CN104211970A - Supermolecular hydrogel material for constructing calixarene and preparation method of supermolecular hydrogel material - Google Patents
Supermolecular hydrogel material for constructing calixarene and preparation method of supermolecular hydrogel material Download PDFInfo
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- CN104211970A CN104211970A CN201410459907.4A CN201410459907A CN104211970A CN 104211970 A CN104211970 A CN 104211970A CN 201410459907 A CN201410459907 A CN 201410459907A CN 104211970 A CN104211970 A CN 104211970A
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- cup
- aromatic hydrocarbons
- dodecyl
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Abstract
The invention discloses a supermolecular hydrogel material for constructing calixarene and a preparation method of the supermolecular hydrogel material. The supermolecular hydrogel material is prepared from dodecyl modified sulfonated calix[4]arene (SC4AD) and methyl viologen modified polyvinyl alcohol under the interaction of supermolecules. The preparation method comprises the steps of self-aggregating SC4AD in a water liquid to form a micelle; and crosslinking the SC4AD micelle through PVA-MV by virtue of the host-guest bonding capacity of viologen and sulfonated calixarene to form the supermolecular hydrogel which is stable at room temperature. The supermolecular hydrogel material which is stable at room temperature is obtained by using a simple, convenient and feasible liquid mixing way by virtue of the advantage that a specific group of the viologen as a guest can be identified by the sulfonated calixarene. Compared with methods for synthesizing other hydrogels, the method disclosed by the invention has the advantages of simplicity in operation and high yield and is a convenient and effective hydrogel preparation method. The supermolecular hydrogel material has a wide application prospect in the field of materials.
Description
Technical field
The invention belongs to intelligent material technical field, particularly a kind of preparation of the supramolecular hydrogel of being constructed by calixarene and application.
Background technology
Water is organic important component part, water reconcile and regulating bioprocess complicated in organism (referring to L. Fang, S. Basu, C. H. Sue, A. C. Fahrenbach, J. F. Stoddart,
j. Am. Chem. Soc. 2011,
133, 396-399.).The gel forming in the aqueous solution, namely hydrogel, since last century the fifties end start, synthetic water gel be just defined as an important field of research (referring to E. A. Appel, J. del Barrio, X. J. Loh, O. A. Scherman,
chem. Soc. Rev. 2012 , 41,6195-6214.).This is mainly because it has very widely application, comprise the material transfer on super water-absorbing material, chemistry and bio-matrix, storage material, bio-pharmaceutical and build bioengineered tissue (referring to M. P. Lutolf,
nat. Mater. 2009,
8, 451-453; (2) K. Y. Lee, D. J. Mooney,
chem. Rev. 2001,
101, 1869-1879.).Due to, the shortcomings such as it is inhomogeneous that the hydrogel that covalent interaction cross-linked polymer segment is constructed has cross-linking density, and preparation is difficult, and light transmission is poor, carry out cross-linked polymer segment with special dynamic noncovalent interaction, developed a brand-new direction-supramolecular hydrogel.The converging network of these waters has formed the interesting soft material of a class, these materials exist attracting character such as stimulating responsive and self-healing properties, promoted they dynamic property and real world applications (referring to L. Yu, J. Ding,
chem. Soc. Rev. 2008,
37, 1473-1481).Visco-elasticity that these materials are expected to be applied to biomedical correlative study and can optionally to imitate human tissue (referring to: M. de Loos, B. L. Feringa, J. H. van Esch,
eur. J. Org. Chem. 2005, 3615-3631.).Therefore, the development of supramolecular hydrogel gets more and more people's extensive concerning.
