CN111269438A - Oriented microfiber hydrogel and preparation method thereof - Google Patents
Oriented microfiber hydrogel and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims description 15
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- 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
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- 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
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Abstract
The invention provides a preparation method of an oriented microfiber hydrogel, which comprises the following steps: mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol; reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer; dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample; placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer; and crosslinking the polymer with a crosslinking solution to obtain the hydrogel of the oriented microfibers. The end group of the polyvinyl alcohol tertiary amine with the structure of the formula (I) is a hydrophobic alkane chain. By pre-stretching the network in the oriented gel, controlling the retraction length when the external force is removed, and realizing controllable fold conformation by covalent crosslinking and fixation when the retraction length is preset; the method realizes the oriented microfiber hydrogel with a wrinkled structure.
Description
Technical Field
The invention relates to the technical field of materials, in particular to an oriented microfiber hydrogel and a preparation method thereof.
Background
Biological soft tissue has comprehensive mechanical properties, and many weighing soft tissues (such as muscles) are complex bodies with certain spatial configuration formed by various cells with specific functions, elastic fibers, collagen fibers, smooth muscles and matrixes. The mechanical properties of soft tissue are mainly determined by the mechanical properties of its components, and most of them have viscoelasticity, which is mainly derived from collagen fibers and smooth muscle. Tear resistance, low mechanical retardation, high elasticity, low modulus and high strength. At present, artificial synthetic materials are rarely used for preparing materials matched with the mechanical properties of muscles. Professor Zhao xuanhe, the institute of technology and technology, massachusetts, recently reported a class of highly oriented polyvinyl alcohol materials (www.pnas.org/cgi/doi/10.1073/pnas.1903019116). However, their strategy relies on repeated pulling, the process is time consuming and energy intensive, not suitable for practical production, and their materials emphasize segment orientation, resulting in limited tensile properties.
At present, two materials for realizing water enrichment through a bionic mechanism have muscle-like mechanical properties, one is to simulate actin on a molecular scale and realize a continuous Markov random process following time evolution; however, these rely on complex organic synthesis processes and are not suitable for large-scale production; the other is to simulate the fiber orientation of the muscle from a higher scale, realize good flexibility and excellent mechanical property, and then develop the muscle into a novel artificial muscle; however, the orientation segment has a low stretching space, the stretching rate is limited, the modulus is generally large, and the orientation segment is not matched with the weak soft mass of the muscle, so that the material cannot well replace the muscle tissue of the human body.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing an oriented microfiber hydrogel, which has good tensile properties and biocompatibility.
The invention provides a preparation method of an oriented microfiber hydrogel, which comprises the following steps:
A) mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol;
B) reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer;
C) dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample;
D) placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer;
E) crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers;
wherein m and n are independently selected from 50-350.
Preferably, the activator in step a) is carbonyldiimidazole, and the solvent is dimethyl sulfoxide; the molar ratio of the polyvinyl alcohol to the activating agent is 1: 0.001 to 1: 0.5; the reaction temperature is 20-30 ℃; the reaction time is 3-4 h.
Preferably, the molar ratio of the activated polyvinyl alcohol in the step B) to the n-octylamine is 0.6; the reaction temperature is 20-30 ℃; the reaction time was 48 hours.
Preferably, the stretching magnification of the step D) is 9-10 times; the controllable release is specifically to control the retraction to 4-8 times of the original length.
Preferably, the solvent in the step D) comprises N, N-2-methylformamide and deionized water; the mass ratio of the N, N-2-methylformamide to the deionized water is 1: 1.
Preferably, the hardening in the step D) is specifically hardening by soaking in water, and the soaking time is 6-24 hours.
Preferably, the step A) is also preceded by heating to dissolve the polyvinyl alcohol having the structure of formula (I) and then cooling; the heating temperature is 85-95 ℃; the molecular weight of the polyvinyl alcohol with the structure of the formula (I) is 14600-18600.
Preferably, the crosslinking solution of step E) comprises isoprene glycol, hydrochloric acid and water; the concentration of the isoprene glycol is 1-2 wt%; the concentration of the hydrochloric acid is 1-2 wt%.
The invention provides an oriented microfiber hydrogel which is prepared by the preparation method in the technical scheme.
The invention provides an adjustable muscle-like mechanical property material, which comprises the oriented microfiber hydrogel prepared by the preparation method of the technical scheme.
