CN116655952A - Visible light driven synthesized hemicellulose-based nano composite hydrogel and preparation method and application thereof - Google Patents
Visible light driven synthesized hemicellulose-based nano composite hydrogel and preparation method and application thereof Download PDFInfo
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- CN116655952A CN116655952A CN202310633836.4A CN202310633836A CN116655952A CN 116655952 A CN116655952 A CN 116655952A CN 202310633836 A CN202310633836 A CN 202310633836A CN 116655952 A CN116655952 A CN 116655952A
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- hemicellulose
- hydrogel
- drug
- nano composite
- visible light
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/7028—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages
- A61K31/7034—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin
- A61K31/704—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin attached to a condensed carbocyclic ring system, e.g. sennosides, thiocolchicosides, escin, daunorubicin
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/14—Hemicellulose; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Epidemiology (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a visible light driven synthesis hemicellulose-based nano composite hydrogel, a preparation method and application thereof, belonging to the technical field of drug carrier materials and adopting a composite photocatalyst alpha-Fe 2 O 3 /rGO/mpg‑C 3 N 4 As a photoinitiator, the straw hemicellulose is used as a raw material, and the hemicellulose-based nano composite hydrogel with good drug slow release performance is synthesized under the action of visible light. The method realizes the visible light driven synthesis of the hemicellulose nano composite hydrogel, has the advantages of green and environment-friendly preparation method and simple operation, solves the difficult problem of green synthesis of bio-based drug carrier materials, breaks through the problem of drug carrier materials which are poor in biocompatibility and not biodegradable, and effectively reduces or avoids the toxic and side effects of the drug. The embedding rate of the anticancer drug doxorubicin can reach 96.5%, and the anticancer drug doxorubicin can be used as a drug carrier, so that the defects of low bioavailability, systemic toxicity of chemotherapeutic drugs, serious side effects and the like can be overcome, the drug release time can be prolonged, the drug concentration of focus parts can be increased, and the anticancer chemical drug therapeutic index can be improved.
Description
Technical Field
The invention belongs to the technical field of drug carrier materials, and particularly relates to a visible light driven synthesis hemicellulose-based nano composite hydrogel and a preparation method and application thereof.
Background
With the continued development of related control studies, chemical drug therapies were found to be one of the very effective methods in clinical tumor treatment. However, most small molecule chemotherapeutic agents have the disadvantages of poor water solubility, poor pharmacokinetic properties, low bioavailability, low targeted delivery efficiency, toxic and side effects on normal cells, easy rapid phagocytosis by macrophages and the like, and greatly limit the treatment of cancers clinically. The anticancer drug delivery system can obviously reduce the toxic and side effects of the drug in the human body delivery process when being applied to the clinic treatment of cancer. In addition, the tumor tissue microenvironment is utilized to prepare the anticancer drug delivery system with stimulus responsiveness, so that the enrichment degree of the drugs in the tumor tissue and the use efficiency of the drugs are obviously improved, and the anticancer drug delivery system has more effective treatment effect and lower toxic and side effects. In the research of a drug slow-release system, the drug delivery system using hydrogel as a material has the characteristics of pH stimulus responsiveness, unique three-dimensional network structure, water retention and the like. Thus, in response to the stimulation of the tumor microenvironment, the unique drug targeting allows for loading of anticancer drugs and delivery of the drugs into cancer cells, tumor tissue. Drug carriers made of micro-scale materials retain near cancer cells due to surface effects resulting from their large specific surface area and quantum effects resulting from their small particle size. When the drug carrier is delivered to a human body, the drug carrier is accumulated near the cancer tissue through the retention effect, and meanwhile, the drug carrier is triggered to carry out drug slow release because the microenvironment of the cancer tissue has weak acidity (pH=5.0-6.5), so that the anticancer treatment of the chemical drugs is carried out. Most of the current drug carrier materials are synthesized mainly by man, resulting in poor biocompatibility and non-biodegradability. The biomass material is directly extracted from renewable resources and is obtained through biological, chemical and physical processing, so that the biomass material has unique biological activity, physiological function and biocompatibility. In such materials, hemicellulose is a heteromultimer composed of several different types of monosaccharides and having hydrophilic properties, and is widely present in plants such as straw, cork, hardwood, grass, etc., and is the main chemical component of plant fiber raw materials. Hemicellulose has the advantages of good biocompatibility, environmental protection, no toxicity and the like, and provides a wide application prospect for natural biological anticancer drug delivery systems. The hemicellulose not only can be used as a drug carrier to prepare functional biopolymer materials, but also can further improve the properties of hemicellulose hydrogel through chemical modification of raw materials, thereby meeting various requirements of the hemicellulose hydrogel in the fields of drug release and the like. Sun X-F et al synthesized biodegradable pH sensitive hemicellulose hydrogel using potassium persulfate and anhydrous sodium sulfite initiation system, achieving 5-6h sustained release of aspirin and theophylline (Sun X-F, wang HH, jin ZX, mohanathas R.Hemicellose-based pH-sensitive and biodegradable hydrogel for controlled drug release. Carbohydrate Polymers,2013, 92:1357-1366.); sun X-F et al take modified xylan hemicellulose and silanized GO as raw materials, and adopt an ammonium persulfate and anhydrous sodium sulfite initiating system to prepare a chemically crosslinked hydrogel, so that the chemically crosslinked hydrogel is applied to removal of copper ions in sewage (Sun X-F, xie, Y.; shan, S.; li, W.; sun, L.chemical ly-crosslinked xylan/graphene oxide composite hydrogel for copper ions remote.J.Polym.environment.2022, 30, 3999-4013.) the preparation of the hemicellulose hydrogel is generally initiated by a toxic reagent such as persulfate and the like to carry out free radical polymerization synthesis, the preparation method is not green and environment-friendly, the drug loading rate of the prepared hemicellulose hydrogel is low, the drug release time is short, and the application of the hemicellulose hydrogel in the field of drug release is limited.
