CN103102512B - Chitosan-fullerene compound and preparation method - Google Patents
Chitosan-fullerene compound and preparation method Download PDFInfo
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- CN103102512B CN103102512B CN201310051831.7A CN201310051831A CN103102512B CN 103102512 B CN103102512 B CN 103102512B CN 201310051831 A CN201310051831 A CN 201310051831A CN 103102512 B CN103102512 B CN 103102512B
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Abstract
The invention discloses a chitosan-fullerene compound and a preparation method, wherein the preparation method comprises the following steps: uniformly mixing the fullerene powder and water-soluble chitosan powder, wherein the mass ratio of fullerene powder to water-soluble chitosan is 1:250-1:20; performing ball milling on the uniformly mixed powder in a bowl mill, wherein the ball milling temperature is kept at 15-20 DEG C; dissolving the fully mixed powder after ball milling in a proper amount of water, fully stirring; filtering the stirred solution to remove the insoluble substances to obtain a chitosan-fullerene compound solution; concentrating and drying the obtained chitosan-fullerene compound solution to obtain the chitosan-fullerene compound solid. The prepared chitosan-fullerene compound has good functions of moisture absorption, moisture retention, conditioning, bacteriostasis and the like, excellent biological activity can be guaranteed, good stability is provided, and the moisture retention and antioxidation activity performance can be provided.
Description
Technical field
The present invention relates to fullerene-based material field, particularly relate to a kind of chitosan-fullerene compound and preparation method thereof.
Background technology
In prior art, address this problem and mainly contain two kinds of methods: 1) chemical modification method, namely utilize chemical reaction hydroxyl or carboxyl on Fullerene Carbon cage is modified outward; 2) water-soluble polymer cladding process, namely utilizes the water soluble molecules such as polyoxyethylene glycol (PEG), polyvinylpyrrolidone (PVP), cyclodextrin to be carried out being wrapped to form water-soluble compound by fullerene molecule).
But above-mentioned two kinds of methods are only improve the solubility property of soccerballene in water, alcohol and ester solvent and certain biocompatibility, but with regard to performance, comparatively single, remain and remove free radical this function anti-oxidant, generally not there is the performances such as moisturizing, so the function singleness of existing soccerballene, Application Areas are narrower, be not fully utilized.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of chitosan-fullerene compound and preparation method thereof, be intended to solve the problem that existing fullerene-based material performance is single, do not have moisturizing and anti-oxidant activity concurrently.
Technical scheme of the present invention is as follows:
A preparation method for chitosan-fullerene compound, wherein, comprises step:
S1, fullerene powder mixed with water-soluble chitosan powder, the mass ratio of described fullerene powder and water-soluble chitosan is 1:250 ~ 1:20;
S2, the powder mixed is carried out ball milling in ball mill, ball milling temperature remains on 15 ~ 20 DEG C;
S3, powder well-mixed after ball milling is dissolved in suitable quantity of water, fully stirs;
S4, by stir after solution carry out filtration treatment, filter out insolubles and obtain chitosan-fullerene compound solution;
S5, the chitosan-fullerene compound solution concentrate drying obtained is obtained the solid of chitosan-fullerene compound.
The preparation method of described chitosan-fullerene compound, wherein, described soccerballene is C
60, C
70or C
60with C
70mixture.
The preparation method of described chitosan-fullerene compound, wherein, the mechanical milling process in described step S2 is intermittent type ball milling, ball mill start and stop once: operate after 1 ~ 20 minute, stop 20 ~ 40 minutes, and circulating start and outage totally 200 ~ 1200 minutes.
The preparation method of described chitosan-fullerene compound, wherein, the churning time in described step S3 is 4 ~ 8 hours.
The preparation method of described chitosan-fullerene compound, wherein, the filter sizes that the filtration treatment in described step S4 adopts is 0.2 ~ 1 micron.
The preparation method of described chitosan-fullerene compound, wherein, described filter sizes is 1 micron.
The preparation method of described chitosan-fullerene compound, wherein, the drying in described step S5 carries out drying under adopting vacuum and low temperature.
The preparation method of described chitosan-fullerene compound, wherein, described water-soluble chitosan is cm-chitosan.
