CN113024732B - Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof - Google Patents
Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN113024732B CN113024732B CN202110167089.0A CN202110167089A CN113024732B CN 113024732 B CN113024732 B CN 113024732B CN 202110167089 A CN202110167089 A CN 202110167089A CN 113024732 B CN113024732 B CN 113024732B
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- mixed solution
- infrared light
- mxene
- isopropyl acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
- A61K47/32—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
- A61K47/38—Cellulose; Derivatives thereof
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a near-infrared light response N-isopropyl acrylamide-based hydrogel and a preparation method and application thereof, wherein the method comprises the following steps: mixing the bacterial cellulose dispersion liquid with MXene suspension liquid to obtain a mixed solution; sequentially adding an N-isopropyl acrylamide monomer and a cross-linking agent into the mixed solution to obtain a precursor solution; and adding a catalyst and an initiator into the precursor solution, and carrying out polymerization reaction to obtain the near-infrared light response N-isopropyl acrylamide-based hydrogel. The semi-interpenetrating network hydrogel is synthesized by simple free radical polymerization, the mechanical strength of the hydrogel is obviously improved by the actions of hydrogen bonds, physical entanglement and the like, and the prepared composite hydrogel is non-toxic and harmless and has good biocompatibility.
Description
Technical Field
The invention relates to the technical field of hydrogel, in particular to near-infrared light response N-isopropyl acrylamide-based hydrogel and a preparation method thereof.
Background
Hydrogel is a material having a three-dimensional network structure and having a high water content and tissue-like elasticity, and is considered as an ideal material for tissue engineering, cell culture, drug carriers, and artificial cartilage. The intelligent hydrogel is a hydrogel with a structure, physical and chemical properties capable of responding according to the change of external environmental stimuli. For example, some smart hydrogels respond with stimuli such as temperature, PH, electric field, magnetic field, light, and ionic strength. In recent years, near-infrared responsive hydrogels have received attention due to their superior tissue penetration ability and good temporal and spatial controllability in physiological environments. Such hydrogels generally consist of two parts, a thermally responsive hydrogel matrix and a near infrared photothermal agent. The near-infrared thermal agent can convert near-infrared light into heat energy, so that the hydrogel matrix is subjected to sol-gel conversion or volume shrinkage and other changes, and intelligent release of a load in gel is realized.
Poly-N-isopropylacrylamide (PNIPAM) is a representative thermal response high molecular polymer, has certain biocompatibility and is widely used as a drug carrier. PNIPAM hydrogels undergo a reversible hydrophilic-hydrophobic phase transition at a Low Critical Solution Temperature (LCST) of about 32 ℃. Below LCST, PNIPAM hydrogels are in a water swollen state, and can carry large amounts of drug molecules. When the temperature is raised above the LCST, the hydrogel undergoes a severe volume contraction, which squeezes to release the loaded drug molecules.
However, one significant drawback of PNIPAM hydrogels is their poor mechanical performance in the swollen state as drug carriers. And due to its non-biodegradable nature, it is necessary to remove the drug from the body after its release, and if the matrix is too soft, it is difficult to remove it completely by conventional surgical methods.
Therefore, the prior art is still subject to further improvement.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a near-infrared light responsive N-isopropyl acrylamide based hydrogel and a preparation method thereof, which are used for solving the problem of poor mechanical properties of the conventional thermal responsive polymer hydrogel in a swollen state.
In a first aspect, an embodiment of the present invention provides a method for preparing a near-infrared light-responsive N-isopropyl acrylamide-based hydrogel, where the method includes:
mixing the bacterial cellulose dispersion liquid with MXene suspension liquid to obtain a mixed solution;
sequentially adding an N-isopropyl acrylamide monomer and a cross-linking agent into the mixed solution to obtain a precursor solution;
and adding a catalyst and an initiator into the precursor solution, and carrying out polymerization reaction to obtain the near-infrared light response N-isopropyl acrylamide-based hydrogel.
Optionally, the preparation method includes the step of mixing the bacterial cellulose dispersion liquid with the MXene suspension to obtain a mixed solution, and specifically includes:
diluting bacterial cellulose with water to obtain a diluent, and dispersing the diluent to obtain a bacterial cellulose dispersion;
mixing MXene suspension with a certain concentration with the bacterial cellulose dispersion liquid to obtain a mixed solution.