Aiming at the technical problems of no green environmental protection, low drug loading rate, short drug slow release time and poor biocompatibility of the existing hemicellulose hydrogel preparation method, a new hemicellulose-based hydrogel is needed to be found to solve the problems, and the application of the hemicellulose hydrogel in the field of drug release is widened.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a visible light driven synthesis hemicellulose-based nano composite hydrogel, and a preparation method and application thereof, so as to solve the difficult problem of green synthesis of a biological-based anticancer drug carrier material, solve the problems of low drug loading rate, short drug slow release time and the like of the drug carrier material, and effectively reduce or avoid toxic and side effects of the drug.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of hemicellulose-based nano composite hydrogel, which comprises the following steps:
1) Dispersing hemicellulose uniformly, adding N, N-methylene bisacrylamide, completely dissolving, and adding alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 After uniform dispersion, adding acrylic acid, homogenizing, and performing ultrasonic treatment to obtain an HC/PAA/FGN composite hydrogel precursor;
2) And (3) irradiating the HC/PAA/FGN composite hydrogel precursor obtained in the step (1) under visible light to obtain the hemicellulose-based nano composite hydrogel.
Preferably, in step 1), hemicellulose: n, N-methylenebisacrylamide: alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 : the mass ratio of the acrylic acid is (0.05-0.25): (0.005-0.04): (0.0005-0.005): (0.5-2.0).
Preferably, in the step 1), the time of the homogenization reaction is 5-10 min; the ultrasonic treatment time is 20-40 min.
Preferably, in step 2), the visible light source is a xenon lamp.
Further preferably, in step 2), the power of the visible light source is 150 to 300W.
Further preferably, in step 2), the irradiation time of the visible light is 3 to 4 hours.
The invention also discloses the hemicellulose-based nano composite hydrogel prepared by the preparation method, the surface of the hemicellulose-based nano composite hydrogel presents a honeycomb micron-sized pore structure, and a large number of nano pores exist inside the hemicellulose-based nano composite hydrogel.
Preferably, the hemicellulose-based nano composite hydrogel is immersed in the doxorubicin solution for drug deposition, and the embedding rate of the hemicellulose-based nano composite hydrogel on the doxorubicin is 87.8% -96.5%.
Preferably, the equilibrium swelling ratio of the hemicellulose-based nanocomposite hydrogel is 9026% -17420%.
The invention also discloses application of the hemicellulose-based nano composite hydrogel in preparation of a bio-based drug carrier material, and the hemicellulose-based nano composite hydrogel is used as a drug carrier for transporting the doxorubicin, so that the doxorubicin can be slowly released for more than 80 hours under the conditions of normal body temperature and tumor tissue pH value microenvironment.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of hemicellulose-based nano composite hydrogel, which takes macromolecule hemicellulose extracted from wheat straw as a raw material, and takes visible light response, nontoxic and environment-friendly alpha-Fe as a raw material 2 O 3 /rGO/mpg-C 3 N 4 The hemicellulose-based nano composite hydrogel is synthesized by visible light initiation as a photocatalyst, has pH sensitivity, can be used as a drug carrier for transporting anticancer drug Doxorubicin (DOX), effectively reduces or avoids toxic and side effects of drugs, and provides a wide application prospect for a drug delivery system; the hemicellulose-based nano composite hydrogel also has a certain antibacterial property, active substances generated in the photocatalysis process can damage cell walls of microorganisms in the preparation process, so that bacterial death and microorganism load reduction are caused, microorganisms and chemical pollution in the hydrogel synthesis process can be effectively reduced, and the problem that microorganisms or chemical reagents are polluted frequently in the traditional medical hydrogel synthesis process can be effectively solved. In addition, the method realizes the visible light driving synthesis of the hemicellulose nano composite hydrogel, has the advantages of green and environment-friendly preparation method and simple operation, can overcome the defects of complex synthesis, toxicity, low bioavailability, serious side effect and the like of common hydrogels, solves the problem of green synthesis of bio-based drug carrier materials, breaks through the drug carrier material problems of poor biocompatibility and short drug release time, effectively reduces or avoids the toxic and side effect of drugs, and can improve the anticancer chemical drug treatment index.
The invention also discloses the hemicellulose-based nano composite hydrogel prepared by the preparation method, which adopts the straw hemicellulose material with certain biological activity, physiological function and biocompatibility as raw material and adopts the alpha-Fe with antibacterial property 2 O 3 /rGO/mpg-C 3 N 4 As a photocatalyst, the synthesized drug-loaded hemicellulose-based nano composite hydrogel is triggered by visible light green. The hemicellulose-based nano composite hydrogel has a honeycomb micron-sized pore structure on the surface, a large number of nano pores exist in the surface, and the remarkably increased specific surface area can improve the drug loading property.
Furthermore, the hemicellulose-based nano composite hydrogel is immersed in an adriamycin solution for drug deposition, the embedding rate of adriamycin serving as an anticancer drug reaches 96.5%, and the adriamycin is loaded on the hemicellulose-based hydrogel to prepare an anticancer drug delivery carrier, so that a closed coating environment is provided for adriamycin before the adriamycin is delivered to targeted lesion tissues, the integrity of the drug can be improved, the high bioactivity of the drug can be maintained, and the toxic and side effects of the drug can be effectively reduced or avoided.
