CN113150324A - TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof - Google Patents

TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof Download PDF

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CN113150324A
CN113150324A CN202110397246.7A CN202110397246A CN113150324A CN 113150324 A CN113150324 A CN 113150324A CN 202110397246 A CN202110397246 A CN 202110397246A CN 113150324 A CN113150324 A CN 113150324A
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millettia speciosa
gellan gum
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宗敏华
陈曦
娄文勇
黄智�
罗思媛
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South China University of Technology SCUT
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Abstract

The invention discloses TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and a preparation method and application thereof. The invention takes Millettia speciosa champ dreg cellulose as raw material to prepare TEMPO oxidized Millettia speciosa champ dreg cellulose, the produced Millettia speciosa champ dreg cellulose is mixed with gellan gum, dispersed in distilled water, heated in hot water bath, cooled to form hydrogel, and then passed through Ca2+And further crosslinking, and freeze-drying to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel. The cellulose used in the invention is derived from the domestic and industrial production waste of the beautiful millettia root residue, has rich and easily obtained materials, is beneficial to the full development of resources, is ecological and environment-friendly, conforms to the characteristics of green chemistry, andthe reaction condition is mild, the process operation is simple, the equipment requirement is low, and the prepared product has good pH responsiveness and high application value in the field of biomedicine.

Description

TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of natural hydrogel, and particularly relates to TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel as well as a preparation method and application thereof.
Background
Hydrogels are defined as three-dimensional networks of hydrophilic polymers that are capable of absorbing and retaining large amounts of water. Hydrogels can be classified as natural polymer-based hydrogels and synthetic polymer-based hydrogels. Hydrogels formed from natural polymers (e.g., cellulose, chitosan, chitin, and sodium alginate) have attracted more researchers' interest in their higher safety, hydrophilicity, and biocompatibility than hydrogels formed from synthetic polymers.
Millettia speciosa is a main variety of south Chinese medicines, belongs to Millettia dielsiana of Papilionaceae of leguminosae, is widely used as a raw material for cooking soup in two broad areas, is used for making medicated diet, medicated wine and the like, and is a famous plant for both medicine and food in the south of Ling. In addition to being used as raw materials for cooking soup and soaking wine, the current production of the beautiful millettia root is mainly focused on the extraction of beautiful millettia root polysaccharide. Beautiful millettia root produces a large amount of waste residues in the production and processing processes of soup cooking, wine soaking and polysaccharide, and the beautiful millettia root residues are usually directly discarded, so that the environment is polluted and the resource waste is also caused. The beautiful millettia root residues contain a large amount of cellulose, and no one pays attention to the cellulose in the beautiful millettia root at present, so that the full utilization of the cellulose has great significance for resource development.
The cellulose is taken as the most abundant renewable natural biological resource on the earth, has simple preparation process and is widely applied to the synthesis of hydrogel with friendly environment and good biocompatibility. In order to realize the efficient utilization of resources, cellulose in the beautiful millettia root residue is utilized to synthesize cellulose hydrogel. In addition, cellulose is an excellent material for synthetic hydrogels. Cellulose molecules contain a large amount of alcoholic hydroxyl groups, and are easy to be oxidized and modified. TEMPO (2,2,6, 6-tetramethyl piperidine-nitrogen-oxide) is a novel selective oxidation catalyst TEMPO/NaBr/NaClO oxidation system, can selectively oxidize primary hydroxyl on a cellulose glucose unit C6, and has the characteristics of high selectivity, mild reaction conditions, low degradation rate, simplicity, high efficiency, energy conservation, environmental protection and the like. After TEMPO catalytic oxidation, carboxyl functional groups are uniformly introduced to the surface of the Millettia speciosa Roxb cellulose to generate the TEMPO oxidized Millettia speciosa Roxb cellulose. Due to the existence of carboxyl in the cellulose molecules of TEMPO oxidized beautiful millettia root, the formed hydrogel has pH responsiveness.
Gellan gum, also known as Keke gum, is a high molecular linear polysaccharide formed by repeating a polymerization of basic units consisting of 4 monosaccharide molecules. The gellan gum is safe, nontoxic, good in heat resistance and acid resistance, high in enzyme stability and biodegradable. Insoluble in nonpolar organic solvent and cold water, but dispersing in water with stirring, heating to dissolve into transparent solution, and cooling to obtain transparent and firm gel. In addition, the gellan gum has excellent gel performance, and can form gel under the condition of small using amount.
Therefore, by utilizing the excellent gel property of the gellan gum, the gellan gum and the TEMPO oxidized millettia speciosa champ cellulose form the composite hydrogel, a toxic chemical cross-linking agent is not required to be added, the formed safe, non-toxic and green hydrogel has pH responsiveness, and the hydrogel can be applied to the field of drug delivery.
