CN112239512A - Synthesis method of active bromine-containing bagasse xylan ester-g-AM - Google Patents
Synthesis method of active bromine-containing bagasse xylan ester-g-AM Download PDFInfo
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Abstract
The invention discloses a method for synthesizing active bromine-containing bagasse xylan ester-g-AM. Bagasse xylan is used as a main raw material, ammonium persulfate/sodium bisulfite is used as an initiator of a redox system, acrylamide is used as a grafting monomer, and a bagasse xylan-grafted acrylamide copolymer, namely bagasse xylan-g-AM, is synthesized in a water solvent through a free radical reaction; further taking 3-bromopyruvic acid as an esterifying agent and 4-dimethylaminopyridine and tetrabutyl titanate as a composite catalyst, and synthesizing the final product, namely the active bromine-containing derivative bagasse xylan bromopyruvate-g-AM, through catalytic esterification. The solubility of the product obtained by the invention in water is improved by 10%, the thermal stability is improved, the biological activity is also improved, and the application of the bagasse xylan in the fields of medicines, high molecular functional materials and the like is widened.
Description
Technical Field
The invention relates to the field of biomass functional materials, in particular to a method for synthesizing active bromine-containing bagasse xylan ester-g-AM.
Background
The strong drug resistance of tumor cells is always a difficult problem in the field of clinical medicine, so that the search for high-efficiency and low-toxicity anticancer drugs is an important direction of the current cancer research. Due to the unique structure, the xylan has various biological functions, such as basically no toxicity, good biodegradability, good biocompatibility, reproducibility, low oxygen osmotic pressure and the like, and particularly has certain capacity of inhibiting cancer cell proliferation. However, hydroxyl groups on C2 and C3 positions of the bagasse xylan easily form a strong hydrogen bond network, so that the activity of the bagasse xylan is low, and the functional application of the bagasse xylan is limited, so that the method for enhancing the activity of the bagasse xylan by chemical modification has important research value. In addition, the water solubility of bagasse xylan derivatives, which are modified by esterification and grafting, is still to be improved. Groups with anticancer activity are introduced by a composite chemical modification means, the solubility of the bagasse xylan is improved by eliminating the effect of hydrogen bonds to a certain extent while the variety of the bagasse xylan branched chains is increased, and the bioactivity is enhanced, so that a foundation is provided for the research of an injection type targeted anticancer drug carrier.
Acrylamide (AM) is used as a grafting monomer, the Acrylamide (AM) and bagasse xylan can be subjected to free radical reaction to synthesize a bagasse xylan copolymer, and a functional monomer mainly occupies hydroxyl on the C2 site of the original bagasse xylan, so that part of hydrogen bond effects in a xylan structure can be weakened, and the solubility of the xylan copolymer in water is improved. On the other hand, the bagasse xylan graft copolymer is further esterified and modified, most of the hydroxyl groups on the C2 and C3 positions are replaced, the strong hydrogen bond network of the bagasse xylan graft copolymer is damaged, the original unique functions of the bagasse xylan and the bagasse xylan graft copolymer are retained, and the water solubility of the bagasse xylan graft copolymer is further improved. In addition, tumor cells are greatly different from normal cells in productivity mechanism, mainly manifested by the aggravation of glycolysis of tumor cells and the provision of energy consumed by rapid cell proliferation through glycolysis, and hexokinase is one of the key enzymes in glycolysis pathway. If an active bromine-containing compound 3-bromopyruvic acid is introduced into the bagasse xylan binary graft copolymer structure through esterification reaction, the esterified product can be combined with the active site of mitochondrial outer membrane hexokinase II to inactivate the hexokinase II, so that the propagation of tumor cells is inhibited, and the aim of improving the bioactivity of the bagasse xylan derivative is fulfilled.
