CN114395142A - Method for preparing anisotropic programmable hydrogel based on borate bond and hydrogel - Google Patents
Method for preparing anisotropic programmable hydrogel based on borate bond and hydrogel Download PDFInfo
- Publication number
- CN114395142A CN114395142A CN202210057151.5A CN202210057151A CN114395142A CN 114395142 A CN114395142 A CN 114395142A CN 202210057151 A CN202210057151 A CN 202210057151A CN 114395142 A CN114395142 A CN 114395142A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- boric acid
- programmable
- anisotropic
- mixed solution
- 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.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
Abstract
The invention provides a method for preparing anisotropic programmable hydrogel based on borate bonds, which comprises the following steps: adding a macromolecular compound into a boric acid solution to react to obtain a macromolecular compound-boric acid mixed solution; standing the macromolecular compound-boric acid mixed solution at room temperature to obtain macromolecular compound-boric acid hydrogel; pressing the hydrogel into a mold, and performing freezing and melting treatment to obtain a hydrogel standard sample strip; directionally stretching the standard sample strip to be threadlike to obtain hydrogel with directionally arranged molecular chains; the hydrogel with the molecular chain in the oriented arrangement realizes a programmable structure by utilizing the self-healing characteristic of a borate bond, and the hydrogel with the programmed and fixed structure is obtained by curing; salting out the hydrogel with the structure programming fixation, and swelling in distilled water to obtain the anisotropic programmable hydrogel. The method has simple process, low cost and no introduction of toxic chemical substances, and can conveniently construct a complex anisotropic hydrogel structure with higher mechanical strength and good biocompatibility.
Description
Technical Field
The invention relates to the fields of intelligent bionic materials, flexible electronic devices and biomedical engineering, in particular to a method for preparing anisotropic programmable hydrogel based on boric acid ester bonds and hydrogel.
Background
The hydrogel is a polymer with a three-dimensional net-shaped and water-rich structure formed by hydrophilic molecules through physical or chemical crosslinking, is similar to biological soft tissue, and has potential application prospects in the fields of biomedicine, bioengineering, intelligent bionic materials, flexible electronic devices and the like due to excellent mechanical properties and good biocompatibility.
The biological soft tissue has unique mechanical property due to the special anisotropy, and has higher strength and toughness even in a high water-containing state, while the biological tissue with ordered layers is essentially hydrogel, and under the background, the anisotropic hydrogel is used as an entry point, and the application research in the fields of biomedical engineering and intelligent bionics is started.
One strategy for achieving anisotropic hydrogels is to stretch the synthesized hydrogel to align the polymer chains along the axial direction of the force field, but traditional hydrogels have difficulty in achieving reorientation and complex structure construction due to their irreversible cross-linking, and the key to solving this problem is the controllable cross-linking between the polymer chains.
The borate bond is a typical dynamic covalent bond, has dynamic reversible characteristics, and is beneficial to realizing the directional arrangement of hydrogel polymer chain conformation on a microscopic level and realizing the fusion of a hydrogel interface on a macroscopic level. Meanwhile, by adjusting the pH value, the boric acid ester bond can quickly realize crosslinking and curing, thereby preventing the shrinkage and curling of molecular chains. In this context, the preparation of highly anisotropic programmable structural hydrogels is achieved by the controllability of dynamic boronic ester bonds.
The methods for preparing the anisotropic PVA hydrogel reported at present roughly comprise an oriented freezing method, a limited domain drying method, a mechanical training method and the like, and the methods are all based on the irreversible crosslinking of the hydrogel, generally, the folded and wound polymer chains are difficult to be sufficiently stretched along the stretching direction, and the complex anisotropic hydrogel structure is difficult to prepare, so that the application of the bionic structure hydrogel is limited to a great extent.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
Still another object of the present invention is to provide a method for preparing an anisotropic programmable hydrogel based on borate bonds, which has the advantages of simple process, low cost and no chemical pollution, and the prepared hydrogel has high mechanical properties, good biocompatibility and flexible structure assembly.