But, be not all noncovalent interactions in the aqueous solution, be all effectively, in order to address this problem, water miscible large ring acceptor, such as cyclodextrin, calixarene and Cucurbituril etc., be used as the novel method of preparing supramolecular hydrogel (referring to J. W. Steed, J. A. Foster
angew. Chem. Int. Ed. 2010,
49, 6718-6724.).The micro-molecular hydrogel of cup [4] aromatic hydrocarbons of modifying based on proline(Pro) get more and more people's extensive concerning (referring to T. Becker, C. Y. Goh, F. Jones, M. J. McIldowie, M. Mocerino, M. I. Ogden,
chem. Commun. 2008,
33, 3900-3092; (2) C. Y. Goh, T. Becker, D. H. Brown, B. W. Skelton, F. Jones, M. Mocerino, M. I. Ogden,
chem. Commun. 2011,
47, 6057-6059; (3) J. Zhang, D. S. Guo, L. H. Wang, Z. Wang, Y. Liu,
soft Mater.
2011,
7, 1756-1762).Sulfonated calixarenes is the important derivative of a class of calixarene, has good water-solublely, there is no hemolytic toxicity, has inclusion character widely.Sulfonated calixarenes is to the stronger binding ability of purpurine class object, provides theoretical foundation (referring to Guo, D.-S., Wang, L.-H., Liu, Y. for we further use Sulfonated calixarenes to construct supramolecular hydrogel
j. Org. Chem. 2007,
72, 7775-7778).But the hydrogel based on sulfonation cup [4] aromatic hydrocarbons still rarely has report.
Summary of the invention
The object of this invention is to provide a kind of supramolecular hydrogel material of being constructed by calixarene and preparation method thereof, this supramolecular hydrogel material is the novel gelatinous material of a class.The interaction of purpurine and Sulfonated calixarenes has conclusive effect to the formation of gel.
Technical scheme of the present invention:
A supramolecular hydrogel material of being constructed by calixarene, modifies sulfonation cup [4] aromatic hydrocarbons (SC4AD) by dodecyl and is interacted and formed by supramolecule with methyl viologen modification polyvinyl alcohol (PVA-MV), and its concrete structure of constructing primitive is as follows:
。
A preparation method for the supramolecular hydrogel material of being constructed by calixarene, comprises the steps:
1) dodecyl is modified the preparation of sulfonation cup [4] aromatic hydrocarbons (SC4AD):
Cup [4] aromatic hydrocarbons is dissolved in acetonitrile, add sodium hydride, under nitrogen protection, reflux is more than 0.5 hour, then add bromododecane hydrocarbon, continue to reflux 48 hours, after being cooled to room temperature, filter and be spin-dried for solvent, add methylene dichloride to dissolve, use respectively 0.2mol/L hydrochloric acid and distilled water wash organic phase 3-5 time, add anhydrous sodium sulfate drying 8-10 hour again, filter out siccative, the crude product in solution after concentrating separates with silicagel column, eluent is that volume ratio is methylene dichloride-petroleum ether solution of 1:1, obtains white dodecyl and modifies cup [4] aromatic hydrocarbons;
Dodecyl obtained above is modified cup [4] aromatic hydrocarbon solid and is dissolved in chloroform, add chlorsulfonic acid, room temperature reaction 4 hours, evaporate chloroform, be dissolved in water and the pH of gained solution be adjusted to neutrality with the sodium hydroxide solution of 1M, be spin-dried for solvent, by gained solid water-ethyl alcohol recrystallization, obtain white dodecyl and modify sulfonation cup [4] aromatic hydrocarbons (SC4AD);
2) methyl viologen is modified the preparation of polyvinyl alcohol (PVA-MV):
Methyl viologen is modified polyvinyl alcohol according to (E. A. Appel, X. J. Loh, S. T. Jones, F. Biedermann, C. A. Dreiss, O. A. Scherman, J. Am. Chem. Soc.
2012,
134, 11767-11773) and synthetic.
3) preparation of supramolecular hydrogel material
Concrete grammar is: SC4AD, PVA-MV are dissolved in respectively in distilled water, are prepared into respectively concentration and are the solution of 0.025g/mL.Two kinds of solution of same volume are added drop-wise to respectively in reagent bottle with the speed of 0.5-1mL/min simultaneously, concussion shake up, leave standstill within 30 seconds, can make supramolecular hydrogel.
