CN113150324B - 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 PDFInfo
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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 Ca 2+ And further crosslinking, and freeze-drying to obtain the 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, namely the beautiful millettia root residue, the material is rich and easy to obtain, the full development of resources is facilitated, the ecological and environment-friendly effects are achieved, the green and chemical characteristics are met, the 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 biological medicine.
Description
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 residues 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, 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 solvents and cold water, but is dispersed in water with slight stirring, heated to dissolve in a clear solution, and cooled to form a clear 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 the millettia speciosa champ cellulose: collecting the rest millettia speciosa champ residue after polysaccharide extraction, then adding alpha-amylase, mixing with distilled water, heating in a water bath, carrying out suction filtration, collecting filter residues, 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 value of the reaction system within the range of 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 root residue cellulose, and recording the TEMPO oxidized millettia speciosa root residue cellulose 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 1-30 g/mL, the water bath heating temperature is 45-65 ℃, and the water bath heating time is 1-3 h.
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; the material-liquid ratio is 1; the temperature of the bleaching treatment is 65-85 ℃, the time of the bleaching treatment is 1-3 h, the rotating speed of the centrifugation is 8000-12000 rpm/min, and the time of the centrifugation 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 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%, when the material-to-liquid ratio of the reactant to the potassium hydroxide solution is 1-30 g/mL, the alkali solution is stirred at room temperature for 10-15 h in the treatment process.
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), the 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 amount of TEMPO is 0.015-0.02 g, the amount of NaBr is 0.08-0.15 g, the amount of distilled water is 80-150 mL, the amount of Millettia speciosa is 0.8-1.5 g, the amount of NaClO is 95-800 μ L, the concentration of NaOH solution is 0.2-1.0 mol/L, the 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 of the hot water bath is carried out for 20-40 min at 85-95 ℃, and the soaking is carried out in CaCl 2 The solution has a period of time of 0.08 to 0.15mol/LCaCl 2 Soaking 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 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 a 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 network 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.
According to the invention, TEMPO oxidized Millettia speciosa champ residue cellulose and gellan gum are used as raw materials to synthesize the hydrogel, the raw materials are safe and nontoxic, the prepared hydrogel has excellent 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 formulations of examples 1-3;
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 below clearly and completely by referring to specific embodiments and accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
(1) Collecting the residual bovine high-strength slag (with the weight of 20 g) after polysaccharide extraction, adding alpha-amylase to remove starch in the raw materials, mixing the alpha-amylase with distilled water, and heating in a water bath at 55 ℃ for 2h when the material-water ratio of reactants to the distilled water is 1. 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. 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 materials, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the feed-liquid ratio of reactants to the potassium hydroxide solution is 1. 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, sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, and recording 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 mixture is uniformly dispersed, then pouring the mixture into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 And (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, then adding alpha-amylase to remove starch in the raw materials, wherein the addition amount of the alpha-amylase is 0.20% (w/w) of the weight of the millettia speciosa champ residue, mixing the alpha-amylase with distilled water, and heating in a water bath at 55 ℃ for 2h when the material-water ratio of reactants to the distilled water is 1. 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. 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 materials, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the feed-liquid ratio of reactants to the potassium hydroxide solution is 1. 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 using 0.5mol/LNaOH solution to maintain the pH value of the reaction system within the range of 10.0 +/-0.2 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 Roxb 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 mixture is uniformly dispersed, then pouring the mixture into a circular mould, cooling to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 And (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 which is 0.20% (w/w) of the weight of the millettia speciosa champ residue, and heating in a water bath at 55 ℃ for 2h when the material-water ratio of reactants to the distilled water is 1. And then, carrying out suction filtration and collecting filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying at 60 ℃ for 16 hours, 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. 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 materials, wherein the mass fraction of the potassium hydroxide solution is 10%, and stirring and reacting for 12 hours at room temperature when the feed-liquid ratio of reactants to the potassium hydroxide solution is 1. 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, sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, and recording 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 using 0.5mol/LNaOH solution to maintain the pH value of the reaction system within the range of 10.0 +/-0.2 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 millettia speciosa champ cellulose in water to prepare dispersion liquid with the mass fraction of 5%, wherein the proportion of the TEMPO millettia speciosa champ cellulose to the gellan gum is 1:4, stirring in a hot water bath at 90 ℃ for 30min until the mixture is uniformly dispersed, then pouring the mixture into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 Soaking in distilled water for 48h after 4h, changing water every 4h, and freeze-drying at-70 deg.C for 18h to obtain TEMPO oxidized Millettia speciosa champ fiberThe pH responsive hydrogel of the plain/gellan gum is designated 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, and heating in a 50 ℃ water bath for 1.5h when the material-water ratio of reactants to the distilled water is 1. 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 the temperature of 70 ℃ when the feed-liquid ratio of a reactant to the sodium chlorite solution is 1. 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 a 60-mesh sieve to obtain the cellulose with lignin removed.
