CN115124740A - Preparation method and application of hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound - Google Patents
Preparation method and application of hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound Download PDFInfo
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Abstract
The invention provides a preparation method of an antioxidant/anti-saccharification hydrogel containing a fullerene-cyclodextrin water-soluble inclusion compound, which loads the fullerene-cyclodextrin inclusion compound with good water solubility on the hydrogel prepared from chitosan and bentonite. The inclusion compound of fullerene and cyclodextrin prepared by using the water-solubility and the unique hydrophobic cavity of cyclodextrin can greatly increase the solubility of fullerene and enhance the bioavailability of fullerene, so that the prepared hydrogel has the cosmetic effects of oxidation resistance, saccharification resistance and the like, and can be applied to cosmetics. The raw materials of the method provided by the invention can be purchased commercially, the cost is low, the preparation is simple, the hydrogel structure is convenient to process, the used raw materials are recorded in the cosmetic raw material record list, the method is safe and reliable, the effects of oxidation resistance, saccharification resistance and the like are good, and the prepared hydrogel is expected to become a cosmetic raw material with excellent performance.
Description
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to a preparation method and application of hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound.
Background
The fullerene is a nano material with wide application prospect in the field of biological medicine. The skin of a human body can generate a large amount of free radicals after being exposed to the sun and light, and the free radicals can attack cell membranes, so that the skin is loose, aged and wrinkled. The fullerene has strong oxidation resistance which is 172 times of that of vitamin C, can be combined with free radicals to form a compound, converts the free radicals in vivo into harmless products through the process of electron transmission, can effectively prevent skin sunburn and aging, and is called as free radical sponge. Meanwhile, the fullerene adsorbs free radicals, so that the generation of in vivo advanced glycosylation end products (AGEs) can be inhibited, the AGEs are products of in vivo glycosylation reaction, and the AGEs can cause in vivo melanin deposition, and are combined with collagen and elastin in the skin to influence the normal function of cells, so that the skin aging is caused. The fullerene has the cosmetic effects of oxidation resistance and saccharification resistance, and is a cosmetic raw material with wide application prospect; however, its application is greatly limited due to its poor water solubility.
Disclosure of Invention
In view of this, an object of the embodiments of the present invention is to provide a method for preparing a hydrogel containing a fullerene-cyclodextrin water-soluble inclusion compound, and an application of the hydrogel.
The invention provides a preparation method of hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound, which comprises the following steps:
and mixing the fullerene-cyclodextrin inclusion compound aqueous solution with the chitosan-bentonite hydrogel to obtain the fullerene-cyclodextrin water-soluble inclusion compound-containing hydrogel.
Preferably, the preparation method of the fullerene-cyclodextrin inclusion compound aqueous solution comprises the following steps:
mixing fullerene and cyclodextrin, and dissolving in water to obtain fullerene-cyclodextrin inclusion compound water solution.
Preferably, the dissolving method is selected from ultrasonic vibration treatment or stirring under the protection of inert gas.
Preferably, the preparation method of the chitosan-bentonite hydrogel comprises the following steps:
mixing a sodium hydroxide solution and a chitosan-bentonite mixed solution to obtain chitosan-bentonite hydrogel;
the mixing was stirred overnight.
Preferably, the preparation method of the chitosan-bentonite mixed solution comprises the following steps:
mixing the bentonite solution and the chitosan solution to obtain a chitosan-bentonite mixed solution;
the solvent in the bentonite solution is water;
the solvent in the chitosan solution is acetic acid aqueous solution;
the mixing was stirred overnight.
Preferably, the mixing further comprises:
and filtering, washing and dialyzing the obtained mixture to obtain the chitosan-bentonite hydrogel.
Preferably, the cyclodextrin is selected from one or more of beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxypropyl gamma-cyclodextrin, sulfobutyl ether beta-cyclodextrin, sulfobutyl ether gamma-cyclodextrin and sulfobutyl beta-cyclodextrin.
Preferably, the mixing further comprises:
mixing the obtained mixture with antibacterial component to obtain hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound;
said antimicrobial component is selected from AgNO 3 And/or Zn (NO) 3 ) 2 。
Preferably, the bentonite in the bentonite solution is modified bentonite.
The present invention provides a cosmetic comprising: the hydrogel containing the fullerene-cyclodextrin water-soluble inclusion compound is prepared by the method in the technical scheme.