Optionally, the preparation method, wherein the step of sequentially adding the N-isopropylacrylamide monomer and the crosslinking agent to the mixed solution to obtain the precursor solution further includes: and purging the precursor liquid by adopting inert gas for removing dissolved oxygen dissolved in the precursor liquid.
Optionally, the preparation method comprises the step of enabling the bacterial cellulose dispersion liquid to be 0.1-0.5% in mass percentage.
Optionally, the preparation method, wherein the substance concentration of the MXene suspension is 0.01-5 mg/mL.
Alternatively, the method of making, wherein the cross-linking agent is selected from N, N' -methylenebisacrylamide.
Optionally, in the preparation method, the catalyst is N, N' -tetramethylethylenediamine, and the initiator is ammonium persulfate.
Optionally, in the preparation method, the MXene is Nb 2 C MXene。
Optionally, in the preparation method, the mass ratio of the N-isopropylacrylamide monomer to the crosslinking agent and the initiator is 80-120: 1-5: 0.5-3.
In a second aspect, an embodiment of the present invention provides a near-infrared light-responsive N-isopropylacrylamide-based hydrogel, wherein the near-infrared light-responsive N-isopropylacrylamide-based hydrogel is prepared by the method described above.
Has the advantages that: the embodiment of the invention provides a near-infrared light response N-isopropyl acrylamide-based hydrogel and a preparation method thereof, wherein the semi-interpenetrating network hydrogel is synthesized through simple free radical polymerization, the mechanical strength of the hydrogel is obviously improved through the actions of hydrogen bonds, physical entanglement and the like, and the prepared composite hydrogel is non-toxic and harmless and has good biocompatibility.
Drawings
Fig. 1 is a flowchart of a method for preparing a near-infrared light-responsive N-isopropylacrylamide-based hydrogel according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a composite hydrogel prepared in example 1;
FIG. 3 is a scanning electron micrograph of the composite hydrogel prepared in example 1 after freeze-drying;
FIG. 4 is a tensile stress strain curve of the composite hydrogel prepared in example 1 with a neat PNIPAM hydrogel (without BC and MXene);
FIG. 5 is a photothermal curve of the composite hydrogel prepared in example 1 and pure water;
fig. 6 shows the drug release curve of the drug-loaded composite hydrogel prepared in example 1 under the control of near infrared light.
Detailed Description
The invention provides a near-infrared light response N-isopropyl acrylamide-based hydrogel and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a near-infrared light-responsive N-isopropyl acrylamide-based hydrogel, including the following steps:
s10, mixing the bacterial cellulose dispersion liquid with the MXene suspension liquid to obtain a mixed solution.
Specifically, the bacterial cellulose dispersion liquid can be prepared by adding water to dilute a Bacterial Cellulose (BC) raw material, and dispersing for 10min at the rotating speed of 15000-. MXene is a novel two-dimensional material consisting of a transition metal carbide, nitride or carbonitride (Advanced Materials,2011,23(37): 4248-. MXene has the general formula Mn +1Xn (n ═ 1-3), where M is an early transition metal (e.g., Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo), and X is carbon or nitrogen, which has a graphene-like structure. MXene has been found to be applied to the fields of energy storage, catalysis, sensing and the like for the first time in 2011.
In this embodiment, MXene is Nb 2 C MXene has abnormally high photothermal conversion efficiency, excellent biocompatibility and physiological stability in a first near infrared region (750-. Nb with the mass concentration of the substance of 0.01-5mg/mL 2 And mixing the C MXene suspension and the BC dispersion liquid, and uniformly dispersing the C MXene suspension and the BC dispersion liquid under magnetic stirring at room temperature to obtain a mixed solution.
And S20, sequentially adding the N-isopropyl acrylamide monomer and the cross-linking agent into the mixed solution to obtain a precursor solution.
