uniformly to prepare a redox system initiator solution, and pouring the redox system initiator solution into a 100mL constant-pressure dropping funnel for later use;
(3) weighing 1.0-3.0 g of acrylamide, respectively weighing 1.0-3.0 mL of analytically pure methyl acrylate and 1.0-3.0 mL of analytically pure benzyl acrylate, and mixing with 10-30 mL of analytically pure benzyl acrylate according to volume ratio V Acetone (II):V Water (W)Putting the water solution of analytically pure acetone prepared in a ratio of 1:3 into a 50mL beaker, stirring and dissolving uniformly to obtain a monomer mixed solution, and pouring the monomer mixed solution into another 100mL constant-pressure dropping funnel for later use;
(4) weighing 12.0-18.0 g of the dry bagasse xylan obtained in the step (1), placing the dry bagasse xylan into a 250mL four-neck flask, adding 60-120 mL of distilled water, heating to 50-55 ℃, and stirring for 20-30 minutes to obtain bagasse xylan activating solution;
(5) firstly, adding one third of the mixed initiator solution obtained in the step (2) to the bagasse xylan activation solution obtained in the step (4), stirring for 10-20 minutes, then synchronously dropwise adding the monomer mixed solution obtained in the step (3) and the rest two thirds of the initiator solution obtained in the step (2), controlling the temperature at 50-65 ℃ and the dropwise adding time at 3-4 hours, continuously reacting for 3-5 hours after dropwise adding is finished, and cooling the obtained material to room temperature;
(6) precipitating the material obtained in the step (5) for 25-35 minutes by using 50-70 mL of analytically pure acetone, and after suction filtration, washing and suction filtering the precipitate for 2-3 times by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol in sequence;
the filter cake is placed in a constant-temperature drying oven at 60 ℃ and dried for 24 hours to constant weight, and a bagasse xylan-g-AM/MA/BzA crude product is obtained;
(7) placing the bagasse xylan-g-AM/MA/BzA crude product obtained in the step (6) into a Soxhlet extractor, and adding 150-200 mL of analytically pure acetone for extraction for 18-24 hours; after extraction, taking out the materials, putting the materials into a watch glass, and drying the materials in a vacuum constant-temperature drying oven at 60 ℃ for 16-24 hours until the weight is constant to obtain pure graft copolymer bagasse xylan-g-AM/MA/BzA;
(8) weighing 2.0-6.0 g of pure bagasse xylan-g-AM/MA/BzA obtained in the step (7) and placing the pure bagasse xylan-g-AM/MA/BzA into a 250mL four-neck flask according to the mass ratiom P-toluenesulfonic acid:m Bagasse xylan-g-AM/MA/BzA=0.1:1 andm 3-Bromopyruvic acid:m Bagasse xylan-g-AM/MA/BzA1.0-3.0 g of esterifying agent 3-bromopyruvic acid, 0.1-0.15 g of catalyst hexadecyltrimethylammonium bromide and 0.05-0.15 g of catalyst p-toluenesulfonic acid are sequentially added according to the proportion of 1:1, and then 50-70 mL of analytically pure dichloroethane is added as a solvent;
heating to 50-75 ℃ under stirring, continuously stirring for reaction for 5-8 hours, and cooling the obtained material to room temperature;
(9) precipitating the material obtained in the step (8) for 25-35 minutes by using 50-70 mL of analytically pure acetone, and after suction filtration, washing and suction filtering the precipitate for 2-3 times by using 50-70 mL of analytically pure acetone and 20-50 mL of absolute ethyl alcohol in sequence;
and (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 18-24 hours to constant weight to obtain the bagasse xylan bromopyruvate-g-AM/MA/BzA product.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3012146A1 (en) * | 2013-10-23 | 2015-04-24 | Ct Tech De L Ind Des Papiers Cartons Et Celluloses | ORGANIC PARTICLES, PREPARATION METHOD AND USE IN THE MANUFACTURE OF PAPER |
| CN107400186A (en) * | 2017-09-15 | 2017-11-28 | 桂林理工大学 | A kind of active bagasse xylan cloves acid esters g AM/ MMA/BA synthetic method |