A kind of chitosan-fullerene compound, wherein, adopts arbitrary described preparation method to obtain.
Beneficial effect: the present invention by soccerballene and chitosan being carried out mix, ball milling, dissolving stirring, filtration treatment, the process such as vacuum-drying, obtained chitosan-fullerene compound, there is good moisture absorption, moisturizing, conditioning, the function such as anti-oxidant, antibacterial, namely ensure that excellent physiologically active, again there is satisfactory stability, had the performance of moisturizing and anti-oxidant activity concurrently, pole is suitable for having the used for cosmetic of complex function as preparation.
Accompanying drawing explanation
Fig. 1 is the moisture retention schematic diagram of the cm-chitosan in embodiment 4.
Fig. 2 is the moisture retention schematic diagram of the cm-chitosan-fullerene complex in embodiment 4.
Fig. 3 is the free radical removal capacity schematic diagram not adding the blank test of any actives in embodiment 5.
Fig. 4 is the schematic diagram of the removal free radical performance after the interpolation cm-chitosan in embodiment 5.
Fig. 5 is the schematic diagram of the removal free radical performance after the interpolation cm-chitosan-fullerene complex in embodiment 5.
Embodiment
The invention provides a kind of chitosan-fullerene compound and preparation method thereof, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The preparation method of a kind of chitosan-fullerene compound provided by the invention, comprises step:
A, fullerene powder mixed with water-soluble chitosan powder, the mass ratio of described fullerene powder and water-soluble chitosan is 1:250 ~ 1:20;
B, the powder mixed is carried out ball milling in ball mill, ball milling temperature remains on 15 ~ 20 DEG C;
C, powder well-mixed after ball milling is dissolved in suitable quantity of water, fully stirs;
D, by stir after solution carry out filtration treatment, filter out insolubles and obtain chitosan-fullerene compound solution;
E, the chitosan-fullerene compound solution concentrate drying obtained is obtained the solid of chitosan-fullerene compound.
Described soccerballene is preferably C
60, C
70or C
60with C
70mixture, C
60molecule is a kind of molecule be made up of 60 carbon atoms, and likeness in form football, is also called football alkene, C
60namely by C
60molecular composition, C
70character similar to C60, the two can carry out compound with water-soluble chitosan.
Fullerene powder wherein and the mass ratio of water-soluble chitosan range preferably from 1:250 ~ 1:20, under this mass ratio, the composite effect of fullerene powder and chitosan is best, and can make full use of the two anti-oxidant activity and performance of keeping humidity, is retained in obtained mixture.
Mechanical milling process is in stepb intermittent type ball milling, ball mill start and stop once: operate after 1 ~ 20 minute, stop 20 ~ 40 minutes, and circulating start and outage totally 200 ~ 1200 minutes.The present invention adopts the mode of circulating start and outage to carry out ball milling, in order to avoid the molecular structure of long-time ball milling to chitosan and soccerballene causes damage, meanwhile, at the heat that tank body produces in the mechanical milling process that also can leave in the time shut down, be conducive to reducing ball milling temperature.Ball mill is preferably temperature controllable ball mill, namely in described ball mill, arranges a temperature-control device, is used for controlling the ball milling temperature of described ball mill, makes it to remain on 15 ~ 20 DEG C, avoids producing molecule thermo-labile in raw material destroying.
Churning time in described step c is 4 ~ 8h, churning time is too short, mixture stirs insufficient, and long words, easily destroy again the physiologically active of raw material, the present invention preferably adopts the churning time of 4 ~ 8h, can obtain preferably mixing effect, is unlikely to again the stability destroying chitosan and soccerballene.
Filtration treatment in described steps d adopts strainer to filter, and its filter sizes is preferably 0.2 ~ 1 micron.Preferably, this filter sizes is 1 micron.
Drying in described step e carries out drying under adopting vacuum and low temperature.Vacuum dehydrating at lower temperature, can chitosan-fullerene compound at low temperatures described in drying, thus avoid the molecular structure of high temperature to the chitosan-fullerene compound finally prepared to damage, thus ensure that the physiologically active of chitosan-fullerene compound.