The amount ratio of described cup [4] aromatic hydrocarbons, acetonitrile, sodium hydride, bromododecane hydrocarbon and methylene dichloride is 1mol:15L: 4.25mol:5mol:37.5L.
The amount ratio that described dodecyl is modified cup [4] aromatic hydrocarbons, chloroform, chlorsulfonic acid is 1mol:3L:4.25mol.
Reaction mechanism of the present invention and product performance:
In the aqueous solution, SC4AD self assembles formation micella, and due to the Subjective and Objective binding ability of purpurine and Sulfonated calixarenes, PVA-MV is by crosslinked together SC4AD micella, thus stable supramolecular hydrogel under formation room temperature.
Advantage of the present invention is:
The present invention utilizes the identification advantage of Sulfonated calixarenes to purpurine object special groups, by simple and feasible solution hybrid mode, has obtained supramolecular hydrogel material stable under a kind of room temperature.Compared with the method for synthetic other hydrogel, that the method has advantages of is simple to operate, productive rate is high, is a kind of method of preparing hydrogel easily and effectively.This supramolecular hydrogel material has broad application prospects at Material Field.
Brief description of the drawings
Fig. 1 is the nuclear magnetic spectrogram that dodecyl is modified sulfonation cup [4] aromatic hydrocarbons.
Fig. 2 is the photo of gel formation.
Fig. 3 is the laser light scattering experiment that dodecyl modification sulfonation cup [4] aromatic hydrocarbons forms micella in the aqueous solution.
Fig. 4 is the AFM pattern that dodecyl modification sulfonation cup [4] aromatic hydrocarbons forms micella in the aqueous solution.
Fig. 5 is the SEM pattern of the calixarene supramolecular hydrogel that obtains.
Embodiment
Embodiment
A preparation method for novel supramolecular hydrogel material, comprises the steps:
1) dodecyl is modified the preparation of sulfonation cup [4] aromatic hydrocarbons:
By 1.7g(4mmol) cup [4] aromatic hydrocarbons be dissolved in 60mL acetonitrile, add 0.41g(17mmol) sodium hydride, reflux 0.5 hour under nitrogen protection.Add afterwards bromododecane hydrocarbon 4.98g(20mmol), continue to reflux 48 hours.Be cooled to room temperature, filter and be spin-dried for solvent, add 100ml methylene dichloride to dissolve, use respectively 0.2mol/L hydrochloric acid (3 × 50mL) and distilled water (50mL) washing organic phase.Add afterwards anhydrous sodium sulfate drying 9h.Filtration drying agent, the crude product after concentrating separates with silicagel column, and eluent is that volume ratio is methylene dichloride-petroleum ether solution of 1:1, obtains white dodecyl and modifies cup [4] aromatic hydrocarbon solid 3.95g, productive rate 90%.
To the above-mentioned solid 1.1g(1.0 mmol that obtains) in add 3mL chloroform to be placed in 10mL round-bottomed flask, room temperature drip 0.50g(4.25mmol) chlorsulfonic acid, react 4 hours.Solvent evaporated, is dissolved in 50ml distilled water, the pH of gained solution is adjusted to neutrality with 1M sodium hydroxide solution.Be spin-dried for solvent, thick product water-ethyl alcohol recrystallization, obtains white powder solid 1.38g, productive rate 92%.Fig. 1 is the nuclear magnetic spectrogram of ethyl bridging sulfonation cup [4] aromatic hydrocarbons, has shown the constitutional features that dodecyl is modified sulfonation cup [4] aromatic hydrocarbons.
2) methyl viologen is modified the preparation of polyvinyl alcohol (PVA-MV):
Methyl viologen is modified polyvinyl alcohol according to (E. A. Appel, X. J. Loh, S. T. Jones, F. Biedermann, C. A. Dreiss, O. A. Scherman, J. Am. Chem. Soc.
2012,
134, 11767-11773) and synthetic.