It is still another object of the present invention to provide an anisotropic programmable hydrogel prepared based on borate bonds, which has excellent mechanical properties, and a breaking strength and Young's modulus in a direction parallel to a stretching direction of up to 8.0MPa and 0.99MPa, respectively, which are 34 times and 12 times as high as those of hydrogels prepared by conventional freeze-thaw methods and salting-out methods. In addition, the hydrogel also has typical anisotropy, flexible programmability, good biocompatibility and chemical stability.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing an anisotropic programmable hydrogel based on borate bonds, comprising the steps of:
step one, adding a high molecular compound into a boric acid solution to react to obtain a high molecular compound-boric acid mixed solution;
standing the macromolecular compound-boric acid mixed solution at room temperature to obtain macromolecular compound-boric acid hydrogel;
pressing the hydrogel into a mold, and performing freezing and melting treatment to obtain a hydrogel standard sample strip;
step four, directionally stretching the hydrogel standard sample strip to be threadlike to obtain hydrogel with molecular chain directionally arranged;
fifthly, utilizing the self-healing characteristic of borate bonds to realize a programmable structure of the hydrogel with the molecular chain in the oriented arrangement, and curing to obtain the hydrogel with the structure programmed and fixed;
and sixthly, salting out the hydrogel with the programmed and fixed structure, and swelling the hydrogel in distilled water to obtain the anisotropic programmable hydrogel.
Preferably, the macromolecular compound is a polysaccharide polymer having an ortho-dihydroxy structure.
Preferably, the polymer compound is polyvinyl alcohol, sodium alginate, hydroxymethyl cellulose or hyaluronic acid.
Preferably, in the first step, the concentration of the polymer compound is 0.02-0.5 g/mL; the concentration of the boric acid solution is 0.01-0.2 mol/L, the pH value is 8-12, the reaction temperature is 30-120 ℃, and the reaction time is 30-120 min.
Preferably, in the second step, the standing time is 5-30 min.
Preferably, in the third step, the freezing temperature is-20 to-80 ℃, and the melting temperature is 10 to 30 ℃.
Preferably, in the fourth step, the oriented stretching mode is stretching along the central axis direction; the stretching speed is 10-150 mm/min; the stretching ratio is 200-1000%.
Preferably, in the fifth step, the programmable structure is one of a net shape, a tubular shape, a multilayer shape, a braided tube and a muscle-like tissue, the curing is realized by adjusting the pH value to 12-14, and the curing time is 10-120 s.
Preferably, in the sixth step, the solvent used for salting out is a mixed solution of sodium chloride and glucose, wherein the concentration of sodium chloride is 0.01-0.1 g/mL; the concentration of glucose is 0.05-0.5 g/mL, the salting-out time is 6-48 h, and the swelling time is 6-48 h.
The object of the present invention is further achieved by an anisotropic programmable hydrogel prepared on the basis of borate bonds.
The invention at least comprises the following beneficial effects:
1. the preparation method is simple and easy to implement and low in cost, and solves the problem that the polymer chain in the existing hydrogel is difficult to be completely oriented, stretched and re-solidified. More importantly, various complex anisotropic hydrogel structures can be conveniently constructed by utilizing the inherent dynamic crosslinking behavior of borate bonds;
2. the hydrogel prepared by the invention has excellent mechanical properties, the breaking strength and Young modulus in the direction parallel to the stretching direction can respectively reach 8.0MPa and 0.99MPa, and the breaking strength and Young modulus are 34 times and 12 times of those of the hydrogel prepared by the traditional freeze-thaw method and salting-out method. In addition, the hydrogel also has typical anisotropy, flexible programmability, good biocompatibility and chemical stability.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic representation of an anisotropic programmable hydrogel prepared in example 1 of the present invention;
FIG. 2 is a fluorescence microscopy image of an anisotropic programmable hydrogel of example 1 of the present invention;
FIG. 3 is a polarization microscope image of an anisotropic programmable hydrogel of example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of an anisotropic programmable hydrogel of example 1 of the present invention;
FIG. 5 is a stress-strain curve of the anisotropic programmable hydrogel of example 1 of the present invention in different directions of stretching;
FIG. 6 is a scanning electron microscope image of the hydrogels prepared in comparative example 1 and comparative example 2;
FIG. 7 is a graph comparing the stress-strain curves of the hydrogels of example 1 of the present invention and the hydrogels prepared in comparative examples 1 and 2;
FIG. 8 is a pictorial representation of a woven tubular hydrogel prepared in example 2;
FIG. 9 is a schematic representation of the tubular hydrogel prepared in example 3.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The following examples are only for explaining the present invention and are not intended to limit the scope of the present invention. All reagents, materials and test equipment used in the examples were not indicated by the manufacturer and were commercially available.