Specifically, N-isopropylacrylamide monomer and N, N' -Methylenebisacrylamide (MBA), which is a crosslinking agent, are added to the mixed solution prepared in step S10, the mixed solution is magnetically stirred at room temperature, and purged with an inert gas (the inert gas may be introduced into the mixed solution while stirring) to remove dissolved oxygen from the mixed solution, and a precursor solution is obtained after the stirring is completed. It is readily understood that the inert gas may be nitrogen, argon, or the like. The cross-linking agent is used for cross-linking the N-isopropylacrylamide monomer.
And S30, adding a catalyst and an initiator into the precursor solution, and carrying out polymerization reaction to obtain the near-infrared light response N-isopropyl acrylamide-based hydrogel.
Specifically, N' -tetramethylethylenediamine (TEMED, catalyst) and ammonium persulfate (APS, initiator) were injected into the precursor solution prepared in step S20, stirred rapidly and uniformly and sonicated to remove air bubbles in the mixed solution, the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the composite hydrogel obtained after polymerization in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel, namely the near-infrared light response N-isopropyl acrylamide-based hydrogel.
In the embodiment, the thermal response hydrogel matrix and the near-infrared photothermal agent are combined to form the composite hydrogel with the semi-interpenetrating network structure by utilizing the free radical reaction, and the hydrogel has good biocompatibility and mechanical property and good near-infrared photoresponse.
Based on the same inventive concept, the embodiment of the application also provides a near-infrared light response N-isopropyl acrylamide-based hydrogel, and the hydrogel can be prepared by the preparation method. For the specific preparation process, reference may be made to the above preparation method, which is not described herein again.
Based on the same inventive concept, the embodiment of the application also provides application of the near infrared light response N-isopropyl acrylamide-based hydrogel used as a drug carrier.
Illustratively, the near-infrared light-responsive N-isopropyl acrylamide-based hydrogel prepared in step S30 is freeze-dried, and then is put into a doxorubicin hydrochloride (DOX) solution of 5mg/mL and soaked at room temperature for 3 days, so as to sufficiently load the DOX drug into the gel, thereby obtaining a drug-loaded composite hydrogel.
The present invention provides a near infrared light responsive N-isopropyl acrylamide based hydrogel and a method for preparing the same, which are further illustrated by the following specific preparation examples.
EXAMPLE 1
(1) Adding 30mL of deionized water into 30mL of BC dispersion raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion at the rotating speed of 20000rpm for 10min by using a high-speed dispersion machine to obtain fully dispersed BC dispersion, and mixing the BC dispersion with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.3 wt% and Nb 2 Mixed solution of C MXene concentration of 0.5 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 20mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly and homogeneously and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel. As shown in fig. 2, a semi-interpenetrating network structure composed of a PNIPAM backbone and a BC segment is formed by in-situ radical polymerization. Nb 2 The doped C MXene nanosheets can be used as a photo-thermal agent, and can form hydrogen bonds with a gel network, so that the mechanical property of the composite hydrogel is further improved.
The PNIPAM/BC/MXene composite hydrogel finally obtained is subjected to freeze drying and then scanning by an electron microscope, and the result is shown in figure 3, wherein the composite hydrogel can be found to have a porous three-dimensional network structure. The inset is a macroscopic photograph of the composite hydrogel due to the incorporation of Nb 2 C MXene, so the entire composite hydrogel appears black.
The final PNIPAM/BC/MXene composite hydrogel and pure PNIPAM hydrogel were subjected to tensile test, and the results are shown in FIG. 4, from which it can be seen that the composite hydrogel has a higher tensile strength than the pure PNIPAM hydrogelIs greatly improved because PNIPAM and BC form a semi-interpenetrating network structure with physical entanglement and hydrogen bonding, and Nb 2 The incorporation of the C MXene nanosheet further enhances the hydrogen bonding effect, so that the mechanical property of the gel is greatly improved.
As shown in FIG. 5, the PNIPAM/BC/MXene composite hydrogel and pure water obtained finally were subjected to photothermal test, and 1cm of the hydrogel was taken 3 The composite hydrogel is placed in a quartz cuvette, 0.5mL of deionized water is added, and when the using wavelength is 1064nm and the power density is 2W/cm 2 When the composite hydrogel is irradiated by the near-infrared laser, the water temperature can be increased to 65 ℃ within 10min, which shows that the composite hydrogel has good photo-thermal property and potential of photo-thermal treatment. Pure water hardly absorbs the near-infrared laser light, so that the temperature rise is insignificant.