The bagasse xylan is used as a main raw material, ammonium persulfate/sodium bisulfite is used as an oxidation-reduction system initiator, acrylamide is used as a grafting monomer, and a bagasse xylan-grafted acrylamide copolymer, namely bagasse xylan-g-AM, is synthesized in a water solvent through a free radical reaction; and further, synthesizing the final product, namely the active bromine-containing derivative bagasse xylan bromopyruvate-g-AM, by catalytic esterification by using the bagasse xylan grafted acrylamide copolymer as an initial raw material, 3-bromopyruvic acid as an esterifying agent and 4-dimethylaminopyridine and tetrabutyl titanate as a composite catalyst.
Disclosure of Invention
The invention aims to provide a method for synthesizing active bromine-containing bagasse xylan ester-g-AM, which introduces a multifunctional group into a bagasse xylan molecular structure through a composite chemical modification means, can achieve the purpose of improving the water solubility of bagasse xylan while increasing the variety of bagasse xylan branched chains, thereby enhancing the biological activity of the bagasse xylan, expanding the application range and providing the method for synthesizing the active bromine-containing bagasse xylan ester-g-AM.
The method comprises the following specific steps:
(1) and (3) drying 12-15 g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to obtain the dry-based bagasse xylan.
(2) Weighing 0.60-1.60 g of ammonium persulfate and 0.30-0.80 g of sodium bisulfite into a 50mL beaker, adding 20-30 mL of distilled water, stirring and dissolving uniformly to prepare a redox system initiator solution, and pouring into a 100mL constant-pressure dropping funnel for later use.
(3) Weighing 3.0-6.0 g of acrylamide in a 100mL beaker, adding 20-40 mL of distilled water, stirring and dissolving uniformly to obtain a monomer solution, and pouring the monomer solution into another 100mL constant-pressure dropping funnel for later use.
(4) Weighing 6.0-12.0 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 ℃, and stirring for 20-30 minutes to obtain the bagasse xylan activating solution.
(5) And (3) synchronously dropwise adding the initiator solution obtained in the step (2) and the monomer solution obtained in the step (3) into the bagasse xylan activation solution obtained in the step (4), controlling the temperature to be 50-65 ℃ and the time to be 3-3.5 hours, and continuously reacting for 1.5-3 hours, and cooling the materials to room temperature.
(6) And (3) precipitating the material obtained in the step (5) for 20-30 minutes by using 40-60 mL of analytically pure acetone, and washing and filtering the precipitate obtained after the filtration for 2-3 times by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol respectively. 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 crude product.
(7) Placing the bagasse xylan-g-AM crude product obtained in the step (6) into a Soxhlet extractor, and adding 150-200 mL of analytically pure acetone for extraction for 16-24 hours; and taking out the extract, putting the extract into a watch glass, and drying the extract in a vacuum constant-temperature drying oven at the temperature of 60 ℃ for 12 to 24 hours until the weight is constant to obtain the pure bagasse xylan-g-AM graft copolymer.
(8) Weighing 2.0-4.0 g of the pure bagasse xylan-g-AM obtained in the step (7), placing the pure bagasse xylan-g-AM into a 250mL four-neck flask, sequentially adding 1.0-4.0 g of an esterifying agent 3-bromopyruvic acid, 0.12-0.20 g of a catalyst 4-dimethylaminopyridine, 0.06-0.10 g of a catalyst tetrabutyl titanate and 50-70 mL of a solvent to analyze pure dichloroethane, heating to 50-70 ℃, stirring for reacting for 6-8 hours, and cooling the material to room temperature.
(9) And (3) precipitating the material obtained in the step (8) for 20-30 minutes by using 40-60 mL of analytically pure acetone, and washing and filtering the precipitate obtained after the filtration for 2-3 times by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol respectively. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a product of the bromine-containing bagasse xylan derivative, namely bagasse xylan bromopyruvate-g-AM.