Disclosure of Invention
The invention aims to provide a pH-sensitive hydrogel prepared by taking TEMPO oxidized millettia speciosa champ cellulose and gellan gum as raw materials and a preparation method thereof, and the pH-sensitive hydrogel has good pH responsiveness.
The invention also aims to provide application of the TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel prepared by the preparation method as a drug carrier in drug delivery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel, which comprises the following steps:
(1) extracting Millettia speciosa champ residue cellulose: collecting the rest radix millettiae speciosae residue after polysaccharide extraction, then adding alpha-amylase, mixing with distilled water, heating in water bath, carrying out suction filtration, collecting filter residue, washing, drying, crushing and screening; then adding a bleaching agent for bleaching treatment, centrifuging to obtain a precipitate, washing, drying, crushing and screening; treating with alkali solution, filtering to obtain residue, washing, drying, pulverizing, and sieving to obtain Millettia speciosa champ residue cellulose (MSCC);
(2) preparing TEMPO oxidized Millettia speciosa champ cellulose: dissolving TEMPO and NaBr in distilled water, adding Millettia speciosa champ cellulose, stirring, adding NaClO into the system, and maintaining the pH of the reaction system within 10.0 +/-0.2 by using NaOH solution. Adding absolute ethyl alcohol into a reaction system after the oxidation reaction is finished to stop the reaction, adjusting the pH value to 7.0 by using an HCl solution, washing the precipitate, and drying to obtain TEMPO oxidized millettia speciosa champ residue cellulose which is recorded as OMSCC;
(3) preparing TEMPO oxidized beautiful millettia root cellulose/gellan gum pH response type hydrogel: dispersing gellan gum and TEMPO oxidized bovine kala efficacious slag cellulose in water, stirring in a hot water bath until the gellan gum and the TEMPO oxidized bovine kala efficacious slag cellulose are uniformly dispersed, pouring the mixture into a mold, and cooling to room temperature to form hydrogel. Soaking the hydrogel in CaCl2 solution for a period of time, transferring the hydrogel into distilled water, soaking and washing, and freeze-drying to obtain TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Further, in the step (1), the addition amount of the alpha-amylase is 0.10-0.30% (w/w) of the weight of the beautiful millettia root, the mixing ratio of the beautiful millettia root and distilled water is 1: 10-30 g/mL, the water bath heating temperature is 45-65 ℃, and the water bath heating time is 1-3 hours.
Further, in the step (1), the washing after the alpha-amylase treatment is to wash the filter residue with distilled water for 2-4 times, wash the filter residue with 95% ethanol for 1 time, dry the filter residue at 50-70 ℃ for 15-20 h, and screen the filter residue through a Chinese herbal medicine pulverizer to pass through a 60-100-mesh sieve.
Further, in the step (1), the bleaching agent is a sodium chlorite solution with the mass fraction of 6.5-8.5%, the pH value is adjusted to 3.8-4.0 by using a hydrochloric acid solution, and the feed-liquid ratio of the reactant to the bleaching agent is 1: 10-30 g/mL; the material-liquid ratio is 1: 10-30 g/mL; the bleaching treatment temperature is 65-85 ℃, the bleaching treatment time is 1-3 h, the centrifugal rotating speed is 8000-12000 rpm/min, and the centrifugal time is 8-12 min.
Further, in the step (1), the washing after the bleaching treatment is to wash the precipitate with distilled water until the supernatant is neutral, wash the precipitate with 95% ethanol for 1 time, dry the precipitate at 50-70 ℃ for 15-20 h, crush the precipitate with a Chinese herbal medicine crusher, and screen the crushed precipitate to pass through a 60-100 mesh sieve.
Further, in the step (1), the alkali solution is a potassium hydroxide solution with a mass fraction of 5-12%, and when the material-to-liquid ratio of the reactant to the potassium hydroxide solution is 1: 10-30 g/mL, the alkali solution is stirred at room temperature for 10-15 hours.
Further, in the step (1), the washing after the alkali solution treatment is to wash the filter residue with distilled water until the supernatant is neutral, wash the filter residue with 95% ethanol for 1 time, dry the filter residue at 50-70 ℃ for 15-20 h, crush the filter residue with a Chinese herbal medicine crusher, and screen the filter residue to pass through a 60-100 mesh sieve.
Further, in the step (2), stirring is carried out at 25-35 ℃ for 8-15 min, the reaction temperature is 25-35 ℃, the reaction time is 5-7 h, and the drying process is carried out at 50-70 ℃ for 15-20 h.
