CN102391415B - Preparation method of thermo-sensitive hydrogel by taking baicalin as template - Google Patents
Preparation method of thermo-sensitive hydrogel by taking baicalin as template Download PDFInfo
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- IKIIZLYTISPENI-ZFORQUDYSA-N baicalin Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC=CC=1)O2 IKIIZLYTISPENI-ZFORQUDYSA-N 0.000 title claims abstract description 63
- 229960003321 baicalin Drugs 0.000 title claims abstract description 63
- AQHDANHUMGXSJZ-UHFFFAOYSA-N baicalin Natural products OC1C(O)C(C(O)CO)OC1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC=CC=1)O2 AQHDANHUMGXSJZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
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- 238000002791 soaking Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
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- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
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- 230000004044 response Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 241001274660 Modulus Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- NLMKTBGFQGKQEV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO NLMKTBGFQGKQEV-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
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- SZMVKWFJCYTPOI-UHFFFAOYSA-N baicaline Natural products N1CCC2=C3OCOC3=C(OC)C3=C2C1CC1=C3C=C(OC)C(OC)=C1 SZMVKWFJCYTPOI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of thermo-sensitive hydrogel by taking baicalin as a template. The hydrogel is prepared from the baicalin, thermo-sensitive monomers, a chemical cross-linking agent, an initiator and an organic solvent according to the ratio by weight percent of (0.1-0.9%):(5-10%):(0.85-5%):(0.05-0.1%):(84-94%). The preparation method comprises the following steps: 1) dissolving the baicalin in the organic solvent; 2) sequentially adding the thermo-sensitive monomers, the chemical cross-linking agent and the initiator into mixed solution in the step 1), and performing free radical polymerization at high temperature after sealing to get yellow gel; and 3) cutting the yellow gel into pieces, soaking and removing impurities. The product according to the invention has thermo-sensitive property, the baicalin plays a role of the template in the gel, the pore size, the thermo-sensitive property and the mechanical properties of the product can be regulated through the using amount of the baicalin, and the product can be used in biological medicine, tissue engineering, protection against drought, anti-waterlogging property, chemical separation and other fields.
Description
Technical field
The present invention relates to pharmaceutical preparation and intelligent macromolecule material field, be specifically related to a kind of preparation method of the temperature-sensitive hydrogel take baicalin as template.
Background technology
Hydrogel (hydrogels) is a kind of wetting ability but water-fast high molecular polymer can be processed into different shape, as column, porous spongy, fibrous, tubulose, hollow form, membranaceous and spherical etc.Intelligent aqueous gel capable is that a class stimulates (as temperature, pH, light, electric field, magnetic field, pressure etc.) can produce the hydrogel of responsive response to external world.The temperature-responsive hydrogel that is subject at present common concern is alkyl acrylamide class hydrogel, NIPA (PNIPAM) particularly is in biological medicine, organizational project, take precautions against drought waterlogging-resistant and the field such as chemical separation has demonstrated good application prospect.
Can obtain having the material of ordered structure as template with the small molecules tensio-active agent in gel.(the chemical journal .2009 such as Lu Cuixiang, 67 (3): 238) take hexadecanol Soxylat A 25-7 (Brij58) as template, use N, N '-methylene-bisacrylamide (MBA) adopts photopolymerization to synthesize polyacrylamide (PAAm) hydrogel of compound with regular structure as linking agent, small structure with homogeneous, internal structure is more regular, orderly, and what kept traditional hydrogel changes the character of response fast to the pH value.In addition, Shen Xinyu etc. (functional materials, 2004,35 (increasing): 2431) with the PAAm hydrogel as template, the biomineralization of simulation calcium carbonate is carried out bionical syntheticly, obtaining diameter is the calcite type near-spherical aggregate of 10～50 μ m.And consist of the monomer size homogeneous, meticulous (50～100nm), and show same orientation on secondary structure unit of this aggregate.Contrast is without the result that obtains under the template to regulate condition, and the PAAm hydrogel template is due to the high-sequential structure that himself exists, and the crystallography orientation of calcium carbonate and granularity, pattern are all had strict control action kou.
