CN103102512B - Chitosan-fullerene compound and preparation method - Google Patents

Abstract

The invention discloses a chitosan-fullerene compound and a preparation method thereof, wherein the preparation method comprises the steps of uniformly mixing fullerene powder and water-soluble chitosan powder, and mixing the fullerene powder and The mass ratio of water-soluble chitosan is 1:250~1:20; the uniformly mixed powder is ball milled in a ball mill, and the ball milling temperature is kept at 15~20°C; the fully mixed powder after ball milling is dissolved in an appropriate amount of water, fully Stirring; filtering the stirred solution, filtering out insolubles to obtain a chitosan-fullerene complex solution; concentrating and drying the obtained chitosan-fullerene complex solution to obtain chitosan-fullerene Composite solids. The chitosan-fullerene compound prepared by the present invention has good functions such as moisture absorption, moisturizing, conditioning and antibacterial, which ensures excellent physiological activity and good stability, and has both moisturizing and antibacterial properties. properties of oxidation activity.

Description

A kind of chitosan-fullerene compound and preparation method thereof

technical field

The invention relates to the field of fullerene materials, in particular to a chitosan-fullerene composite and a preparation method thereof.

Background technique

In the prior art, there are two main methods to solve this problem: 1) chemical modification method, that is, using chemical reaction to modify the hydroxyl or carboxyl group outside the fullerene carbon cage; 2) water-soluble polymer coating method, that is, using Water-soluble molecules such as polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and cyclodextrin wrap fullerene molecules to form a water-soluble complex).

However, the above two methods only improve the solubility of fullerene in water, alcohol and ester solvents and certain biocompatibility, but in terms of performance, they are relatively simple, and they still have the function of removing free radicals and anti-oxidation. , generally do not have properties such as moisturizing, so the existing fullerenes have single functions and narrow application fields, and have not been fully utilized.

Therefore, the prior art still needs to be improved and developed.

Contents of the invention

In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a chitosan-fullerene composite and a preparation method thereof, aiming at solving the problem that the existing fullerene materials have single performance, do not have both moisturizing and anti-oxidation properties. The question of activity.

Technical scheme of the present invention is as follows:

A kind of preparation method of chitosan-fullerene compound, wherein, comprise steps:

S1, mixing fullerene powder and water-soluble chitosan powder evenly, the mass ratio of described fullerene powder and water-soluble chitosan is 1:250～1:20;

S2. Milling the uniformly mixed powder in a ball mill, keeping the milling temperature at 15-20°C;

S3. Dissolve the fully mixed powder after ball milling in an appropriate amount of water and stir thoroughly;

S4, filtering the stirred solution, filtering out insolubles to obtain a chitosan-fullerene complex solution;

S5. Concentrating and drying the obtained chitosan-fullerene complex solution to obtain a solid chitosan-fullerene complex.

The preparation method of the chitosan-fullerene complex, wherein the fullerene is C ₆₀ , C ₇₀ or a mixture of C ₆₀ and C ₇₀ .

The preparation method of the chitosan-fullerene compound, wherein, the ball milling process in the step S2 is intermittent ball milling, and the ball mill is started and stopped once: after running for 1 to 20 minutes, stop for 20 to 40 minutes, and Cycle start and stop for a total of 200~1200 minutes.

The preparation method of the chitosan-fullerene complex, wherein the stirring time in the step S3 is 4 to 8 hours.

The preparation method of the chitosan-fullerene complex, wherein the filter membrane pore size used in the filtration treatment in the step S4 is 0.2-1 micron.

The preparation method of the chitosan-fullerene complex, wherein the filter membrane pore size is 1 micron.

The preparation method of the chitosan-fullerene complex, wherein, the drying in the step S5 is carried out under vacuum and low temperature.

The preparation method of the chitosan-fullerene complex, wherein the water-soluble chitosan is carboxymethyl chitosan.

A kind of chitosan-fullerene complex, wherein, adopt any described preparation method to make.

Beneficial effects: the chitosan-fullerene complex prepared by the present invention has good hygroscopicity, moisture retention, Conditioning, anti-oxidation, antibacterial and other functions, not only ensure excellent physiological activity, but also have good stability, and have the performance of moisturizing and anti-oxidation activity, which is very suitable for the preparation of cosmetics with complex functions.

Description of drawings

Fig. 1 is the moisture retention schematic diagram of the carboxymethyl chitosan in embodiment 4.

Figure 2 is a schematic diagram of the moisture retention of the carboxymethyl chitosan-fullerene complex in Example 4.

Fig. 3 is a schematic diagram of the free radical removal performance of the blank test without adding any active substance in Example 5.

Figure 4 is a schematic diagram of the free radical removal performance after adding carboxymethyl chitosan in Example 5.

FIG. 5 is a schematic diagram of the free radical removal performance after adding carboxymethyl chitosan-fullerene complex in Example 5. FIG.

Detailed ways

The present invention provides a chitosan-fullerene complex and a preparation method thereof. In order to make the purpose, technical scheme and effect of the present invention clearer and clearer, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

A kind of preparation method of chitosan-fullerene compound provided by the invention comprises steps:

A, mixing fullerene powder and water-soluble chitosan powder evenly, the mass ratio of described fullerene powder and water-soluble chitosan is 1:250～1:20;

b. Mill the uniformly mixed powder in a ball mill, and keep the milling temperature at 15-20°C;

c. Dissolve the fully mixed powder after ball milling in an appropriate amount of water and stir thoroughly;

d, the stirred solution is filtered, and the insolubles are filtered out to obtain a chitosan-fullerene complex solution;

e. Concentrating and drying the obtained chitosan-fullerene complex solution to obtain a solid chitosan-fullerene complex.

The fullerene is preferably C ₆₀ , C ₇₀ or a mixture of C ₆₀ and C _70. The C ₆₀ molecule is a molecule made of 60 carbon atoms, resembling a football, also known as footballene, and C ₆₀ consists of The molecular composition of C ₆₀ and the properties of C ₇₀ are similar to those of C60, both of which can be compounded with water-soluble chitosan.

Wherein the range of the mass ratio of fullerene powder and water-soluble chitosan is preferably 1:250～1:20, under this mass ratio, the composite effect of fullerene powder and chitosan is the best, and can make full use of The antioxidant activity and moisturizing properties of both are retained in the resulting complex.

The ball milling process in step b is intermittent ball milling, and the ball mill is started and stopped once: after running for 1 to 20 minutes, stop for 20 to 40 minutes, and cycle the start and stop for a total of 200 to 1200 minutes. The present invention adopts the mode of cycle start-stop to carry out ball milling, in order to avoid damage to the molecular structure of chitosan and fullerene caused by ball milling for a long time, and at the same time, it can also dissipate the oil generated in the tank during the ball milling process during the stoppage of operation. The heat is beneficial to reduce the temperature of ball milling. The ball mill is preferably a temperature-controllable ball mill, that is, a temperature control device is installed in the ball mill to control the milling temperature of the ball mill to keep it at 15-20°C to avoid damage to heat-labile molecules in the raw material.

The stirring time in the step c is 4 ~ 8h, if the stirring time is too short, the stirring of the mixture is insufficient, and if it is too long, it is easy to destroy the physiological activity of the raw material. The present invention preferably adopts the stirring time of 4 ~ 8h, which can A better stirring effect can be obtained without destroying the stability of chitosan and fullerene.

The filtration treatment in the step d is to use a filter to filter, and the filter membrane pore size is preferably 0.2-1 micron. Preferably, the filter membrane has a pore size of 1 micron.

The drying in the step e is carried out under vacuum and low temperature. Vacuum low-temperature drying can dry the chitosan-fullerene complex at a low temperature, thereby avoiding high temperature damage to the molecular structure of the final prepared chitosan-fullerene complex, thereby ensuring chitosan Physiological activity of sugar-fullerene complexes.

Among the present invention, described water-soluble chitosan is preferably carboxymethyl chitosan, and carboxymethyl chitosan has multiple excellent properties, such as moisture absorption and moisture retention, strong antibacterial property, etc., and carboxymethyl chitosan The properties are stable and can be used as an excellent compound raw material. It can be seen that those skilled in the art can choose various other water-soluble chitosans to prepare the chitosan-fullerene complex in the present invention, that is, all of them can realize the present invention.

Based on the above preparation method, the present invention also provides a chitosan-fullerene composite, which is prepared by the above preparation method.

The present invention will be described in detail below by way of examples.

Example 1

After 5g of carboxymethyl chitosan and 20mg of C ₆₀ fullerene are mixed evenly, move to the ball mill. Set the temperature of the ball mill to 15°C, set the ball mill to the intermittent mode, and start and stop the ball mill 10 times: every time it runs for 10 minutes, it stops for 20 minutes. After fully mixing evenly, move the fully mixed powder into a blender, add 250ml of water, and stir thoroughly for 4 hours. A filter membrane with a pore size of 1 um was selected, and the insoluble matter was removed by suction filtration under reduced pressure to obtain a clear solution, which was a carboxymethyl chitosan-fullerene complex solution. When the carboxymethyl chitosan-fullerene complex solution is concentrated to 1/3 of the original volume, it is placed in a freeze dryer to remove water, and the carboxymethyl chitosan-fullerene complex can be obtained solid. Because there is basically no insoluble matter in the filtration process, the mass percentage of fullerene in the composite is 0.4%.

Example 2

After 5g of carboxymethyl chitosan and 100mg of C ₆₀ fullerene were mixed uniformly, they were transferred to a ball mill. Set the temperature of the ball mill to 15°C, set the ball mill to intermittent mode, and start and stop the ball mill 20 times: every time it runs for 10 minutes, it stops for 20 minutes. After fully mixing evenly, move the fully mixed powder into a blender, add 250ml of water, and stir thoroughly for 8 hours. Select a filter membrane with a pore size of 1 um, remove the insoluble matter by suction filtration under reduced pressure, and obtain a clear solution that is the carboxymethyl chitosan-fullerene complex solution. The carboxymethyl chitosan-fullerene complex solution When it is concentrated to 1/3 of the original volume, it is placed in a freeze dryer to remove water, and the carboxymethyl chitosan-fullerene complex solid can be obtained. During the preparation process, the insoluble matter obtained by filtration is fullerene solid, which weighs about 20 mg after drying, so the percentage of fullerene in the carboxymethyl chitosan-fullerene composite is about 1.6%. .

Example 3

After 5g carboxymethyl chitosan and 250mg C ₆₀ fullerene are mixed uniformly, move in the ball mill. Set the temperature of the ball mill to 15°C, set the ball mill to the intermittent mode, and start and stop the ball mill 20 times: every time it runs for 20 minutes, it stops for 40 minutes. After fully mixing evenly, move the mixed powder to a blender, add 250ml of water, and stir thoroughly for 8 hours. A filter membrane with a pore size of 1 um was selected, and the insoluble matter was removed by vacuum filtration to obtain a clear solution, which was the carboxymethyl chitosan-fullerene complex solution. When the carboxymethyl chitosan-fullerene complex solution is concentrated to 1/3 of the original volume, it is placed in a freeze dryer to remove water, and the carboxymethyl chitosan-fullerene complex can be obtained solid. The insoluble matter obtained by filtration is fullerene solid, which weighs about 50 mg after drying. Therefore, in the carboxymethyl chitosan-fullerene composite, the percentage of fullerene is about 5%.

Example 4

Humidity test of carboxymethyl chitosan-fullerene complex:

formula , S _i : moisture retention rate of the sample, %, H _n : water content after storage, H ₀ : water content before storage.

Accurately take by weighing 0.5 g of the carboxymethyl chitosan-fullerene compound gained in Example three, after fully drying, put into a weighing bottle with a diameter of 3 cm, add the deionized water whose mass fraction is 10% of the sample amount, Put it in a desiccator equipped with dry silica gel, take it out and weigh the sample at 4, 12, 24, 36, 48, 60, 72, 84, and 96 hours, and calculate the water content at this time, and calculate the moisture content according to the formula Rate, take the average value of two experiments, and make a graph. Figure 1 shows the moisture retention of carboxymethyl chitosan, and Figure 2 shows the moisture retention of carboxymethyl chitosan-fullerene complex. It can be seen from the figure that the carboxymethyl chitosan-fullerene composite prepared by the present invention has excellent moisturizing properties.

Example 5

Free radical removal performance test of carboxymethyl chitosan-fullerene complex:

The free radical removal effect was measured by spin trap method (ESR). The test principle is: for the free radicals generated by the reaction of hydrogen peroxide and ferrous ions, use DMPO (5,5-dimethyl-1-pyrroline-N-oxide) as a spin trapping agent to detect the free radicals of DMPO and hydroxyl The signal of the product DMPO-OH formed by the radical reaction.

In the actual test: the concentration of ferrous sulfate heptahydrate is 0.4 mmol/L, the mass concentration of hydrogen peroxide is 5%, the pH value of PBS (phosphate buffer saline) is 7.4, and the concentration of chitosan-fullerene complex is 25mmol/L, and the concentration of DMPO was 0.4mol/L. Take 50 μL of each of the above five solutions and mix them evenly before testing. Fig. 3 is the blank test result without adding any active substances, Fig. 4 is a schematic diagram of the free radical removal performance after adding 5000umol/L carboxymethyl chitosan 50μL, Fig. 5 is the addition of 5000umol/L carboxymethyl chitosan- Schematic diagram of the free radical removal performance of 50 μL of fullerene complex. From the figure, it can be seen that the free radical removal performance (relative strength) of the carboxymethyl chitosan-fullerene complex is greatly improved compared with the free radical removal performance (relative strength) of the blank and carboxymethyl chitosan Improvement, that is, the antioxidant activity is improved and the performance is more stable.

In summary, the present invention is through processes such as mixing fullerene and chitosan, ball milling, dissolving and stirring, filtering treatment, vacuum drying, etc., and the chitosan-fullerene compound prepared has good moisture absorption and moisturizing properties. , conditioning, antibacterial and other functions, not only ensure excellent physiological activity, but also have good stability, and have the performance of moisturizing and anti-oxidation activity, which is very suitable for the preparation of cosmetics with complex functions.

It should be understood that the application of the present invention is not limited to the above examples, and those skilled in the art can make improvements or transformations according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended 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.