Further, the hemicellulose-based nanocomposite hydrogel has a maximum equilibrium swelling ratio of 17420%; hemicellulose, α -Fe in hydrogel at ph=11.0 2 O 3 /rGO/mpg-C 3 N 4 When the contents of the acrylic acid and the N, N-methylene bisacrylamide are respectively 0.2g, 0.001g, 1.0g and 0.03g, the equilibrium swelling ratio of the hemicellulose-based nano composite hydrogel reaches the maximum value, and the maximum equilibrium swelling ratio is 17420%.
The invention also discloses application of the hemicellulose-based nano composite hydrogel in preparation of a bio-based drug carrier material, and the hemicellulose-based nano composite hydrogel is used as a drug carrier for transporting anticancer drug doxorubicin, and the doxorubicin can be controllably released for more than 80 hours under the conditions of approaching the normal body temperature of a human body and approaching the pH value microenvironment of tumor tissues. Can overcome the defects of low bioavailability, systemic toxicity of chemotherapy drugs, serious side effects and the like, prolong the drug release time, increase the drug concentration at focus parts and improve the therapeutic index of anticancer chemical drugs. The anticancer drug DOX is loaded on hemicellulose-based hydrogel to prepare a drug delivery carrier, so that a closed coating environment is provided for the anticancer drug DOX before the anticancer drug DOX is delivered to targeted pathological tissues, and the integrity, the structure and the high bioactivity of the anticancer drug DOX can be well maintained. As a drug carrier for transporting the anticancer drug doxorubicin, the drug carrier can overcome the defects of low bioavailability, systemic toxicity of chemotherapeutic drugs, serious side effects and the like, and can prolong the drug release time, increase the drug concentration at focus positions and improve the therapeutic index of the anticancer chemical drugs. Most importantly, the hemicellulose-based nano composite hydrogel synthesized by visible light green initiation effectively reduces or avoids toxic and side effects of the drug.
Drawings
FIG. 1 is a reaction mechanism diagram of a hemicellulose-based nanocomposite hydrogel according to the present disclosure;
FIG. 2 shows hemicellulose, alpha-Fe prepared in examples 1 and 2 2 O 3 /rGO/mpg-C 3 N 4 Infrared spectrograms of hydrogels Gel-2 and Gel-7;
FIG. 3 is an SEM image of various samples prepared in examples 1 and 2; wherein (a) is hemicellulose and (b) is alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 (c) is a Gel-8 enlarged view, and (d) is Gel-8;
FIG. 4 is a TEM image of various samples obtained in example 1; wherein (a) is nano hemicellulose and (b) is alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 (c) is Gel-1;
FIG. 5 is a peak-split fitting spectrum of XPS spectrum and C, N, O of the hemicellulose-based nanocomposite hydrogel prepared in example 1; wherein, (a) is an XPS full spectrum of the hemicellulose-based nanocomposite hydrogel, (b) is a C1s high-resolution XPS spectrum of the hemicellulose-based nanocomposite hydrogel, (C) is an N1s high-resolution XPS spectrum of the hemicellulose-based nanocomposite hydrogel, and (d) is an O1s high-resolution XPS spectrum of the hemicellulose-based nanocomposite hydrogel;
FIG. 6 is an XRD pattern of various samples prepared in examples 1 and 4; wherein (a) is hemicellulose, and (b) is graphite, GO, mpg-C 3 N 4 And alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 (c) is Gel-13;
FIG. 7 is the effect of varying AA levels on swelling properties of hemicellulose-based nanocomposite hydrogels of example 1;
FIG. 8 shows a different alpha-Fe of example 2 2 O 3 /rGO/mpg-C 3 N 4 Influence of the content on the swelling property of the hemicellulose-based nanocomposite hydrogel;
FIG. 9 is the effect of varying hemicellulose content on the swelling properties of hemicellulose-based nanocomposite hydrogels of example 3;
FIG. 10 is a graph showing the effect of varying N, N-methylenebisacrylamide content on swelling properties of hemicellulose-based nanocomposite hydrogels of example 4;
FIG. 11 is a kinetic profile of DOX loaded on the hemicellulose-based nanocomposite hydrogel prepared in example 1;
FIG. 12 is the effect of pH of different release media prepared in example 1 on the slow release of hemicellulose-based nanocomposite hydrogel drug; wherein, (a) is slow release of drugs with different pH values at 25 ℃, and (b) is slow release of drugs with different pH values at 37 ℃;
FIG. 13 is a graph showing 1 the effect of varying initial acrylic acid content on hemicellulose-based nanocomposite hydrogel drug release;
FIG. 14 shows the different alpha-Fe values obtained in example 2 2 O 3 /rGO/mpg-C 3 N 4 Influence of initial content on sustained release of hemicellulose-based nanocomposite hydrogel drug;
FIG. 15 is a graph showing the effect of the initial hemicellulose content on the slow release of hemicellulose-based nanocomposite hydrogel drug prepared in example 3;
FIG. 16 shows the effect of initial levels of N, N-methylenebisacrylamide on the sustained release of hemicellulose-based nanocomposite hydrogel drug prepared in example 4.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
at present, most of drug carrier materials are mainly synthesized by artificial chemistry, and the components of the drug carrier materials are poor in biocompatibility, non-biodegradable, complex in synthesis method and toxic. The invention adopts natural straw hemicellulose material, is suitable for biomedical engineering application, in particular to the synthesis of hemicellulose-based nano composite hydrogel by adopting visible light initiation, is environment-friendly, is simple to operate, and uses composite photocatalyst alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 As an initiator and hemicellulose are used as raw materials, and the hemicellulose-based nano composite hydrogel with excellent performances such as good degradability, biocompatibility and the like is synthesized under the action of visible light.