< example 1>
An anisotropic programmable polyvinyl alcohol hydrogel (APH) prepared based on borate linkages by the method of:
step one, adjusting the pH value of 20mL boric acid solution (0.02mol/L) to 10 by using 10mol/L sodium hydroxide solution, adding 3.0g of polyethylene Particles (PVA) into the boric acid solution to obtain a mixed solution, sealing the mixed solution, placing the sealed mixed solution in a water bath at 90 ℃ for magnetic stirring, and reacting for 80min to obtain a polyethylene-boric acid mixed solution;
step two, standing the polyethylene-boric acid mixed solution at room temperature for 10min to make the polyethylene-boric acid mixed solution lose fluidity, so as to obtain polyethylene-boric acid hydrogel (PBH);
pressing PBH into a mold, freezing at-20 ℃, carrying out melting treatment at 20 ℃, and standing for 10min to obtain a standard sample strip;
step four, slowly stretching the standard sample strip to be threadlike along the central axis direction, and regulating and controlling the cross-linking state of a molecular chain through a borate bond to obtain the anisotropic hydrogel, wherein the stretching speed is 50 mm/min; the stretching ratio is 5 times;
fifthly, programming the hydrogel obtained in the fourth step into a net structure by utilizing the self-healing characteristic of a borate bond, and curing by adjusting the pH value to 12 to obtain the polyvinyl alcohol hydrogel with the structure programmed and fixed, wherein the curing time is 5 min;
and sixthly, salting out the polyvinyl alcohol hydrogel with the programmed and fixed structure for 24 hours in a mixed solution of 0.01g/mL sodium chloride and 0.05g/mL glucose, swelling the polyvinyl alcohol hydrogel in distilled water for 24 hours, and removing small molecules such as salt ions, glucose and boric acid through diffusion to obtain the stable and pure reticular anisotropic programmable polyvinyl alcohol hydrogel APH.
FIG. 2 is a fluorescence microscope image of the hydrogel APH prepared in this example, which shows that the fibrils composed of the molecular chains of the fluorescent markers in the hydrogel have obvious directional arrangement; fig. 3 is a polarization microscope image of the hydrogel APH prepared in this example, and it is observed that the interference colors at different angles are significantly changed, which indirectly reflects the highly uniform orientation of the polymer; FIG. 4 is a scanning electron microscope image of the hydrogel APH prepared in this example, showing a pattern consisting of a tightly packed nanofiber structure, such a perfectly oriented pattern indicating a high degree of crystallinity of the polymer; fig. 5 is a stress-strain curve of the hydrogel APH prepared in this example in different stretching directions, and it can be seen that the breaking strength in the parallel stretching direction is about 4.4 times of that in the perpendicular stretching direction, and meanwhile, compared with fig. 7, it is found that the tensile strength of the anisotropic PVA hydrogel in the parallel direction is about 34 times and 12 times of that of the freeze-thaw PVA hydrogel and the isotropic hydrogel, respectively, which indicates that the anisotropic structure of the hydrogel has a significant effect on the mechanical properties thereof, and also indicates that the oriented structure and the high crystallinity are important factors for improving the mechanical properties of the hydrogel.
< example 2>
An anisotropic programmable polyvinyl alcohol hydrogel (APH) prepared based on borate bonds, prepared in the same manner as in example 1, except that:
step five, winding and weaving the hydrogel obtained in the step four on the surface of a columnar mould to form a tubular structure, and curing by adjusting the pH value to 12 to obtain the polyvinyl alcohol hydrogel with the structure programmed and fixed, wherein the curing time is 5 min;
a physical diagram of the woven tubular hydrogel prepared in this example is shown in FIG. 8.
< example 3>
An anisotropic programmable polyvinyl alcohol hydrogel (APH) prepared based on borate bonds, prepared in the same manner as in example 1, except that:
fifthly, programming the tubular structure of the hydrogel obtained in the fourth step by utilizing the self-healing characteristic of the borate bond, and curing by adjusting the pH value to 12 to obtain the polyvinyl alcohol hydrogel with the programmed and fixed structure, wherein the curing time is 5 min;
a physical diagram of the woven tubular hydrogel prepared in this example is shown in FIG. 9.