The invention relates to a preparation method of a supramolecular inclusion compound based on cyclodextrin and the technical field of supramolecular polysaccharide biological hydrogel; provides a preparation method of fullerene-cyclodextrin inclusion compound and chitosan-bentonite hydrogel, and the application of the fullerene-cyclodextrin inclusion compound and the chitosan-bentonite hydrogel in the cosmetic fields of oxidation resistance, saccharification resistance and the like. The invention effectively improves the water solubility of fullerene through supermolecular inclusion, and plays an important role in the aspects of increasing the bioavailability, playing the anti-oxidation/anti-saccharification property and the like.
The inclusion compound of fullerene and cyclodextrin prepared by utilizing the water solubility and the unique cavity of cyclodextrin can effectively increase the water solubility of fullerene and enhance the biocompatibility of the fullerene, and is expected to become a cosmetic auxiliary agent with excellent performance.
Drawings
FIG. 1 is a schematic diagram of a hydrogel prepared according to an embodiment of the present invention and a schematic diagram of a preparation route of a fullerene and hydroxypropyl beta-cyclodextrin inclusion compound;
fig. 2 is a picture of an aqueous solution of fullerene and hydroxypropyl beta-cyclodextrin inclusion compound and a freeze-dried solution prepared in example 1 of the present invention;
FIG. 3 is a schematic thermogravimetric diagram of an inclusion compound of fullerene, hydroxypropyl β -cyclodextrin, fullerene and hydroxypropyl β -cyclodextrin in example 1 of the present invention;
fig. 4 is an ultraviolet spectrum of fullerene and aqueous solution of fullerene and cyclodextrin inclusion compound in examples 1 and 3 of the present invention, including: ultraviolet spectrum of fullerene with concentration of 0.02g/L in cyclohexane solution; ultraviolet spectrum of fullerene prepared in example 1 diluted 3 times with hydroxypropyl β -cyclodextrin inclusion aqueous solution; ultraviolet spectrum of fullerene with high fullerene content prepared in example 3 diluted 10 times with hydroxypropyl β -cyclodextrin inclusion compound aqueous solution; ultraviolet spectrum of fullerene with high fullerene content prepared in example 3 diluted 10 times with hydroxypropyl γ -cyclodextrin inclusion compound aqueous solution; ultraviolet spectrum of fullerene with high fullerene content prepared in example 3 diluted 10 times with aqueous solution of γ -cyclodextrin inclusion compound;
FIG. 5 is a photograph of a hydrogel prepared in example 2 of the present invention, including: a chitosan-bentonite hydrogel picture; AgNO loaded 3 A picture of chitosan-bentonite hydrogel of an aqueous solution; a picture of chitosan-bentonite hydrogel loaded with fullerene and hydroxypropyl beta-cyclodextrin inclusion compound;
FIG. 6 is an image of energy modulus as a function of strain for chitosan-bentonite hydrogel prepared in example 2 of the present invention, (a) is an image of G' (storage modulus) and G "(loss modulus); (b) images of G' (storage modulus) and G "(loss modulus) as a function of frequency;
fig. 7 is an image of energy modulus function of chitosan-bentonite hydrogel loaded with fullerene and hydroxypropyl β -cyclodextrin inclusion compound prepared in example 2 of the present invention, (a) is an image of G' (storage modulus) and G "(loss modulus) as a function of strain; (b) images of G' (storage modulus) and G "(loss modulus) as a function of frequency;
fig. 8 shows the effect of ORAC test on scavenging oxygen radicals of fullerene and hydroxypropyl β -cyclodextrin inclusion compound prepared in example 1 of the present invention and the effect of hydroxypropyl β -cyclodextrin blank control group on scavenging oxygen radicals;
FIG. 9 is a graph showing the results of an anti-glycation test performed on the chitosan-bentonite hydrogel prepared in example 2 of the present invention;
fig. 10 is a graph showing the results of an anti-glycation test performed on the hydrogel loaded with fullerene and hydroxypropyl β -cyclodextrin inclusion compound prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound, which comprises the following steps:
and mixing the fullerene-cyclodextrin inclusion compound aqueous solution with the chitosan-bentonite hydrogel to obtain the fullerene-cyclodextrin water-soluble inclusion compound-containing hydrogel.
In the present invention, it is preferable to add a certain amount of the fullerene-cyclodextrin inclusion complex aqueous solution to the chitosan-bentonite hydrogel to obtain an antioxidant/anti-glycation hydrogel containing a fullerene-cyclodextrin water-soluble inclusion complex, as shown in fig. 1.
