CN112675051A - Preparation method of water-soluble fullerene lysine-based solution - Google Patents
Preparation method of water-soluble fullerene lysine-based solution Download PDFInfo
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Abstract
The invention discloses a preparation method of a water-soluble fullerene lysine-based solution, which relates to the technical field of skin care products, has simple preparation operation steps, can realize large-scale production, has good water solubility and biocompatibility, greatly improves the solubility of fullerene in a polar solution, and has good radiation resistance and excellent performance in the aspect of removing free radicals; the synthesis method of the invention is applicable to various amino acids, and further, various fullerene amino acid derivatives can be obtained.
Description
Technical Field
The invention relates to the field of skin care products, in particular to a preparation method of a water-soluble fullerene lysine amino solution.
Background
Free radicals (active oxygen) of human skin are a fuse for causing various skin problems such as wrinkles, darkness, color spots, dryness and the like, fullerene is the most effective component for solving the skin free radical problem at present, has super-strong capacity of absorbing and eliminating free radicals, can absorb and eliminate the free radicals like sponge water absorption, thereby cutting off the source of the skin problem, recalling young healthy skin, improving the self-resistance of the skin, subverting the free radical revolution by the fullerene, and the oxidation resistance is 172 times of vitamin C! Fullerene mainly has the effects of resisting aging, whitening skin, removing freckles, shrinking pores, inhibiting acne, removing wrinkles, maintaining after laser phototherapy operation and the like, and in the field of cosmetics, fullerene is a high-end anti-aging raw material, can well remove free radicals, has extremely strong oxidation resistance, and plays a role in activating skin cells and preventing skin aging.
However, the hydrophobic property of the fullerene directly influences the exertion of the biological activity, particularly the exertion of the biological activity under the condition of water solubility. In order to better promote absorption, the fullerene is prepared into a small-particle-size solution type which is easy to be absorbed by skin quickly, and is in a molecular state, so that the fullerene is a good choice, however, the fullerene is insoluble in water, and a special technology is needed to obtain water-soluble fullerene molecules. In general, water-soluble fullerenes can be obtained by the following 4 methods: firstly, preparing a fullerene water-soluble inclusion complex, such as wrapping fullerene molecules in a hydrophilic compound by utilizing liposome, cyclodextrin and the like, although the water solubility of fullerene is partially increased, the method is still severely limited in biomedical application, firstly, the efficiency of wrapping the fullerene is low, secondly, many materials for preparing the inclusion complex have toxicity to cells, thirdly, the operation procedure is complex and is difficult to apply to practice, and therefore, the method is mainly applied to basic theory research of a cell-free system; secondly, fullerene hydrosol is prepared, fullerene exists in the aqueous solution in a cluster form, the ion concentration in the prepared hydrosol is difficult to control mainly under the action of strong acid and strong alkali in the preparation process, and the biological application of the hydrosol is severely limited; thirdly, water-soluble groups are added on the fullerene carbon cage to synthesize and prepare the water-soluble derivative of the fullerene. The method improves the water solubility of the fullerene, simultaneously can retain part of the activity of the fullerene per se by the added water-soluble group, adjusts the derivative group of the fullerene, can reduce or even avoid the toxic effect of the fullerene, and can be used for a cell system and even for general experimental research.
Amino acid and polypeptide are very important substances in organisms, have strong water solubility, if the amino acid, the polypeptide and the fullerene are connected, the water solubility of the fullerene can be greatly improved, the amino group on the amino acid contains lone pair electrons and has strong nucleophilic ability, and the amino acid and the polypeptide can perform nucleophilic addition reaction with the fullerene with electron-deficient olefin property, so that fullerene amino acid derivatives or fullerene polypeptide derivatives are obtained, and after the fullerene is combined with hydrophilic biomolecules, the fullerene can easily permeate a biological membrane, so that the utilization rate of biological tissues on fullerene hydrophilic derivatives can be increased.
Many methods for improving the water solubility of fullerenes by adding water-soluble groups include an adduct group, a shuttle group, an amino group, and a sulfonamide group. However, many derivatives have low water solubility, are difficult to meet the requirements of biological experiments, some derivatives have increased biotoxicity while improving water solubility, and some derivatives have complex synthesis and are difficult to meet the requirements of large-scale industrial production. The fullerene lysine derivative has high water solubility, and the synthesis method is simple and direct and can be used for large-scale industrial production. Different fullerene derivatives have very different radical scavenging ability and water solubility. At present, most of fullerene and amino acid are synthesized through indirect reaction, namely, a group is connected to fullerene firstly, and then the group is utilized to react with the amino acid.