Referring to FIG. 1, a reaction mechanism diagram of a hemicellulose-based nanocomposite hydrogel according to the present disclosure; as can be seen from the figures: the polymerization process mainly comprises the following three stages; firstly, in a chain initiation stage, under the initiation of visible light, when illumination energy is larger than the forbidden bandwidth of a photocatalyst, electron hole pairs generated by the photocatalyst react with water molecules and dissolved oxygen in an aqueous solution to generate primary active free radicals; subsequently, the chain growth stage is that the primary active free radical reacts with the monomer acrylic acid to generate a monomer free radical, the monomer free radical reacts with the adjacent monomer to complete chain growth, and the cross-linking agent also participates in polymerization while the chain growth is carried out, so that a porous three-dimensional network structure is formed; meanwhile, FGN and HC can form hydrogen bonds to be doped into the hydrogel structure, so that the crosslinking density of the hydrogel is further improved; eventually, the chain termination stage, the amount of monomeric acrylic acid will decrease as the polymer continues to react, until the reaction is completed.
Wherein HC is hemicellulose; MBA is N, N-methylene bisacrylamide; FGN is alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the AA is acrylic acid; PAA is polyacrylic acid after polymerization.
The invention discloses a preparation method of hemicellulose-based nano composite hydrogel, which comprises the following steps:
1) Weighing 0.05-0.25 g of Hemicellulose (HC) in a 10-50 mL beaker, adding 10-30 mL of deionized water, and carrying out ultrasonic treatment for 20-40 min until the HC is uniformly dispersed;
2) Then adding 0.005-0.04 g of N, N-Methylene Bisacrylamide (MBA), adding 0.0005-0.005 g of alpha-Fe after complete dissolution 2 O 3 /rGO/mpg-C 3 N 4 (FGN) uniformly dispersed using a high-speed homogenizer;
3) Adding 0.5-2.0 g of Acrylic Acid (AA) into the dispersion liquid, homogenizing and dispersing for 5-10 min at high speed, and then carrying out ultrasonic treatment for 20-40 min;
4) And placing the beaker under a 150-300W xenon lamp and irradiating for 3-4 hours to obtain the uniformly molded hemicellulose-based nano composite hydrogel.
Wherein, alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 The preparation method of the (C) comprises the following steps:
1) Preparation of protonated mpg-C 3 N 4 (pCN): weighing 10g urea, placing into a ceramic crucible with a cover, heating to 600deg.C at a heating rate of 10deg.C/min, heating for 4 hr, cooling to room temperature, taking out, and grinding to obtain mpg-C 3 N 4 . Preparing 0.3mol/L dilute hydrochloric acid solution, taking 200mL of dilute hydrochloric acid, adding 1g of prepared mpg-C 3 N 4 Ultrasonic treatment is carried out for 0.5h, and then the mixed solution is vigorously stirred for 4h by using a constant-speed stirrer; the mixed solution is taken out and filtered, washed to be neutral by deionized water, and dried for 12 hours in an oven at 70 ℃ to obtain the protonated mpg-C 3 N 4 (pCN)；
2) Preparation of alpha-Fe by hydrothermal method 2 O 3 /RGO/mpg-C 3 N 4 Nanocomposite material: 100mg of protonated mpg-C was weighed 3 N 4 15mg of alpha-Fe 2 O 3 Nanoparticle, 50mg of RGO powder and 0.1g of Sodium Dodecyl Benzene Sulfonate (SDBS) are dispersed in 20mL of deionized water, and ultrasonic treatment is carried out for 30min; transferring the mixture to highIn an autoclave, reacting for 6 hours at 180 ℃; the product was washed with deionized water and absolute ethanol, respectively, filtered and freeze-dried for 12h. By controlled addition of rGO and alpha-Fe 2 O 3 The quality of the nano particles is finally prepared into alpha-Fe 2 O 3 Is 10% of alpha-Fe by mass 2 O 3 /rGO/mpg-C 3 N 4 A nanocomposite.
Example 1
(1) A method for preparing hemicellulose-based nanocomposite hydrogel, comprising the steps of:
1) Weighing 0.2g of HC in a 50mL beaker, adding 10mL of deionized water, and performing ultrasonic treatment for 20min until the HC is uniformly dispersed;
2) Weighing 0.03g of MBA, adding the MBA into the solution in the step 1), carrying out ultrasonic treatment, and adding 0.001g of alpha-Fe after complete dissolution 2 O 3 /rGO/mpg-C 3 N 4 Uniformly dispersing by using a high-speed homogenizer;
3) Adding a certain amount of AA into the dispersion liquid, homogenizing for 5min, and then performing ultrasonic treatment for 20min;
4) And placing the beaker under a 150W xenon lamp and irradiating for 3 hours to obtain the uniformly molded hemicellulose-based nano composite hydrogel.
A series of composite hydrogels with different AA contents, named Gel 2, gel 3, gel1 and Gel 4, were prepared by changing the AA content of the Gel system to 0.5g, 0.75g, 1.0g and 2.0g, respectively.
Referring to FIG. 2, HC, α -Fe is prepared according to examples 1 and 2 2 O 3 /rGO/mpg-C 3 N 4 Infrared spectra of hydrogels Gel-2 and Gel-7. As can be seen from the figures: HC and alpha-Fe in the IR spectra of hydrogels Gel-2 and Gel-7 2 O 3 /rGO/mpg-C 3 N 4 The characteristic absorption peaks of (2) indicate that the two materials are well fused into the hydrogel. At 3558cm -1 And 2935cm -1 The absorption peaks of the telescopic vibration respectively belonging to O-H and C-H appear at 1733cm -1 The carboxyl group was located at the carbonyl stretching vibration absorption peak, and the hydrogel was 1600cm in length -1 There was no strong absorption peak attributed to acrylic acid c=c in the vicinity, indicating that the monomer had reacted completely. At 1453cm -1 The absorption peak at which corresponds to bending vibration (-C-O-H), 1261cm -1 And 1172cm -1 The place is asymmetric stretching vibration of carboxylate, 805cm -1 At CH 2 The unit deforms and swings and vibrates.