(10) Benefit toAnd (3) measuring the esterification substitution degree of the bagasse xylan bromopyruvate-g-AM obtained in the step (9) by using an acid-base titration method, which comprises the following specific steps: accurately weighing about 0.5g of product sample into a 50mL conical flask, adding 20mL of distilled 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 condition, carrying out blank titration by using bagasse xylan-g-AM, and recording the volume V of the consumed hydrochloric acid standard solution0. Mass fraction (w) of carboxylic acid acyl groups in the target productc) Bagasse xylan bromopyruvate-g-AM degree of substitution by esterification (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 substitution by esterification of bagasse xylan bromopyruvate-g-AM;
m and 132-acyl group of Carboxylic acid esterifying agent and relative molecular mass of the bagasse xylan anhydroxylose unit.
(11) And (3) determining the solubility of the dry-base bagasse xylan obtained in the step (1) and the product bagasse xylan bromopyruvate-g-AM obtained in the step (9). The procedure for determining the solubility of the product obtained is as follows: placing a round-bottom flask in an electromagnetic constant-temperature stirring water bath at room temperature, adding 10mL of distilled water into the flask, adding the product obtained in the step (9) in batches, namely the bagasse xylan bromopyruvate-g-AM, recording the mass of each addition, uninterruptedly sampling, observing the shape and the dissolution degree of crystals under a polarizing microscope until the crystals are not dissolved any more, and stopping stirring. Separating the undissolved product by centrifuge according to the mass (m) of added bagasse xylan bromopyruvate-g-AM1) And mass (m) of distilled water0) The solubility (S) of the bagasse xylan bromopyruvate-g-AM in water at room temperature was calculated. The calculation formula is as follows:
in the formula:
m1-mass of bagasse xylan bromopyruvate-g-AM in g;
m0-mass of distilled water in g;
s-solubility of bagasse xylan bromopyruvate-g-AM in water.
The invention synthesizes the bagasse xylan bromopyruvate-g-AM containing the bromine derivative by chemical modification methods such as grafting, esterification and the like. Compared with the original bagasse xylan, under the combined action of functional groups such as acrylamide, 3-bromopyruvic acid and the like, the solubility of the bagasse xylan in water at room temperature is improved by about 10%, and the thermal stability is also improved, so that the biological activity of the bagasse xylan is improved. The application of the product can not only improve the economic value of the bagasse xylan and promote the reasonable utilization of agricultural and forestry waste resources, but also widen the functional application of the bagasse xylan in the fields of medicines, foods, functional materials 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 synthesized by the example of the present invention.
FIG. 3 is an IR chart of raw bagasse xylan and bagasse xylan bromopyruvate-g-AM synthesized by an example of the present invention; a is an IR picture of original bagasse xylan, and b is an IR picture of bagasse xylan bromopyruvate-g-AM synthesized by the example 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 synthesized in accordance with an embodiment of the present invention.
FIG. 6 is a graph showing TG and DTG curves of raw bagasse xylan.
FIG. 7 shows TG and DTG curves of bagasse xylan bromopyruvate-g-AM synthesized in accordance with an embodiment of the present invention.
Detailed Description
Example (b):
(1) and (3) placing 15g 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 1.2g of ammonium persulfate and 0.80g of sodium bisulfite in a 50mL beaker, adding 30mL 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) 5.0g of acrylamide is weighed into a 100mL beaker, 30mL of distilled water is added, the mixture is stirred and dissolved uniformly to obtain a monomer solution, and the monomer solution is poured into another 100mL constant-pressure dropping funnel for standby.
(4) Weighing 10.0g of the dry bagasse xylan obtained in the step (1), placing the dry bagasse xylan into a 250mL four-neck flask, adding 90mL of distilled water, heating to 50 ℃, and stirring for 25 minutes to obtain the bagasse xylan activation solution.
(5) Synchronously dropwise adding the initiator solution obtained in the step (2) and the monomer solution obtained in the step (3) into the bagasse xylan activation solution obtained in the step (4), controlling the temperature at 50 ℃ and the time at 3 hours, continuously reacting for 3 hours, and cooling the materials to room temperature.