(3) And (3) freeze-drying the prepared composite hydrogel, putting the composite hydrogel into 5mg/mL DOX solution, and stirring in a rotary stirrer for 3 days to obtain the drug-loaded composite hydrogel.
As shown in figure 6, the obtained drug-loaded composite hydrogel was tested for drug release under the control of near infrared light, and 1cm was taken 3 The drug-loaded composite hydrogel is placed in a quartz cuvette, 0.5mL of deionized water is added, the use wavelength is 1064nm, and the power density is 2W/cm 2 The near-infrared laser irradiates the gel, controls the on-off of the laser, and calculates the release rate of the drug according to the ultraviolet absorption value of DOX released in the composite hydrogel under different states. It can be seen that the amount of drug released increases significantly under the irradiation of the laser in the near-infrared region two, whereas the drug release is very slow without laser irradiation. The reasons for this are: because the composite hydrogel contains Nb with higher photo-thermal conversion rate 2 When the C MXene nanosheet is irradiated by near-infrared laser, light is converted into heat, the gel temperature is rapidly increased, when the temperature is higher than the Lower Critical Solution Temperature (LCST) of the composite hydrogel, the hydrogel is subjected to hydrophilic-to-hydrophobic transition, the volume is rapidly shrunk, the internal water is released, and in the process, drug molecules are released along with the hydrophilic-to-hydrophobic transition, so that the drug is rapidly released. In the absence of near infrared light, the drug molecules can only pass throughDiffusion is released from the inside of the gel and the process is therefore slow. Therefore, the composite hydrogel system can be used for realizing near infrared light controlled drug release and realizing the synergistic treatment of photothermal treatment and chemotherapy, and has certain application value in the field of biomedicine.
Example 2:
(1) adding 30mL of deionized water into 30mL of BC dispersion liquid raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion liquid for 10min at the rotating speed of 15000rpm by using a high-speed dispersion machine to obtain fully dispersed BC dispersion liquid, and mixing the BC dispersion liquid with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain a mixture with the mass fraction of BC of 0.2 wt% and Nb 2 Mixed solution of C MXene concentration of 0.25 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 20mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu.L of LN, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were poured into the mixed solution, stirred rapidly and homogenized and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the composite hydrogel obtained after polymerization in deionized water for 2 days, and changing water every 6 hours to remove redundant monomers and impurities, thereby finally obtaining the PNIPAM/BC/MXene composite hydrogel.
(3) And (3) freeze-drying the prepared composite hydrogel, putting the composite hydrogel into 5mg/mL DOX solution, and stirring in a rotary stirrer for 3 days to obtain the drug-loaded composite hydrogel.
EXAMPLE 3
(1) Adding 30mL of deionized water into 30mL of BC dispersion raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion at the rotating speed of 20000rpm for 15min by using a high-speed dispersion machine to obtain fully dispersed BC dispersion, and mixing the BC dispersion with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.1 wt% and Nb 2 Mixed solution of C MXene concentration of 0.01 mg/mL.