Disclosure of Invention
The present invention has been made to overcome the above problems of the prior art, and an object of the present invention is to provide a method for easily synthesizing a fullerene lysine derivative, in which fullerene and lysine are directly reacted with each other to add a chemical group, thereby improving the water solubility of fullerene, and the functionality of the fullerene derivative can be improved by the addition of lysine.
In order to realize the purpose, the preparation of the fullerene lysine derivative is specifically carried out by the following steps:
firstly, dissolving fullerene in an organic solvent;
mixing with a water-alcohol solution of lysine, wherein the fullerene and the lysine have certain solubility in the mixed solution, the fullerene and the lysine dissolved in the mixed solution can react in the solution, a reaction product is separated out in the mixed solution due to poor solubility, and the separation of the reaction product promotes undissolved reactants to enter the mixed solution for reaction;
the initial reaction product is refined by dissolving it in water and alcohol as precipitant, and the water is the benign solvent of fullerene lysine derivative and the alcohol is the precipitant.
The method comprises the following specific steps:
step1, weighing a certain mass of fullerene, dissolving the fullerene in an organic solvent, and performing ultrasonic dispersion to form a liquid with violet color;
furthermore, the particle size of the fullerene is generally selected to be less than 200nm, and the small particle size enables the prepared water-soluble derivative to be absorbed more easily;
further, the organic solvent may be selected from commonly used organic solvents for dissolving fullerene, for example, toluene, methanol, and the like. The organic solvent is used in an amount that can ensure that the fullerene is completely immersed, and for example, the mass ratio of the fullerene to the toluene may be 1:0.5 to 1. The frequency of the ultrasonic dispersion can be 100-150 times/min.
Further, ultrasonically dispersing until no fullerene is attached to the surface of the container and the solution in the container is not layered, wherein the dispersing time is 1-3 h generally;
step2, weighing a certain mass of lysine and NaOH, dissolving in deionized water, adding a certain mass of dispersing solvent, and stirring at room temperature for 1-3 h to completely dissolve;
further, lysine: NaOH and deionized water in a mass ratio of (3-5) to (1-2) to (4-6), wherein the addition amount of the dispersing solvent is 2-5 times of that of the mixed solution prepared in the previous step;
the dispersant can be selected from any one or more of chlorotoluene, chloroform, toluene and ethanol, and preferably, the dispersant is ethanol;
step3, slowly dripping the fullerene organic solution into the lysine solution, carrying out ultrasonic dispersion for 10-15 h, and then carrying out centrifugal layering until the pH value of the upper-layer solution is 6.5-7.5;
further, the preparation mass ratio of the fullerene organic solution to the lysine solution is (3-5): 1;
further, the centrifugation can precipitate the resulting fullerene lysine derivative having a relatively large molecular weight in the lower layer by the action of gravity, and the organic solvent having a relatively small molecular weight and the dispersant are dispersed in the solution in the upper layer. And when the pH value of the upper layer solution is 6.5-7.5, the organic solvent and the dispersing agent in the system are basically removed completely. The centrifugation times can be 2-4 times, the centrifugation speed can be 6000-7500 rpm, the time of each centrifugation can be 5-10 min, and the volume ratio of the deionized water added during each centrifugation to the dispersion solution before centrifugation can be 1/3-1/2: 1.
Step4, layering to obtain an upper organic layer which is nearly colorless and a lower water-alcohol mixed phase which is brownish black, and separating the water-alcohol mixed phase by using a separating funnel;
step5, extracting trace C60 in the water-alcohol mixed phase by using an extracting agent;
further, the extractant can be selected from toluene, xylene, chlorobenzene, preferably toluene;
further, the extraction times are 2-4 times;
furthermore, the volume ratio of the extracting agent to the water-alcohol mixed phase is generally (8-5): 1;
step6 removing the solvent under reduced pressure by a rotary evaporator to obtain a black viscous solid;
further, the mass ratio of the solid obtained by rotary evaporation to water can be 0.5-1: 10;
further, the temperature of the rotary evaporation is 50-100 ℃, and optionally 60-80 ℃, the temperature can ensure the efficiency of the rotary evaporation, the performance of the fullerene derivative cannot be changed, and the rotating speed can be 100-200 r/min;
step7 adding a certain amount of deionized water into the solid after rotary evaporation to completely dissolve the solid, adding a certain amount of absolute ethyl alcohol, and oscillating to obtain a brown sandy precipitate.