< example 4>
An anisotropic programmable sodium alginate hydrogel prepared based on borate bonds is prepared by the following method:
step one, adjusting the pH value of 20mL boric acid solution (0.15mol/L) to 10 by using 10mol/L sodium hydroxide solution, adding 1.0g sodium alginate powder into the boric acid solution to obtain a mixed solution, sealing the mixed solution, placing the sealed mixed solution in a water bath at 90 ℃ for magnetic stirring, and reacting for 80min to obtain a sodium alginate-boric acid mixed solution;
standing the sodium alginate-boric acid mixed solution at room temperature for 10min to ensure that the sodium alginate-boric acid mixed solution loses fluidity, so as to obtain sodium alginate-boric acid hydrogel;
pressing the sodium alginate-boric acid hydrogel into a mold, freezing at the temperature of minus 20 ℃, performing melting treatment at the temperature of 20 ℃, and standing for 10min to obtain a standard sample strip;
step four, slowly stretching the standard sample strip to be threadlike along the central axis direction, and regulating and controlling the cross-linking state of a molecular chain through a borate bond to obtain the anisotropic hydrogel, wherein the stretching speed is 50 mm/min; the stretching ratio is 5 times;
fifthly, programming the hydrogel obtained in the fourth step into a net structure by utilizing the self-healing characteristic of a borate bond, and curing by adjusting the pH value to 12 to obtain the sodium alginate hydrogel with a programmed and fixed structure, wherein the curing time is 5 min;
and sixthly, salting out the sodium alginate hydrogel with the programmed and fixed structure for 24 hours in a mixed solution of 0.01g/mL sodium chloride and 0.05g/mL glucose, swelling the sodium alginate hydrogel in distilled water for 24 hours, and removing small molecules such as salt ions, glucose and boric acid through diffusion to obtain the stable and pure reticular anisotropic programmable sodium alginate hydrogel.
< example 5>
An anisotropic programmable hydroxymethylcellulose hydrogel prepared based on boronic ester linkages, prepared by a process comprising:
step one, adjusting the pH value of 20mL boric acid solution (0.15mol/L) to 10 by using 10mol/L sodium hydroxide solution, adding 1.0g of hydroxymethyl cellulose powder into the boric acid solution to obtain a mixed solution, sealing the mixed solution, placing the sealed mixed solution into a water bath at 90 ℃ for magnetic stirring, and reacting for 80min to obtain hydroxymethyl cellulose-boric acid mixed solution;
standing the hydroxymethyl cellulose-boric acid mixed solution at room temperature for 10min to make the hydroxymethyl cellulose-boric acid mixed solution lose fluidity, so as to obtain hydroxymethyl cellulose-boric acid hydrogel;
pressing the hydroxymethyl cellulose-boric acid hydrogel into a mold, freezing at-20 ℃, performing melting treatment at 20 ℃, and standing for 10min to obtain a standard sample strip;
step four, slowly stretching the standard sample strip to be threadlike along the central axis direction, and regulating and controlling the cross-linking state of a molecular chain through a borate bond to obtain the anisotropic hydrogel, wherein the stretching speed is 50 mm/min; the stretching ratio is 5 times;
fifthly, programming the hydrogel obtained in the fourth step into a net structure by utilizing the self-healing characteristic of a borate bond, and curing by adjusting the pH value to 12 to obtain the hydroxymethyl cellulose hydrogel with a programmed and fixed structure, wherein the curing time is 5 min;
and sixthly, salting out the hydroxymethyl cellulose hydrogel with the programmed and fixed structure for 24 hours in a mixed solution of 0.01g/mL sodium chloride and 0.05g/mL glucose, swelling the hydroxymethyl cellulose hydrogel in distilled water for 24 hours, and removing small molecules such as salt ions, glucose and boric acid through diffusion to obtain the stable and pure reticular anisotropic programmable hydroxymethyl cellulose hydrogel.