(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 feed-liquid ratio of a reactant to the potassium hydroxide solution is 1. 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 using 0.5mol/LNaOH solution to maintain the pH value of the reaction system within the range of 10.0 +/-0.2 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 Roxb 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 mixture is uniformly dispersed, then pouring the mixture into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 And (3) soaking and washing the solution for 3 hours in distilled water for 36 hours, changing water every 4 hours, and freeze-drying the solution at-70 ℃ for 16 hours 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, then adding alpha-amylase to remove starch in the raw material, wherein the addition amount of the alpha-amylase is 0.25% (w/w) of the weight of the millettia speciosa champ residue, mixing the alpha-amylase with distilled water, and heating in a water bath at 65 ℃ for 2.5 hours when the material-water ratio of reactants to the distilled water is 1. And then, carrying out suction filtration and collecting filter residues, washing the filter residues with distilled water for 3 times, washing the filter residues with 95% ethanol for 1 time, drying for 20 hours at 65 ℃, 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. 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 14h at room temperature when the material-liquid ratio of a reactant to the potassium hydroxide solution is 1. 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 Roxb 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 1:5, 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/LCaCl 2 And (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) Taking the TEMPO oxidized beautiful millettia root cellulose/gellan gum pH response type hydrogel OGH prepared in the examples 1 to 3 for infrared spectrogram analysis:
the infrared spectra of the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogels prepared in examples 1-3 were measured by FT-IR spectroscopy, and the results are shown in FIG. 1, in which OGH1, OGH2, and OGH3 represent the hydrogels prepared in examples 1-3, respectively.
3400cm in the figure -1 Is the stretching vibration peak of O-H, and 1720cm -1 The nearby peak is the stretching vibration peak of C = O, which indicates thatThe existence of carboxyl in the hydrogel indicates that hydroxyl in the millettia speciosa root residue cellulose is successfully oxidized into carboxyl. Due to the existence of carboxyl, the prepared hydrogel OGH 1-3 shrinks under the low pH environment and swells under the high pH environment, and the responsiveness to pH is reflected.
(2) The TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH responsive hydrogel OGH prepared in examples 1 to 3 was subjected to morphological analysis:
SEM images of the TEMPO oxidized Millettia speciosa cellulose/gellan gum pH-responsive hydrogels prepared in examples 1 to 3 were measured by scanning electron microscopy, and the results are shown in FIGS. 2a to 2c, where FIGS. 2a, 2b, and 2c represent the pH-responsive hydrogels prepared in examples 1 to 3, respectively. OGH1, OGH2 and OGH3 present a regular net structure, and the pore diameter is 400-500 μm.