Further, deionized water is added until the solid is completely dissolved, and the volume ratio of the deionized water to the absolute ethyl alcohol is generally 1 (10-15);
step8, filtering the precipitate, washing the precipitate for 2-4 times by using absolute ethyl alcohol, and drying the precipitate to obtain brownish black solid powder, namely the fullerene lysine derivative;
the drying conditions may include: the temperature is 20-30 ℃ and the time is 3-5 hours. For example, the temperature is 22-25 ℃; the time is 4-5 hours.
The synthesis method of the fullerene amino acid derivative provided by the embodiment of the invention has the advantages that the water solubility of the synthesized product is high, the method is simple, in addition, the biotoxicity of the preparation is reduced or even avoided by adjusting the derivative group, the harm to human cells is reduced, and meanwhile, if a certain proportion of the derivative is added into the skin care lotion, the radiation protection effect on gamma-ray irradiated cells can be improved, and the radiation resistance of a human body can be improved.
Drawings
FIG. 1 shows the synthesis equation of the fullerene lysine derivative of the present invention.
FIG. 2 is a manufacturing process of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Examples
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, all methods used are conventional in the art, and all reagents used are commercially available.
Example 1
The synthesis method of the fullerene amino acid derivative comprises the following steps:
s1: weighing a certain mass of fullerene, dissolving the fullerene in organic solvent toluene, and performing ultrasonic dispersion to form liquid with violet color, wherein the mass ratio of the fullerene to the toluene can be 1:0.5, the frequency of ultrasonic dispersion can be 100 times/min, and the dispersion time is 1H;
s2: weighing lysine and NaOH and dissolving in deionized water, wherein the weight ratio of lysine: adding a certain mass of dispersion solvent absolute ethyl alcohol into NaOH and deionized water according to the mass ratio of 3.5:1:4, wherein the addition amount of the dispersion solvent absolute ethyl alcohol is 2 times of the volume of the mixed solution, and stirring for 1 hour at room temperature to completely dissolve the mixed solution;
s3: slowly and dropwisely adding the fullerene organic solution in the S1 into the lysine solution S2, wherein the preparation mass ratio of the fullerene organic solution to the lysine solution is 3:1, carrying out ultrasonic dispersion for 10 hours, and then carrying out centrifugal layering, wherein the centrifugation frequency can be 2 times, the centrifugation speed can be 6000rpm, the time of each centrifugation can be 10min, and the volume ratio of deionized water added in each centrifugation to the dispersion solution before centrifugation can be 1/3:1 until the pH of the upper layer solution is 6.5-7.5;
s4: after layering, the upper layer is nearly colorless, the lower layer is brownish black, and a separating funnel is used for separating the water-alcohol mixed phase;
s5: extracting trace C60 in the water-alcohol mixed phase by using a toluene extractant, wherein the volume ratio of the extractant to the water-alcohol mixed phase is generally 8:1, and extracting for 2 times;
s6: removing solvent under reduced pressure with a rotary evaporator to obtain black viscous solid, wherein the rotary evaporation temperature is 60 deg.C, and the rotation speed can be 100r/min to obtain black viscous solid and liquid at a mass ratio of 0.5: 2;
s7: and adding a certain amount of deionized water into the solid after rotary evaporation to completely dissolve the solid, adding a certain amount of absolute ethyl alcohol, adding deionized water and absolute ethyl alcohol according to the volume ratio of 1:10, and oscillating to obtain brown sandy precipitate.
S8: filtering the precipitate, washing the precipitate for 2-4 times by using absolute ethyl alcohol, and drying the precipitate under the following drying conditions: the temperature is 25 ℃, the nitrogen environment is kept for 4 hours, and the obtained brown-black solid powder is the fullerene lysine derivative.
Example 2
The synthesis method of the fullerene amino acid derivative comprises the following steps:
s1: weighing a certain mass of fullerene, dissolving the fullerene in an organic solvent methanol, and performing ultrasonic dispersion to form a liquid with violet color, wherein the mass ratio of the fullerene to the methanol can be 1:0.8, the frequency of ultrasonic dispersion can be 100 times/min, and the dispersion time is 1H;
s2: weighing lysine and NaOH and dissolving in deionized water, wherein the weight ratio of lysine: adding a certain mass of dispersion solvent absolute ethyl alcohol into NaOH and deionized water according to the mass ratio of 3.5:1:4, wherein the addition amount of the dispersion solvent absolute ethyl alcohol is 3 times of the volume of the mixed solution, and stirring for 1.5H at room temperature to completely dissolve the mixed solution;
s3: slowly and dropwisely adding the fullerene organic solution in the S1 into the lysine solution S2, wherein the preparation mass ratio of the fullerene organic solution to the lysine solution is 3:1, carrying out ultrasonic dispersion for 10 hours, and then carrying out centrifugal layering, wherein the centrifugation frequency can be 2 times, the centrifugation speed can be 6500rpm, the time of each centrifugation can be 10min, and the volume ratio of deionized water added during each centrifugation to the dispersion solution before centrifugation can be 1/3:1 until the pH of the upper layer solution is 6.5-7.5;
s4: after layering, the upper layer is nearly colorless, the lower layer is brownish black, and a separating funnel is used for separating the water-alcohol mixed phase;
s5: extracting trace C60 in the water-alcohol mixed phase by using a toluene extractant, wherein the volume ratio of the extractant to the water-alcohol mixed phase is generally 7:1, and extracting for 2 times;
s6: removing the solvent by rotary evaporator under reduced pressure to obtain black viscous solid, wherein the rotary evaporation temperature is 70 deg.C, and the rotation speed can be 100r/min to obtain black viscous solid and liquid at a mass ratio of 1: 10;
s7: and adding a certain amount of deionized water into the solid after rotary evaporation to completely dissolve the solid, adding a certain amount of absolute ethyl alcohol, adding deionized water and absolute ethyl alcohol according to the volume ratio of 1:10, and oscillating to obtain brown sandy precipitate.
S8: filtering the precipitate, washing with anhydrous ethanol for 2 times, and drying under the following conditions: the temperature is 25 ℃, the nitrogen environment is kept for 4 hours, and the obtained brown-black solid powder is the fullerene lysine derivative.
Example 3
The synthesis method of the fullerene amino acid derivative comprises the following steps:
s1: weighing fullerene with a certain mass, dissolving the fullerene in organic solvent toluene, and performing ultrasonic dispersion to form liquid with violet color, wherein the mass ratio of the fullerene to the toluene can be 1:1, the frequency of ultrasonic dispersion can be 150 times/min, and the dispersion time is 2H;
s2: weighing lysine and NaOH and dissolving in deionized water, wherein the weight ratio of lysine: adding a certain mass of dispersion solvent absolute ethyl alcohol into NaOH and deionized water according to the mass ratio of 3.5:1:4, wherein the addition amount of the dispersion solvent absolute ethyl alcohol is 3 times of the volume of the mixed solution, and stirring at room temperature for 2 hours to completely dissolve the mixed solution;
s3: slowly and dropwisely adding the fullerene organic solution in the S1 into the lysine solution S2, wherein the preparation mass ratio of the fullerene organic solution to the lysine solution is 3:1, after ultrasonic dispersion is carried out for 10 hours, carrying out centrifugal layering, wherein the centrifugation frequency can be 3 times, the centrifugation speed can be 6500rpm, the time of each centrifugation can be 10min, and the volume ratio of deionized water added during each centrifugation to the dispersion solution before centrifugation can be 1/2:1 until the pH value of the upper layer solution is 6.5-7.5;
s4: after layering, the upper layer is nearly colorless, the lower layer is brownish black, and a separating funnel is used for separating the water-alcohol mixed phase;
s5: extracting trace C60 in the water-alcohol mixed phase by using a toluene extractant, wherein the volume ratio of the extractant to the water-alcohol mixed phase is generally 8:1, and extracting for 4 times;
s6: removing solvent under reduced pressure with a rotary evaporator to obtain black viscous solid, wherein the rotary evaporation temperature is 80 deg.C, the rotation speed can be 200r/min, and the mass ratio of black viscous solid to liquid is about 0.5: 10;
s7: and adding a certain amount of deionized water into the solid after rotary evaporation to completely dissolve the solid, adding a certain amount of absolute ethyl alcohol, adding deionized water and absolute ethyl alcohol according to the volume ratio of 1:10, and oscillating to obtain brown sandy precipitate.
S8: filtering the precipitate, washing with anhydrous ethanol for 4 times, and drying under the following conditions: the temperature is 30 ℃, the nitrogen environment is kept for 5 hours, and the obtained brown-black solid powder is the fullerene lysine derivative.