See fig. 3 for SEM images of the various samples prepared in examples 1 and 2; wherein, (a) is an SEM image of HC, from which it can be seen that HC is in the form of a fiber rod-like structure, and a large amount of HC is intertwined; (b) Is alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 It can be seen from SEM image of the reduced graphene oxide and graphite phase carbon nitride that the lamellar structure is interlaced with each other, and that the particle size of alpha-Fe is 50-100nm 2 O 3 The nano particles are in uniform spherical shape and are adsorbed on the surface of the sheet layer of the reduced graphene oxide; (c) And (d) SEM image of hemicellulose-based nanocomposite hydrogel Gel-8 and its magnified image, the hydrogel sample exhibiting a cellular structure with few redundant nodules, presumably alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 . From the figure, the hydrogel surface contains a large number of micron-sized pore sizes, and the significantly increased specific surface area will improve the drug loading performance.
Referring to fig. 4, TEM images of various samples prepared in example 1; wherein, (a) is a TEM image of nano hemicellulose, and the prepared nano hemicellulose is in a fiber rod-shaped structure and has particle size in the range of 30nm-90 nm; (b) Is alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 TEM image of nanocomposite material, it can be seen that after the reaction, α -Fe 2 O 3 And mpg-C 3 N 4 Nanoparticles are attached to RGO; (c) In addition to the rod-like hemicellulose contained in Gel-1, TEM image of hydrogel Gel-1 shows that a large number of nanopores are present in the interior of the hydrogel in addition to the micropores formed in the Gel network.
Referring to fig. 5, an XPS spectrum and a peak-splitting fitting spectrum of C, N, O of the hemicellulose-based nanocomposite hydrogel prepared in example 1; (a) XPS full spectrum of hemicellulose-based nano composite hydrogel, the spectrum shows that the hydrogel mainly contains C, N, O elements, and the synthetic hemicellulose hydrogelWhen only a trace amount of photocatalyst alpha-Fe is added 2 O 3 /rGO/mpg-C 3 N 4 The photocatalyst only contains trace Fe element, so that the characteristic peak of Fe2p is hardly distinguished in the full spectrum; (b) C1s high-resolution XPS spectrum of hemicellulose-based nano composite hydrogel, and mpg-C in photocatalyst is assigned to characteristic absorption peak with binding energy of 285.4eV 3 N 4 C-N bond of (C); the characteristic absorption peak at a binding energy of 284.6eV is assigned to the C-C bond on the HC and AA backbones; the characteristic absorbance peak at binding energy 288.6eV is assigned to the c=o bond on the AA backbone and in MBA; (c) N1s high-resolution XPS spectrum of hemicellulose-based nano composite hydrogel, and characteristic absorption peak with the binding energy of 399.6eV is attributed to-NH-bond of MBA in the crosslinking agent; (d) The O1s high-resolution XPS spectrum of the hemicellulose-based nano composite hydrogel is characterized in that the characteristic absorption peak with the binding energy of 533.2eV is attributed to a C-O-H bond on HC; the characteristic absorbance peak at binding energy 531.6eV is assigned to the c=o bond on the AA backbone and in MBA.
Referring to fig. 6, XRD patterns of various samples prepared in examples 1 and 4; wherein, (a) is an XRD pattern of HC, and from characteristic peaks in the pattern, HC has no obvious crystallization, almost amorphous structure and only trace microcrystalline structure, and the purity of the purified hemicellulose is very high without mixing with cellulose; (b) Is graphite, GO, g-C 3 N 4 And alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 According to the diffraction peaks of graphite and GO in the figure, the diffraction peak of graphite becomes the (001) crystal plane diffraction peak of GO sheet; g-C 3 N 4 The characteristic peak of the sample at 12.7℃is attributed to g-C 3 N 4 And at g-C 3 N 4 The (002) crystal plane lamellar structure showed a strong characteristic peak stacking peak at 27.3 °. alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4( FGN) spectral line crystal plane data with g-C 3 N 4 Is hardly different. However, with the compounding of the three materials, g-C in the sample 3 N 4 The crystal plane peak of (C) is slowly moved to a smaller angle from g-C 3 N 4 Gradually moving to 26.9 degrees of FGN nanocomposite, the interlayer distance of crystal face is substituted into Bragg formulaThe distance was increased from 0.326nm to 0.331nm. Illustrating alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 mpg-C after nanocomposite is compounded 3 N 4 The interlayer spacing will gradually increase and the stack will become more relaxed. FIG. (c) is an XRD pattern of Gel-13 hydrogel, in which the peak of the photocatalyst substantially disappeared in the diffraction pattern of Gel-13, since only a trace amount of photocatalyst was added during the synthesis, which also shows that HC, AA and MBA also reacted, and the characteristic peak appearing at 20.7 had no apparent crystalline structure.
(2) Swelling property test of hemicellulose-based nanocomposite hydrogel
The swelling ratio of the hemicellulose-based nanocomposite hydrogel was measured by a gravimetric method, and the specific procedure was as follows: accurately weighing xerogel with a certain mass, putting the xerogel into a beaker filled with 25mL of deionized water to enable the xerogel to absorb water and swell, taking out hydrogel at regular intervals, sucking the water on the surface by using filter paper, and putting the filter paper on an electronic balance for weighing. The swelling ratio was calculated by the ratio of the mass difference before and after swelling to the mass of the gel before swelling.