(2) 15mL of the above mixed solution was taken, and 0.8g N-isopropylacrylamide monomer (NIPAM) and 10mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.25mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly until uniform and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and allowed to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
EXAMPLE 4
(1) Adding 30mL of deionized water into 30mL of BC dispersion raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion at the rotating speed of 20000rpm for 15min by using a high-speed dispersion machine to obtain fully dispersed BC dispersion, and mixing the BC dispersion with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.1 wt% and Nb 2 Mixed solution with the concentration of C MXene of 2 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 20mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly until uniform and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and allowed to polymerize at room temperature for 22 h. And soaking the polymerized composite hydrogel in deionized water for 1.5 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
EXAMPLE 5
(1) Adding 30mL of deionized water into 30mL of BC dispersion liquid raw material with the mass fraction of 0.65 wt% for dilution, and dispersing the BC dispersion liquid raw material for 10min at the rotating speed of 20000rpm by using a high-speed dispersion machine to obtain full dispersionAnd mixing it with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.3 wt% and Nb 2 Mixed solution with the concentration of C MXene of 2 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 20mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly and homogeneously and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
EXAMPLE 6
(1) Adding 30mL of deionized water into 30mL of BC dispersion liquid raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion liquid for 10min at the rotating speed of 20000rpm by using a high-speed dispersion machine to obtain fully dispersed BC dispersion liquid, and mixing the BC dispersion liquid with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.5 wt% and Nb 2 C MXene concentration of 5 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 20mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 0.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly and homogeneously and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
EXAMPLE 7
(1) Adding 30mL of deionized water into 30mL of BC dispersion liquid raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion liquid for 10min at the rotating speed of 20000rpm by using a high-speed dispersion machine to obtain fully dispersed BC dispersion liquid, and mixing the BC dispersion liquid with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.3 wt% and Nb 2 Mixed solution of C MXene concentration of 0.5 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1g N-isopropylacrylamide monomer (NIPAM) and 30mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 1mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly and homogenized and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and left to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
EXAMPLE 8
(1) Adding 30mL of deionized water into 30mL of BC dispersion raw material with the mass fraction of 0.65 wt% for dilution, dispersing the BC dispersion at the rotating speed of 20000rpm for 10min by using a high-speed dispersion machine to obtain fully dispersed BC dispersion, and mixing the BC dispersion with Nb 2 Mixing the C MXene suspension, and magnetically stirring at room temperature for 20min to obtain BC with mass fraction of 0.3 wt% and Nb 2 Mixed solution of C MXene concentration of 0.5 mg/mL.
(2) 15mL of the above mixed solution was taken, and 1.2g N-isopropylacrylamide monomer (NIPAM) and 50mg of N, N' -methylenebisacrylamide (MBA, crosslinking agent) were added thereto in this order, stirred at room temperature, and purged with nitrogen for 30min to remove dissolved oxygen in the mixed solution. Then 15. mu. L N, N, N ', N' -tetramethylethylenediamine (TEMED, catalyst) and 1.5mL of a 20mg/mL ammonium persulfate solution (APS, initiator) were injected into the mixed solution, stirred rapidly until uniform and bubbles were removed from the mixed solution by sonication, and then the vessel was sealed and allowed to polymerize at room temperature for 24 hours. And soaking the polymerized composite hydrogel in deionized water for 2 days, and replacing water every 6 hours to remove redundant monomers and impurities to finally obtain the PNIPAM/BC/MXene composite hydrogel.
In summary, the invention provides a near-infrared light responsive N-isopropyl acrylamide based hydrogel, a preparation method and an application thereof, wherein the method comprises the following steps: mixing the bacterial cellulose dispersion liquid with MXene suspension liquid to obtain a mixed solution; sequentially adding an N-isopropyl acrylamide monomer and a cross-linking agent into the mixed solution to obtain a precursor solution; and adding a catalyst and an initiator into the precursor solution, and carrying out polymerization reaction to obtain the near-infrared light response N-isopropyl acrylamide-based hydrogel. The semi-interpenetrating network hydrogel is synthesized by simple free radical polymerization, the mechanical strength of the hydrogel is obviously improved by the actions of hydrogen bonds, physical entanglement and the like, and the prepared composite hydrogel is non-toxic and harmless and has good biocompatibility. In particular, since Nb 2 The characteristics of the C MXene are that the composite hydrogel has good photo-thermal effect no matter in a near infrared first region (750-. When the composite hydrogel is irradiated by near-infrared laser, the temperature of the composite hydrogel is obviously increased, and when the temperature is increased to be higher than LCST, the gel is violently contracted to release the internally loaded medicine. Therefore, the composite hydrogel can be used as a drug transport carrier to realize accurate control of drug release, and in addition, the composite hydrogel can also realize the synergistic treatment of photothermal treatment and chemotherapy, and has certain research value in the biomedical field.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A method for preparing a near-infrared light-responsive N-isopropyl acrylamide-based hydrogel, which is characterized by comprising the following steps:
mixing the bacterial cellulose dispersion liquid with MXene suspension liquid to obtain a mixed solution;
sequentially adding an N-isopropyl acrylamide monomer and a cross-linking agent into the mixed solution to obtain a precursor solution;
adding a catalyst and an initiator into the precursor solution, and carrying out polymerization reaction to obtain a near-infrared light response N-isopropyl acrylamide hydrogel;
the MXene is Nb 2 C MXene；
The step of mixing the bacterial cellulose dispersion liquid with the MXene suspension to obtain a mixed solution specifically comprises the following steps:
diluting bacterial cellulose with water to obtain a diluent, and dispersing the diluent to obtain a bacterial cellulose dispersion;
mixing MXene suspension with a certain concentration with the bacterial cellulose dispersion liquid to obtain a mixed solution; the mass concentration of the MXene suspension is 0.01-5 mg/mL;
and forming a semi-interpenetrating network structure consisting of a poly-N-isopropylacrylamide framework and bacterial cellulose chain segments through in-situ free radical polymerization.