(6) And (3) precipitating the material obtained in the step (5) by using 50mL of analytically pure acetone for 25 minutes, and washing and filtering precipitates obtained after suction filtration by using 70mL of analytically pure acetone and 50mL of analytically pure absolute ethyl alcohol for 3 times respectively. 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 crude product.
(7) Placing the bagasse xylan-g-AM crude product obtained in the step (6) into a Soxhlet extractor, and adding 180mL of analytically pure acetone for extraction for 18 hours; and taking out the extract, putting the extract into a watch glass, and putting the watch glass in a vacuum constant-temperature drying oven at 60 ℃ for drying for 24 hours until the weight is constant, thereby obtaining the pure bagasse xylan-g-AM graft copolymer.
(8) Weighing 4.0g of the pure bagasse xylan-g-AM obtained in the step (7), placing the pure bagasse xylan-g-AM in a 250mL four-neck flask, sequentially adding 3.2g of an esterifying agent 3-bromopyruvic acid, 0.15g of a catalyst 4-dimethylaminopyridine, 0.08g of a catalyst tetrabutyl titanate and 60mL of a solvent analytically pure dichloroethane, heating to 60 ℃, stirring for reacting for 6 hours, and cooling the material to room temperature.
(9) And (3) precipitating the material obtained in the step (8) for 25 minutes by using 50mL of analytically pure acetone, and washing and filtering precipitates obtained after filtration for 2 times by using 70mL of analytically pure acetone and 50mL of analytically pure absolute ethyl alcohol respectively. And (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a product of the bromine-containing bagasse xylan derivative, namely bagasse xylan bromopyruvate-g-AM.
(10) Measuring the esterification substitution degree of the bagasse xylan bromopyruvate-g-AM obtained in the step (9) by adopting an acid-base titration method to obtain DScIs 0.375.
(11) And (3) measuring the solubilities of the dry bagasse xylan obtained in the step (1), the intermediate product pure bagasse xylan-g-AM obtained in the step (7) and the product bagasse xylan bromopyruvate-g-AM obtained in the step (9), wherein the measured solubilities are 0.3%, 2.6% and 10.3% respectively.
SEM analysis on the product bagasse xylan bromopyruvate-g-AM shows that the particles are irregular in shape, uneven in surface and more in hole folds, and the surface structure of the product is obviously different from that of the original bagasse xylan particles. Through IR analysis, compared with the original bagasse xylan, the obtained bagasse xylan bromopyruvate-g-AM is increased by 3208.84cm-1associated-NH in acrylamide2Characteristic absorption peak vibration absorption peak, 1736.61cm-11667.92cm, which is the coincidence peak of the ester group of (A) and the C ═ O stretching vibration absorption peak of the carbonyl group in 3-bromopyruvic acid-1The absorption peaks of C-N and C ═ C bond stretching vibration in acrylamide (655.52 cm)-1The carbon-bromine bond stretching vibration absorption peak in the 3-bromopyruvic acid, and the like; the characteristic peaks show that the grafting monomer acrylamide and the esterified carboxylic acid 3-bromopyruvic acid are reacted with hydroxyl on xylan, and AM and characteristic groups of 3-bromopyruvic acid are introduced into the molecular chain of the xylan. XRD analysis shows that the bromine-containing bagasse xylan ester-g-AM has more obvious diffraction peaks at 11.0 degrees, 12.5 degrees, 19.1 degrees, 22.6 degrees, 25.5 degrees, 31.8 degrees and 34.0 degrees; compared with the original bagasse xylan, the modified bagasse xylan bromopyruvate-g-AM has small change of diffraction peaks within an angle of 10-30 degrees, and new diffraction peaks of 31.8 degrees and 34.0 degrees appear after 30 degrees, which indicates that the modified bagasse xylan forms a new crystallization area and the crystallinity is increased. The TG-DTG curve of the analyzed product has the advantages that the process of the change of the product quality along with the temperature can be divided into four stages, the mass loss of the first stage in the range of 0-100 ℃ is about 5 percent, and the first stage is mainly caused by the volatilization of residual water in the product; the loss in the second stage is 20% in the range of 100 ℃ to 180 ℃, mainly due to the loss of crystal water in the product and the breakage of hydrogen bonds for the reaction; the loss in the third stage is about 70% in the range of 180 ℃ to 500 ℃, probably due to breakage of xylan glycosidic bonds and modified branches; the fourth stage has basically unchanged quality in the temperature range of 500-800 deg.c. The comparison with the original bagasse xylan shows that the 3-bromopyruvic acid and the acrylamide group introduced by esterification graft modification change the thermal decomposition process and the mass loss rate of the bagasse xylan, and improve the thermal stability of the xylan.