In the invention, after the fullerene-cyclodextrin water-soluble inclusion compound is loaded on the hydrogel, the structure of the hydrogel is not destroyed, and rheological test results show that the gel still has stable gel performance after the fullerene inclusion compound is loaded. The anti-oxidation/anti-saccharification hydrogel containing the fullerene-cyclodextrin water-soluble inclusion compound has the effects of scavenging free radicals, resisting oxidation, resisting saccharification and the like, is safe and reliable, and is expected to become a cosmetic raw material with excellent performance.
In the invention, the hydrogel is a three-dimensional network which can keep high water content and biological fluidity, and is also a functional polymer material similar to natural biological tissues; the supramolecular biological hydrogel based on cyclodextrin combines the advantages of hydrogel and cyclodextrin, has excellent biocompatibility and high water content, and has excellent application prospect in the aspect of cosmetics.
In the invention, the fullerene-cyclodextrin inclusion compound aqueous solution is prepared from cyclodextrin and fullerene; the preparation method of the fullerene-cyclodextrin inclusion compound aqueous solution preferably comprises the following steps:
mixing fullerene and cyclodextrin, and dissolving in water to obtain fullerene-cyclodextrin inclusion compound water solution.
In the invention, the cyclodextrin is preferably selected from one or more of beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxypropyl gamma-cyclodextrin, sulfobutyl ether beta-cyclodextrin, sulfobutyl ether gamma-cyclodextrin and sulfobutyl beta-cyclodextrin, the inclusion effect and the price factor are combined, and the hydroxypropyl beta-cyclodextrin is most preferably selected.
In the invention, beta-cyclodextrin, gamma-cyclodextrin, hydroxypropyl beta-cyclodextrin, hydroxypropyl gamma-cyclodextrin, sulfobutyl ether beta-cyclodextrin, sulfobutyl ether gamma-cyclodextrin, sulfobutyl beta-cyclodextrin and other cyclodextrins with the same mass are selected to be included with fullerene with the same mass, and all the cyclodextrins can form inclusion compounds with better water solubility, but the inclusion compounds of sulfobutyl beta-cyclodextrin and fullerene are unstable when passing through a 0.8 mu m microporous filter membrane; determining the inclusion rate of cyclodextrin and fullerene through ultraviolet-visible spectrum, and integrating the inclusion effect and price of different types of cyclodextrin, most preferably hydroxypropyl beta-cyclodextrin.
In the invention, the dosage proportion of the fullerene, the cyclodextrin and the water is preferably (0.1-10) mg: (10-100) mg: (5-15) mL, more preferably (0.5-8) mg: (20-80) mg: (8-12) mL, more preferably (1-6) mg: (20-60) mg: 10mL, more preferably (1-4) mg: (20-40) mg: 10mL, most preferably 1 mg: 20 mg: 10 mL.
In the invention, hydroxypropyl beta-cyclodextrin with different mass is used to be included with fullerene with the same mass, the inclusion rate of the cyclodextrin and the fullerene is determined by ultraviolet-visible spectrum, the inclusion effect and the price of hydroxypropyl beta-cyclodextrin with different mass are integrated, and the optimal dosage ratio is that 20mg of hydroxypropyl beta-cyclodextrin and 1mg of fullerene are included.
In the present invention, the fullerene and cyclodextrin mixture preferably includes:
fully grinding the fullerene, adding cyclodextrin for continuously grinding, and then mixing.
In the present invention, the dissolving method is preferably selected from ultrasonic vibration treatment or stirring under the protection of inert gas.
In the present invention, the water is preferably distilled water.
In the present invention, it is preferable that the mixture further comprises:
the resulting mixture was filtered to remove solids, and the filtered precipitate was collected to obtain unreacted fullerene.
In the invention, the filtration is preferably a filter membrane, and more preferably a disposable needle filter membrane; the aperture of the disposable needle filter membrane is preferably 0.6-1.0 μm, more preferably 0.7-0.9 μm, and most preferably 0.8 μm.
In the present invention, it is preferable that the filtration further comprises:
the obtained filtrate was lyophilized to obtain a yellow powder of fullerene-cyclodextrin inclusion compound.
In the present invention, the lyophilization is preferably performed under vacuum.
In the present invention, the preparation method of the fullerene-cyclodextrin inclusion compound aqueous solution preferably includes:
and dissolving the fullerene-cyclodextrin inclusion compound in water to obtain the fullerene-cyclodextrin inclusion compound aqueous solution.
In the present invention, the mass content of the fullerene-cyclodextrin inclusion compound in the fullerene-cyclodextrin inclusion compound aqueous solution is preferably 3.0 to 25.0%, more preferably 5 to 20%, and most preferably 10 to 15%.