< example 6>
An anisotropic programmable hyaluronic acid hydrogel prepared based on a borate bond, which is prepared by the following method:
step one, adjusting the pH value of 20mL boric acid solution (0.15mol/L) to 10 by using 10mol/L sodium hydroxide solution, adding 1.0g of hyaluronic acid powder into the boric acid solution to obtain a mixed solution, sealing the mixed solution, placing the sealed mixed solution in a water bath at 90 ℃ for magnetic stirring, and reacting for 80min to obtain a hyaluronic acid-boric acid mixed solution;
standing the hyaluronic acid-boric acid mixed solution at room temperature for 10min to lose fluidity, so as to obtain hyaluronic acid-boric acid hydrogel;
pressing the hyaluronic acid-boric acid hydrogel into a mold, freezing at-20 ℃, performing melting treatment at 20 ℃, and standing for 10min to obtain a standard sample strip;
step four, slowly stretching the standard sample strip to be threadlike along the central axis direction, and regulating and controlling the cross-linking state of a molecular chain through a borate bond to obtain the anisotropic hydrogel, wherein the stretching speed is 50 mm/min; the stretching ratio is 5 times;
fifthly, programming the network structure of the hydrogel obtained in the fourth step by utilizing the self-healing characteristic of the borate bond, and curing by adjusting the pH value to 12 to obtain the hyaluronic acid hydrogel with the structure programmed and fixed, wherein the curing time is 5 min;
and sixthly, salting out the hyaluronic acid hydrogel with the programmed and fixed structure for 24 hours in a mixed solution of 0.01g/mL sodium chloride and 0.05g/mL glucose, swelling the hyaluronic acid hydrogel in distilled water for 24 hours, and removing small molecules such as salt ions, glucose and boric acid through diffusion to obtain the stable and pure reticular anisotropic programmable hyaluronic acid hydrogel.
< comparative example 1>
An isotropic polyvinyl alcohol hydrogel prepared by the method comprising:
1) the pH of 20mL of a boric acid solution (0.02mol/L) was adjusted to 10 with 10mol/L sodium hydroxide solution, and then 3.0g of polyvinyl alcohol Particles (PVA) were added to the boric acid solution to seal.
2) Sealing the mixed solution, placing the mixed solution in a water bath with the temperature of 90 ℃ for magnetic stirring, reacting for 80min to obtain a polyethylene-boric acid mixed solution, and then placing the mixed solution at room temperature for 10min to gradually lose fluidity to obtain the polyethylene-boric acid hydrogel (PBH).
3) Pressing PBH into a mold, freezing at-20 ℃, performing melting treatment at 20 ℃, and standing for 10min to obtain a standard sample strip.
4) Self-healing the unstretched hydrogel obtained in the step 3) by utilizing a boric acid ester bond to realize programming of a net structure, realizing curing for 5min by adjusting the pH value to 12, salting out the cured hydrogel in a mixed solution of 0.01g/mL sodium chloride and 0.05g/mL glucose for 24h, and obtaining isotropic hydrogel through physical crosslinking;
5) swelling the hydrogel obtained in the step 4) in distilled water for 24 hours, and removing salt ions and micromolecules such as glucose, boric acid and the like to obtain pure isotropic hydrogel.
< comparative example 2>
A virgin freeze-thaw polyvinyl alcohol hydrogel prepared by a method comprising:
adding 3.0g of polyvinyl alcohol Particles (PVA) into 20mL of distilled water, placing the distilled water in a water bath at 90 ℃ for magnetic stirring until the PVA is completely dissolved, then injecting the solution into a mould, and performing freeze-thaw treatment to obtain the original freeze-thaw PVA hydrogel.
Fig. 6 is a scanning electron microscope image of the hydrogels prepared in comparative examples 1 and 2, in which fig. 6A is a scanning electron microscope image of the hydrogel prepared in comparative example 1, and fig. 6B is a scanning electron microscope image of the hydrogel prepared in comparative example 2, and it was observed that the fibers formed by the molecular chains of the hydrogel prepared in comparative example 1 had a significant alignment and the pattern had no significant texture orientation, and further, the breaking strength of the hydrogel prepared in comparative example 1 in the parallel stretching direction was about 0.67MPa (refer to the stress-strain curve of fig. 7), indicating that the pre-stretching process was omitted so that the polymer chains were loosely disordered during the preparation of the isotropic hydrogel.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations described and illustrated herein, but fall within the scope of the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing anisotropic programmable hydrogel based on borate bond comprises the following steps:
step one, adding a high molecular compound into a boric acid solution to react to obtain a high molecular compound-boric acid mixed solution;
standing the macromolecular compound-boric acid mixed solution at room temperature to obtain macromolecular compound-boric acid hydrogel;
pressing the hydrogel into a mold, and performing freezing and melting treatment to obtain a hydrogel standard sample strip;
step four, directionally stretching the hydrogel standard sample strip to be threadlike to obtain hydrogel with molecular chain directionally arranged;
fifthly, utilizing the self-healing characteristic of borate bonds to realize a programmable structure of the hydrogel with the molecular chain in the oriented arrangement, and curing to obtain the hydrogel with the structure programmed and fixed;
and sixthly, salting out the hydrogel with the programmed and fixed structure, and swelling the hydrogel in distilled water to obtain the anisotropic programmable hydrogel.