Baicalin (baicalin) another name baicaline is for the dry root of the dicotyledons Labiatae root of large-flowered skullcap extracts a kind of flavonoid compound that gets.Baicalin molecular formula C
21H
18O
11Molecular weight 446.37, light yellow crystalline powder, 223～225 ℃ of fusing points, be soluble in dimethyl formamide, pyridine, dissolve in the basic solutions such as sodium bicarbonate, sodium carbonate, sodium hydroxide, but unstable in alkali lye, the gradual change burgundy, be slightly soluble in hot Glacial acetic acid, be insoluble in formic acid, acetic acid, acetone, water-soluble hardly, ether, benzene, chloroform etc.That baicalin has is anticancer, antibiotic, antiviral, remove oxyradical and anti-oxidant, analgesic, anti-arrhythmia, step-down and calmness, adjusting immunologic function, suppress vascular smooth muscle cell proliferation, regulate the effects such as blood fat, atherosclerosis.
Because baicalin is small molecules, add reaction system in gel preparation course, reacting complete mode by immersion can ooze out from the hole of gel, thereby forms the gel pattern of different bore hole sizes.The present invention has considered the temperature sensitivity of hydrogel and the pore of baicalin, near utilize alkyl acrylamide class hydrogel to stretch or shrink volume phase transition temperature (VPTT) conformational change, add baicalin in the hydrogel preparation process, jointly be dissolved in organic solvent, prepare hydrogel under high temperature, by change baicalin consumption, but the internal structure of Effective Regulation gel and hole form.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of temperature-sensitive hydrogel take baicalin as template, gained gel transparency is high, temperature-responsive is sensitive, bore hole size is adjustable.
The preparation method of a kind of temperature-sensitive hydrogel take baicalin as template of the present invention comprises the steps:
1) under 20～25 ℃, the yellow powder baicalin is dissolved in organic solvent, is mixed with the organic solvent solution that the baicalin mass concentration is 0.1-0.9%, magnetic agitation 15～30min forms yellow transparent solution;
2) under nitrogen protection, temperature sensitive monomer and chemical cross-linking agent are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 20～40min, add the initiator solid particulate, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 24～36h carries out radical polymerization, control temperature of reaction at 65～80 ℃, react and obtain yellow gel after complete;
3) yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of organic solvent, then take out and be soaked in 1-2 week in deionized water, at interval of changing organic solvent or deionized water in 5-8 hour, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
The mass percent of described baicalin, temperature sensitive monomer, chemical cross-linking agent, initiator and organic solvent is baicalin: 0.1-0.9%, temperature sensitive monomer: 5-10%, chemical cross-linking agent: 0.85-5%, initiator: 0.05-0.1%, organic solvent: 84-94%.
Described baicalin can be dissolved in organic solvent fully, realizes the function of template in the gel-purified process by the mode of soaking.
Described organic solvent is any one in dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or pyridine.
Described temperature sensitive monomer is a kind of of NIPA or isopropyl methyl acrylamide, owing to both having contained hydrophilic amide group in the monomer whose structure, contain again hydrophobic sec.-propyl or methyl group, thereby have volume phase transition temperature (VPTT), when lower than this temperature, hydrophilic interaction power plays a major role, the molecular chain full extension, and when higher than this temperature, hydrogen bond is destroyed, hydrophobic interaction power increases, and molecular chain shrinks.
Described chemical cross-linking agent is any one in methylene-bisacrylamide (MBA), ethylene glycol dimethacrylate (EDGMA) or bismethacryloyloxyphenyl propane.
Described initiator is any one in Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMBN), dibenzoyl peroxide (BPO) or the peroxidation isocaprylic acid tert-butyl ester (TBPO).
As yellow, be light yellow after immersion after described temperature-sensitive hydrogel reaction take baicalin as template is complete, and near the water white transparency shape.
According to the preferred method of the present invention, first baicalin is added and form transparent and homogeneous solution in organic solvent, add function monomer and chemical cross-linking agent and other raw material to form mixed reaction solution, high temperature radical polymerization prepares the temperature-sensitive hydrogel that obtains take baicalin as template under the initiator effect at last again.
Described temperature-sensitive hydrogel inner void take baicalin as template is of a size of 50～500 μ m, and volume phase transition temperature (VPTT) is positioned at 30～34 ℃, presents the low-temperature transparent swelling, the characteristics that high temperature bleaches and shrinks.
