CN104327284A - Preparation method of supramolecular hydrogel - Google Patents
Preparation method of supramolecular hydrogel Download PDFInfo
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- CN104327284A CN104327284A CN201410593092.9A CN201410593092A CN104327284A CN 104327284 A CN104327284 A CN 104327284A CN 201410593092 A CN201410593092 A CN 201410593092A CN 104327284 A CN104327284 A CN 104327284A
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Abstract
The invention relates to a preparation method of a supramolecular hydrogel. The preparation method is characterized by comprising the following steps: 1) by using beta-cyclodextrin as a raw material, synthesizing mono-(6-oxo-6-para-tolylsulfonyl)-beta-cyclodextrin and synthesizing mono-(6-deoxidized-6-sulfydryl)-beta-cyclodextrin on the basis; 2) dropwise adding a 1*10<-3>mol/l silver nitrate aqueous solution into an isovolumetric 4*10<-3>mol/l sodium borohydride aqueous solution under a stirring condition of an ice-salt bath (-1 to 0 DEG C), wherein the dropping time is controlled within 30 minutes, then maintaining the ice bath temperature all the way along with the reaction system, and continuously stirring for 10 hours to prepare a nanosilver particle hydrosol; and 3) after uniformly mixing the nanosilver particle hydrosol with EO-PO type polyether F127, adding the mono-(6-deoxidized-6-sulfydryl)-beta-cyclodextrin synthesized in the step 1) and uniformly stirring, and after centrifugalizing for 90 seconds at a rotating speed of 1500-3000rpm, standing for 30-120 minutes to obtain the supramolecular hydrogel. The method provided by the invention is simple and the prepared supramolecular hydrogel shows intellectuality.
Description
Technical field
The present invention relates to a kind of preparation method of supramolecular hydrogel, belong to supramolecular materials preparation field.
Background technology
Hydrogel, because of its good bio-compatibility, can be used for the biological medicine Application Areass such as medicine transport, organizational project and causes general concern.A large amount of about temperature sensitive, photosensitive and that pH is responsive aquogel system by wide coverage.On the other hand, the superior physics and chemistry character that also possesses because of itself of Nano silver grain and be applied to Science and Technology field more and more.Therefore, build a kind of supramolecular hydrogel if hydrogel and Nano silver grain combined, and be applied to biological and pharmaceutical field and will be one and significantly work.
Summary of the invention
The object of this invention is to provide that a kind of technique is simple, cost of investment is low, good biocompatibility, medicine carrying are for a long time active and there is the preparation method of intelligent supramolecular hydrogel.Its technology contents is:
A kind of preparation method of supramolecular hydrogel, it is characterized in that adopting following steps: 1) take beta-cyclodextrin as Material synthesis list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin, then be Material synthesis list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin; 2) under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1boron hydracid sodium water solution in, time for adding 15-30min, continues to stir 10h, the obtained Nano silver grain water-sol; 3) after the Nano silver grain water-sol being mixed with EO-PO type polyethers F127, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin of synthesizing stirring, under 1500-3000rpm rotating speed after centrifugal 90-150s, leave standstill 30-120min again, obtain supramolecular hydrogel.
For realizing goal of the invention; the preparation method of described supramolecular hydrogel; step 1) in the preparation process of list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin be: by beta-cyclodextrin and p-methyl benzene sulfonic chloride in molar ratio 1:1.5 be dissolved in deionized water; the add-on of deionized water and the mass ratio of beta-cyclodextrin are 24:1; stir after 2 ~ 3h, adding be 10:1 concentration with beta-cyclodextrin mol ratio is 2.5mol.l
-1the NaOH aqueous solution, continue stir 30min, impurity screening obtains filtrate; The 1mol.l with amount of substances such as NaOH is added in filtrate
-1hydrochloric acid, adjust ph to 8; Filter after gained solution is placed in refrigerator 12-24h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
For realizing goal of the invention, the preparation method of described supramolecular hydrogel, step 1) in the preparation process of list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin be: by list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and the thiocarbamide mixed in molar ratio according to 1:20, add with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin mass ratio is that (methyl alcohol and water volume ratio are 80:20 for the mixed solvent of 40:1 again, density is 0.85g/ml), rotary evaporation after above-mentioned solution return 48h is obtained solid; Add in above-mentioned solid with mixed solvent volume ratio be 1:4 methyl alcohol and leave standstill 1 day after stirring 1 ~ 3h, then rotary evaporation obtains white solid; Being dissolved in by white solid with the mass ratio of list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin is that in the NaOH aqueous solution of 35:1, (NaOH massfraction is 10%, density is 1.05g/ml), 50 DEG C are stirred 5h, then being adjusted to pH with the HCl solution of massfraction 10% is 2, the trieline (density is 1.46g/ml) that to add with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin mass ratio be again 4:1 stirs 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
For realizing goal of the invention, the preparation method of described supramolecular hydrogel, step 3) in the mass ratio 1:4 ~ 1:7 of EO-PO type polyethers F127 and the Nano silver grain water-sol, the mass ratio of list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin and the Nano silver grain water-sol is 1:15 ~ 1:20.