Compared with the prior art, the invention provides a preparation method of an oriented microfiber hydrogel, which comprises the following steps: A) mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol; B) reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer; C) dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample; D) placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer; E) crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers; wherein m and n are independently selected from 50-350. The end group of the polyvinyl alcohol tertiary amine with the structure of formula (I) is a hydrophobic alkane chain, and the derivative is water-insoluble. The preparation of the gel and the achievement of the desired mechanical properties are achieved by gelling and post-treatment of the polyvinyl alcohol graft polymer. By pre-stretching the network in the oriented gel, controlling the retraction length when the external force is removed, and carrying out covalent crosslinking and fixation when the retraction length is preset, the controllable fold conformation is realized; the method realizes the oriented microfiber hydrogel with a wrinkled structure. The material with adjustable muscle-like mechanical properties is prepared. By regulating the wrinkle degree, the invention can realize the strain hardening characteristic of the muscle-like muscle and can also regulate and control the modulus transformation of the material.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of PVA-C8-x;
FIG. 2 is a schematic diagram of a preparation scheme of a high tensile hydrogel with near-skeletal muscle mechanical properties;
FIG. 3 is a graph of tensile testing of a sample;
FIG. 4 is a graph showing the mechanical elongation of PVA-C8-L0/L;
FIG. 5 is a graph of the cyclic stretch profile of PVA-C8-16-10;
FIG. 6 toxicity of 3T3 cells measured by thiazole blue colorimetry;
FIG. 7 hydrogel extraction environmental solution, 3T3 cells cultured for 24 hours and then images taken with a standard bright field microscope;
FIG. 83T 3 cells were photographed 48 hours after propagation using a standard bright field microscope;
FIG. 9 hydrogel extraction Environment solution, 3T3 cells were cultured for 48 hours and then imaged using a standard bright field microscope.
Detailed Description
The invention provides an oriented microfiber hydrogel and a preparation method thereof, and a person skilled in the art can use the content to reference the text and appropriately improve the process parameters to realize the oriented microfiber hydrogel. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a preparation method of an oriented microfiber hydrogel, which comprises the following steps:
A) mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol;
B) reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer;
C) dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample;
D) placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer;
E) crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers;
wherein m and n are independently selected from 50-350.
The invention firstly provides polyvinyl alcohol with a structure of formula (I). The source of the present invention is not limited, and may be commercially available or prepared according to a method known to those skilled in the art.
Mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol. The activator of the present invention is preferably carbonyldiimidazole, and the solvent is preferably dimethyl sulfoxide.
Firstly, heating and dissolving polyvinyl alcohol with a structure shown in a formula (I), and then cooling; the heating temperature is 85-95 ℃; the molecular weight of the polyvinyl alcohol with the structure of the formula (I) is 14600-18600.
The preferable steps are as follows: stirring and dissolving PVA by using dimethyl sulfoxide (DMSO) as a solvent at the temperature of 80-90 ℃; after the PVA solution is cooled to room temperature, a proper amount of N, N' -Carbonyldiimidazole (CDI) is added for reaction, and the PVA is activated.
The molar ratio of polyvinyl alcohol to activator is preferably 1: 0.001 to 1: 0.5; the reaction temperature is preferably 20-30 ℃; the reaction time is preferably 3-4 h.
And reacting the activated polyvinyl alcohol with n-octylamine to obtain the polyvinyl alcohol graft polymer.
The molar ratio of the activated polyvinyl alcohol to the n-octylamine is 0.6; the reaction temperature is 20-30 ℃; the reaction time was 48 h.
Adding a proper amount of ammonia water to stop the reaction, and then dropping the obtained solution into deionized water to precipitate the modified PVA-C8-DS. The ammonia in the precipitate was then washed away with deionized water. Freeze-drying, weighing and reserving. The present invention is not limited to the above-described operation, and those skilled in the art will be familiar with the operation.
And dissolving the polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample.
The sample was dissolved using N, N-Dimethylformamide (DMF) as a solvent. Pumping the air of the solution by a water pump, pouring the solution into a mould, carrying out water exchange for a period of time, gelling, and taking out the soaked water to obtain a sample.
The dissolving temperature is 30-60 ℃. The time is 3 h. The vacuumizing pressure is 0-0.05 MPa.
The time for the water exchange was 12 h.
The hydrogel samples were placed in a solvent to swell.
And taking the obtained hydrogel sample out of the mold, and then putting the hydrogel sample into a mixed solution of N, N-2-methylformamide and deionized water for swelling.
In the present invention, the solvent includes N, N-2-methylformamide and deionized water; the mass ratio of the N, N-2-methylformamide to the deionized water is preferably 1: 1.
The stretching magnification is 9-10 times;
the stretching of the present invention is preferably as follows: the hydrogel from which DMF had been removed was prepared; the resulting film was softened by being put in a mixture of DMF and water, and the longest stretch length was 900 to 1000% of the original length, and the film was stretched to 800% of the original length, and then cut off.
Hardening after stretching. The effective stretching portion is stretched and fixed to a jig with an adhesive tape, and is hardened by being put into water.