(3) The TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH responsive hydrogel OGH prepared in examples 1 to 3 was subjected to pH sensitivity test:
the pH responsiveness of the pH-responsive hydrogels prepared in examples 1 to 3 was investigated by measuring their swelling degrees at different pH, 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 change of the swelling degree of OGH1, OGH2 and OGH3 along with the change of the pH value in the environment shows a similar trend, namely, the swelling degree is firstly increased and then decreased along with the increase of the pH value of 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 Millettia speciosa cellulose/gellan gum pH responsive hydrogel OGH prepared in examples 1-3 was taken for the 5-Fu delivery performance measurement:
taking the TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH-responsive hydrogel prepared in examples 1 to 3, respectively soaking the hydrogel in 5-Fu solutions with the concentration of 1mg/mL, adsorbing at room temperature for 72h, taking out the hydrogel, and freeze-drying to obtain the 5-Fu-loaded hydrogel. The gastric juice-like substance is put into simulated gastric juice, and the release process of 5-Fu in the stomach is simulated at 37 ℃ and 100 rpm. After 2h, the hydrogel was removed, and simulated intestinal fluid was added to simulate the release of 5-Fu in the intestine at 37 ℃ and 100 rpm. The release rate of the hydrogel to 5-Fu was calculated by measuring the concentration of 5-Fu in the release medium, and the results are shown in FIG. 4, in which OGH1, OGH2 and OGH3 represent the pH-responsive hydrogels prepared in examples 1 to 3, respectively, in which the release rate of OGH2 to 5-Fu was 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 (2)
1. A preparation method of TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel is characterized by comprising one of the following methods:
(1) Collecting the residual millettia speciosa champ residue after polysaccharide extraction, then adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water in an amount which is 0.20 percent (w/w) of the weight of the millettia speciosa champ residue, and heating in a water bath at 55 ℃ for 2 hours when the material-water ratio of reactants to the distilled water is 1; then, carrying out suction filtration and collecting filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying for 16h 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 a reactant to the sodium chlorite solution is 1; 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 materials, 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; 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, sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, and recording 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 is finished, 10mL of absolute ethyl alcohol is added into the reaction system to stop the reaction, and the pH value is adjusted to 7.0 by using 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 Roxb 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 mixture is uniformly dispersed, then pouring the mixture into a circular mould, cooling to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 Soaking and washing the solution for 4h, transferring the solution into 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;
or
(1) Collecting 20g of the residual millettia speciosa champ after polysaccharide extraction, then adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water, and heating in a water bath at 55 ℃ for 2h when the material-water ratio of reactants to the distilled water is 1; then, carrying out suction filtration and collecting filter residue, washing the filter residue with distilled water for 2 times, washing the filter residue with 95% ethanol for 1 time, drying for 16h 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 a reactant to the sodium chlorite solution is 1; 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 lignin-removed cellulose;
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw materials, 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; 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, sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, and recording as MSCC;
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa champ cellulose, 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 is finished, 10mL of absolute ethyl alcohol is added into the reaction system to stop the reaction, and the pH value is adjusted to 7.0 by using 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 millettia speciosa champ cellulose in water to prepare dispersion liquid with the mass fraction of 5%, wherein the proportion of the TEMPO millettia speciosa champ cellulose to the gellan gum is 1:4, stirring in a hot water bath at 90 ℃ for 30min until the mixture is uniformly dispersed, then pouring the mixture into a round mould to cool to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 Transferring the solution into distilled water for soaking and washing for 48 hours, changing water every 4 hours, and freeze-drying at-70 ℃ for 18 hours to obtain TEMPO oxidized millettia speciosa champ cellulose/gellan gum pH response type hydrogel which is recorded as OGH;
or
(1) Collecting 20g of the residual millettia speciosa champ after polysaccharide extraction, then adding alpha-amylase to remove starch in the raw material, mixing the alpha-amylase with distilled water, and heating in a water bath at 55 ℃ for 2h when the material-water ratio of reactants to the distilled water is 1; then, carrying out suction filtration and collecting 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 a reactant to the sodium chlorite solution is 1; 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 lignin-removed cellulose;
(3) Mixing 20g of lignin-removed cellulose with a potassium hydroxide solution to remove hemicellulose in the raw materials, 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; 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, sieving with 100 mesh sieve to obtain Millettia speciosa champ residue cellulose, and recording as MSCC;
(4) Weighing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of distilled water, adding 1g of Millettia speciosa champ cellulose, 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 is finished, 10mL of absolute ethyl alcohol is added into the reaction system to stop the reaction, and the pH value is adjusted to 7.0 by using 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 Roxb 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 mixture is uniformly dispersed, then pouring the mixture into a circular mould, cooling to room temperature, and soaking the obtained hydrogel in 0.1mol/LCaCl 2 Soaking and washing the solution for 4h, transferring the solution into 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;
the hydrogel shrinks under a low pH environment and swells under a high pH environment, so that the responsiveness to pH is reflected, the hydrogel has a regular net structure, and the pore diameter is 400-500 mu m; 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.
2. Use of the TEMPO oxidized beautiful millettia root cellulose/gellan gum pH-responsive hydrogel according to claim 1 in the field of drug delivery.
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