Further, in the step (2), the use amount of TEMPO is 0.015-0.02 g, the use amount of NaBr is 0.08-0.15 g, the use amount of distilled water is 80-150 mL, the use amount of Millettia speciosa is 0.8-1.5 g, the use amount of NaClO is 95-800 muL, the concentration of NaOH solution is 0.2-1.0 mol/L, the use amount of absolute ethyl alcohol is 5-15 mL, and the concentration of HCl solution is 0.2-1.0 mol/L.
Further, in the step (3), the stirring in the hot water bath is performed for 20-40 min at 85-95 ℃, and the soaking is performed in CaCl2The solution is kept for a period of time of 0.08 to 0.15mol/LCaCl2Soaking in the solution for 3-5 h, and soaking in distilled waterThe washing is to soak the fabric in distilled water for 36-60 h, and the distilled water is replaced every 3-5 h, and the freeze drying is to freeze dry the fabric for 16-20 h at-60 to-70 ℃.
Further, in the step (3), the mass fraction of the TEMPO oxidized Millettia speciosa champ slag cellulose/gellan gum dispersion is 4.0-6.0%, wherein the ratio of the TEMPO oxidized Millettia speciosa champ slag cellulose to gellan gum is 1: 3 to 5.
In a second aspect, the invention provides TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH responsive hydrogel prepared by the preparation method, wherein the hydrogel shrinks under a low pH environment and swells under a high pH environment, so that the pH responsiveness is reflected, the hydrogel has a regular net structure, and the pore diameter is 400-500 μm; the hydrogels exhibit low swelling at low pH (pH < 4) and reduced swelling at too high pH (pH > 10).
In a third aspect, the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel provided by the invention can be applied to the field of drug delivery.
Compared with the prior art, the invention has the following beneficial effects:
the cellulose for preparing the hydrogel is derived from the beautiful millettia root residue which is a waste in life and industrial production, the material is rich and easy to obtain, and the waste recycling is favorable for the full development and high-valued application of resources.
The method adopts a TEMPO/NaBr/NaClO oxidation system to selectively oxidize the primary hydroxyl on the cellulose glucose unit C6, and has the characteristics of high selectivity, mild reaction conditions, low degradation rate, simplicity, high efficiency, energy conservation, environmental protection and the like.
The TEMPO oxidized millettia speciosa champ residue cellulose and the gellan gum are used as raw materials to synthesize the hydrogel, the raw materials are safe and non-toxic, the prepared hydrogel is excellent in structural characteristics, and reagents and reaction conditions used in the reaction process are mild, ecological and environment-friendly, and accord with the characteristics of green chemistry.
The method has simple process operation and low equipment requirement, and carboxyl in TEMPO oxidized Millettia speciosa champ cellulose molecules endows hydrogel with good pH responsiveness, and has high application value in the field of drug delivery.
Drawings
FIG. 1 is an infrared spectrum of a hydrogel prepared in examples 1 to 3;
FIG. 2a is a scanning electron micrograph of the hydrogel prepared in example 1;
FIG. 2b is a scanning electron micrograph of the hydrogel prepared in example 2;
FIG. 2c is a scanning electron micrograph of the hydrogel prepared in example 3;
FIG. 3 is a graph of pH response performance of the samples prepared in examples 1 to 3;
FIG. 4 is a graph showing the effect of the hydrogels prepared in examples 1-3 on the delivery of 5-Fu.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following specific embodiments, which are obviously only a part of embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Collecting residual ox gallnut residues (with the weight of 20g) after polysaccharide extraction, adding alpha-amylase to remove starch in the raw materials, mixing the alpha-amylase with distilled water until the material-water ratio of reactants to the distilled water is 1:20g/mL, and heating in a water bath at 55 ℃ for 2h, wherein the addition amount of the alpha-amylase is 0.20% (w/w) of the weight of the ox gallnut residues. And then, carrying out suction filtration and collecting the filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying for 16 hours at 60 ℃, crushing by using a Chinese herbal medicine crusher, and sieving by using a 80-mesh sieve to obtain the millettia speciosa champ crude cellulose.
(2) Mixing 20g of millettia speciosa champ crude cellulose with a sodium chlorite solution for bleaching treatment to remove lignin in the raw material, wherein the mass fraction of the sodium chlorite solution is 7.5%, adjusting the pH to 4.0 by hydrochloric acid, and treating for 2 hours at 75 ℃ when the feed-liquid ratio of reactants to the sodium chlorite solution is 1:20 g/mL. Centrifuging the reacted mixed solution at 10000rpm/min for 10min, washing the precipitate with distilled water until the supernatant is neutral, washing the precipitate with 95% ethanol for 1 time, drying at 60 ℃ for 16h, crushing with a Chinese herbal medicine crusher, and sieving with a 80-mesh sieve to obtain the lignin-removed cellulose.