2. The method according to claim 1, wherein in the first step, the polymer compound is a polysaccharide polymer having a vicinal dihydroxy structure.
3. The method according to claim 2, wherein the polymer compound is polyvinyl alcohol, sodium alginate, hydroxymethyl cellulose, or hyaluronic acid.
4. The method according to claim 1, wherein in the first step, the concentration of the polymer compound is 0.02-0.5 g/mL; the concentration of the boric acid solution is 0.01-0.2 mol/L, the pH value is 8-12, the reaction temperature is 30-120 ℃, and the reaction time is 30-120 min.
5. The method according to claim 1, wherein in the second step, the standing time is 5-30 min.
6. The method according to claim 1, wherein in the third step, the freezing temperature is-20 to-80 ℃, and the melting temperature is 10 to 30 ℃.
7. The method according to claim 1, wherein in the fourth step, the directional stretching is stretching along the central axis; the stretching speed is 10-150 mm/min; the stretching ratio is 200-1000%.
8. The method as claimed in claim 1, wherein in the fifth step, the programmable structure is one of a net shape, a tube shape, a multi-layer shape, a braided tube and a muscle-like tissue, and the curing is realized by adjusting the pH to 12-14 and the curing time is 10-120 s.
9. The method according to claim 1, wherein in the sixth step, the solvent for salting out is a mixed solution of sodium chloride and glucose, wherein the concentration of sodium chloride is 0.01-0.1 g/mL; the concentration of glucose is 0.05-0.5 g/mL, the salting-out time is 6-48 h, and the swelling time is 6-48 h.
10. An anisotropic programmable hydrogel prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210057151.5A CN114395142B (en) | 2022-01-18 | 2022-01-18 | Method for preparing anisotropic programmable hydrogel based on borate ester bond and hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210057151.5A CN114395142B (en) | 2022-01-18 | 2022-01-18 | Method for preparing anisotropic programmable hydrogel based on borate ester bond and hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114395142A true CN114395142A (en) | 2022-04-26 |
| CN114395142B CN114395142B (en) | 2022-11-08 |
Family
ID=81231179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210057151.5A Active CN114395142B (en) | 2022-01-18 | 2022-01-18 | Method for preparing anisotropic programmable hydrogel based on borate ester bond and hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395142B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115337452A (en) * | 2022-09-05 | 2022-11-15 | 武汉诺曼医疗科技有限公司 | Tissue engineering material and preparation method thereof |
| CN115364279A (en) * | 2022-09-22 | 2022-11-22 | 山西浙大新材料与化工研究院 | Preparation method of polymer composite material with orthotropic structure |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610724A (en) * | 2001-10-29 | 2005-04-27 | 纳米体系研究公司 | Reinforced, laminated, impregnated and composite-like materials as crosslinked polyvinyl alcohol hydrogel structures |
| US20090214623A1 (en) * | 2005-03-30 | 2009-08-27 | Wankei Wan | Anisotropic hydrogels |
| US20090252800A1 (en) * | 2003-08-13 | 2009-10-08 | Wan-Kei Wan | Anisotropic nanocomposite hydrogel |
| CN110229374A (en) * | 2019-06-30 | 2019-09-13 | 北方民族大学 | A kind of preparation method and application of high intensity orientating type polyvinyl alcohol hydrogel |
| CN112321978A (en) * | 2020-11-13 | 2021-02-05 | 四川大学 | Anisotropic high-strength high-toughness organic hydrogel and preparation method and application thereof |
| CN112552533A (en) * | 2020-12-15 | 2021-03-26 | 中山大学 | Preparation method of high-strength anisotropic crystal hydrogel |
-
2022
- 2022-01-18 CN CN202210057151.5A patent/CN114395142B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610724A (en) * | 2001-10-29 | 2005-04-27 | 纳米体系研究公司 | Reinforced, laminated, impregnated and composite-like materials as crosslinked polyvinyl alcohol hydrogel structures |
| US20090252800A1 (en) * | 2003-08-13 | 2009-10-08 | Wan-Kei Wan | Anisotropic nanocomposite hydrogel |
| US20090214623A1 (en) * | 2005-03-30 | 2009-08-27 | Wankei Wan | Anisotropic hydrogels |