Compared with prior art, tool has the following advantages in the present invention:
1, the present invention's supramolecular hydrogel containing Nano silver grain that to have utilized a kind of simple and easy method to prepare novel, this supramolecular hydrogel has the potential using value as pharmaceutical carrier.
2, production technique of the present invention is simple, and facility investment is few, and production cost is low, easily realizes industrialization.Only need a generic centrifuge and little process matched therewith and equipment, just can prepare that effluent consistency is good, medicine carrying is active of a specified duration and have intelligent supramolecular hydrogel.
Embodiment
Embodiment 1:
Step 1): 30.0g beta-cyclodextrin and 7.6g p-methyl benzene sulfonic chloride are added in 720mL deionized water.After stirring 2 ~ 3h, add 2.5mol.l
-1naOH aqueous solution 105ml, continue to stir 30min, impurity screening obtains filtrate; In filtrate, add 262ml concentration is 1mol.l
-1hydrochloric acid, reconcile pH value to 8; Filter after gained solution is placed in refrigerator 12h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
Take 2.0g mono--(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and 2.4g thiocarbamide, (methyl alcohol and water volume ratio are 80:20 to add 94ml mixed solvent again, density is 0.85g/ml), rotary evaporation after above-mentioned solution return 48h is obtained solid; In above-mentioned solid, add 24ml methyl alcohol and leave standstill 1 day after stirring 1h, then rotary evaporation obtains white solid; White solid is dissolved in (density is 1.05g/ml) in the NaOH solution of 67ml massfraction 10%, 50 DEG C are stirred 5h, then being adjusted to pH with the HCl solution of massfraction 10% is 2, add 5.5ml trieline (density is 1.46g/ml) again and stir 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
Step 2): under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by 20ml concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1in boron hydracid sodium water solution, time for adding 15-30min, continues to stir 10h, prepares the Nano silver grain water-sol.
Step 3): after the 0.85g Nano silver grain water-sol and 0.14g EO-PO type polyethers F127 are mixed, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin 0.05g of synthesizing stirring, centrifugal 150s under 1500rpm rotating speed, leave standstill 30min again, obtain supramolecular hydrogel.
Embodiment 2:
Step 1): 40.0g beta-cyclodextrin and 10.1g p-methyl benzene sulfonic chloride are added in 960ml deionized water.After stirring 2 ~ 3h, add 2.5mol.l
-1naOH aqueous solution 141ml, continue to stir 30min, impurity screening obtains filtrate; In filtrate, add 352ml concentration is 1mol.l
-1hydrochloric acid, reconcile pH value to 8; Filter after gained solution is placed in refrigerator 16h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
Take 3.0g mono--(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and 3.6g thiocarbamide, (methyl alcohol and water volume ratio are 80:20 to add 141ml mixed solvent again, density is 0.85g/ml), rotary evaporation after above-mentioned solution return 48h is obtained solid; In above-mentioned solid, add 35ml methyl alcohol and leave standstill 1 day after stirring 1.5h, then rotary evaporation obtains white solid; White solid is dissolved in (density is 1.05g/ml) in the NaOH solution of 100ml massfraction 10%, 50 DEG C are stirred 5h, then being adjusted to pH with the HCl solution of massfraction 10% is 2, add 8.2ml trieline (density is 1.46g/ml) again and stir 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
Step 2): under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by 25ml concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1in boron hydracid sodium water solution, time for adding 15-30min, continues stirring 10
h, prepares the Nano silver grain water-sol.