Referring to FIG. 7, the effect of varying AA levels on the swelling properties of hemicellulose-based nanocomposite hydrogels of example 1; when the AA content was increased from 0.5g to 1.0g, the hemicellulose-based nanocomposite hydrogel increased in water absorption to a medium solution having ph=11.0, reaching a maximum swelling ratio of 17420%. This is due to the fact that at high AA levels more-COO is dissociated - The osmotic pressure in the solution increases with the mutual repulsion between ions. And the carboxyl on AA can form hydrogen bond with water molecules, thereby enhancing the hydrophilicity of the hydrogel. With further increases in AA content, water absorption decreases due to an increase in hydrogel crosslink density, which results in a decrease in swelling properties. Thus, after the AA content exceeds a certain value, the influence of the crosslink density in the swelling property of the hydrogel is dominant. The difference in AA content causes-COO in the polymer - The swelling properties of the hydrogels are affected by the different amounts.
(3) Hemicellulose-based nanocomposite hydrogel drug loading efficiency study
The hemicellulose-based nanocomposite hydrogel is immersed in a DOX solution for drug deposition. The hemicellulose-based nano composite hydrogel contains a carboxyl group with anions, and DOX is a cationic anticancer drug containing terminal amino groups, so that the positively charged anticancer drug DOX can generate electrostatic association with a negatively charged main chain to spontaneously deposit into the hydrogel.
Referring to fig. 11, there is a kinetic curve of the hemicellulose-based nanocomposite hydrogel prepared in example 1 loaded with DOX. As can be seen from the figure, the spontaneous deposition rate of DOX is higher in the first 8 hours, the incubation time is 24 hours later, the embedding rate of DOX can reach 96.5% and the embedding amount is 96.5mg DOX/g Gel. The reason for the high entrapment of DOX in hemicellulose-based nanocomposite hydrogels is: first, DOX small molecules can enter a large number of three-dimensional network nano holes in the hydrogel under the action of capillary force. Secondly, positively charged DOX small molecules are electrostatically attracted by negatively charged carboxyl groups in the hydrogel and the photocatalytic graphite phase carbon nitride.
(4) Drug sustained release performance of hemicellulose-based nanocomposite hydrogels
Referring to fig. 12, there are graphs showing the sustained-release cumulative release of the drug at pH values of 7.4, 6.0 and 3.6 at 25 ℃ and 37 ℃ respectively after loading DOX with the hemicellulose-based nanocomposite hydrogel prepared in example 1; it can be seen from (a) that the DOX release rate was higher and then gradually smoothed over the first 24 hours. At pH 7.4, the accumulated release of DXO was 18.3%, indicating that DOX was not released prematurely and the drug-loaded hemicellulose-based nanocomposite hydrogel remained highly stable. And when the pH value is 6.0, the accumulated release of DOX can reach 37.9%, which means that the drug-loaded hemicellulose-based nano composite hydrogel has certain pH sensitivity and can be released stably for more than 80 hours. The release rate in a buffer solution with a pH value of 3.6 is faster, the accumulated release amount is more, and the intelligent pH responsiveness of the hemicellulose-based nano composite hydrogel mainly has the following reasons: first, due to the electrostatic interaction between AA and DOX, electrostatic adsorption between the administered DOX is impaired at lower pH values, thereby promoting slow release of the drug. Finally, at low pH, hydrogen bonding with DOX inside the hemicellulose-based nanocomposite hydrogel can be broken, thereby causing drug release. The sustained release performance of the hydrogel drug at various pH values (7.4, 6.0 and 3.6) was evaluated at 37℃near the normal body temperature of the human body. In-vitro drug release simulation is performed under the condition that the pH value of the cell is 7.4 lower than that of normal tissue cells of a human body, and the micro environment of the tumor often shows the characteristic of low pH value because various ion exchangers are arranged on a cell membrane system of tumor tissue. At 37 ℃, the accumulated slow release amount of the drug is larger than the slow release amount at 25 ℃, which indicates that the drug is easier to release from the carrier at higher temperature. The accumulated release of the medicine can reach more than 45.7 percent under the condition that the pH value microenvironment approaches to tumor tissue under the condition of approaching to the normal body temperature of human body.
See fig. 13 for the effect of varying AA initial content on hemicellulose-based nanocomposite hydrogel drug release; as can be seen from the figure, as the initial AA content increases, the cumulative release amount and release rate of DOX from the drug-loaded hemicellulose-based nanocomposite hydrogel decrease. This is because an increase in the initial AA content results in an increase in the carboxyl content, an increase in the crosslink density of the hemicellulose-based nanocomposite hydrogel, and a decrease in the release rate of DOX.
Example 2
(1) A method for preparing hemicellulose-based nanocomposite hydrogel, comprising the steps of:
1) Weighing 0.2g of HC in a 50mL beaker, adding 20mL of deionized water, and performing ultrasonic treatment for 30min until the HC is uniformly dispersed;
2) Weighing 0.03g of MBA, adding the MBA into the solution obtained in the step 1), carrying out ultrasonic treatment, adding a certain amount of FGN after complete dissolution, and uniformly dispersing by using a high-speed homogenizer;
3) Adding 1.0g of AA into the dispersion liquid, homogenizing for 5min, and then carrying out ultrasonic treatment for 30min;
4) And (3) placing the beaker under a 300W xenon lamp and irradiating for 4 hours to obtain the uniformly molded hemicellulose-based nano composite hydrogel.
A series of hemicellulose-based nanocomposite hydrogels with different FGN contents, named Gel 5, gel 6, gel 7, and Gel 8, were prepared by changing the FGN content in the Gel system to 0.0005g, 0.002g, 0.003g, and 0.005g, respectively.