In the present invention, the preparation method of the fullerene-cyclodextrin inclusion compound aqueous solution preferably includes:
fully grinding fullerene, adding cyclodextrin for continuous grinding, dissolving the uniformly ground mixture in a proper amount of distilled water, and then performing ultrasonic oscillation treatment or stirring under the protection of inert gas; filtering with disposable needle filter membrane with pore diameter of 0.8 μm to remove solid in the solution, and collecting filtered precipitate as unreacted fullerene; and freeze-drying the filtrate under vacuum condition to obtain yellow powder, namely the fullerene-cyclodextrin inclusion compound.
In the present invention, the method for preparing the fullerene-cyclodextrin inclusion compound aqueous solution more preferably includes:
fully grinding 0.1-10 mg, preferably 1mg, of fullerene, adding 10-100 mg, preferably 20mg, of cyclodextrin, continuously grinding, dissolving the uniformly ground mixture in 10mL of distilled water, and then performing ultrasonic oscillation treatment, or stirring under the protection of inert gas; filtering with disposable needle filter membrane with pore diameter of 0.8 μm to remove solid in the solution, and collecting filtered precipitate as unreacted fullerene; and freeze-drying the filtrate under vacuum condition to obtain yellow powder, namely the fullerene-cyclodextrin inclusion compound.
In the present invention, the method for preparing the chitosan-bentonite hydrogel preferably comprises:
and mixing the sodium hydroxide solution and the chitosan-bentonite mixed solution to obtain the chitosan-bentonite hydrogel.
In the invention, the sodium hydroxide solution is preferably an aqueous sodium hydroxide solution, and the concentration of the sodium hydroxide solution is preferably 0.3-0.7 mol/L, more preferably 0.4-0.6 mol/L, and most preferably 0.5 mol/L.
In the present invention, the preparation method of the chitosan-bentonite mixed solution preferably includes:
and mixing the bentonite solution and the chitosan solution to obtain a chitosan-bentonite mixed solution.
In the present invention, the solvent in the bentonite solution is preferably water, more preferably distilled water, and preferably bentonite is dissolved in distilled water, and the upper suspension is taken to obtain a bentonite solution; the preferable dosage ratio of the bentonite to the water is (300-500) mg: (20-40) mL, more preferably (350-450) mg: (25-35) mL, most preferably 450 mg: 30 mL.
In the invention, the bentonite in the bentonite solution is preferably modified bentonite, more preferably modified bentonite prepared by adding a modifier into the bentonite, and the physical and chemical properties of the hydrogel can be optimized; the above-mentionedThe modifier is preferably selected from sodium modifiers, such as NaCl, Na 2 CO 3 、Na 2 SO 4 Magnesium modifiers, e.g. MgSO 4 、Mg(NO 3 ) 2 And the like.
In the invention, the solvent in the chitosan solution is preferably an acetic acid aqueous solution, more preferably a dilute acetic acid aqueous solution, and the volume concentration of the acetic acid aqueous solution is preferably 1-2%, more preferably 1.5%; the preferable dosage ratio of the chitosan to the acetic acid aqueous solution is (100-1000) mg: (10-30) mL, more preferably (200-800) mg: (15-25) mL, more preferably (300-600) mg: 20mL, most preferably 300 mg: 20 mL.
In the invention, the volume ratio of the bentonite solution to the chitosan solution is preferably (10-30): (10-30), more preferably (15-25): (15-25), most preferably 20: 20.
in the invention, the chitosan is prepared by deacetylating chitin rich in crustacean organisms in nature, is used as a natural polymer, has excellent biological functionality and biocompatibility, is safe and reliable, has excellent moisture retention and antibacterial property in the aspect of cosmetics, can effectively improve the moisture retention performance of the cosmetics, and can inhibit skin inflammation and eliminate acne by eliminating microorganisms such as bacteria, fungi and the like; meanwhile, the chitosan can improve the metabolism and regeneration speed of skin cells, thereby slowing down aging and playing a role in beautifying.
In the present invention, the bentonite solution and the chitosan solution are preferably mixed with stirring overnight.
In the invention, the volume ratio of the sodium hydroxide solution to the chitosan-bentonite mixed solution is preferably (20-40): (30-50), more preferably (25-35): (35-45), most preferably 30: 40.
in the present invention, the sodium hydroxide solution and the chitosan-bentonite mixed solution are mixed, preferably stirred overnight.
In the present invention, it is preferable that the sodium hydroxide solution and the chitosan-bentonite mixed solution further include, after mixing:
and filtering, washing and dialyzing the obtained mixture to obtain the chitosan-bentonite hydrogel.