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw material, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the material-liquid ratio of reactants to the potassium hydroxide solution is 1:20 g/mL. Collecting the filter residue, washing the filter residue with distilled water until the filtrate is neutral, washing the filter residue with 95% ethanol for 1 time, drying at 60 deg.C for 16h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, which is recorded as MSCC.
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa Roxb, stirring for 10min at 30 ℃, dropwise adding 95 mu of LNaClO into the system, reacting for 6h at 30 ℃, and maintaining the pH of the reaction system within the range of 10.0 +/-0.2 by using 0.5mol/LNaOH solution in the reaction process. After the reaction was completed, 10mL of anhydrous ethanol was added to the reaction system to stop the reaction, and the pH was adjusted to 7.0 with 0.5mol/L HCl solution. Washing the precipitate with distilled water for 2 times, washing the precipitate with 95% ethanol for 1 time, and drying the precipitate at 60 deg.C for 16h to obtain TEMPO oxidized Millettia speciosa champ residue cellulose, which is recorded as OMSCC.
(5) Dispersing gellan gum and TEMPO oxidized millettia speciosa champ cellulose in water to prepare a dispersion liquid with the mass fraction of 5%, wherein the proportion of the TEMPO oxidized millettia speciosa champ cellulose to the gellan gum is 1: 4, stirring in a hot water bath at 90 ℃ for 30min until the dispersion is uniform, then pouring into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl2And (3) soaking and washing the solution for 4h in distilled water for 48h, changing water every 4h, and freeze-drying the solution at-70 ℃ for 18h to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Example 2
(1) Collecting 20g of millettia speciosa champ residue after polysaccharide extraction, adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water in an amount of 0.20% (w/w) of the weight of the millettia speciosa champ residue, and heating in a water bath at 55 ℃ for 2h until the material-water ratio of reactants to the distilled water is 1:20 g/mL. And then, carrying out suction filtration and collecting the filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying for 16 hours at 60 ℃, crushing by using a Chinese herbal medicine crusher, and sieving by using a 80-mesh sieve to obtain the millettia speciosa champ crude cellulose.
(2) Mixing 20g of millettia speciosa champ crude cellulose with a sodium chlorite solution for bleaching treatment to remove lignin in the raw material, wherein the mass fraction of the sodium chlorite solution is 7.5%, adjusting the pH to 4.0 by hydrochloric acid, and treating for 2 hours at 75 ℃ when the feed-liquid ratio of reactants to the sodium chlorite solution is 1:20 g/mL. Centrifuging the reacted mixed solution at 10000rpm/min for 10min, washing the precipitate with distilled water until the supernatant is neutral, washing the precipitate with 95% ethanol for 1 time, drying at 60 ℃ for 16h, crushing with a Chinese herbal medicine crusher, and sieving with a 80-mesh sieve to obtain the lignin-removed cellulose.
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw material, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the material-liquid ratio of reactants to the potassium hydroxide solution is 1:20 g/mL. Collecting the filter residue, washing the filter residue with distilled water until the filtrate is neutral, washing the filter residue with 95% ethanol for 1 time, drying at 60 deg.C for 16h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, which is recorded as MSCC.
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa Roxb, stirring for 10min at 30 ℃, dropwise adding 383 mu of LNaClO into the system, reacting for 6h at 30 ℃, and maintaining the pH of the reaction system within the range of 10.0 +/-0.2 by using 0.5mol/LNaOH solution in the reaction process. After the reaction was completed, 10mL of anhydrous ethanol was added to the reaction system to stop the reaction, and the pH was adjusted to 7.0 with 0.5mol/L HCl solution. Washing the precipitate with distilled water for 2 times, washing the precipitate with 95% ethanol for 1 time, and drying the precipitate at 60 deg.C for 16h to obtain TEMPO oxidized Millettia speciosa champ residue cellulose, which is recorded as OMSCC.