In the present invention, described water-soluble chitosan is preferably cm-chitosan, and cm-chitosan has multiple advantageous property, such as moisture absorbability and moisture retentivity, and germ resistance is strong, and the stable in properties of cm-chitosan, can be used as excellent compound material.Visible is, those of ordinary skill in the art, other water-soluble chitosan multiple can be selected to prepare the chitosan-fullerene compound in the present invention, namely all can realize the present invention.
Based on above-mentioned preparation method, the present invention also provides a kind of chitosan-fullerene compound, and it adopts described preparation method to prepare.
Below by embodiment, the present invention is specifically described.
Embodiment 1
5g cm-chitosan and 20mgC
60after soccerballene mixes, move in ball mill.Setting ball mill temperature 15 DEG C, setting ball mill is intermittent type pattern, ball mill start and stop 10 times: often operate 10 minutes, stop 20 minutes.After fully mixing, well-mixed powder is moved in agitator, add 250ml water, fully stir 4h.Select aperture to be the filter membrane of 1 um, decompress filter removes insolubles, and obtaining settled solution, is cm-chitosan-fullerene complex solution.When cm-chitosan-fullerene complex solution is concentrated into 1/3 volume of original volume, is placed in freeze drier and removes moisture, cm-chitosan-fullerene complex solid can be obtained.Because substantially do not have insolubles in filtration procedure, therefore in mixture, the mass percentage of soccerballene is 0.4%.
Embodiment 2
5g cm-chitosan and 100mg C
60after soccerballene mixes, move in ball mill.Setting ball mill temperature 15 DEG C, setting ball mill is intermittent type pattern, ball mill start and stop 20 times: often operate 10 minutes, stop 20 minutes.After fully mixing, well-mixed powder is moved in agitator, add 250ml water, fully stir 8h.Aperture is selected to be the filter membrane of 1 um, decompress filter removes insolubles, obtain settled solution and be cm-chitosan-fullerene complex solution. when cm-chitosan-fullerene complex solution is concentrated into 1/3 volume of original volume, be placed in freeze drier and remove moisture, cm-chitosan-fullerene complex solid can be obtained.In preparation process, filtering the insolubles obtained is soccerballene solid, and weighing after drying is about 20mg, and therefore in cm-chitosan-fullerene complex, the percentage composition of soccerballene is about 1.6%.
Embodiment 3
5g cm-chitosan and 250mg C
60after soccerballene mixes, move in ball mill.Setting ball mill temperature 15 DEG C, setting ball mill is intermittent type pattern, ball mill start and stop 20 times: often operate 20 minutes, stop 40 minutes.After fully mixing, mixed powder is moved in agitator, add 250ml water, fully stir 8h.Select aperture to be the filter membrane of 1 um, decompress filter removes insolubles, obtains settled solution and is cm-chitosan-fullerene complex solution.When cm-chitosan-fullerene complex solution is concentrated into 1/3 volume of original volume, is placed in freeze drier and removes moisture, cm-chitosan-fullerene complex solid can be obtained.Filtering the insolubles obtained is soccerballene solid, and weighing after drying is about 50mg, and therefore, in cm-chitosan-fullerene complex, the percentage composition of soccerballene is about 5%.
Embodiment 4
The moisture retention test of cm-chitosan-fullerene complex:
Formula
, S
i: sample moisturizing rate, %, H
n: moisture content amount after placing, H
0: moisture content amount before placing.
Accurately take embodiment three gained cm-chitosan-fullerene complex 0.5g, after abundant drying, put into the weighing bottle that diameter is 3cm, add the deionized water that massfraction is sample size 10%, be placed in the moisture eliminator that dry silica gel is housed, weigh example weight 4,12,24,36,48,60,72,84,96 little taking-ups constantly respectively, and calculate now water-content, according to formulae discovery moisturizing rate, get the mean value of twice experiment, and be figure.Fig. 1 is the moisture retention of cm-chitosan, and Fig. 2 is the moisture retention of cm-chitosan-fullerene complex.As can be seen from the figure, cm-chitosan-fullerene complex that the present invention prepares has excellent performance of keeping humidity.