The bore hole size of the temperature-sensitive hydrogel take baicalin as template of the present invention, Thermo-sensitive and mechanical property can be regulated by the baicalin consumption.No matter the baicalin mass percent is in any numerical value of 0.1-0.9%, its volume phase transition temperature is all 32 ℃ of left and right, but temperature response speed increases with content of baicalin and improves, when without baicalin, the hydrogel bore hole size is 70～100 μ m approximately, and 15 ℃ of storage moduluss are about 1.6MPa, when the baicalin mass percent is 4%, hydrogel hole chi is up to 400 μ m, and 15 ℃ of storage moduluss are about 6MPa, and this has important reference for form and the performance regulation and control of hydrogel from now on application.
Description of drawings
Fig. 1 is without the hydrogel of baicalin and the electron scanning micrograph of the hydrogel take baicalin as template.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Under 22 ℃, the 0.02g baicalin is dissolved in the 10mL dimethyl sulfoxide (DMSO), magnetic agitation 20min forms yellow transparent solution;
Under nitrogen protection, 0.90g N-isopropylacrylamide and 0.18g methylene-bisacrylamide are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 25min, add the 0.009g 2,2'-Azobis(2,4-dimethylvaleronitrile), after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 30h carries out radical polymerization, control temperature of reaction at 70 ℃, react and obtain yellow gel after complete;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of dimethyl sulfoxide (DMSO), then take out and be soaked in 1 week in deionized water, at interval of changing dimethyl sulfoxide (DMSO) or deionized water in 8 hours, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
Adopt scanning electronic microscope, differential scanning calorimeter and dynamic thermomechanometry test, gained hydrogel bore hole size is 80 μ m, and the volume phase transition temperature is 32.0 ℃, and storage modulus is 3.7MPa.
Embodiment 2
Under 23 ℃, the 0.04g baicalin is dissolved in the 10mL dimethyl formamide, magnetic agitation 25min forms yellow transparent solution;
Under nitrogen protection, 1.0g N-isopropylacrylamide and 0.2g methylene-bisacrylamide are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 30min, add the 0.01g Diisopropyl azodicarboxylate, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 32h carries out radical polymerization, control temperature of reaction at 73 ℃, react and obtain yellow gel after complete;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of dimethyl formamide, then take out and be soaked in 1 week in deionized water, at interval of changing dimethyl formamide or deionized water in 7 hours, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
Adopt scanning electronic microscope, differential scanning calorimeter and dynamic thermomechanometry test, gained hydrogel bore hole size is 400 μ m, and the volume phase transition temperature is 31.8 ℃, and storage modulus is 6.3MPa.
Embodiment 3
Under 25 ℃, the 0.06g baicalin is dissolved in the 11mL pyridine, magnetic agitation 30min forms yellow transparent solution;
Under nitrogen protection, 0.95g isopropyl methyl acrylamide and 0.19g ethylene glycol dimethacrylate are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 35min, add the 0.0095g peroxidation isocaprylic acid tert-butyl ester, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 34h carries out radical polymerization, control temperature of reaction at 75 ℃, react and obtain yellow gel after complete;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of dimethyl formamide, then take out and be soaked in 2 weeks in deionized water, at interval of changing pyridine or deionized water in 6 hours, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
Adopt scanning electronic microscope, differential scanning calorimeter and dynamic thermomechanometry test, gained hydrogel bore hole size is 460 μ m, and the volume phase transition temperature is 31.6 ℃, and storage modulus is 7.1MPa.
Embodiment 4
Under 23 ℃, the 0.08g baicalin is dissolved in the 12mL dimethyl formamide, magnetic agitation 30min forms yellow transparent solution;
Under nitrogen protection, 1.1g N-isopropylacrylamide and 0.2g ethylene glycol dimethacrylate are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 40min, add the 0.010g dibenzoyl peroxide, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 36h carries out radical polymerization, control temperature of reaction at 75 ℃, react and obtain yellow gel after complete;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of dimethyl formamide, then take out and be soaked in 2 weeks in deionized water, at interval of changing dimethyl formamide or deionized water in 5 hours, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
Adopt scanning electronic microscope, differential scanning calorimeter and dynamic thermomechanometry test, gained hydrogel bore hole size is 510 μ m, and the volume phase transition temperature is 31.2 ℃, and storage modulus is 5.6MPa.