In the invention, the washing is preferably performed by using distilled water, and the number of washing is preferably 1 to 3, and more preferably 2. In the present invention, the dialysis is preferably performed for 5 days or more using distilled water to remove excess sodium hydroxide; the dialysis preferably further comprises: and filtering the dialyzed solution to obtain the chitosan-bentonite hydrogel.
In the present invention, the method for preparing the chitosan-bentonite hydrogel preferably comprises:
dissolving bentonite in distilled water, and taking an upper suspension; dissolving chitosan in 1-2% dilute acetic acid aqueous solution, adding bentonite suspension uniformly dispersed in distilled water, and stirring overnight; adding 0.5mol/L sodium hydroxide aqueous solution into the chitosan-bentonite mixed solution, stirring overnight, filtering, washing twice with distilled water, dialyzing with distilled water for more than 5 days to remove excessive sodium hydroxide, and filtering the dialyzed solution to obtain the chitosan-bentonite hydrogel.
In the present invention, the method for preparing the chitosan-bentonite hydrogel more preferably comprises:
dissolving 300-500 mg, preferably 450mg of bentonite in 30mL of distilled water, and taking an upper suspension; dissolving 100-1000 mg, preferably 300mg of chitosan in 20mL of 1-2% dilute acetic acid aqueous solution, adding 20mL of bentonite suspension uniformly dispersed in distilled water, and stirring overnight; adding 30mL of 0.5mol/L sodium hydroxide aqueous solution into the chitosan-bentonite mixed solution, stirring overnight, filtering, washing twice with distilled water, dialyzing with distilled water for more than 5 days to remove excessive sodium hydroxide, and filtering the dialyzed solution to obtain the chitosan-bentonite hydrogel.
In the present invention, the mass ratio of the fullerene-cyclodextrin inclusion compound aqueous solution to the chitosan-bentonite hydrogel is preferably (1 to 10): (10-1000), more preferably (2-8): (50-900), more preferably (3-6): (100-800), more preferably (4-5): (200-700), more preferably (4-5): (300-600), most preferably 1: 10.
in the present invention, it is preferable that the aqueous fullerene-cyclodextrin inclusion compound solution and the chitosan-bentonite hydrogel further include, after mixing:
mixing the obtained mixture with antibacterial component to obtain hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound;
the antimicrobial component is selected from AgNO 3 And/or Zn (NO) 3 ) 2 。
In the present invention, the AgNO 3 Preferably AgNO 3 An aqueous solution; said Zn (NO) 3 ) 2 Zn (NO) is preferred 3 ) 2 An aqueous solution; addition of AgNO to hydrogels 3 Or Zn (NO) 3 ) 2 The metal ion doped hydrogel with the antibacterial effect can be obtained by using the aqueous solution.
In the invention, the chitosan-bentonite hydrogel is doped with AgNO 3 Or Zn (NO) 3 ) 2 The hydrogel carrier with good antibacterial performance can be obtained without destroying the original gel structure.
The present invention provides a cosmetic comprising: the hydrogel containing the fullerene-cyclodextrin water-soluble inclusion compound is prepared by the method in the technical scheme.
The invention provides an application of an antioxidant/anti-saccharification hydrogel containing a fullerene-cyclodextrin water-soluble inclusion compound in cosmetics. Compared with other cosmetic raw materials, the anti-oxidation/anti-saccharification hydrogel used in the invention has excellent beautifying effect due to the free radical scavenging capacity and biocompatibility of the water-soluble fullerene, and the used chitosan-bentonite hydrogel carrier is safe and reliable, is easy to prepare, and also has a certain beautifying antibacterial effect. The raw materials for preparing the hydrogel are commercially available, the cost is low, the preparation is simple, the hydrogel structure is convenient to process, the used raw materials are recorded in the cosmetic raw material record list, the hydrogel is safe and reliable, the cosmetic effects of oxidation resistance, saccharification resistance and the like are excellent, and the hydrogel is expected to become a cosmetic raw material with excellent performance.
The invention utilizes the water solubility and unique cavity of cyclodextrin to prepare the fullerene-cyclodextrin inclusion compound, can effectively increase the water solubility of fullerene, and simultaneously uses chitosan and bentonite to prepare hydrogel with beauty treatment effect for loading the fullerene-cyclodextrin inclusion compound.