3) preparation of the supramolecular hydrogel of being constructed by calixarene, modifying sulfonation cup [4] aromatic hydrocarbons (SC4AD) by dodecyl is interacted and is formed by supramolecule with methyl viologen modification polyvinyl alcohol, concrete grammar is: 25 mg SC4AD are added in 1 mL water and to dissolve the micellar solution that makes SC4AD, Fig. 3 is the laser light scattering experiment of micellar solution, the AFM morphology characterization that Fig. 4 is micella.25mgPVA-MV is added in 1 mL water and makes solution.Two kinds of solution are added drop-wise to respectively in reagent bottle with the speed of 0.5-1mL/min simultaneously, concussion shake up, leave standstill within 30 seconds, can make supramolecular hydrogel.Fig. 5 is the SEM pattern of calixarene supramolecular hydrogel.
Claims (4)
1. a supramolecular hydrogel material of being constructed by calixarene, modifies sulfonation cup [4] aromatic hydrocarbons (SC4AD) by dodecyl and is interacted and formed by supramolecule with methyl viologen modification polyvinyl alcohol (PVA-MV), and its concrete structure of constructing primitive is as follows:
。
2. a preparation method for the supramolecular hydrogel of being constructed by calixarene described in claim 1, modifies sulfonation cup [4] aromatic hydrocarbons (SC4AD) by dodecyl and is interacted and formed by supramolecule with methyl viologen modification polyvinyl alcohol, and concrete grammar is:
1) dodecyl is modified the preparation of sulfonation cup [4] aromatic hydrocarbons (SC4AD)
Cup [4] aromatic hydrocarbons is dissolved in acetonitrile, add sodium hydride, under nitrogen protection, reflux is more than 0.5 hour, then add bromododecane hydrocarbon, continue to reflux 48 hours, after being cooled to room temperature, filter and be spin-dried for solvent, add methylene dichloride to dissolve, use respectively 0.2mol/L hydrochloric acid and distilled water wash organic phase 3-5 time, add anhydrous sodium sulfate drying 8-10 hour again, filter out siccative, the crude product in solution after concentrating separates with silicagel column, eluent is that volume ratio is methylene dichloride-petroleum ether solution of 1:1, obtains white dodecyl and modifies cup [4] aromatic hydrocarbons;
Dodecyl obtained above is modified cup [4] aromatic hydrocarbon solid and is dissolved in chloroform, add chlorsulfonic acid, room temperature reaction 4 hours, evaporate chloroform, be dissolved in water and the pH of gained solution be adjusted to neutrality with the sodium hydroxide solution of 1M, be spin-dried for solvent, by gained solid water-ethyl alcohol recrystallization, obtain white dodecyl and modify sulfonation cup [4] aromatic hydrocarbons (SC4AD);
2) preparation of supramolecular hydrogel material
SC4AD, methyl viologen are modified to polyvinyl alcohol (PVA-MV) and be dissolved in respectively in distilled water, be prepared into respectively concentration and be the solution of 0.025g/mL; Two kinds of solution of same volume are added drop-wise to respectively in reagent bottle with the speed of 0.5-1mL/min simultaneously, concussion shake up, leave standstill within 30 seconds, can make supramolecular hydrogel.
3. method according to claim 2, is characterized in that: the amount ratio of described cup [4] aromatic hydrocarbons, acetonitrile, sodium hydride, bromododecane hydrocarbon and methylene dichloride is 1mol:15L: 4.25mol:5mol:37.5L.