Claims (1)
1. A method for preparing active bromine-containing bagasse xylan ester-g-AM is characterized by comprising the following specific steps:
(1) drying 12-15 g of bagasse xylan in a vacuum constant-temperature drying oven at 60 ℃ for 24 hours to obtain dry-based bagasse xylan;
(2) weighing 0.60-1.60 g of ammonium persulfate and 0.30-0.80 g of sodium bisulfite in a 50mL beaker, adding 20-30 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 3.0-6.0 g of acrylamide in a 100mL beaker, adding 20-40 mL of distilled water, stirring and dissolving uniformly to obtain a monomer solution, and pouring the monomer solution into another 100mL constant-pressure dropping funnel for later use;
(4) weighing 6.0-12.0 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 ℃, and stirring for 20-30 minutes to obtain bagasse xylan activating solution;
(5) synchronously dropwise adding the initiator solution obtained in the step (2) and the monomer solution obtained in the step (3) into the bagasse xylan activation solution obtained in the step (4), controlling the temperature to be 50-65 ℃ and the time to be 3-3.5 hours, and simultaneously finishing dropwise adding, continuously reacting for 1.5-3 hours, and cooling the materials to room temperature;
(6) precipitating the material obtained in the step (5) for 20-30 minutes by using 40-60 mL of analytically pure acetone, sequentially washing and filtering the precipitate by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol for 2-3 times;
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 crude product is obtained;
(7) placing the bagasse xylan-g-AM crude product obtained in the step (6) into a Soxhlet extractor, and adding 150-200 mL of analytically pure acetone for extraction for 16-24 hours; taking out the extract, putting the extract into a watch glass, and drying the extract in a vacuum constant-temperature drying oven at the temperature of 60 ℃ for 12 to 24 hours until the weight is constant to obtain a pure bagasse xylan-g-AM graft copolymer;
(8) weighing 2.0-4.0 g of pure bagasse xylan-g-AM obtained in the step (7), placing the pure bagasse xylan-g-AM into a 250mL four-neck flask, sequentially adding 1.0-4.0 g of esterifying agent 3-bromopyruvic acid, 0.12-0.20 g of catalyst 4-dimethylaminopyridine, 0.06-0.10 g of catalyst tetrabutyl titanate and 50-70 mL of solvent analysis pure dichloroethane, heating to 50-70 ℃, stirring for reacting for 6-8 hours, and cooling the material to room temperature;
(9) precipitating the material obtained in the step (8) for 20-30 minutes by using 40-60 mL of analytically pure acetone, sequentially washing and filtering the precipitate by using 60-80 mL of analytically pure acetone and 30-60 mL of analytically pure absolute ethyl alcohol for 2-3 times;
and (3) drying the filter cake in a constant-temperature drying oven at 60 ℃ for 24 hours to constant weight to obtain a product of the bromine-containing bagasse xylan derivative, namely bagasse xylan bromopyruvate-g-AM.
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