(5) Dispersing gellan gum and TEMPO oxidized bovine kale cellulose in water to prepare a dispersion liquid with the mass fraction of 5%, wherein the TEMPO oxidized bovine kale cellulose isThe ratio of the vigorous slag cellulose to the gellan gum is 1: 4, stirring in a hot water bath at 90 ℃ for 30min until the dispersion is uniform, then pouring into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl2And (3) soaking and washing the solution for 4h in distilled water for 48h, changing water every 4h, and freeze-drying the solution at-70 ℃ for 18h to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Example 3
(1) Collecting 20g of millettia speciosa champ residue after polysaccharide extraction, adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water in an amount of 0.20% (w/w) of the weight of the millettia speciosa champ residue, and heating in a water bath at 55 ℃ for 2h until the material-water ratio of reactants to the distilled water is 1:20 g/mL. And then, carrying out suction filtration and collecting the filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying for 16 hours at 60 ℃, crushing by using a Chinese herbal medicine crusher, and sieving by using a 80-mesh sieve to obtain the millettia speciosa champ crude cellulose.
(2) Mixing 20g of millettia speciosa champ crude cellulose with a sodium chlorite solution for bleaching treatment to remove lignin in the raw material, wherein the mass fraction of the sodium chlorite solution is 7.5%, adjusting the pH to 4.0 by hydrochloric acid, and treating for 2 hours at 75 ℃ when the feed-liquid ratio of reactants to the sodium chlorite solution is 1:20 g/mL. Centrifuging the reacted mixed solution at 10000rpm/min for 10min, washing the precipitate with distilled water until the supernatant is neutral, washing the precipitate with 95% ethanol for 1 time, drying at 60 ℃ for 16h, crushing with a Chinese herbal medicine crusher, and sieving with a 80-mesh sieve to obtain the lignin-removed cellulose.
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw material, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the material-liquid ratio of reactants to the potassium hydroxide solution is 1:20 g/mL. Collecting the filter residue, washing the filter residue with distilled water until the filtrate is neutral, washing the filter residue with 95% ethanol for 1 time, drying at 60 deg.C for 16h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, which is recorded as MSCC.
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa Roxb, stirring for 10min at 30 ℃, dropwise adding 766 mu of LNaClO into the system, reacting for 6h at 30 ℃, and maintaining the pH of the reaction system within the range of 10.0 +/-0.2 by using 0.5mol/LNaOH solution in the reaction process. After the reaction was completed, 10mL of anhydrous ethanol was added to the reaction system to stop the reaction, and the pH was adjusted to 7.0 with 0.5mol/L HCl solution. Washing the precipitate with distilled water for 2 times, washing the precipitate with 95% ethanol for 1 time, and drying the precipitate at 60 deg.C for 16h to obtain TEMPO oxidized Millettia speciosa champ residue cellulose, which is recorded as OMSCC.
(5) Dispersing gellan gum and TEMPO oxidized millettia speciosa champ cellulose in water to prepare a dispersion liquid with the mass fraction of 5%, wherein the proportion of the TEMPO oxidized millettia speciosa champ cellulose to the gellan gum is 1: 4, stirring in a hot water bath at 90 ℃ for 30min until the dispersion is uniform, then pouring into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl2And (3) soaking and washing the solution for 4h in distilled water for 48h, changing water every 4h, and freeze-drying the solution at-70 ℃ for 18h to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Example 4
(1) Collecting 20g of millettia speciosa champ residue after polysaccharide extraction, adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water in an amount of 0.15% (w/w) of the weight of the millettia speciosa champ residue, and heating in a water bath at 50 ℃ for 1.5h until the material-water ratio of reactants to the distilled water is 1:15 g/mL. And then, carrying out suction filtration and collecting filter residue, washing the filter residue with distilled water for 1 time, washing the filter residue with 95% ethanol for 1 time, drying at 55 ℃ for 16 hours, crushing by using a Chinese herbal medicine crusher, and sieving by using a 60-mesh sieve to obtain the millettia speciosa champ crude cellulose.
(2) Mixing 20g of millettia speciosa champ crude cellulose with a sodium chlorite solution for bleaching treatment to remove lignin in the raw material, wherein the mass fraction of the sodium chlorite solution is 7.0%, adjusting the pH to 3.8 by hydrochloric acid, and treating for 1.5h at 70 ℃ until the material-liquid ratio of reactants to the sodium chlorite solution is 1:15 g/mL. Centrifuging the reacted mixed solution at 8000rpm/min for 8min, washing the precipitate with distilled water until the supernatant is neutral, washing the precipitate with 95% ethanol for 1 time, drying at 55 deg.C for 16h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 60 mesh sieve to obtain lignin-removed cellulose.
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw material, wherein the mass fraction of the potassium hydroxide solution is 8%, and stirring and reacting for 10 hours at room temperature when the material-liquid ratio of reactants to the potassium hydroxide solution is 1:15 g/mL. Collecting the filter residue, washing the filter residue with distilled water until the filtrate is neutral, washing the filter residue with 95% ethanol for 1 time, drying at 55 deg.C for 16h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with a 60 mesh sieve to obtain Millettia speciosa champ residue cellulose, which is recorded as MSCC.
