CN103553021A - Water-soluble poly gamma cyclodextrin-C60 supermolecule clathrate compound as well as preparation method thereof - Google Patents
Water-soluble poly gamma cyclodextrin-C60 supermolecule clathrate compound as well as preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble poly gamma cyclodextrin-C60 supermolecule clathrate compound as well as a preparation method thereof, and relates to the technical field of supramolecular chemistry. The preparation method comprises the following steps of: placing the poly gamma cyclodextrin and fullerene C60 in ultrasonic treatment after mixing and stirring by using water as a solvent, and carrying out rotary evaporation until the mixture is thick; and then, obtaining the water-soluble poly gamma cyclodextrin-C60 supermolecule clathrate compound through vacuum-drying. The prepared clathrate compound contains a complex of 1wt%-50wt% of the poly gamma cyclodextrin, and concentration of the lathrate compound for dispersing the fullerene C60 in water is 10g/L. According to the invention, non-covalent bonds interact, water is used as the solvent, and the poly gamma cyclodextrin is used as a solubilizer, so that negative ion liquor pretreatment does not needed to be carried out onto C60, and the structure of the C60 is not damaged. The method disclosed by the invention is simple and convenient to operate, easily controllable in condition and capable of realizing industrialization.
Description
Technical field
The present invention relates to supramolecular chemistry technical field, particularly there is the production technical field of the cyclodextrin of hydrophobic cavity, also relate to and improve soccerballene C
60water miscible technical field.
Background technology
Supramolecular chemistry is about some chemical species, by molecular interaction, to combine formed, and has the chemistry of higher complexity and certain systematical integral body.In this integral body, each component also keeps some intrinsic physics and chemistry character, simultaneously again because of to each other influence each other or disturbance shows some allomeric function.The microscopic units of supramolecular system be can Individual existence by the molecule of some and even various different compounds or ion or other the particles agglomerate with certain chemical property form.Aggregation number can determine or be uncertain, and this and a part Atom number are strictly determined and had essential distinction.The Host-guest Recognition of ring molecule is to form supramolecular one of them important means, it is found that the ring molecule that contains hollow endoporus as: crown ether, cyclodextrin, Cucurbituril, Polycyclic aromatic hydrocarbons etc. are due to its unique hollow inner hole structure, can with the form of self-assembly, be combined together to form molecular assembly body, i.e. supramolecule with specific molecule.
Cyclodextrin has hydrophobic cavity as the s-generation " supramolecule ", and can inclusion many inorganic, organic and chirality guest molecules form host-guest or super molecular complexes, so it is used widely in supramolecular chemistry research.γ-cyclodextrin (being called for short γ-CD) is by cyclodextrin glycosyltransferase, to act on starch to produce, " cone bucket " the shape molecule being combined into α-Isosorbide-5-Nitrae glycosidic link by 7 D-glucopyranose units.The special molecular structure of its " interior hydrophobic, outer hydrophilic ", can, as different " object " compound of " host " envelope, form the inclusion complex of special construction.Along with going deep into of Cyclodextrin Chemistry research, cyclodextrin is divided into from structure: the pendant type bonding on linear macromolecular chain, with the network that chemical bond is fixed in the middle of net high-polymer chain, bifunctional monomer and cyclodextrin hydroxyl crosslinking polymerization, linear macromolecular chain embed macromolecular chain through most cyclodextrin moleculars, cyclodextrin molecular with intermolecular forces, neutralize that with physical method, to be fixed to natural polymer subchain first-class.The theoretical investigation of γ-CD and derivative thereof and practical application development are rapidly.
Soccerballene C
60after diamond and graphite, British scientist Harod W. Kroto and American scientist Robert F. Curl, Richard E. Smalley equal a kind of atom family material being comprised of 60 carbon atoms of finding near the forming process of carbon atom family simulation interplanetary and fixed star in 1985, the third allotropic substance of the carbon of similar Association football.In recent years, the biological activity of fullerene compound attracts much attention gradually, and the aspect such as that preliminary study shows is viral, antitumor at HIV, inhibition of enzyme activity, cutting DNA, photodynamic therapy has unique effect.This compounds all shows tempting application prospect in fields such as superconduction, electricity, magnetics, optics, catalysis, polymer, materialogy, biochemistry, medical science, pharmacology.Estimate C
60in high-tech sectors such as type material, computer and full optical communications, also will be widely used.