The hardening is specifically hardening by soaking in water, and the soaking time is 6-24 hours.
And then a controlled release. After release its titin expands into a polymer with filaments and cross-links.
The controllable release is specifically to control the retraction to 4-8 times of the original length.
The release of the invention is specifically as follows: when the external force is removed, the retraction length is controlled, and when the retraction length is preset, covalent crosslinking fixation is carried out, so that controllable fold conformation is realized.
Crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers; the crosslinking solution of the present invention comprises isovaleraldehyde, hydrochloric acid and water.
The method specifically comprises the following steps: the samples with different retraction ratios are subjected to isoprenoid crosslinking under the condition of keeping the stretching. The crosslinking solution was: 1-2 wt.% of isovaleraldehyde, 1-2 wt.% of hydrochloric acid and the balance of water.
The crosslinking solution comprises isovaleraldehyde, hydrochloric acid and water; the concentration of the isovaleraldehyde is 1-2 wt%; the concentration of the hydrochloric acid is 1-2 wt%.
The invention provides an oriented microfiber hydrogel which is prepared by the preparation method in the technical scheme.
The invention provides an adjustable muscle-like mechanical property material, which comprises the oriented microfiber hydrogel prepared by the preparation method of the technical scheme.
The invention provides a preparation method of an oriented microfiber hydrogel, which comprises the following steps: A) mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol; B) reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer; C) dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample; D) placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer; E) crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers; wherein m and n are independently selected from 50-350. The end group of the polyvinyl alcohol tertiary amine with the structure of formula (I) is a hydrophobic alkane chain, and the derivative is water-insoluble. The preparation of the gel and the achievement of the desired mechanical properties are achieved by gelling and post-treatment of the polyvinyl alcohol graft polymer. By pre-stretching the network in the oriented gel, controlling the retraction length when the external force is removed, and carrying out covalent crosslinking and fixation when the retraction length is preset, the controllable fold conformation is realized; the method realizes the oriented microfiber hydrogel with a wrinkled structure. The material with adjustable muscle-like mechanical properties is prepared. By regulating the wrinkle degree, the invention can realize the strain hardening characteristic of the muscle-like muscle and can also regulate and control the modulus transformation of the material.
In order to further illustrate the present invention, the following will describe an oriented microfiber hydrogel and a method for preparing the same in detail with reference to the following examples.
Example 1
Stirring and dissolving PVA at 90 ℃ by using dimethyl sulfoxide (DMSO) as a solvent; after the PVA solution is cooled to room temperature, a proper amount of N, N' -Carbonyldiimidazole (CDI) is added for reaction for 3 hours, and the PVA is activated. Adding a proper amount of n-octylamine to modify PVA, and reacting for a period of time. Adding a proper amount of ammonia water to stop the reaction, and then dropping the obtained solution into deionized water to precipitate the modified PVA-C8-DS. FIG. 1 is a nuclear magnetic resonance spectrum of PVA-C8-x; FIG. 2 is a scheme for preparing a high tensile hydrogel with near-skeletal muscle mechanical properties. The sample prepared by this stretching method is designated PVA-C8-L0/L, wherein, panel a depicts oriented PVA-C8; panel b depicts the introduction of wrinkles in oriented fibers.
The ammonia in the precipitate was washed away with deionized water. Freeze-dried, weighed, and the sample dissolved using N, N-Dimethylformamide (DMF) as a solvent. Pumping the air of the solution by a water pump, pouring the solution into a mould, carrying out water exchange for a period of time, gelling, and taking out the soaked water to obtain a sample. Taking the obtained hydrogel sample from the die, putting the hydrogel sample into a mixed solution of N, N-2-methylformamide and deionized water for swelling, and stretching by different times; the stretching specifically comprises the following steps: the hydrogel (about 5cm long) which had been prepared with the DMF removed was put in a mixture of DMF and water to soften it, and we could stretch it to 800% of the original length according to its longest stretched length of 900% to 1000% of the original length, cut 3cm (remove the part fixed at both ends to the unstretched part, the effective stretched part was 2cm) and stretch the effective stretched part to 16cm and fix it on a jig of 17cm length with an adhesive tape, put in water to harden it. After release its titin expands into a polymer with filaments and cross-links.
Example 2
Preparing a crosslinking solution, wherein the volume ratio of water to the isovaleraldehyde is 9: and 1, adding 4-6 drops of hydrochloric acid, uniformly stirring, stretching the swelled substances to a plurality of samples with the original length of 8 times, and respectively retracting part of the samples by 4 times, retracting part of the samples by 6 times and keeping part of the samples by 8 times under the action of external force after releasing. And (3) crosslinking the samples with different lengths in the crosslinking solution for 30min, taking out the samples, withdrawing the external force, and soaking the samples in water for 3h to leach out the crosslinking solution in the samples. And (6) performing a tensile test. The results are shown in FIG. 3.