4. method according to claim 2, is characterized in that: the amount ratio that described dodecyl is modified cup [4] aromatic hydrocarbons, chloroform, chlorsulfonic acid is 1mol:3L:4.25mol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672167A (en) * | 2015-02-13 | 2015-06-03 | 安徽师范大学 | Preparation method of aminothiazole five-membered heterocyclic compound |
| CN104826562A (en) * | 2015-04-21 | 2015-08-12 | 西北师范大学 | Preparation method of supramolecular copolymerization column five-aromatic hydrocarbon gel |
| CN104841342A (en) * | 2015-05-08 | 2015-08-19 | 南开大学 | Fluorescent injectable supramolecular hydrogel and preparation method thereof |
| CN105130882A (en) * | 2015-07-15 | 2015-12-09 | 天津师范大学 | Construction of sulfonated calyx[4]arene-methyl-naphthyl-viologen simulative biologic region selective recognition bionic system |
| CN107033281A (en) * | 2017-05-05 | 2017-08-11 | 南开大学 | Excellent fluorescence hydrogel of a kind of swelling behavior and preparation method thereof |
| CN108586659A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of aromatic modified temperature-sensitive hydrogel of cup [6] and its synthetic method and application |
| CN109206576A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of hybrid cross-linked dynamic aggregation object |
| WO2024027193A1 (en) * | 2022-08-03 | 2024-02-08 | 苏州隽德生物科技有限公司 | Skin-care product composition and pharmaceutical composition comprising sulfonated calixarene, and use of sulfonated calixarene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6069150A (en) * | 1983-09-26 | 1985-04-19 | Kuraray Co Ltd | Modified polyvinyl alcohol composition and use thereof as electron transferring medium |
| CN102304141A (en) * | 2011-05-06 | 2012-01-04 | 南开大学 | Calixarene constructed supramolecular polymer material and preparation method thereof |
| CN102379840A (en) * | 2011-10-17 | 2012-03-21 | 南开大学 | Preparation and application of micromolecular hydrogel with electroresponsive characteristic |
-
2014
- 2014-09-11 CN CN201410459907.4A patent/CN104211970B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6069150A (en) * | 1983-09-26 | 1985-04-19 | Kuraray Co Ltd | Modified polyvinyl alcohol composition and use thereof as electron transferring medium |
| CN102304141A (en) * | 2011-05-06 | 2012-01-04 | 南开大学 | Calixarene constructed supramolecular polymer material and preparation method thereof |
| CN102379840A (en) * | 2011-10-17 | 2012-03-21 | 南开大学 | Preparation and application of micromolecular hydrogel with electroresponsive characteristic |
Non-Patent Citations (1)
| Title |
|---|
| 王魁等: "磺化杯芳烃与紫精客体键合的热力学", 《南师范大学学报（自然科学版）》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672167A (en) * | 2015-02-13 | 2015-06-03 | 安徽师范大学 | Preparation method of aminothiazole five-membered heterocyclic compound |
| CN104826562A (en) * | 2015-04-21 | 2015-08-12 | 西北师范大学 | Preparation method of supramolecular copolymerization column five-aromatic hydrocarbon gel |
| CN104826562B (en) * | 2015-04-21 | 2017-01-04 | 西北师范大学 | A kind of preparation method of supermolecule copolymerization post 5 aromatic hydrocarbons gel |
| CN104841342A (en) * | 2015-05-08 | 2015-08-19 | 南开大学 | Fluorescent injectable supramolecular hydrogel and preparation method thereof |
| CN105130882A (en) * | 2015-07-15 | 2015-12-09 | 天津师范大学 | Construction of sulfonated calyx[4]arene-methyl-naphthyl-viologen simulative biologic region selective recognition bionic system |
| CN107033281A (en) * | 2017-05-05 | 2017-08-11 | 南开大学 | Excellent fluorescence hydrogel of a kind of swelling behavior and preparation method thereof |
| CN107033281B (en) * | 2017-05-05 | 2019-01-15 | 南开大学 | A kind of fluorescence hydrogel and preparation method thereof that swelling behavior is excellent |
| CN109206576A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of hybrid cross-linked dynamic aggregation object |
| CN108586659A (en) * | 2018-04-23 | 2018-09-28 | 佛山市功能高分子材料与精细化学品专业中心 | A kind of aromatic modified temperature-sensitive hydrogel of cup [6] and its synthetic method and application |
| WO2024027193A1 (en) * | 2022-08-03 | 2024-02-08 | 苏州隽德生物科技有限公司 | Skin-care product composition and pharmaceutical composition comprising sulfonated calixarene, and use of sulfonated calixarene |
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