Example 1 preparation of Water-soluble Fullerene
Fully grinding 1mg of fullerene, adding 20mg of hydroxypropyl beta-cyclodextrin for continuous grinding, dissolving the uniformly ground mixture in 10mL of distilled water, and then performing ultrasonic oscillation treatment for more than 6 hours, or stirring for more than 24 hours under the protection of inert gas; filtering with disposable needle filter membrane with pore diameter of 0.8 μm to remove solid in the solution, and collecting filtered precipitate as unreacted fullerene; and freeze-drying the filtrate under vacuum condition to obtain yellow powder, namely the fullerene-hydroxypropyl beta-cyclodextrin inclusion compound.
20mg of the fullerene-hydroxypropyl beta-cyclodextrin inclusion compound was dissolved in 1mL of water to obtain an aqueous fullerene-hydroxypropyl beta-cyclodextrin inclusion compound solution.
Example 2
Dissolving 450mg of bentonite in 30mL of distilled water, and taking an upper suspension; dissolving 300mg of chitosan into 20mL of dilute acetic acid water solution with volume concentration of 1.5%, adding 20mL of bentonite suspension uniformly dispersed in distilled water, and stirring overnight; adding 30mL of 0.5mol/L sodium hydroxide aqueous solution into the chitosan-bentonite mixed solution, stirring overnight, filtering, washing twice with distilled water, dialyzing with distilled water for more than 5 days to remove excessive sodium hydroxide, and filtering the dialyzed solution to obtain chitosan-bentonite hydrogel;
an aqueous solution containing 20mg of the fullerene-cyclodextrin inclusion compound prepared in example 1 in 1mL was added to 10-15 g of chitosan-bentonite hydrogel to obtain an antioxidant hydrogel containing the fullerene-cyclodextrin water-soluble inclusion compound.
20g of chitosan-bentonite hydrogel and 1mL of AgNO with the mass concentration of 0.2 percent 3 Mixing the aqueous solution to obtain the loaded AgNO 3 Aqueous chitosan solution-bentonite hydrogel.
Example 3 preparation of high Fullerene content Water-soluble Fullerene
Fully grinding 2mg of fullerene, adding 5mg of hydroxypropyl beta-cyclodextrin for continuous grinding, dissolving the uniformly ground mixture in 10mL of distilled water, and then performing ultrasonic oscillation treatment for more than 6 hours, or stirring for more than 24 hours under the protection of inert gas; filtering with disposable needle filter membrane with pore diameter of 0.8 μm to remove solid in the solution, and collecting filtered precipitate as unreacted fullerene; and freeze-drying the filtrate under vacuum condition to obtain yellow powder, namely the fullerene-hydroxypropyl beta-cyclodextrin inclusion compound with high fullerene content.
Replacing hydroxypropyl beta-cyclodextrin with hydroxypropyl gamma-cyclodextrin or gamma-cyclodextrin by the same method to obtain fullerene-hydroxypropyl gamma-cyclodextrin inclusion compound and fullerene-gamma-cyclodextrin inclusion compound with high fullerene content;
20mg of the fullerene-cyclodextrin inclusion compound prepared above was dissolved in 1mL of water to obtain an aqueous fullerene-cyclodextrin inclusion compound solution.
Performance detection
Fig. 2 shows pictures of the fullerene and hydroxypropyl β -cyclodextrin inclusion compound aqueous solution and the lyophilized solution prepared in example 1, and it can be seen that the powder of the aqueous solution and the lyophilized solution is yellow, and the color change can indicate that the cyclodextrin and the fullerene are successfully included.
Thermogravimetric detection is carried out on the fullerene, hydroxypropyl beta-cyclodextrin, fullerene and hydroxypropyl beta-cyclodextrin inclusion compound in example 2 by using a Mettler Toledo TGA 2 type thermogravimetric analyzer (TGA) of Mettler Toledo company of Switzerland Torland at a test temperature of 40-800 ℃ under a nitrogen atmosphere, and a detection result is shown in figure 3.
Using a Shimadazu UV-3600 spectrometer (temperature control device: PTC-348WI) UV-visible spectrophotometer, using a quartz cuvette with an optical path length of 1 cm, UV spectrum detection was performed on fullerene, fullerene and an aqueous solution of an inclusion compound of fullerene and hydroxypropyl β -cyclodextrin in examples 1 and 3, and the detection results are shown in fig. 4, and it can be seen that by comparing the UV spectrum of 0.02g/L of fullerene in a cyclohexane solution with the UV spectrum of fullerene diluted 3 times with an aqueous solution of an inclusion compound of hydroxypropyl β -cyclodextrin, the concentration of fullerene in the aqueous solution of the inclusion compound in example 1 can be calculated according to the lambert beer's law, and the calculated encapsulation rate is 75 to 79%, that is, 3.61 to 3.80mg of fullerene is contained in each 100mg of the inclusion compound; calculating the fullerene concentration in the aqueous solution of the three clathrates in the embodiment 3, wherein the calculated encapsulation rate of the fullerene-hydroxypropyl beta-cyclodextrin clathrate is 71.5-72.5%, namely, each 100mg of clathrate contains 22.20-22.48 mg of fullerene; the encapsulation rate of the fullerene-hydroxypropyl gamma-cyclodextrin inclusion compound is 62.5-64.1%, namely, each 100mg of inclusion compound contains 20.00-20.38 mg of fullerene; the encapsulation rate of the fullerene-gamma-cyclodextrin inclusion compound is 89.5-91.0%, namely, each 100mg of inclusion compound contains 26.36-26.70 mg of fullerene.