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa Roxb, stirring for 10min at 30 ℃, dropwise adding 766 mu of LNaClO into the system, reacting for 6h at 30 ℃, and maintaining the pH of the reaction system within the range of 10.0 +/-0.2 by using 0.5mol/LNaOH solution in the reaction process. After the reaction was completed, 10mL of anhydrous ethanol was added to the reaction system to stop the reaction, and the pH was adjusted to 7.0 with 0.5mol/L HCl solution. Washing the precipitate with distilled water for 2 times, washing the precipitate with 95% ethanol for 1 time, and drying the precipitate at 60 deg.C for 16h to obtain TEMPO oxidized Millettia speciosa champ residue cellulose, which is recorded as OMSCC.
(5) Dispersing gellan gum and TEMPO oxidized millettia speciosa champ cellulose in water to prepare a dispersion liquid with the mass fraction of 5%, wherein the proportion of the TEMPO oxidized millettia speciosa champ cellulose to the gellan gum is 1: 3, stirring in a hot water bath at 90 ℃ for 30min until the dispersion is uniform, then pouring into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl2And (3) soaking and washing the solution for 3h, then transferring the solution into distilled water, changing water every 4h, and freeze-drying the solution at-70 ℃ for 16h to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Example 5
(1) Collecting 20g of millettia speciosa champ residue after polysaccharide extraction, adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water until the material-water ratio of reactants to the distilled water is 1:25g/mL, wherein the addition amount of the alpha-amylase is 0.25% (w/w) of the weight of the millettia speciosa champ residue, and heating in a 65 ℃ water bath for 2.5 hours. And then, carrying out suction filtration and collecting filter residue, washing the filter residue with distilled water for 3 times, washing the filter residue with 95% ethanol for 1 time, drying at 65 ℃ for 20 hours, crushing by using a Chinese herbal medicine crusher, and sieving by using a 100-mesh sieve to obtain the millettia speciosa champ crude cellulose.
(2) Mixing 20g of millettia speciosa champ crude cellulose with a sodium chlorite solution for bleaching treatment to remove lignin in the raw material, wherein the mass fraction of the sodium chlorite solution is 8.0%, adjusting the pH to 4.0 by hydrochloric acid, and treating for 2.5 hours at 80 ℃ when the feed-liquid ratio of reactants to the sodium chlorite solution is 1:25 g/mL. Centrifuging the reacted mixed solution at 12000rpm/min for 12min, washing the precipitate with distilled water until the supernatant is neutral, washing the precipitate with 95% ethanol for 1 time, drying at 65 deg.C for 20h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 100 mesh sieve to obtain the lignin-removed cellulose.
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw material, wherein the mass fraction of the potassium hydroxide solution is 12%, and stirring and reacting for 14 hours at room temperature when the material-liquid ratio of reactants to the potassium hydroxide solution is 1:25 g/mL. Collecting the filter residue, washing the filter residue with distilled water until the filtrate is neutral, washing the filter residue with 95% ethanol for 1 time, drying at 65 deg.C for 20h, pulverizing with a Chinese herbal medicine pulverizer, and sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, which is recorded as MSCC.
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa Roxb, stirring for 10min at 30 ℃, dropwise adding 766 mu of LNaClO into the system, reacting for 6h at 30 ℃, and maintaining the pH of the reaction system within the range of 10.0 +/-0.2 by using 0.5mol/LNaOH solution in the reaction process. After the reaction was completed, 10mL of anhydrous ethanol was added to the reaction system to stop the reaction, and the pH was adjusted to 7.0 with 0.5mol/L HCl solution. Washing the precipitate with distilled water for 2 times, washing the precipitate with 95% ethanol for 1 time, and drying the precipitate at 60 deg.C for 16h to obtain TEMPO oxidized Millettia speciosa champ residue cellulose, which is recorded as OMSCC.
(5) Dispersing gellan gum and TEMPO oxidized millettia speciosa champ cellulose into water to prepare a dispersion liquid with the mass fraction of 5%, wherein the TEMPO oxidized millettia speciosa champ cellulose and the TEMPO oxidized millettia speciosa champ cellulose are mixed with each otherThe proportion of gellan gum is 1: 5, stirring in a hot water bath at 90 ℃ for 30min until the dispersion is uniform, then pouring into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl2And (3) soaking and washing the solution for 3h, then transferring the solution into distilled water, changing water every 4h, and freeze-drying the solution at-70 ℃ for 20h to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH.