C
60these characteristics caused biologist, medicine scholar's great interest.Existing many research groups biological activity of soccerballene and derivative thereof that begins one's study in the past few years, and obtained some challenging results.Yet, C
60intrinsic hydrophobicity, is restricted its research and application in various fields.Therefore, how to increase C
60water-solublely become a difficult problem in the urgent need to address.
Summary of the invention
The object of the invention is to propose a kind of C that do not destroy
60under the prerequisite of self structure, solve C
60the water-soluble poly γ cyclodextrin-C of the solvability in water and stability
60super molecule inclusion compound.
The mixture that contains the poly-γ cyclodextrin of 1～50 wt% in inclusion compound of the present invention, inclusion compound disperses soccerballene C in water
60concentration be 10 g/L.
In inclusion compound of the present invention, poly-γ cyclodextrin plays the effect of solubilising, makes poly-γ cyclodextrin-C
60super molecule inclusion compound has well water-soluble, and does not destroy C
60intrinsic characteristic.Poly-γ cyclodextrin and C
60between there is non-covalent interaction, under ultrasound condition, just can in water, form stable, homodisperse inclusion complex in solution.
The advantage of inclusion compound of the present invention is, C
60this solvability in water is very poor, and poly-γ cyclodextrin and C
60the solubleness of inclusion compound in water be 10 g/L.Soccerballene is only soluble in some nonpolar and organic solvents low-pole, as benzene, toluene, etc., in water isopolarity solvent, be difficult to dissolve, but living things system is all the water-soluble system that obtains, this has hindered the development of soccerballene at biomedicine field, so the synthetic of water-soluble fullerene is the prerequisite that soccerballene is applied in biological medicine.
The present invention also proposes the preparation method of above inclusion compound.
The present invention is usingd water as solvent, will gather γ cyclodextrin and soccerballene C
60after mix and blend, be placed in after supersound process, then be rotated and be evaporated to thickly, then through vacuum-drying, obtain water-soluble poly γ cyclodextrin-C
60super molecule inclusion compound.
The present invention utilizes non-covalent interaction, usings water as solvent, serves as solubilizing agent, to C to gather γ cyclodextrin
60without carrying out negative solution pre-treatment, do not destroy C
60the structure of self.Method is easy and simple to handle, and condition is easily controlled, and can realize industrialization.
Concrete steps of the present invention comprise:
1) stirring at room, is dissolved in the NaOH aqueous solution γ cyclodextrin, then, under 30 ℃ of envrionment temperatures, adds epoxy chloropropane, after mixing, is cooled to room temperature, obtains mixing solutions; By dialysis method, remove after the salt in mixing solutions, then mixing solutions steamed to thick, then add dehydrated alcohol to separate out white solid, more after filtration, vacuum-drying, obtain water-soluble poly γ cyclodextrin;
2) by soccerballene C
60even with water-soluble poly γ cyclodextrin mixed grinding, obtain C
60mixture with poly-γ cyclodextrin;
3) by C
60mix with water with the mixture of poly-γ cyclodextrin, at room temperature stir, obtain brown yellow solution, then by brown yellow solution sonic oscillation at room temperature, obtain stable C
60the aqueous solution;
4) by C
60the aqueous solution be rotated be evaporated to thick, and then vacuum-drying.
Separately, γ cyclodextrin of the present invention and soccerballene C
60the mass ratio that feeds intake be 400 ︰ 1.The advantage of this ingredient proportion is to make the purity of the final inclusion compound obtaining the highest.
The concentration of the aqueous solution of NaOH described in step 1) is 30wt%, and the ratio of mixture of γ cyclodextrin and the NaOH aqueous solution is 1g ︰ 2 mL.The concentration advantage of this NaOH aqueous solution is that the solubleness of γ cyclodextrin in the NaOH aqueous solution is best.
The advantage of above blending ratio is easy control of reaction system, and the product purity of acquisition is higher, and inclusion compound is water-soluble better.
Vacuum drying vacuum tightness described in step 1) is 1200～4800Pa, and temperature is 50～70 ℃.The dry rate of drying that can accelerate sample under the condition of vacuum, temperature is arranged between 50～70 ℃ can guarantee that inclusion compound can be not destroyed because of excess Temperature.
The feed ratio of the γ cyclodextrin in water described in step 3) and step 1) is 1g ︰ 5mL.The advantage of this feed ratio is that γ cyclodextrin can well be dispersed in solution.
The frequency of step 3) sonic oscillation is 60KHz.The advantage of this ultrasonic frequency is to obtain the stable C60 aqueous solution, and can not destroy inclusion compound.