| CN107417857A (en) * | 2017-09-15 | 2017-12-01 | 桂林理工大学 | Active anticancer derivative bagasse xylan cloves acid esters g AM/MMA synthetic method |
| CN107540789A (en) * | 2017-09-15 | 2018-01-05 | 桂林理工大学 | Biologically active derivatives bagasse xylan cloves acid esters g AM synthetic method |
| WO2018036025A1 (en) * | 2016-08-22 | 2018-03-01 | 华南理工大学 | Xylan-based double network nanocomposite hydrogel and preparation and application thereof |
| CN109369828A (en) * | 2018-10-21 | 2019-02-22 | 桂林理工大学 | A kind of synthetic method of anti-lung cancer activity bagasse xylan caffeic acid ester-g-AM |
| CN109400768A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of bioactivity bagasse xylan -4- acetylamino cinnamate-g-AM/MMA |
| CN109400812A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of anti-tumor activity crosslinking bagasse xylan caffeic acid ester-g-AM/BA |
| CN109400767A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method being crosslinked bagasse xylan -4- acetylamino cinnamate-g-AM |
| CN109400757A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan o-toluic acid esterification-g-AM |
| CN109400769A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan o-toluic acid ester-g-AM/MMA/BA |
| CN109400770A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of anticancer activity bagasse xylan -4- acetylamino cinnamate-g-AM/BA |
| CN109400759A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of bagasse xylan o-toluic acid ester-g-AM/MMA |
-
2020
- 2020-09-06 CN CN202010925070.3A patent/CN112250797A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3012146A1 (en) * | 2013-10-23 | 2015-04-24 | Ct Tech De L Ind Des Papiers Cartons Et Celluloses | ORGANIC PARTICLES, PREPARATION METHOD AND USE IN THE MANUFACTURE OF PAPER |
| WO2018036025A1 (en) * | 2016-08-22 | 2018-03-01 | 华南理工大学 | Xylan-based double network nanocomposite hydrogel and preparation and application thereof |
| CN107400186A (en) * | 2017-09-15 | 2017-11-28 | 桂林理工大学 | A kind of active bagasse xylan cloves acid esters g AM/ MMA/BA synthetic method |
| CN107417857A (en) * | 2017-09-15 | 2017-12-01 | 桂林理工大学 | Active anticancer derivative bagasse xylan cloves acid esters g AM/MMA synthetic method |
| CN107540789A (en) * | 2017-09-15 | 2018-01-05 | 桂林理工大学 | Biologically active derivatives bagasse xylan cloves acid esters g AM synthetic method |
| CN109400768A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of bioactivity bagasse xylan -4- acetylamino cinnamate-g-AM/MMA |
| CN109369828A (en) * | 2018-10-21 | 2019-02-22 | 桂林理工大学 | A kind of synthetic method of anti-lung cancer activity bagasse xylan caffeic acid ester-g-AM |
| CN109400812A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of anti-tumor activity crosslinking bagasse xylan caffeic acid ester-g-AM/BA |
| CN109400767A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method being crosslinked bagasse xylan -4- acetylamino cinnamate-g-AM |
| CN109400757A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan o-toluic acid esterification-g-AM |
| CN109400769A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of activity bagasse xylan o-toluic acid ester-g-AM/MMA/BA |
| CN109400770A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of anticancer activity bagasse xylan -4- acetylamino cinnamate-g-AM/BA |
| CN109400759A (en) * | 2018-10-21 | 2019-03-01 | 桂林理工大学 | A kind of synthetic method of bagasse xylan o-toluic acid ester-g-AM/MMA |
Non-Patent Citations (10)
| Title |
|---|
| JINGXIA QIAN等: "Methacrylic acid/butyl acrylate onto feruloylated bagasse xylan: Graft copolymerization and biological activity", 《MATERIALS SCIENCE & ENGINEERING C》 * |
| 严家文等: "靶向肿瘤糖酵解途径用于肿瘤治疗的研究进展", 《中国新药杂志》 * |
| 左凯等: "蔗渣木聚糖没食子酸酯－ｇ－ＬＭＥ／ＡＡ／ＡＭ复合功能性衍生物", 《化工新型材料》 * |
| 曾常茜等: "3-溴丙酮酸抗肿瘤作用及机制研究", 《中国新药杂志》 * |
| 李和平等: "ＡＭ／ＭＭＡ－ＢＸ交联型接枝共聚物的合成与表征", 《化工新型材料》 * |
| 李和平等: "交联AA/AM-g-黄原酸酯化氰乙基木薯淀粉的合成与表征", 《化学反应工程与工艺》 * |
| 李和平等: "交联型木薯淀粉黄原酸酯－ｇ－ＡＡ／ＡＭ 微球的合成与表征", 《化工新型材料》 * |
| 李和平等: "木聚糖的化学修饰及其衍生物的应用研究进展", 《化工进展》 * |
| 李和平等: "蔗渣木聚糖-丙烯酰胺/丙烯酸丁酯三元接枝共聚物的合成与表征", 《化工新型材料》 * |
| 钱敬侠等: "蔗渣木聚糖没食子酸酯-g-MAA/BA 的合成及抗癌活性", 《精细化工》 * |
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