Performance testing and applications
(1) Carrying out infrared spectrogram analysis on the TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel OGH prepared in the embodiment 1-3:
an infrared spectrogram of the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel prepared in examples 1 to 3 is measured by an FT-IR spectrometer, and the results are shown in FIG. 1, wherein OGH1, OGH2 and OGH3 respectively represent the hydrogel prepared in examples 1 to 3.
3400cm in the figure-1Is the stretching vibration peak of O-H, and 1720cm-1The nearby peak is the stretching vibration peak of C ═ O, which indicates the existence of carboxyl in the hydrogel, and indicates that the hydroxyl in the Millettia speciosa cellulose is successfully oxidized into carboxyl. Due to the existence of carboxyl, the prepared hydrogel OGH 1-3 shrinks under a low pH environment and swells under a high pH environment, and the responsiveness to pH is reflected.
(2) Carrying out morphological analysis on the TEMPO oxidized beautiful millettia root cellulose/gellan gum pH response type hydrogel OGH prepared in the embodiment 1-3:
SEM images of the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel prepared in examples 1-3 are determined by scanning electron microscopy, and the results are shown in FIGS. 2 a-2 c, wherein FIGS. 2a, 2b and 2c represent the pH-responsive hydrogels prepared in examples 1-3, respectively. OGH1, OGH2 and OGH3 are regular net-shaped structures, and the pore diameter is 400-500 μm.
(3) Carrying out pH sensitivity test on the TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel OGH prepared in the embodiment 1-3:
the pH responsiveness of the pH responsive hydrogels prepared in examples 1 to 3 was investigated by measuring the swelling degrees at different pH values, and the results are shown in FIG. 3, in which OGH1, OGH2 and OGH3 represent the pH responsive hydrogels prepared in examples 1 to 3, respectively. The changes of the swelling degrees of OGH1, OGH2 and OGH3 show similar trends along with the changes of the pH values in the environment, namely, the swelling degrees are firstly increased and then decreased along with the increase of the pH values in the environment. This is because the carboxyl groups in the OGH are protonated in the hydrogel under a low pH environment, and the hydrogel shrinks and has a low swelling degree. As the pH value is increased, the carboxyl groups are deprotonated, the electrostatic repulsion between the groups in the hydrogel is increased, and the swelling degree of the hydrogel is increased. And when the pH is too high, the charge shielding effect of the cations weakens the electrostatic repulsion among the groups in the hydrogel, and the swelling degree is reduced.
(4) The TEMPO oxidized beautiful millettia root cellulose/gellan gum pH response type hydrogel OGH prepared in the examples 1 to 3 is used for carrying out 5-Fu delivery performance measurement:
taking the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel prepared in the embodiment 1-3, respectively soaking the hydrogel in 5-Fu solution with the concentration of 1mg/mL, adsorbing for 72h at room temperature, taking out the hydrogel, and freeze-drying to obtain the 5-Fu-loaded hydrogel. It was placed in simulated gastric fluid to simulate the release of 5-Fu in the stomach at 37 deg.C and 100 rpm. After 2h, the hydrogel was removed, simulated intestinal fluid was added, and the release of 5-Fu in the intestine was simulated at 37 ℃ and 100 rpm. The release rate of the hydrogel to 5-Fu is calculated by measuring the concentration of 5-Fu in the release medium, and the result is shown in fig. 4, wherein OGH1, OGH2 and OGH3 respectively represent the pH response type hydrogel prepared in examples 1-3, and the release rate of OGH2 to 5-Fu is low.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A preparation method of TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel is characterized by comprising the following steps:
(1) extracting Millettia speciosa champ residue cellulose: collecting the rest radix millettiae speciosae residue after polysaccharide extraction, then adding alpha-amylase, mixing with distilled water, heating in water bath, carrying out suction filtration, collecting filter residue, washing, drying, crushing and screening; then adding a bleaching agent for bleaching treatment, centrifuging to obtain a precipitate, washing, drying, crushing and screening; treating with alkali solution, filtering to obtain residue, washing, drying, pulverizing, and sieving to obtain Millettia speciosa champ residue cellulose;
(2) preparing TEMPO oxidized Millettia speciosa champ cellulose: dissolving TEMPO and NaBr in distilled water, adding the Millettia speciosa champ cellulose obtained in the step (1), adding NaClO into a system after stirring, and maintaining the pH of the reaction system within a range of 10.0 +/-0.2 by using a NaOH solution; adding absolute ethyl alcohol into a reaction system after the oxidation reaction is finished to stop the reaction, adjusting the pH value to 7.0 by using an HCl solution, washing the precipitate and drying to obtain TEMPO oxidized millettia speciosa champ residue cellulose;
(3) preparing TEMPO oxidized beautiful millettia root cellulose/gellan gum pH response type hydrogel: dispersing gellan gum and the TEMPO oxidized bovine kala efficacious slag cellulose obtained in the step (2) in water, stirring in a hot water bath until the gellan gum and the TEMPO oxidized bovine kala efficacious slag cellulose are uniformly dispersed, pouring the mixture into a mold, cooling to room temperature to form hydrogel, and soaking the hydrogel in CaCl2And transferring the solution into distilled water for soaking and washing, and freeze-drying to obtain TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel.