Vacuum drying vacuum tightness described in step 4) is 1200～4800Pa, and temperature is 50～70 ℃, and the time is 24 h.The advantage of this vacuum-drying condition is the dry rate of drying that can accelerate sample under the condition of vacuum, and temperature is arranged between 50～70 ℃ can guarantee that inclusion compound can be not destroyed because of excess Temperature.
Accompanying drawing explanation
Fig. 1 is poly-γ cyclodextrin-C prepared by the present invention
60the digital photograph figure of the super molecule inclusion compound aqueous solution.
Fig. 2 is poly-γ cyclodextrin-C prepared by the present invention
60the ultraviolet-visible absorption spectroscopy figure of super molecule inclusion compound.
Embodiment
One, prepare water-soluble poly γ cyclodextrin-C
60super molecule inclusion compound
1, prepare water-soluble γ-CD polymkeric substance
20 g γ-CD are added in the 40 mL 30wt% NaOH aqueous solution, and stirring at room treats that γ-CD dissolves.Under 30 ℃ of water-baths, then 15 mL epoxy chloropropane are added in mixture, stir 24 h, be cooled to room temperature.First by dialysis method except after desalting, then solution is steamed to thick, add dehydrated alcohol to separate out white solid, filter, vacuum-drying 24 h(vacuum tightnesss are 1200～4800 Pa, drying temperature is 50～70 ℃), obtain water-soluble γ-CD polymkeric substance.
2, preparation C
60mixture with poly-γ cyclodextrin
Take 50 mg C
60water-soluble γ-CD polymkeric substance 300～500 mg with upper step is made, are placed in agate mortar, grind 10～15 min, and it is mixed, and obtain C
60mixture with poly-γ cyclodextrin.
3, preparation C
60the aqueous solution
By the C of above-mentioned acquisition
60be placed in 100 mL water with the mixture of poly-γ cyclodextrin, at room temperature stir, 100～150 revs/min of stirring velocitys, stir 2～3 h, obtain brown yellow solution.Again by brown yellow solution sonic oscillation 1～2 h(sonic oscillation frequency 60KHz at room temperature), obtain stable C
60the aqueous solution.
4, prepare water-soluble poly γ cyclodextrin-C
60super molecule inclusion compound
By C
60the aqueous solution is rotated evaporation, is distilled to thickly, and then to carry out vacuum-drying 24 h(vacuum tightnesss be 1200～4800Pa, and drying temperature is 50～70 ℃), last product is brown color solid, i.e. poly-γ cyclodextrin-C
60super molecule inclusion compound.
Two, product performance
1, the product of making is carried out to digital photographing, see the digital photograph of Fig. 1.
2, the product of making is carried out to spectroscopic analysis,, as can be seen from Fig. 2, there are two C at wavelength approximately 275 nm and 350 nm places in ultraviolet-visible absorption spectroscopy figure as shown in Figure 2
60charateristic avsorption band, poly-γ cyclodextrin-C is described
60super molecule inclusion compound has the water miscible C that simultaneously do not destroy
60intrinsic characteristic.
3, the mixture that contains the poly-γ cyclodextrin of 1～50 wt% in inclusion compound, inclusion compound disperses soccerballene C in water
60concentration be 10 g/L.
Three, product application prospect example
Preliminary study shows that the aspects such as fullerene compound is viral, antitumor at HIV, inhibition of enzyme activity, cutting DNA, photodynamic therapy have unique effect.Poly-γ cyclodextrin-C that the present invention synthesizes
60super molecule inclusion compound greatly increases C
60water-soluble, can effectively solve the problem of biocompatibility.For example, in tumour cell, add the synthetic inclusion compound of the present invention, under illumination, C
60can produce the oxygen of singlet, can kill tumour cell, therefore, this inclusion compound has good application prospect aspect therapeutic treatment.
Claims (9)
1. a water-soluble poly γ cyclodextrin-C
60super molecule inclusion compound, is characterized in that: in inclusion compound, contain the mixture of the poly-γ cyclodextrin of 1～50 wt%, inclusion compound disperses soccerballene C in water
60concentration be 10 g/L.
2. water-soluble poly γ cyclodextrin-C as claimed in claim 1
60the preparation method of super molecule inclusion compound, is characterized in that: using water as solvent, will gather γ cyclodextrin and soccerballene C
60after mix and blend, be placed in after supersound process, then be rotated and be evaporated to thickly, then vacuum-drying, obtains water-soluble poly γ cyclodextrin-C
60super molecule inclusion compound.