Step 3): after the 1.0g Nano silver grain water-sol and 0.18g EO-PO type polyethers F127 are mixed, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin 0.06g of synthesizing stirring, centrifugal 130s under 2000rpm rotating speed, leave standstill 60min again, obtain supramolecular hydrogel.
Embodiment 3:
Step 1): 50.0g beta-cyclodextrin and 12.6g p-methyl benzene sulfonic chloride are added in 1200ml deionized water.After stirring 2 ~ 3h, add 2.5mol.l
-1naOH aqueous solution 176ml, continue to stir 30min, impurity screening obtains filtrate; In filtrate, add 440ml concentration is 1mol.l
-1hydrochloric acid, reconcile pH value to 8; Filter after gained solution is placed in refrigerator 20h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
Take 4.0g mono--(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and 4.7g thiocarbamide, (methyl alcohol and water volume ratio are 80:20 to add l88ml mixed solvent again, density is 0.85g/ml), rotary evaporation after above-mentioned solution return 48h is obtained solid; In above-mentioned solid, add 47ml methyl alcohol and leave standstill 1 day after stirring 2h, then rotary evaporation obtains white solid; White solid is dissolved in (density is 1.05g/ml) in the NaOH solution of 133ml massfraction 10%, 50 DEG C are stirred 5h, then being adjusted to pH with the HCl solution of massfraction 10% is 2, add 11.0ml trieline (density is 1.46g/ml) again and stir 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
Step 2): under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by 30ml concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1in boron hydracid sodium water solution, time for adding 15-30min, continues to stir 10h, prepares the Nano silver grain water-sol.
Step 3) the 1.2g Nano silver grain water-sol and 0.28g EO-PO type polyethers F127 are mixed after, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin 0.08g of synthesizing stirring, centrifugal 110s under 2500rpm rotating speed, leave standstill 90min again, obtain supramolecular hydrogel.
Embodiment 4:
Step 1): 60.0g beta-cyclodextrin and 15.1g p-methyl benzene sulfonic chloride are added in 1440ml deionized water.After stirring 2 ~ 3h, add 2.5mol.l
-1naOH aqueous solution 211ml, continue to stir 30min, impurity screening obtains filtrate; In filtrate, add 527ml concentration is 1mol.l
-1hydrochloric acid, reconcile pH value to 8; Filter after gained solution is placed in refrigerator 20h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
Take 5.0g mono--(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and 5.9g thiocarbamide, (methyl alcohol and water volume ratio are 80:20 to add 235ml mixed solvent again, density is 0.85g/ml), rotary evaporation after above-mentioned solution return 48h is obtained solid; In above-mentioned solid, add 59ml methyl alcohol and leave standstill 1 day after stirring 3h, then rotary evaporation obtains white solid; White solid is dissolved in (density is 1.05g/ml) in the NaOH solution of 167ml massfraction 10%, 50 DEG C are stirred 5h, then being adjusted to pH with the HCl solution of massfraction 10% is 2, add 13.7ml trieline (density is 1.46g/ml) again and stir 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
Step 2): under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by 40ml concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1in boron hydracid sodium water solution, time for adding 15-30min, continues to stir 10h, prepares the Nano silver grain water-sol.
Step 3) the 1.4g Nano silver grain water-sol and 0.31g EO-PO type polyethers F127 are mixed after, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin 0.07g of synthesizing stirring, centrifugal 90s under 3000rpm rotating speed, leave standstill 120min again, obtain supramolecular hydrogel.
Claims (4)
1. the preparation method of a supramolecular hydrogel, it is characterized in that adopting following steps: 1) take beta-cyclodextrin as Material synthesis list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin, then be Material synthesis list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin; 2) under-1 ~ 0 DEG C of cryosel bath agitation condition, be 1 × 10 by concentration
-3mol.l
-1silver nitrate aqueous solution to be added drop-wise to equal-volume concentration be 4 × 10
-3mol.l
-1boron hydracid sodium water solution in, time for adding 15-30min, continues to stir 10h, the obtained Nano silver grain water-sol; 3) after the Nano silver grain water-sol being mixed with EO-PO type polyethers F127, add step 1) list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin of synthesizing stirring, under 1500-3000rpm rotating speed after centrifugal 90-150s, leave standstill 30-120min again, obtain supramolecular hydrogel.