2. The preparation method of the TEMPO oxidized Millettia speciosa Roxb/gellan gum pH-responsive hydrogel as claimed in claim 1, wherein in step (1), the mixing ratio of the Millettia speciosa Roxb and distilled water is 1: 10-30 g/mL, the addition amount of the alpha-amylase is 0.10-0.30% of the weight of the Millettia speciosa Roxb, the water bath heating temperature is 45-65 ℃, and the water bath heating time is 1-3 h.
3. The method for preparing the TEMPO oxidized Millettia speciosa Roxb/gellan gum pH-responsive hydrogel according to claim 1, wherein in the step (1), the bleaching agent is a sodium chlorite solution with a mass fraction of 6.5-8.5%, the pH is adjusted to 3.8-4.0 by a hydrochloric acid solution, and the addition amount of the bleaching agent is as follows: when the material-liquid ratio of the reactant to the bleaching agent is 1: 10-30 g/mL; the bleaching treatment temperature is 65-85 ℃, the bleaching treatment time is 1-3 h, the centrifugal rotating speed is 8000-12000 rpm/min, and the centrifugal time is 8-12 min.
4. The method for preparing the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel according to claim 1, wherein in the step (1), the alkali solution is a potassium hydroxide solution with a mass fraction of 5-12%; the addition amount of the alkali solution meets the following requirements: when the material-liquid ratio of the reactant to the alkali solution is 1: 10-30 g/mL, the alkali solution is stirred for 10-15 h at room temperature.
5. The preparation method of the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel as claimed in claim 1, wherein in the step (1), the drying process is drying at 50-70 ℃ for 15-20 h, and the sieving process is passing through a 60-100 mesh sieve.
6. The preparation method of TEMPO oxidized Millettia speciosa F.S.A. pulchrum cellulose/gellan gum pH responsive hydrogel according to claim 1, wherein in the step (2), the stirring is performed at 25-35 ℃ for 8-15 min, the reaction temperature is 25-35 ℃, the reaction time is 5-7 h, and the drying is performed at 50-70 ℃ for 15-20 h;
the TEMPO solution is 0.015-0.02 g, the NaBr solution is 0.08-0.15 g, the distilled water solution is 80-150 mL, the Millettia speciosa cellulose solution is 0.8-1.5 g, the NaClO solution is 95-800 mu L, the NaOH solution concentration is 0.2-1.0 mol/L, the anhydrous ethanol solution concentration is 5-15 mL, and the HCl solution concentration is 0.2-1.0 mol/L.
7. The preparation method of the TEMPO oxidized Millettia speciosa C/gellan gum pH-responsive hydrogel as claimed in claim 1, wherein in step (3), the hot water bath stirring is performed at 85-95 ℃ for 20-40 min, and the hydrogel is soaked in CaCl2The time in the solution is 0.08-0.15 mol/LCaCl2Soaking in the solution for 3-5 h, wherein the soaking and washing in distilled water is to soak in distilled water for 36-60 h, and the distilled water is replaced every 3-5 h, and the freeze drying is to freeze dry at-60 to-70 ℃ for 16-20 h.
8. The preparation method of the TEMPO oxidized Millettia speciosa slag cellulose/gellan gum pH-responsive hydrogel according to claim 1, wherein in the step (3), the mass fraction of the TEMPO oxidized Millettia speciosa slag cellulose and gellan gum in water is 4.0-6.0%, wherein the mass ratio of the TEMPO oxidized Millettia speciosa slag cellulose to gellan gum is 1: 3 to 5.
9. The TEMPO oxidized millettia speciosa cellulose/gellan gum pH-responsive hydrogel obtained by the preparation method of any one of claims 1 to 8, wherein the hydrogel shrinks under a low pH environment and swells under a high pH environment, and shows pH responsiveness, and the hydrogel has a regular network structure and the pore diameter is 400 to 500 μm; the hydrogel has a low swelling degree at a pH of less than 4 and a reduced swelling degree at a pH of more than 10.
10. Use of the TEMPO oxidized beautiful millettia root cellulose/gellan gum pH-responsive hydrogel according to claim 9 in the field of drug delivery.
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