2. The method according to claim 1, wherein the step of sequentially adding an N-isopropylacrylamide monomer and a crosslinking agent to the mixed solution to obtain a precursor solution further comprises: and purging the precursor liquid by adopting inert gas for removing dissolved oxygen dissolved in the precursor liquid.
3. The method according to claim 1, wherein the bacterial cellulose dispersion is 0.1 to 0.5% by mass.
4. The method of claim 1, wherein the cross-linking agent is N, N ' -methylenebisacrylamide, the catalyst is N, N, N ', N ' -tetramethylethylenediamine, and the initiator is ammonium persulfate.
5. The preparation method according to claim 1, wherein the mass ratio of the N-isopropylacrylamide monomer to the crosslinking agent and the initiator is 80 to 120: 1-5: 0.5-3.
6. A near-infrared light response N-isopropyl acrylamide-based hydrogel, which is characterized in that the near-infrared light response N-isopropyl acrylamide-based hydrogel is prepared by the method of any one of claims 1 to 5.
7. Use of the near-infrared light-responsive N-isopropylacrylamide-based hydrogel according to claim 6 as a carrier for a drug.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110167089.0A CN113024732B (en) | 2021-02-05 | 2021-02-05 | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110167089.0A CN113024732B (en) | 2021-02-05 | 2021-02-05 | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113024732A CN113024732A (en) | 2021-06-25 |
| CN113024732B true CN113024732B (en) | 2022-08-16 |
Family
ID=76460291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110167089.0A Active CN113024732B (en) | 2021-02-05 | 2021-02-05 | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113024732B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667146A (en) * | 2021-10-09 | 2021-11-19 | 武夷学院 | Preparation method of interpenetrating network polymer hydrogel with temperature responsiveness |
| CN113999476B (en) * | 2021-12-21 | 2022-10-21 | 太原理工大学 | Dual-stimulation-responsive conductive composite hydrogel and preparation method and application thereof |
| CN114588311A (en) * | 2022-03-31 | 2022-06-07 | 南京鼓楼医院 | Dynamic responsiveness stent for flap repair and preparation method thereof |
| CN117065036B (en) * | 2023-09-28 | 2024-04-26 | 广州医科大学附属第三医院（广州重症孕产妇救治中心、广州柔济医院） | Nanometer preparation of vanadium carbide coated doxorubicin and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105816881A (en) * | 2015-12-29 | 2016-08-03 | 温州生物材料与工程研究所 | Composite system based on near-infrared photothermal agent and temperature-sensitive polymer, drug carrier and preparation method |
| CN109232916A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application |
| CN109998988A (en) * | 2019-04-19 | 2019-07-12 | 福建农林大学 | A kind of cellulose/n-isopropyl acrylamide drug controlled release hydrogel and preparation method thereof |
| CN110952308A (en) * | 2019-11-26 | 2020-04-03 | 华南理工大学 | Flame-retardant conductive photothermal response shape memory paper and preparation method and application thereof |
| CN112011094A (en) * | 2020-09-07 | 2020-12-01 | 江南大学 | Nano cellulose MXene gel and preparation method and application thereof |
-
2021
- 2021-02-05 CN CN202110167089.0A patent/CN113024732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105816881A (en) * | 2015-12-29 | 2016-08-03 | 温州生物材料与工程研究所 | Composite system based on near-infrared photothermal agent and temperature-sensitive polymer, drug carrier and preparation method |
| CN109232916A (en) * | 2018-08-17 | 2019-01-18 | 东华大学 | A kind of compound thermal response-type hydrogel of Mxene/PNIPAM/ alginate and its preparation and application |
| CN109998988A (en) * | 2019-04-19 | 2019-07-12 | 福建农林大学 | A kind of cellulose/n-isopropyl acrylamide drug controlled release hydrogel and preparation method thereof |