(2) Swelling Properties of hemicellulose-based nanocomposite hydrogels
See FIG. 8 for a different α -Fe of example 2 2 O 3 /rGO/mpg-C 3 N 4 Influence of the content on the swelling property of the hemicellulose-based nanocomposite hydrogel; the swelling ratio of the hemicellulose-based nanocomposite hydrogel was measured in the same manner as in example 1, and it can be seen from the graph that as the FGN content was increased from 0.0005g to 0.001g, the water absorption of the hemicellulose-based nanocomposite hydrogel to a medium solution having ph=11.0 was increased to reach a swelling ratio of 17420%. The method is characterized in that along with the increase of the dosage of the photocatalyst, the free radicals generated in the free radical polymerization reaction process are increased, so that the polymerization reaction between monomers and between the monomers and HC is facilitated, the polymer chain is continuously increased, and the swelling performance of the hemicellulose-based nanocomposite hydrogel is improved. As the content of the photocatalyst rises again, excessive free radicals are generated in the polymerization process, so that the monomers instantaneously polymerize to form excessive polymerization centers, the chain length of the polymer is shortened, the molecular weight is reduced, and the swelling performance of the hydrogel is further weakened. Furthermore, FGN not only plays a role of an initiator, but also partially plays a role of a crosslinking agent, and a negative charge exists on the surface. Thus, the difference in FGN content causes a difference in the cross-linking density of the polymer network and electrostatic repulsive interaction, so that the swelling performance of the hemicellulose-based nanocomposite hydrogel is affected.
(3) Drug sustained release performance of hemicellulose-based nanocomposite hydrogels
Referring to FIG. 14, the effect of the initial content of FGN on the sustained release of hemicellulose-based nanocomposite hydrogel drug is shown in example 2; with the increase of the initial content of FGN, the accumulated release amount and release rate of the drug-loaded hemicellulose-based nano composite hydrogel to DOX are increased slightly. This is because the FGN content increases, more active radicals are generated under the action of the optical disc drive, and excessive radicals are generated to cause instantaneous polymerization of the monomers to form excessive polymerization centers, so that the chain length of the polymer becomes shorter, the wrapping capability for DOX is reduced, and the drug release amount is increased. However, because of negative charges on the surface of FGN, the gel has certain attraction to DOX, but is far smaller than the influence of hemicellulose-based nano composite hydrogel structure on drug slow release. So the accumulated release amount and release rate of the drug-loaded hemicellulose-based nano composite hydrogel to DOX are increased in small amplitude along with the increase of the initial content of FGN.
Example 3
(1) A method for preparing hemicellulose-based nanocomposite hydrogel, comprising the steps of:
1) Weighing a certain amount of HC in a 50mL beaker, adding 30mL of deionized water, and performing ultrasonic treatment for 30min until HC is uniformly dispersed;
2) Weighing 0.03g of MBA, adding the MBA into the solution in the step 1), carrying out ultrasonic treatment, and adding 0.001g of alpha-Fe after complete dissolution 2 O 3 /rGO/mpg-C 3 N 4 Uniformly dispersing by using a high-speed homogenizer;
3) Adding 1.0g of AA into the dispersion liquid, homogenizing for 10min, and then carrying out ultrasonic treatment for 40min;
4) And (3) placing the beaker under a 300W xenon lamp and irradiating for 4 hours to obtain the uniformly molded hemicellulose-based nano composite hydrogel.
A series of composite hydrogels with different HC contents, named Gel 9, gel 10, gel 11 and Gel 12, are prepared by changing the HC contents in the Gel system to be 0.05g, 0.1g, 0.15g and 0.25g respectively.
(2) Swelling Properties of hemicellulose-based nanocomposite hydrogels
Referring to FIG. 9, the effect of varying HC levels on swelling properties of hemicellulose-based nanocomposite hydrogels of example 3; the swelling ratio of the hemicellulose-based nanocomposite hydrogel was measured in the same manner as in example 1, and it can be seen from the graph that when the HC content was increased from 0.05g to 0.2g, the water absorption of the hemicellulose-based nanocomposite hydrogel to a medium solution having ph=11.0 was increased to reach the maximum swelling ratio 17420%. This is because HC contains a large number of hydrophilic groups, hydroxyl groups, which react with the monomer to enhance the hydrophilicity of the hydrogel. As the HC content further increases beyond the optimum value, the water absorption decreases. This is because an excessive increase in the HC content results in an increase in the crosslink density of the hydrogel, which makes the polymer network structure compact, thereby weakening the swelling properties of the hydrogel. Furthermore, the addition of too much HC results in a decrease in the relative ratio of hydrophilic groups such as-OH, -COOH, and-COO-in the hydrogel, and a decrease in swelling properties.
(3) Drug sustained release performance of hemicellulose-based nanocomposite hydrogels
Referring to FIG. 15, the effect of different initial HC levels on the slow release of hemicellulose-based nanocomposite hydrogel drug prepared in example 3; with the increase of the initial HC content, the accumulated DOX release amount and the DOX release rate of the drug-loaded hemicellulose-based nano composite hydrogel are reduced. The initial HC content is increased, and the hydroxyl content is increased, so that the formed gel network structure is more compact, and the DOX release rate is reduced.
Example 4
(1) A method for preparing hemicellulose-based nanocomposite hydrogel, comprising the steps of:
1) Weighing 0.2g of HC in a 50mL beaker, adding 30mL of deionized water, and performing ultrasonic treatment for 40min until the HC is uniformly dispersed;
2) Weighing a certain amount of MBA, adding the MBA into the solution obtained in the step 1), carrying out ultrasonic treatment, and adding 0.002g of alpha-Fe after complete dissolution 2 O 3 /rGO/mpg-C 3 N 4 Uniformly dispersing by using a high-speed homogenizer; the method comprises the steps of carrying out a first treatment on the surface of the
3) Adding 1.0g of AA into the dispersion liquid, homogenizing for 10min, and then carrying out ultrasonic treatment for 20min;
4) And placing the beaker under a 200W xenon lamp and irradiating for 3 hours to obtain the uniformly molded hemicellulose-based nano composite hydrogel.