| CN110229374A (en) * | 2019-06-30 | 2019-09-13 | 北方民族大学 | A kind of preparation method and application of high intensity orientating type polyvinyl alcohol hydrogel |
| CN112321978A (en) * | 2020-11-13 | 2021-02-05 | 四川大学 | Anisotropic high-strength high-toughness organic hydrogel and preparation method and application thereof |
| CN112552533A (en) * | 2020-12-15 | 2021-03-26 | 中山大学 | Preparation method of high-strength anisotropic crystal hydrogel |
Non-Patent Citations (1)
| Title |
|---|
| 肖长发: "高强度聚乙烯醇纤维结构与性能研究", 《高科技纤维与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115337452A (en) * | 2022-09-05 | 2022-11-15 | 武汉诺曼医疗科技有限公司 | Tissue engineering material and preparation method thereof |
| CN115337452B (en) * | 2022-09-05 | 2024-01-19 | 武汉诺曼医疗科技有限公司 | Tissue engineering material and preparation method thereof |
| CN115364279A (en) * | 2022-09-22 | 2022-11-22 | 山西浙大新材料与化工研究院 | Preparation method of polymer composite material with orthotropic structure |
| CN115364279B (en) * | 2022-09-22 | 2023-08-08 | 山西浙大新材料与化工研究院 | Preparation method of polymer composite material with orthotropic structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114395142B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114395142B (en) | Method for preparing anisotropic programmable hydrogel based on borate ester bond and hydrogel | |
| Darabi et al. | An alkaline based method for generating crystalline, strong, and shape memory polyvinyl alcohol biomaterials | |
| Kargarzadeh et al. | Recent developments in nanocellulose-based biodegradable polymers, thermoplastic polymers, and porous nanocomposites | |
| Chen et al. | Bacterial cellulose-based biomaterials: From fabrication to application | |
| Li et al. | Preparation and properties of cellulose nanocrystals reinforced collagen composite films | |
| Gomri et al. | Recent progress on chemical modification of cellulose nanocrystal (CNC) and its application in nanocomposite films and membranes-A comprehensive review | |
| Huang et al. | Recent advances in bacterial cellulose | |
| Zhu et al. | Cellulose/chitosan composite multifilament fibers with two-switch shape memory performance | |
| EP2476729B1 (en) | Method for producing stereo complex crystals of polylactic acid, polylactic acid, and molded body, synthetic fiber, porous body and ion conductor comprising same | |
| CN107619482B (en) | Preparation method of anisotropic double-crosslinked cellulose hydrogel and membrane material | |
| Pan et al. | Bacterial cellulose hydrogel for sensors | |
| Vega-Cázarez et al. | Preparation and properties of chitosan–PVA fibers produced by wet spinning | |
| CN106310380A (en) | Nano-fibrosis silk fibroin gel and preparation method thereof | |
| CN101053670A (en) | Silk fibroin and polymeric lactic acid compound film and its preparation method | |
| CN110218339B (en) | Beaded nano-cellulose microfiber, preparation method and application thereof in preparation of composite hydrogel | |
| CN112143002A (en) | Preparation method of multi-dimensional oriented cellulose hydrogel | |
| Quan et al. | Bacterial cellulose modification using static magnetic field | |
| John et al. | Nanocellulose-based hydrogels for biomedical applications | |
| Ju et al. | Strong silk fibroin/PVA/chitosan hydrogels with high water content inspired by straw rammed earth brick structures | |
| Zhijiang et al. | Retracted: Preparation and characterization of a bacterial cellulose/chitosan composite for potential biomedical application | |
| CN111793224B (en) | Preparation method and application of bionic fiber web hydrogel with self-repairing performance | |
| Sultan et al. | Three-Dimensional Printing of Nanocellulose-Based Hydrogels | |
| Shi et al. | Recent developments in synthesis, properties, and biomedical applications of cellulose-based hydrogels | |
| Xia et al. | Tough and Strong All-Biomass Plastics from Agricultural and Forest Wastes via Constructing an Aggregate of Hydrogen-Bonding Networks | |
| CN111424337B (en) | Method for preparing chiral reversal graphene liquid crystal through nano fluid rectification |
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 |