2. the preparation method of supramolecular hydrogel according to claim 1; it is characterized in that step 1) in the preparation process of list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin be: by beta-cyclodextrin and p-methyl benzene sulfonic chloride in molar ratio 1:1.5 be dissolved in deionized water; the add-on of deionized water and beta-cyclodextrin mass ratio are 24:1; stir after 2 ~ 3h, adding be 10:1 concentration with beta-cyclodextrin mol ratio is 2.5mol.l
-1the NaOH aqueous solution, continue stir 30min, impurity screening obtains filtrate; The 1mol.l with amount of substances such as NaOH is added in filtrate
-1hydrochloric acid, adjust ph to 8; Filter after gained solution is placed in refrigerator 12-24h, then use water recrystallization again with after distilled water wash solid 2 ~ 3 times; By the 50 DEG C of vacuum-dryings of crystallization after product, obtained list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin.
3. the preparation method of supramolecular hydrogel according to claim 1, it is characterized in that step 1) in the preparation process of list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin be: by list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin and the thiocarbamide mixed in molar ratio according to 1:20, adding with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin mass ratio is again the mixed solvent of 40:1, mixed solvent is made up of methyl alcohol and water, both volume ratios are 80:20, density is 0.85g/ml, and rotary evaporation after above-mentioned solution return 48h is obtained solid; Add in above-mentioned solid with mixed solvent volume ratio be 1:4 methyl alcohol and leave standstill 1 day after stirring 1 ~ 3h, then rotary evaporation obtains white solid; Being dissolved in by white solid with the mass ratio of list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin is in the NaOH aqueous solution of 35:1,50 DEG C are stirred 5h, wherein in the NaOH aqueous solution, NaOH massfraction is 10%, density is 1.05g/ml, then being adjusted to pH with the HCl solution of massfraction 10% is 2, adding with list-(6-oxygen-6-p-toluenesulfonyl)-beta-cyclodextrin mass ratio is again the trieline of 4:1, wherein the density of trieline is 1.46g/ml, stir 24h, separate out white solid, after suction filtration, product is with water recrystallization; By the 50 DEG C of vacuum-dryings of crystallization after product, final obtained list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin.
4. the preparation method of supramolecular hydrogel according to claim 1, it is characterized in that: step 3) in the mass ratio 1:4 ~ 1:7 of EO-PO type polyethers F127 and the Nano silver grain water-sol, the mass ratio of list-(6-deoxidation-6-sulfydryl)-beta-cyclodextrin and the Nano silver grain water-sol is 1:15 ~ 1:20.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001354A (en) * | 2015-08-13 | 2015-10-28 | 安徽世华化工有限公司 | Synthetic method for mono-6-mercapto-beta-cyclodextrin |
| CN108276589A (en) * | 2018-01-11 | 2018-07-13 | 浙江农林大学 | A kind of preparation method of modified cyclodextrin polyalcohol hydrogel and application |
| CN109079153A (en) * | 2018-07-24 | 2018-12-25 | 江汉大学 | A kind of supramolecular hydrogel preparation method of silver-containing nanoparticles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516739A (en) * | 2011-12-13 | 2012-06-27 | 中国科学院成都生物研究所 | Multiple sensitive hydrogel material and preparation method thereof |
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2014
- 2014-10-28 CN CN201410593092.9A patent/CN104327284A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516739A (en) * | 2011-12-13 | 2012-06-27 | 中国科学院成都生物研究所 | Multiple sensitive hydrogel material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 靖波: "基于环糊精包结和离子自组装的超分子结构构建", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001354A (en) * | 2015-08-13 | 2015-10-28 | 安徽世华化工有限公司 | Synthetic method for mono-6-mercapto-beta-cyclodextrin |
| CN108276589A (en) * | 2018-01-11 | 2018-07-13 | 浙江农林大学 | A kind of preparation method of modified cyclodextrin polyalcohol hydrogel and application |
| CN109079153A (en) * | 2018-07-24 | 2018-12-25 | 江汉大学 | A kind of supramolecular hydrogel preparation method of silver-containing nanoparticles |
| CN109079153B (en) * | 2018-07-24 | 2022-03-29 | 江汉大学 | Preparation method of supramolecular hydrogel containing silver nanoparticles |
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