A series of composite hydrogels with different MBA contents, named Gel 13, gel 14, gel 15 and Gel16, are prepared by changing the MBA contents in the Gel system to be 0.005g, 0.01g, 0.02g and 0.04g respectively.
(2) Swelling Properties of hemicellulose-based nanocomposite hydrogels
Referring to FIG. 10, the effect of varying MBA content on the swelling properties of hemicellulose-based nanocomposite hydrogels of example 4; the swelling ratio of the hemicellulose-based nanocomposite hydrogel was measured in the same manner as in example 1, and it can be seen from the graph that when the MBA content was increased from 0.005g to 0.03g, the water absorption of the hemicellulose-based nanocomposite hydrogel to a medium solution having ph=11.0 was increased to reach the maximum swelling ratio 17420%. Through Floy' theory, the increase of the content of the cross-linking agent can improve the cross-linking node number and the cross-linking density of the hydrogel, which is beneficial to the adsorption and the maintenance of the medium solution. As the MBA content rises again, hydrogel crosslinking nodes increase to increase the crosslinking density of the hydrogel, so that the polymer network structure becomes compact and the elasticity decreases, and the swelling performance of the hydrogel is weakened.
(3) Drug sustained release performance of hemicellulose-based nanocomposite hydrogels
Referring to fig. 16, which shows the effect of the initial content of MBA on the slow release of hemicellulose-based nanocomposite hydrogel drug, the cumulative release amount of DOX from the drug-loaded hemicellulose-based nanocomposite hydrogel is greatly reduced and the release rate is reduced with the increase of the initial content of MBA. When the initial content of the cross-linking agent is increased, the cross-linking density of the hemicellulose-based nano composite hydrogel formed by cross-linking of the AA monomer and the MBA is increased, and the DOX release rate is reduced.
Therefore, the invention uses the composite photocatalyst alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 As an initiator and hemicellulose are used as raw materials, and the hemicellulose-based composite hydrogel with good drug slow release performance is synthesized under the action of visible light. The prepared hydrogel has pH stimulation response and can be used as a drug carrier for transporting anticancer drug Doxorubicin (DOX). The preparation method is environment-friendly, and the photoinitiated synthetic hemicellulose-based nano composite hydrogel material is combined with an anticancer drug with strong side effect, so that a wide application prospect is provided for a nano material drug delivery system. The method is a method for crosslinking a polymer under the initiation of low-intensity visible light, and compared with physical crosslinking, the photochemical crosslinking reaction process is easy to control, high in reaction efficiency and high in temperature, and few in by-products are formed. The photocrosslinked hydrogel can be applied to an anticancer drug delivery system, and can be crosslinked into a polymer with a three-dimensional network structure through chemical bond interaction under the condition of visible light irradiation. Photocrosslinked hydrogels are stored in a network after loading with a drug and based on environmental changesA stimulus response is elicited, followed by a sustained drug release to the targeted tissue.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing hemicellulose-based nanocomposite hydrogel, comprising the steps of:
1) Dispersing hemicellulose uniformly, adding N, N-methylene bisacrylamide, completely dissolving, and adding alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 After uniform dispersion, adding acrylic acid, homogenizing, and performing ultrasonic treatment to obtain an HC/PAA/FGN composite hydrogel precursor;
2) And (3) irradiating the HC/PAA/FGN composite hydrogel precursor obtained in the step (1) under visible light to obtain the hemicellulose-based nano composite hydrogel.
2. The method for preparing a hemicellulose-based nanocomposite hydrogel according to claim 1, wherein in step 1), hemicellulose: n, N-methylenebisacrylamide: alpha-Fe 2 O 3 /rGO/mpg-C 3 N 4 : the mass ratio of the acrylic acid is (0.05-0.25): (0.005-0.04): (0.0005-0.005): (0.5-2.0).
3. The method for preparing hemicellulose-based nanocomposite hydrogel according to claim 1, wherein in step 1), the time of the homogenizing reaction is 5-10 min; the ultrasonic treatment time is 20-40 min.
4. The method for preparing a hemicellulose-based nanocomposite hydrogel according to claim 1, wherein in step 2), the visible light source is a xenon lamp.
5. The method of preparing a hemicellulose-based nanocomposite hydrogel according to claim 4, wherein in step 2), the power of the visible light source is 150-300W.
6. The method for preparing a hemicellulose-based nanocomposite hydrogel according to claim 4, wherein in step 2), the irradiation time of visible light is 3-4 hours.
7. The hemicellulose-based nano composite hydrogel prepared by the preparation method according to any one of claims 1 to 6, wherein the surface of the hemicellulose-based nano composite hydrogel presents a honeycomb micron-sized pore structure, and a large number of nanopores exist inside the surface.
8. The hemicellulose-based nanocomposite hydrogel according to claim 7, wherein the hemicellulose-based nanocomposite hydrogel is immersed in a doxorubicin solution for drug deposition, and the hemicellulose-based nanocomposite hydrogel has an entrapment rate of 87.8% -96.5% of doxorubicin.
9. The hemicellulose-based nanocomposite hydrogel according to claim 7, wherein the equilibrium swelling ratio of the hemicellulose-based nanocomposite hydrogel is from 9026% to 17420%.
10. The application of the hemicellulose-based nano composite hydrogel in preparing a bio-based drug carrier material according to any one of claims 7-9, which is characterized in that the hemicellulose-based nano composite hydrogel is used as a drug carrier for transporting doxorubicin, and the doxorubicin can be slowly released for more than 80 hours under the conditions of normal body temperature and tumor tissue pH value microenvironment.
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