| CN110952308A (en) * | 2019-11-26 | 2020-04-03 | 华南理工大学 | Flame-retardant conductive photothermal response shape memory paper and preparation method and application thereof |
| CN112011094A (en) * | 2020-09-07 | 2020-12-01 | 江南大学 | Nano cellulose MXene gel and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Ti2C3Tx nanosheets as photothermal agents for near-infrared responsive hydrogels;Changyu Yang et al.;《Nanoscale》;20180719;第10卷;第15387-15392页 * |
| 增强型纳米复合水凝胶的制备与表征;张晶晶;《中国优秀硕士学位论文全文数据库工程I辑》;20111015(第10期);第B020-122页 * |
| 细菌纤维素/聚N-异丙基丙烯酰胺复合水凝胶的制备及载药研究;周倩;《中国优秀硕士学位论文全文数据库工程科技I辑》;20160815(第8期);第B016-393页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113024732A (en) | 2021-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113024732B (en) | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof | |
| Mota-Morales et al. | Free-radical polymerizations of and in deep eutectic solvents: Green synthesis of functional materials | |
| CN109705370B (en) | Preparation method and application method of TEMPO nano-cellulose-polyacrylic acid gel | |
| Zhu et al. | Temperature/near-infrared light-responsive conductive hydrogels for controlled drug release and real-time monitoring | |
| Xiao et al. | Mechano-responsive hydrogels crosslinked by block copolymer micelles | |
| Hu et al. | Tough and stretchable Fe3O4/MoS2/PAni composite hydrogels with conductive and magnetic properties | |
| CN106861565B (en) | Preparation method of high-strength hydrogel with fluorescence property | |
| CN102558412B (en) | Preparation method of high-strength titanium dioxide nano-grade composite hydrogel | |
| CN102516479B (en) | Graphene-based nano particle composite hydrogel and preparation method thereof | |
| CN112870449B (en) | Intelligent response hydrogel for constructing 3D tissue engineering graft and preparation method and application thereof | |
| CN104448161B (en) | Organic composite hydrogel cross-linked by modified gelatin nano-microsphere and preparation method of organic composite hydrogel | |
| CN105949364A (en) | Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof | |
| Zhong et al. | Tough superabsorbent poly (acrylic acid) nanocomposite physical hydrogels fabricated by a dually cross-linked single network strategy | |
| CN113999476A (en) | Dual-stimulus-responsive conductive composite hydrogel and preparation method and application thereof | |
| CN104356319A (en) | Porous biological material using modified gelatin as crosslinking agent and preparation method of porous biological material | |
| Zhang et al. | Synthesis of multi-amine functionalized hydrogel for preparation of noble metal nanoparticles: utilization as highly active and recyclable catalysts in reduction of nitroaromatics | |
| CN108659237B (en) | Nanofiber composite hydrogel with conductivity tuned with temperature as well as preparation method and application thereof | |
| CN111171342A (en) | High-toughness self-repairing fluorescent double-network hydrogel and preparation method thereof | |
| Chen et al. | Green sustainable photothermal materials by spent coffee grounds | |
| CN110013808A (en) | The preparation method of polyalcohol stephanoporate microballoons with triple responsiveness | |
| CN103214625A (en) | Thermo-sensitive grafted hydrogel with function of resisting protein adsorption and preparation method thereof | |
| CN102516473B (en) | Copolymerized nano composite hydrogel for intelligent separation of cell sheets as well as preparation method and application thereof | |
| CN106317714B (en) | The low-temperature plasma modified processing method of nano-aluminium oxide | |
| CN110669184B (en) | Preparation method of shape memory polymer material with drug release function, obtained product and application | |
| CN109758608B (en) | Printable composite hydrogel with high toughness, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |