Polysaccharide substance modified water-soluble fullerene, preparation method thereof and application of polysaccharide substance modified water-soluble fullerene in cosmetics with anti-wrinkle and anti-aging effects

Abstract

The invention discloses polysaccharide substance modified water-soluble fullerene, a preparation method of the polysaccharide substance modified water-soluble fullerene and application of the polysaccharide substance modified water-soluble fullerene in cosmetics with wrinkle-removing and anti-aging effects. The water-soluble fullerene provided by the invention takes polysaccharide substances as raw materials, and the prepared water-soluble fullerene has the advantages of good water solubility, good dispersity, strong stability, clear and transparent aqueous solution and the like. Meanwhile, polysaccharide substances have low irritation, relieving and repairing effects and an excellent moisturizing effect, and have important application value in the aspects of cosmetics, biomedicine and the like. The invention provides a method for simply preparing water-soluble fullerene without toxic and harmful solvents, and no toxic and harmful solvent is left in the preparation process. The water-soluble fullerene disclosed by the invention has excellent hydroxyl radical scavenging capacity and has wide application potential in biomedicine and cosmetic industries.

Description

Technical Field

[0001] The invention belongs to the field of cosmetic raw materials, and specifically relates to a water-soluble fullerene modified by a polysaccharide substance, a preparation method thereof, and an application thereof in cosmetics with anti-wrinkle and anti-aging effects. Background Art

[0002] Water-soluble fullerene is a fullerene compound with good dispersibility and stability in water phase. Fullerene itself is composed of 60 carbon atoms, forming various forms such as spheres and tubes, and has unique physical and chemical properties, such as efficient electron mobility, good chemical activity and optical properties. Therefore, fullerene has important applications in electronic devices, photovoltaic materials, biomedicine, cosmetics and other fields.

[0003] However, the traditional preparation method of water-soluble fullerene has many problems, such as high temperature and high pressure conditions, complex production, low yield, introduction of toxic and harmful solvents such as toluene, etc., which limits its application in chemical production. Therefore, researchers are committed to developing water-soluble fullerene in order to overcome these limitations and expand its application in electronic devices, photovoltaic materials, biomedicine, cosmetics and other fields.

[0004] There are many methods for preparing water-soluble fullerenes. One common method is to introduce hydrophilic functional groups on the surface of fullerenes through chemical modification. For example, hydrophilic groups such as hydroxyl (-OH) and carboxyl (-COOH) are introduced on the surface of fullerene molecules to make them hydrophilic, so that they can form a stable dispersion system in water. In addition, polymer segments and surfactants can be introduced on fullerene molecules to increase their ability to interact with water and improve their dispersion and stability in water.

[0005] However, for fullerene surface modification and grafting to enhance the water solubility of fullerene, the main surface treatment agents on the market are polyvinyl pyrrolidone (PVP), squalane and other substances. However, due to the limitations of preparation process and composite performance, the proportion of fullerene in the water-soluble fullerene prepared by polyvinyl pyrrolidone (PVP) is relatively low. The solubility of fullerene in squalane is low, and squalane is an oily substance, which limits its use in the biomedical and cosmetic industries.

[0006] Polysaccharides are natural and environmentally friendly, and can improve dry skin, soften the stratum corneum, and promote skin metabolism. In this study, polysaccharides were modified and grafted with fullerene to prepare water-soluble fullerene. At the same time, a green ball milling method without organic solvent addition was used to modify fullerene to obtain a water-soluble fullerene material with high content, good water solubility, and excellent free radical scavenging ability. Summary of the invention

[0007] The present invention aims to provide a method for preparing water-soluble fullerenes by using polysaccharides as surface modification materials. The water-soluble fullerenes disclosed in this patent have good water solubility, can be stably dispersed in water, and their aqueous solutions are clear and transparent. They also have efficient free radical scavenging activity and are suitable for the fields of biomedicine and cosmetics.

[0008] The purpose of the present invention is achieved by at least one of the following technical solutions.

[0009] The present invention provides a method for preparing water-soluble fullerene modified by polysaccharide, comprising the following steps:

[0010] Step 1: Place fullerene powder and polysaccharide in a ball mill for ball milling to form a stable mixture;

[0011] Step 2: taking out the stable mixture obtained in step 1, adding water to dissolve it, and stirring it thoroughly to obtain a water-soluble fullerene solution;

[0012] Step 3: filtering the water-soluble fullerene solution obtained in step 2 for multiple times to remove the fullerene that has not reacted with the polysaccharide substance, and the obtained solution is the water-soluble fullerene solution after the polysaccharide substance is modified;

[0013] Step 4: The water-soluble fullerene solution modified by the polysaccharide substance obtained in step 3 is evaporated to remove the solvent, and then freeze-dried to obtain the water-soluble fullerene powder modified by the polysaccharide substance.

[0014] Further preferably, in step one, during the ball milling process in step one, cooling is required to prevent the temperature in the ball mill from being too high, resulting in oxidation of the fullerene powder. Based on this, the ball mill in the present invention uses a cold air omnidirectional ball mill to ensure that the fullerene powder and the polysaccharide substance are fully contacted and modified. In order to prevent the high-temperature oxidation and denaturation of fullerene powder and polysaccharide substances, the cooling temperature during ball milling needs to be controlled at 5-45°C, preferably 15-25°C; in order to allow fullerene and biological polysaccharide substances to fully react, the speed during ball milling is controlled at 100-500r / min, and further, the speed should be controlled at 200-300 rpm; the ball milling time is 4-48h, and further, the ball milling time should preferably be 8-24h.

[0015] More preferably, the polysaccharide substance is selected from one or more of structural polysaccharides, storage polysaccharides and heteropolysaccharides.

[0016] More preferably, the structural polysaccharide is selected from at least one of starch, glycogen and inulin.

[0017] More preferably, the storage polysaccharide is selected from one or more of cellulose, chitin and heteropolysaccharides.

[0018] Further preferably, the heteropolysaccharide is selected from one or more of phosphate-modified dextran, sulfonated dextran, Tremella polysaccharide, activated carboxyl-modified galactose, maleimide-modified galactose, amino-modified galactose, and biopolysaccharide gum.

[0019] More preferably, the polysaccharide substance is selected from one or more of amino-modified galactose, biopolysaccharide gum, sulfonated polyglucose, and Tremella polysaccharide.

[0020] Further preferably, the fullerene is a hollow fullerene or a metal fullerene, including but not limited to C 2n 、M@C 2n 、MA@C 2n 、M2@C 2n 、M3N@C 2n 、M2C2@C 2n 、M2O@C 2n Any one of, wherein M and A both represent metal elements, selected from any one of Sc, Y and lanthanide metals; 30≤n≤70.

[0021] Further preferably, the water-soluble fullerene of the present invention is selected from hollow fullerene C 2n One or more of , where 30≤n≤70.

[0022] More preferably, the fullerene selected in the present invention is C 60 , C 70 , C 76 , C 78 , C 84 One or more of the .

[0023] Further preferably, the mass ratio of fullerene to polysaccharide in the present invention should be 1:20-1:300, preferably 1:20-1:200; further, the mass ratio of fullerene to polysaccharide should be any one of 1:40-1:250, 1:50-1:200, 1:30-1:150, 1:20-1:120, 1:70-1:140, more preferably, the mass ratio of fullerene to polysaccharide is any one of 1:50-1:200, 1:20-1:120 and 1:70-1:140.

[0024] Further preferably, in step 2, to prevent the fullerene powder and polysaccharide from oxidative deterioration, the stirring water temperature is controlled at 15-35° C., and further, the water temperature should be controlled at 20-30° C. To ensure sufficient and uniform mixing during stirring, the stirring time is controlled at 20-120 min, and further, the stirring time should be controlled at 30-90 min.

[0025] Further preferably, in step three, in order to remove the incompletely modified fullerenes and polysaccharides in the solution, the required filtration pore size is 0.4-1.5 μm, and further, the filtration pore size needs to be 0.6-1.2 μm.

[0026] A water-soluble fullerene is obtained by chemically grafting a polysaccharide substance with fullerene, has high free radical scavenging ability, has good water solubility, can be quickly dissolved in water, and the solution is clear and transparent.

[0027] The present invention provides a simple, efficient and environmentally friendly process for preparing water-soluble fullerenes. At present, water-soluble fullerenes are prepared by dissolving fullerenes in an organic solvent, and then mixing and stirring with a water-soluble substance to finally obtain a water-soluble fullerene material. The organic solvents currently used are mainly aromatic hydrocarbons such as toluene, xylene, benzene, and chlorobenzene, or halogenated hydrocarbons such as chloroform, dichloromethane, and 1,2-dichloroethane, which put forward higher requirements for the purification of the final product and the removal of toxic and harmful solvents, and also pose certain production risks to production enterprises. Therefore, the present invention provides a method for simply preparing water-soluble fullerenes without toxic and harmful solvents. The water-soluble fullerenes prepared by this method have the advantages of high dispersibility, strong free radical scavenging ability, good stability, etc., and no toxic and harmful solvents remain.

[0028] Compared with the existing steps, the preparation steps of the present invention have the following more excellent effects:

[0029] 1. The method for preparing water-soluble fullerenes provided by the present invention does not contain any toxic or harmful organic reagents. Therefore, problems such as organic solvent residues will not occur during the production process, and the safety for human body and environment is better.

[0030] 2. The method for preparing water-soluble fullerene provided by the present invention does not require a subsequent process for removing toxic and harmful organic solvents, and the overall process is simple and has low energy consumption. It is a safe and environmentally friendly method for preparing water-soluble fullerene.

[0031] 3. The present invention adopts ball milling, i.e. mechanical grinding, to prepare water-soluble fullerenes. The water-soluble substances and fullerenes are chemically grafted and modified by rapid grinding in a ball mill. The method is simple to operate and easy to promote and use.

[0032] 4. The method for preparing water-soluble fullerenes used in the present invention can prepare water-soluble fullerenes with better dispersibility and greater stability in water.

[0033] 5. In the preparation method provided by the present invention, the unmodified fullerene powder can be recovered by extraction and reused.

[0034] 6. Since both polysaccharides and fullerenes have antioxidant effects, the water-soluble fullerenes prepared by the preparation method provided by the present invention have excellent wrinkle-removing and anti-aging effects.

[0035] 7. Polysaccharides have excellent moisturizing, soothing sensitivity, and promoting absorption. Therefore, the water-soluble fullerene prepared by the present invention has important application value in the field of cosmetics. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Table 1 is the formula table of the eye cream in Example 6;

[0037] Figure 1 This is a diagram of the preparation of a water-soluble fullerene solution by combining PVP and fullerene in Comparative Example 1;

[0038] Figure 2 This is a diagram of preparing a water-soluble fullerene solution by combining biopolysaccharide gum with fullerene in Example 1;

[0039] Figure 3 This is a diagram of preparing a water-soluble fullerene solution by combining Tremella polysaccharide and fullerene in Example 2;

[0040] Figure 4 The infrared spectra of the drugs used in Example 1 and Example 2 and the water-soluble fullerenes obtained;

[0041] Figure 5 This is a graph showing the hydroxyl radical scavenging ability of water-soluble fullerene prepared by combining PVP and fullerene in Comparative Example 1;

[0042] Figure 6 The hydroxyl radical scavenging ability of water-soluble fullerene prepared by ball milling PVP and fullerene in Comparative Examples 1-4 at different times is shown in FIG.

[0043] Figure 7 This is a graph showing the hydroxyl radical scavenging ability of water-soluble fullerene prepared by combining biopolysaccharide gum with fullerene in Example 1;

[0044] Figure 8 This is a graph showing the hydroxyl radical scavenging ability of water-soluble fullerene prepared by combining Tremella polysaccharide with fullerene in Example 2;

[0045] Fig. 9 is the average length of wrinkles around the eyes after using eye cream in Example 6;

[0046] Fig.10 is the improvement rate of the length of periocular wrinkles after using the eye cream in Example 6;

[0047] Fig.11 is the average value of the width of wrinkles around the eyes after using the eye cream in Example 6;

[0048] Fig.12is the improvement rate of the width of periocular wrinkles after using the eye cream in Example 6;

[0049] Fig.13 This is a graph showing the changes in wrinkles around the eyes over time after the volunteers used eye cream in Example 6. Specific implementation methods

[0051] According to the above contents disclosed in the present invention, according to the common technical knowledge and customary means in the art, without departing from the above basic technical ideas disclosed in the present invention, other various forms of modification, replacement or change may be made.

[0052] In the present invention, the term "fullerene" includes a series of molecules consisting of an even number of carbon atoms, containing 12 five-membered rings and the rest being six-membered rings. Among them, fullerene includes hollow fullerene and endohedral metal fullerene.

[0053] The term "endohedral metallofullerene" refers to a fullerene that contains metal ions within the carbon cage structure of the fullerene, usually represented by M@C 2n Indicates, where M represents a metal element.

[0054] The term "biological polysaccharides", also known as polysaccharides, is a high molecular substance composed of many monosaccharide units and is the main form of sugar in nature.

[0055] The preparation method provided by the present invention is further described by way of examples. In particular, the following examples are only used to explain the preparation method of water-soluble fullerenes of the present invention, but the present invention is not limited thereto. The experimental conditions are conventional conditions unless otherwise specified, and the reactants can be obtained from public commercial channels.

[0056] The water-soluble fullerene prepared by the embodiment of the present invention was tested by infrared spectroscopy. The results showed that the polysaccharide and the fullerene were successfully grafted through chemical bonds. Dissolution and EPR tests showed that the water-soluble fullerene prepared by the embodiment had good water solubility, stable dispersibility and excellent free radical scavenging ability.

[0057] At present, PVP is widely used as a water-soluble modifier in water-soluble fullerenes. Therefore, the present invention selects a composite material of PVP and fullerene as a comparative example, and compares the appearance, aqueous solution stability, and free radical scavenging activity to verify the stability and high-efficiency free radical scavenging activity of the water-soluble fullerene prepared by the present invention.

[0058] Comparative Example 1

[0059] (1) 5.0 g PVP and 37.5 mg C 60Place it in a ball mill and add stainless steel balls to grind it for 16 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0060] (2) The ground mixture was dissolved in 150 mL of water and stirred thoroughly for 1 h.

[0061] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0062] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0063] Its appearance and free radical scavenging activity are Figure 1 and Figure 5 As shown, the solution is brown, and the EPR spectrum shows that the EPR signal peak of the material has decreased, indicating that the solution has a certain free radical scavenging ability.

[0064] Comparative Example 2

[0065] (1) 5.0 g PVP and 37.5 mg C 60 Place it in a ball mill and add stainless steel balls to grind it for 4 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0066] (2) The ground mixture was dissolved in 150 mL of water and stirred thoroughly for 1 h.

[0067] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0068] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0069] Comparative Example 3

[0070] (1) 5.0 g PVP and 37.5 mg C 60Place it in a ball mill and add stainless steel balls to grind it for 8 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0071] (2) The ground mixture was dissolved in 150 mL of water and stirred thoroughly for 1 h.

[0072] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0073] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0074] Comparative Example 4

[0075] (1) 5.0 g PVP and 37.5 mg C 60 Place it in a ball mill and add stainless steel balls to grind for 12 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0076] (2) The ground mixture was dissolved in 150 mL of water and stirred thoroughly for 1 h.

[0077] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0078] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0079] The free radical scavenging ability of Comparative Examples 1-4 is as follows Figure 6 As shown, the results show that within 4-12 hours, as the ball milling time increases, the EPR signal peak decreases, indicating that the free radical scavenging ability of the solution increases with the ball milling time, and the EPR signal of the solution after 16 hours of ball milling is stronger than that of the solution after 12 hours of ball milling, indicating that the free radical scavenging ability after 16 hours of ball milling is weaker. It can be inferred from Comparative Examples 1-4 that 12 hours is the optimal ball milling time.

[0080] Example 1

[0081] (1) Mix 5.0 g of biopolysaccharide gel with 37.5 mg of C 60 Place it in a ball mill and add stainless steel balls to grind for 12 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0082] (2) The ground mixture was dissolved in 150 mL of water at 25°C and stirred for 1 h.

[0083] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0084] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0085] The results show that the water-soluble fullerene prepared by the method provided by the present invention by composite modification of biopolysaccharide gum and fullerene has good water solubility, can be quickly dissolved in water, and the solution is clear and transparent. Figure 2 As shown. After high-speed centrifugation, no precipitation was produced, indicating that its aqueous solution has good stability. Figure 4 As shown, the results show that the material -1 、1427cm -1 The characteristic peak of fullerene is shown at 1000-1200 cm -1 1300~1800cm -1 It shows the characteristic peaks of biopolysaccharide gum, indicating that C 60 The chemical bond grafting with biopolysaccharide glue was successfully carried out. At the same time, the EPR spectrum shows that the EPR signal peak of the material is lower, indicating that it has good free radical scavenging activity, such as Figure 7 shown.

[0086] Example 2

[0087] (1) 5.0 g Tremella polysaccharide powder and 37.5 mg C 60 Place it in a ball mill and add stainless steel balls to grind it for 16 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0088] (2) The ground mixture was dissolved in 150 mL of water at 25°C and stirred for 1 h.

[0089] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0090] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0091] The results show that the water-soluble fullerene prepared by the composite modification of Tremella polysaccharide and fullerene by the method provided by the present invention has good water solubility, can be quickly dissolved in water, and the solution is clear and transparent. Figure 3 As shown. After high-speed centrifugation, no precipitation was produced, indicating that its aqueous solution has good stability. Figure 4 As shown, the results show that the material -1 、1427cm -1 The characteristic peak of fullerene is shown at 1000-1200 cm -1 1300~1800cm -1 The characteristic peaks of Tremella polysaccharide were shown, indicating that C 60 The chemical bond grafting was successfully carried out with Tremella polysaccharide. At the same time, the EPR spectrum shows that the EPR signal peak of the material is lower, indicating that it has good free radical scavenging activity, such as Figure 8 shown.

[0092] Example 3

[0093] (1) Mix 5.0 g of biopolysaccharide gel with 62.5 mg of C 60 Place it in a ball mill and add stainless steel balls to grind for 12 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0094] (2) The ground mixture was dissolved in 150 mL of water and stirred thoroughly for 1 h.

[0095] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0096] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0097] Example 4

[0098] (1) Mix 3.0 g starch with 25.0 mg C 60 Place it in a ball mill and add stainless steel balls to grind for 12 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0099] (2) The ground mixture was dissolved in 150 mL of water at 25°C and stirred for 1 h.

[0100] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0101] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0102] Example 5

[0103] (1) 4.0 g of cellulose and 50.0 mg of C 60 Place it in a ball mill and add stainless steel balls to grind for 12 hours. During the ball milling process, a cooling system is required to ensure that the temperature is around 20°C to ensure C 60 The powder is not oxidized.

[0104] (2) The ground mixture was dissolved in 150 mL of water at 25°C and stirred for 1 h.

[0105] (3) The uniformly mixed solution obtained by stirring is filtered, and the pore size used for filtering is 0.8 μm. The brown liquid obtained is the fullerene aqueous solution. The solid filtered out is the fullerene solid that failed to react with the water-soluble substance and can be subsequently recycled.

[0106] (4) The fullerene aqueous solution is heated to evaporate the solution, and then freeze-dried using a freeze dryer to obtain powdered water-soluble fullerene.

[0107] Example 6

[0108] (1) According to the formula in Table 1, eye creams containing water-soluble fullerene and eye creams without water-soluble fullerene were prepared for efficacy testing, wherein raw materials 1-5 are emulsifiers and dispersants, raw materials 7-10 are softeners, raw materials 6, 11, and 12 are antibacterial agents, raw material 13 is a bioactive substance, and raw material 15 is an exfoliating component, wherein raw materials 13 and 15 do not have anti-aging and firming effects. The blank eye cream does not contain raw material 14, and raw material 14 is the water-soluble fullerene prepared in Example 1, which is added to the fullerene anti-aging and firming eye cream.

[0109] (2) Subject screening conditions:

[0110] ①Number of subjects: 20 subjects, 10 in each of the blank group and the control group.

[0111] ② Inclusion criteria: aged 18 to 60 years old, with intact facial skin, without any scars, injuries or other factors that affect the assessment, both men and women are eligible, with good overall health and no major systemic diseases.

[0112] ③Exclusion criteria: women who are currently pregnant, breastfeeding or preparing for pregnancy; those with forearm damage, scars or other skin diseases; those with highly sensitive constitution or cosmetic allergies.

[0113] (3) Test environment: Real-time dynamic monitoring is carried out under the conditions of 20-22°C and 40%-60% humidity.

[0114] (4) Product Usage: Samples were tested against blank samples and control samples. Volunteers cleaned their faces and used skin lotion in the morning and evening, then applied the eye cream around the eyes and gently massaged until absorbed.

[0115] (5) Objective quantitative evaluation: 30 minutes after facial cleansing, a multifunctional 3D skin imaging analyzer was used to collect periocular images and wrinkle data in the test area as the initial value (D0). Then, the sample was used in the selected area, and the subjects were tested for the same indicators 4 weeks (D28), 6 weeks (D42), and 8 weeks (D56) after using the sample. Each area was measured at least 3 times each time, and the data were recorded and the average value was calculated.

[0116] Testing of the same subject must be completed by the same tester using the same instrument.

[0117] The test results are as follows Figure 9-12 As shown, Figure 9-10 The results showed that compared with the blank anti-aging and firming eye cream, the length of skin wrinkles in the test area of ​​the fullerene anti-aging and firming eye cream was significantly reduced at D28, D42, and D56, with improvements of 30.93%, 37.47%, and 30.46%, respectively, indicating that water-soluble fullerene in the eye cream can effectively reduce the length of wrinkles.

[0118] Figure 11-12 The results showed that compared with the blank anti-aging and firming eye cream, the width of skin wrinkles in the test area of ​​the fullerene anti-aging and firming eye cream was significantly reduced at D28, D42, and D56, with improvements of 2.93%, 2.09%, and 1.97%, respectively, indicating that water-soluble fullerene in the eye cream can effectively reduce the width of wrinkles.

[0119] Fig.13 The results showed that there was a substantial reduction in the wrinkles around the eyes of the volunteers, indicating that the fullerene anti-aging and firming eye cream has a certain anti-wrinkle effect.

[0120] Table 1

[0121]

[0122] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A method for preparing water-soluble fullerene modified by polysaccharide, characterized in that: The steps include: Step 1: Place fullerene powder and polysaccharide in a ball mill for ball milling to form a stable mixture; Step 2: taking out the stable mixture obtained in step 1, adding water to dissolve it, and stirring it thoroughly to obtain a water-soluble fullerene solution; Step 3: filtering the water-soluble fullerene solution obtained in step 2 for multiple times to remove the fullerene that has not reacted with the polysaccharide substance, and the obtained solution is the water-soluble fullerene solution after the polysaccharide substance is modified; Step 4: The water-soluble fullerene solution modified by the polysaccharide substance obtained in step 3 is evaporated to remove the solvent, and then freeze-dried to obtain the water-soluble fullerene powder modified by the polysaccharide substance.

2. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: In step 1, the cooling temperature during ball milling is 5-45° C.; the rotation speed during ball milling is controlled at 100-500 r / min; and the ball milling time is 4-48 h.

3. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: The polysaccharide substance is selected from one or more of structural polysaccharides, storage polysaccharides and heteropolysaccharides; The structural polysaccharide is selected from one or more of starch, glycogen and inulin; The storage polysaccharide is selected from one or more of cellulose, chitin, and heteropolysaccharides; The heteropolysaccharide is selected from one or more of phosphate-modified dextran, sulfonated dextran, Tremella polysaccharide, activated carboxyl-modified galactose, maleimide-modified galactose, amino-modified galactose and biopolysaccharide gum.

4. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: The polysaccharide substance is selected from one or more of amino-modified galactose, biopolysaccharide gum, sulfonated polyglucose and Tremella polysaccharide.

5. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: The fullerene is a hollow fullerene or a metal fullerene, including C 2n 、M@C 2n 、MA@C 2n 、M2@C 2n 、M3N@C 2n 、M2C2@C 2n 、M2O@C 2n Any one of, wherein M and A both represent metal elements, selected from any one of Sc, Y and lanthanide metals, 30≤n≤70.

6. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: In step 1, the mass ratio of the fullerene powder to the polysaccharide substance is 1:20-1:

200.

7. The method for preparing a water-soluble fullerene modified by a polysaccharide substance according to claim 1, characterized in that: In step 2, the stirring water temperature is 15-35°C; and the stirring time is 20-120min.

8. The method for preparing water-soluble fullerene modified by polysaccharide according to claim 1, characterized in that: In step three, the filter pore size is 0.4-1.5 μm.

9. The water-soluble fullerene modified with polysaccharide prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The water-soluble fullerene is obtained by grafting polysaccharides and fullerenes through chemical bonds, has high free radical scavenging ability, has good water solubility, can be quickly dissolved in water, and the solution is clear and transparent.

10. The water-soluble fullerene according to claim 9 is used in the field of biomedicine or anti-wrinkle and anti-aging cosmetics.

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