Embodiment 5
Under 25 ℃, the 0.10g baicalin is dissolved in the 13mL dimethyl sulfoxide (DMSO), magnetic agitation 30min forms yellow transparent solution;
Under nitrogen protection, 0.90g N-isopropylacrylamide and 0.20g ethylene glycol dimethacrylate are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 30min, add the 0.009g dibenzoyl peroxide, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 32h carries out radical polymerization, control temperature of reaction at 76 ℃, react and obtain yellow gel after complete;
Yellow gel is cut into the approximately thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of dimethyl formamide, then take out and be soaked in 1 week in deionized water, at interval of changing organic solvent or deionized water in 5 hours, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
Adopt scanning electronic microscope, differential scanning calorimeter and dynamic thermomechanometry test, gained hydrogel bore hole size is 610 μ m, and the volume phase transition temperature is 32.3 ℃, and storage modulus is 6.7MPa.
Claims (9)
1. the preparation method of the temperature-sensitive hydrogel take baicalin as template, comprise the steps:
1) under 20～25 ℃, the yellow powder baicalin is dissolved in organic solvent, is mixed with the organic solvent solution that the baicalin mass concentration is 0.1-0.9%, magnetic agitation 15～30min forms yellow transparent solution;
2) under nitrogen protection, temperature sensitive monomer and chemical cross-linking agent are joined in above-mentioned yellow transparent solution successively, after magnetic agitation 20～40min, add the initiator solid particulate, after stirring again 20min, reaction solution is poured in glass mold, be positioned over after sealing that in constant temperature oven, 24～36h carries out radical polymerization, control temperature of reaction at 65～80 ℃, react and obtain yellow gel after complete;
3) yellow gel is cut into the thick thin slice of 2mm diameter 13mm that is, first be soaked in 1 week of organic solvent, then take out and be soaked in 1-2 week in deionized water, at interval of changing organic solvent or deionized water in 5-8 hour, to remove unreacted monomer, linking agent and various impurity, obtain described temperature-sensitive hydrogel take baicalin as template.
2. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, it is characterized in that, the mass percent of described baicalin, temperature sensitive monomer, chemical cross-linking agent, initiator and organic solvent is baicalin: 0.1-0.9%, temperature sensitive monomer: 5-10%, chemical cross-linking agent: 0.85-5%, initiator: 0.05-0.1%, organic solvent: 84-94%.
3. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, is characterized in that, described baicalin can be dissolved in organic solvent fully, realizes the function of template in the gel-purified process by the mode of soaking.
4. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, is characterized in that, described organic solvent is any one in dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or pyridine.
5. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, is characterized in that, the temperature sensitive monomer in described step 2 is a kind of of NIPA or isopropyl methyl acrylamide.
6. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, it is characterized in that, the chemical cross-linking agent in described step 2 is any one in methylene-bisacrylamide (MBA), ethylene glycol dimethacrylate (EDGMA) or bismethacryloyloxyphenyl propane.
7. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, it is characterized in that, the initiator in described step 2 is any one in Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide (BPO) or the peroxidation isocaprylic acid tert-butyl ester (TBPO).
8. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, is characterized in that, as yellow, is light yellow after immersion after described temperature-sensitive hydrogel reaction take baicalin as template is complete, and near the water white transparency shape.
9. the preparation method of a kind of temperature-sensitive hydrogel take baicalin as template according to claim 1, it is characterized in that, described temperature-sensitive hydrogel inner void take baicalin as template is of a size of 50～500 μ m, volume phase transition temperature (VPTT) is positioned at 30～34 ℃, present the low-temperature transparent swelling, the characteristics that high temperature bleaches and shrinks.
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| CN101851318A (en) * | 2010-05-20 | 2010-10-06 | 北京化工大学 | Preparation method of punicalagin molecular imprinted polymer microspheres |
| CN101974123A (en) * | 2010-09-10 | 2011-02-16 | 天津工业大学 | Liquid crystal-enhanced fast response temperature sensitive hydrogel and preparation method thereof |
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| CN101851318A (en) * | 2010-05-20 | 2010-10-06 | 北京化工大学 | Preparation method of punicalagin molecular imprinted polymer microspheres |
| CN101974123A (en) * | 2010-09-10 | 2011-02-16 | 天津工业大学 | Liquid crystal-enhanced fast response temperature sensitive hydrogel and preparation method thereof |
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| 卢翠香等.溶致液晶作模板水凝胶的制备及其表征.《化学学报》.2009,第67卷(第3期),238-244. |
| 溶致液晶作模板水凝胶的制备及其表征;卢翠香等;《化学学报》;20091231;第67卷(第3期);238-244 * |
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