Example 2 preparation of Chitosan-Bentonite hydrogel, AgNO Supported 3 Fig. 5 shows pictures of chitosan-bentonite hydrogel in aqueous solution and chitosan-bentonite hydrogel loaded with fullerene and hydroxypropyl beta-cyclodextrin inclusion compound, and it can be seen that chitosan and bentonite can form stable hydrogel and loaded with AgNO 3 The aqueous solution and the inclusion compound of the fullerene and the hydroxypropyl beta-cyclodextrin do not damage the structure of the hydrogel.
An AR 2000ex (TA Instrument) rheometer is used to make strain function images of the storage modulus and the loss modulus of the chitosan-bentonite hydrogel prepared in example 2 on a 40mm flat plate, at 25 ℃, the scanning frequency is fixed at 1Hz, and the strain function images are obtained by performing an oscillation experiment on the gel within the range of 0.1-100%; using an AR 2000ex (TA Instrument) rheometer to make frequency function images of the storage modulus and the loss modulus of the chitosan-bentonite hydrogel on a 40mm flat plate, wherein the fixed stress is 1.0% at 25 ℃, and the frequency function images are obtained by performing oscillation experiments on the gel within the range of 0.1-100.0 rad/s; the detection results are shown in FIG. 6; it can be seen that as the strain increases, G' (storage modulus) is always greater than G "(loss modulus) over a wide range of 0.1 to 100%; in the sweep frequency plot, the relatively large G' and relatively small G "gradually increase and remain substantially parallel as the frequency increases from 0.1rad/s to 100 rad/s; these results are sufficient to demonstrate the high stability of the three-dimensional network of the hydrogel.
According to the method, strain function images and frequency function images are made of the storage modulus and the loss modulus of the chitosan-bentonite hydrogel loaded with the fullerene and hydroxypropyl beta-cyclodextrin inclusion compound prepared in the example 2; the detection results are shown in FIG. 7; it can be seen that as the strain increases, G' (storage modulus) is always greater than G "(loss modulus) over a wide range of 0.1 to 100%; in the sweep frequency curve, the relatively large G' and relatively small G "gradually increase and remain substantially parallel as the frequency increases from 0.1rad/s to 100 rad/s; these results are sufficient to demonstrate the high stability of the three-dimensional network of the hydrogel; meanwhile, the fullerene water-soluble inclusion compound is loaded on the hydrogel, so that the structure of the hydrogel is not destroyed, and the gel still has stable gel performance after the fullerene inclusion compound is loaded.
The ORAC method is adopted to test the scavenging effect of the fullerene-hydroxypropyl beta-cyclodextrin inclusion compound prepared in example 1 on oxygen free radicals and the scavenging effect of hydroxypropyl beta-cyclodextrin as a blank control group, and the detection result is shown in figure 8; AAPH is a free radical initiator which can release free radicals at the temperature of more than 37 ℃, the free radicals can quench the fluorescence emitted by fluorescein, and after an antioxidant substance is added, the antioxidant substance can absorb the free radicals to prevent the free radicals from quenching the fluorescein, and as can be seen from figure 8, the fluorescence quenching speed is slowed down due to the addition of the inclusion compound, which shows that the inclusion compound can eliminate the free radicals and has antioxidant property; the inclusion compound solution added in the detection process is 10 mu L of 1g/L fullerene-hydroxypropyl beta-cyclodextrin inclusion compound solution; in order to demonstrate the effect of fullerene in the inclusion complex on fluorescence quenching, and to exclude the effect of hydroxypropyl β -cyclodextrin itself on the ORAC test, a control experiment was conducted, and it was found that the trend of fluorescence change with time after addition of hydroxypropyl β -cyclodextrin was substantially the same as that without addition, demonstrating that the inclusion complex is indeed antioxidant.