FIG. 3 shows that the method has the characteristics of simplicity, easy control, high efficiency and the like. The resulting gel has high water content (> 80%), high strength (4MPa), low modulus (0.4 MPa).
Taking PVA-C8-1.2 as an example, the test was carried out after the sample was pre-stretched t times for a certain period of time and then relaxed in water for 5 hours. As shown in FIG. 4, the invention is shown in FIG. 4, which is a mechanical tensile curve of PVA-C8-L0/L. As can be seen from the graph, the strength of the PVA-C8-L0/L series hydrogel reaches 4MPa, and the hydrogel shows a strain hardening tendency. The strength of PVA-C8 hydrogel which is not stretched is only 0.4MPa,
the sample is subjected to cyclic stretching, the testing stretching length is respectively 1 time and 2 times of the original length of the sample, and the cycle times are both 100. FIG. 5: the cyclic extension curve of PVA-C8-16-10. As can be seen from FIG. 5, the fatigue resistance of the product is good, and the stress-strain curve of the product fluctuates in a range and the fluctuation is weak after multiple cycles.
To further verify the biocompatibility of the gel material, the inventors adopted the toxicity of thiazole blue colorimetric method to 3T3 cells. Results are shown in FIG. 6, which is a photograph of 3T3 cells taken with a standard bright field microscope after 24 hours of proliferation in the presence of hydrogel + dimethylsulfoxide (1.5%) + vehicle, and cells treated with different concentrations of hydrogel (mg/mL).
FIG. 7 shows the results of treating cells with different volume ratios of the environmental solution in the case of hydrogel immersion in the environmental solution + medium, 3T3 cells were cultured for 24 hours and then photographed by a standard bright field microscope.
As can be seen in FIG. 8, 3T3 cells were photographed with a standard bright field microscope after 48 hours of proliferation in the presence of PVA-C8+ dimethylsulfoxide (1.5%) + vehicle, and the cells were treated with different concentrations of hydrogel (mg/mL).
As can be seen in FIG. 9, 3T3 cells were cultured for 48 hours and then imaged with a standard bright field microscope using different volume ratios of the environmental solution in the hydrogel plus vehicle.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an oriented microfiber hydrogel comprises the following steps:
A) mixing polyvinyl alcohol with a structure shown in formula (I), a solvent and an activating agent for reaction to obtain activated polyvinyl alcohol;
B) reacting the activated polyvinyl alcohol with n-octylamine to obtain a polyvinyl alcohol graft polymer;
C) dissolving a polyvinyl alcohol graft polymer by adopting a solvent, vacuumizing and exchanging water to obtain a hydrogel sample;
D) placing the hydrogel sample in a solvent for swelling, stretching, hardening and controllably releasing to obtain a polymer;
E) crosslinking the polymer with a crosslinking solution to obtain hydrogel of the oriented microfibers;
wherein m and n are independently selected from 50-350.
2. The method of claim 1, wherein the activator of step a) is carbonyldiimidazole, and the solvent is dimethyl sulfoxide; the molar ratio of the polyvinyl alcohol to the activating agent is 1: 0.001 to 1: 0.5; the reaction temperature is 20-30 ℃; the reaction time is 3-4 h.
3. The method according to claim 1, wherein the molar ratio of the activated polyvinyl alcohol to the n-octylamine in the step B) is 0.6; the reaction temperature is 20-30 ℃; the reaction time was 48 hours.
4. The method according to claim 1, wherein the stretching ratio in step D) is 9 to 10 times; the controllable release is specifically to control the retraction to 4-8 times of the original length.
5. The method according to claim 1, wherein the solvent of step D) comprises N, N-2-methylformamide and deionized water; the mass ratio of the N, N-2-methylformamide to the deionized water is 1: 1.
6. The preparation method according to claim 1, wherein the hardening in step D) is specifically hardening by soaking in water, and the soaking time is 6-24 h.
7. The method according to claim 1, wherein step a) is preceded by heating to dissolve the polyvinyl alcohol having the structure of formula (I) and cooling; the heating temperature is 85-95 ℃; the molecular weight of the polyvinyl alcohol with the structure of the formula (I) is 146000-186000.
8. The method of claim 1, wherein the crosslinking solution of step E) comprises isoprene glycol, hydrochloric acid and water; the concentration of the isoprene glycol is 1-2 wt%; the concentration of the hydrochloric acid is 1-2 wt%.
9. An oriented microfiber hydrogel produced by the production method according to any one of claims 1 to 8.
10. A controllable muscle-like mechanical property material, which is characterized in that the material comprises the oriented microfiber hydrogel prepared by the preparation method of any one of claims 1 to 8.
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