Embodiment 5
Cm-chitosan-fullerene complex removes free radical performance test:
Spin trapping method (ESR) is adopted to measure free radical removal effect.Test philosophy is: react for hydrogen peroxide and ferrous ion the free radical produced, utilize DMPO (5,5-dimethyl-1-pyrroline-N-oxide compound) as spin trapping agent, the signal of the product D MPO-OH that detection DMPO and hydroxyl radical reaction generate.
In actual test: the concentration of ferrous sulfate is 0.4 mmol/L, the mass concentration of hydrogen peroxide is 5%, PBS(phosphate buffered saline buffer) pH value be 7.4, the concentration of chitosan-fullerene compound is 25mmol/L, the concentration of DMPO is 0.4 mol/L, respectively gets after above five kinds of solution 50 μ L mix and tests.Fig. 3 is the blank test result not adding any actives, Fig. 4 is the schematic diagram of the removal free radical performance after adding 5000umol/L cm-chitosan 50 μ L, and Fig. 5 adds the schematic diagram that 5000umol/L cm-chitosan-fullerene complex 50 μ L removes free radical performance.From figure, can find out, the removal free radical performance (relative intensity) of cm-chitosan-fullerene complex, greatly improve relative to free radical removal capacity (relative intensity) that is blank and cm-chitosan, namely anti-oxidant activity is improved and shows more stable.
Described in summary, the present invention by soccerballene and chitosan being carried out mix, ball milling, dissolving stirring, filtration treatment, the process such as vacuum-drying, obtained chitosan-fullerene compound, there is good moisture absorption, moisturizing, conditioning, the function such as antibacterial, namely ensure that excellent physiologically active, have satisfactory stability again, had the performance of moisturizing and anti-oxidant activity concurrently, pole is suitable for having the used for cosmetic of complex function as preparation.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (8)
1. a preparation method for chitosan-fullerene compound, is characterized in that, comprises step:
S1, fullerene powder mixed with water-soluble chitosan powder, the mass ratio of described fullerene powder and water-soluble chitosan is 1:250 ~ 1:20;
S2, the powder mixed is carried out ball milling in ball mill, ball milling temperature remains on 15 ~ 20 DEG C;
S3, powder well-mixed after ball milling is dissolved in suitable quantity of water, fully stirs;
S4, by stir after solution carry out filtration treatment, filter out insolubles and obtain chitosan-fullerene compound solution;
S5, the chitosan-fullerene compound solution concentrate drying obtained is obtained the solid of chitosan-fullerene compound;
Mechanical milling process in described step S2 is intermittent type ball milling, ball mill start and stop once: operate after 1 ~ 20 minute, stop 20 ~ 40 minutes, and circulating start and outage totally 200 ~ 1200 minutes.
2. the preparation method of chitosan-fullerene compound according to claim 1, is characterized in that, described soccerballene is C
60, C
70or C
60with C
70mixture.
3. the preparation method of chitosan-fullerene compound according to claim 1, is characterized in that, the churning time in described step S3 is 4 ~ 8 hours.
4. the preparation method of chitosan-fullerene compound according to claim 1, is characterized in that, the filter sizes that the filtration treatment in described step S4 adopts is 0.2 ~ 1 micron.
5. the preparation method of chitosan-fullerene compound according to claim 4, is characterized in that, described filter sizes is 1 micron.
6. the preparation method of chitosan-fullerene compound according to claim 1, is characterized in that, the drying in described step S5 carries out drying under adopting vacuum and low temperature.
7. the preparation method of chitosan-fullerene compound according to claim 1, is characterized in that, described water-soluble chitosan is cm-chitosan.
8. a chitosan-fullerene compound, is characterized in that, adopt as arbitrary in claim 1 to 7 as described in preparation method obtain.
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| CN109077052B (en) * | 2017-06-14 | 2021-09-14 | 北京福纳康生物技术有限公司 | Fullerene structure-based preservative with reduced cytotoxicity and preparation method thereof |
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| CN108904302B (en) * | 2018-08-02 | 2021-01-29 | 北京福纳康生物技术有限公司 | Water-soluble fullerene external composition |
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