The chitosan-bentonite hydrogel prepared in example 2 was subjected to an anti-glycation test, and the detection method was: glycosylation end products (AGEs) generated by saccharification reaction have fluorescence characteristics, and when the excitation wavelength is 370nm, an obvious fluorescence peak is formed at the position of the emission wavelength of 440 nm; incubating bovine serum albumin and glucose to generate AGEs, incubating a mixed solution of the bovine serum albumin, the glucose and a sample to be detected in a phosphate buffer solution, and evaluating the inhibition effect of the sample to be detected on the AGEs in a reaction solution by testing the fluorescence value of the AGEs, namely the anti-saccharification capacity of the sample to be detected; adopting 1% aminoguanidine hydrochloride as a positive control group as a sample to be tested for testing; the results are shown in FIG. 9, which shows that the chitosan-bentonite hydrogel has anti-glycation ability.
As shown in fig. 10, the anti-glycation test was performed on the hydrogel loaded with fullerene and hydroxypropyl β -cyclodextrin inclusion compound prepared in example 2, and the result of the test is shown in fig. 10, which shows that the anti-glycation effect is improved compared with the case where no fullerene inclusion compound is added, indicating that the fullerene inclusion compound also has anti-glycation ability; the chitosan-bentonite hydrogel loaded with the fullerene and hydroxypropyl beta-cyclodextrin inclusion compound has excellent anti-saccharification capacity.
The invention provides an application of an antioxidant/anti-saccharification hydrogel containing a fullerene-cyclodextrin water-soluble inclusion compound in cosmetics. Compared with other cosmetic raw materials, the anti-oxidation/anti-saccharification hydrogel used in the invention has excellent beautifying effect due to the free radical scavenging capacity and biocompatibility of the water-soluble fullerene, and the used chitosan-bentonite hydrogel carrier is safe and reliable, is easy to prepare, and also has a certain beautifying antibacterial effect. The raw materials for preparing the hydrogel are commercially available, the cost is low, the preparation is simple, the hydrogel structure is convenient to process, the used raw materials are recorded in the cosmetic raw material record list, the hydrogel is safe and reliable, the cosmetic effects of oxidation resistance, saccharification resistance and the like are excellent, and the hydrogel is expected to become a cosmetic raw material with excellent performance.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A method for preparing hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound comprises the following steps:
and mixing the fullerene-cyclodextrin inclusion compound aqueous solution with the chitosan-bentonite hydrogel to obtain the fullerene-cyclodextrin water-soluble inclusion compound-containing hydrogel.
2. The method of claim 1, wherein the preparation of the aqueous fullerene-cyclodextrin inclusion solution comprises:
mixing fullerene and cyclodextrin, and dissolving in water to obtain fullerene-cyclodextrin inclusion compound water solution.
3. The method according to claim 2, wherein the dissolving is performed by a method selected from ultrasonic vibration treatment or stirring under an inert gas shield.
4. The method of claim 1, wherein the chitosan-bentonite hydrogel is prepared by a method comprising:
mixing a sodium hydroxide solution and a chitosan-bentonite mixed solution to obtain chitosan-bentonite hydrogel;
the mixing was stirred overnight.
5. The method according to claim 4, wherein the chitosan-bentonite mixed solution is prepared by a method comprising:
mixing the bentonite solution and the chitosan solution to obtain a chitosan-bentonite mixed solution;
the solvent in the bentonite solution is water;
the solvent in the chitosan solution is acetic acid aqueous solution;
the mixing was stirred overnight.
6. The method of claim 4, further comprising, after said mixing:
and filtering, washing and dialyzing the obtained mixture to obtain the chitosan-bentonite hydrogel.
7. The method according to claim 2, wherein the cyclodextrin is selected from one or more of β -cyclodextrin, γ -cyclodextrin, hydroxypropyl β -cyclodextrin, hydroxypropyl γ -cyclodextrin, sulfobutyl ether β -cyclodextrin, sulfobutyl ether γ -cyclodextrin, sulfobutyl β -cyclodextrin.
8. The method of claim 1, further comprising, after said mixing:
mixing the obtained mixture with antibacterial component to obtain hydrogel containing fullerene-cyclodextrin water-soluble inclusion compound;
the antimicrobial component is selected from AgNO 3 And/or Zn (NO) 3 ) 2 。
9. The method according to claim 3, wherein the bentonite in the bentonite solution is a modified bentonite.
10. A cosmetic product comprising: the hydrogel containing a fullerene-cyclodextrin water-soluble inclusion compound prepared by the method of claim 1.
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