3. preparation method according to claim 2, is characterized in that comprising the following steps:
1) stirring at room, is dissolved in the NaOH aqueous solution γ cyclodextrin, then, under 30 ℃ of envrionment temperatures, adds epoxy chloropropane, after mixing, is cooled to room temperature, obtains mixing solutions; By dialysis method, remove after the salt in mixing solutions, then mixing solutions steamed to thick, then add dehydrated alcohol to separate out white solid, more after filtration, vacuum-drying, obtain water-soluble poly γ cyclodextrin;
2) by soccerballene C
60even with water-soluble poly γ cyclodextrin mixed grinding, obtain C
60mixture with poly-γ cyclodextrin;
3) by C
60mix with water with the mixture of poly-γ cyclodextrin, at room temperature stir, obtain brown yellow solution, then by brown yellow solution sonic oscillation at room temperature, obtain stable C
60the aqueous solution;
4) by C
60the aqueous solution be rotated be evaporated to thick, and then vacuum-drying.
4. preparation method according to claim 3, is characterized in that described γ cyclodextrin and soccerballene C
60the mass ratio that feeds intake be 400 ︰ 1.
5. preparation method according to claim 3, the concentration that it is characterized in that the aqueous solution of NaOH described in step 1) is 30wt%, the ratio of mixture of γ cyclodextrin and the NaOH aqueous solution is 1g ︰ 2 mL.
6. preparation method according to claim 3, is characterized in that vacuum drying vacuum tightness described in step 1) is 1200～4800Pa, and temperature is 50～70 ℃.
7. preparation method according to claim 3, the feed ratio that it is characterized in that the γ cyclodextrin in water described in step 3) and step 1) is 1 g ︰ 5 mL.
8. preparation method according to claim 3, the frequency that it is characterized in that step 3) sonic oscillation is 60KHz.
9. preparation method according to claim 3, is characterized in that vacuum drying vacuum tightness described in step 4) is 1200～4800Pa, and temperature is 50～70 ℃, and the time is 24 h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105267975A (en) * | 2015-10-10 | 2016-01-27 | 扬州大学 | Preparation method of poly gamma cyclodextrin-paclitaxel supermolecular anticancer drug |
| CN106491547A (en) * | 2016-11-25 | 2017-03-15 | 北京福纳康生物技术有限公司 | A kind of endohedral tablet and preparation method |
| CN110105585A (en) * | 2019-06-04 | 2019-08-09 | 南开大学 | A kind of polyrotaxane shape two dimension supermolecule nano assembly system and preparation method and application of light reaction driving |
| CN110339821A (en) * | 2019-08-08 | 2019-10-18 | 卫革 | A kind of method and apparatus preparing adsorbent for heavy metal using fullerene |
| CN112442304A (en) * | 2020-11-23 | 2021-03-05 | 成都市富百乐装饰材料实业有限公司 | Multifunctional ecological negative ion coating and preparation method thereof |
| CN114085298A (en) * | 2021-11-30 | 2022-02-25 | 扬州大学 | Water-soluble supramolecular inclusion compound DPG and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105267975A (en) * | 2015-10-10 | 2016-01-27 | 扬州大学 | Preparation method of poly gamma cyclodextrin-paclitaxel supermolecular anticancer drug |
| CN106491547A (en) * | 2016-11-25 | 2017-03-15 | 北京福纳康生物技术有限公司 | A kind of endohedral tablet and preparation method |
| CN110105585A (en) * | 2019-06-04 | 2019-08-09 | 南开大学 | A kind of polyrotaxane shape two dimension supermolecule nano assembly system and preparation method and application of light reaction driving |
| CN110105585B (en) * | 2019-06-04 | 2021-06-29 | 南开大学 | Photoreaction-driven poly-rotaxane-shaped two-dimensional supramolecular nano assembly system and preparation method and application thereof |
| CN110339821A (en) * | 2019-08-08 | 2019-10-18 | 卫革 | A kind of method and apparatus preparing adsorbent for heavy metal using fullerene |
| CN112442304A (en) * | 2020-11-23 | 2021-03-05 | 成都市富百乐装饰材料实业有限公司 | Multifunctional ecological negative ion coating and preparation method thereof |
| CN112442304B (en) * | 2020-11-23 | 2021-08-31 | 成都市富百乐装饰材料实业有限公司 | Multifunctional ecological negative ion coating and preparation method thereof |
| CN114085298A (en) * | 2021-11-30 | 2022-02-25 | 扬州大学 | Water-soluble supramolecular inclusion compound DPG and preparation method and application thereof |
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Application publication date: 20140205 |