Example 4
This example differs from example 1 only in that: in the step S3, the preparation mass ratio of the fullerene organic solution to the lysine solution is 5:1, ultrasonic dispersing for 10 h.
Example 5
This example differs from example 1 only in that: step S2, adding a certain mass of chloroform as a dispersion solvent, wherein the addition amount is 2 times of the volume of the mixed solution, and stirring for 1 hour at room temperature to completely dissolve the chloroform; .
Example 6
This example differs from example 1 only in that: in step S1, the organic solvent in which the fullerene is dissolved is methanol, and the mass ratio of the fullerene to the methanol is still 1: 0.5.
Comparative example 1
A water-soluble fullerene preparation was prepared in the same manner as in example 1, except that no lysine was added.
Performance testing
Solubility test
TABLE 1
| Solubility mg/ml | |
| Example 1 | 1.63 |
| Example 2 | 1.56 |
| Example 3 | 1.65 |
| Example 4 | 1.60 |
| Example 5 | 1.58 |
| Example 6 | 1.57 |
| Comparative example 1 | 1.13 |
As can be seen from table 1, the solubility of the fullerene formulations of the examples of the present invention is significantly improved compared to the comparative examples;
and the higher the preparation mass ratio of the fullerene organic solution to the lysine solution in the dissolution range, the longer the ultrasonic dispersion time is required, and meanwhile, the organic solvent for dissolving the fullerene and the lysine has certain influence on the solubility of the final preparation, and toluene and absolute ethyl alcohol are respectively preferred.
Claims (9)
1. A method for preparing a water-soluble fullerene lysine-based solution is characterized by providing a simple synthesis method, wherein fullerene and lysine are directly reacted, a chemical group is added to improve the water solubility of fullerene, and the addition of lysine can improve the functionality of a fullerene derivative;
the method comprises the following steps:
firstly, dissolving fullerene in an organic solvent;
mixing with water-alcohol solution of lysine, wherein the fullerene and the lysine have certain solubility in the mixed solution, and the fullerene and the lysine dissolved in the mixed solution can react in the solution;
the reaction product is separated out due to poor solubility in the mixed solution, the separation of the reaction product promotes undissolved reactants to enter the mixed solution for reaction, and a crude product can be obtained through centrifugation, layering, extraction and rotary evaporation;
the crude reaction product is refined by dissolving it in water and alcohol, the water is the good solvent of fullerene lysine derivative, and the alcohol is precipitant.
2. The method of claim 1, wherein dissolving fullerenes in an organic solvent comprises:
weighing a certain mass of fullerene, and dissolving the fullerene in an organic solvent toluene, wherein the mass ratio of the fullerene to the toluene is 1:0.5 to 1, and/or
And carrying out ultrasonic dispersion with the frequency of 100-150 times/min and the dispersion time of 1-3 h to form the liquid with the violet color.
3. The method of claim 1, wherein the preparing of the hydroalcoholic solution of lysine comprises:
weighing lysine and NaOH and dissolving in deionized water, wherein the weight ratio of lysine: NaOH and deionized water in a mass ratio of (3-5) to (1-2) to (4-6), and/or
Adding a certain mass of dispersing solvent, wherein the dispersing agent can be one or more of chlorotoluene, chloroform, toluene and ethanol, and the adding amount is 2-5 times of the volume of the mixed solution, and/or
Stirring for 1-3 h at room temperature to completely dissolve the materials.
4. The method of claim 1, wherein the preparing of the mixed solution of fullerene and lysine comprises:
slowly dropping a fullerene organic solution into a lysine solution, wherein the preparation mass ratio of the fullerene organic solution to the lysine solution is (3-5): 1, and/or
After ultrasonic dispersion for 10-15 h, and/or
And (3) carrying out centrifugal layering for 2-4 times, wherein the centrifugal speed can be 6000-7500 rpm, the time of each centrifugation can be 5-10 min, and the volume ratio of the deionized water added during each centrifugation to the dispersion solution before centrifugation can be 1/3-1/2: 1 until the pH value of the upper layer solution is 6.5-7.5.
5. The method of claim 1, wherein the post-centrifugation phase separation comprises:
the upper layer is nearly colorless after layering, the lower layer is brownish black, and the water-alcohol mixed phase is separated by a separating funnel.
6. The method of claim 1, wherein the post-phase separation extraction comprises:
extracting trace C60 in water-alcohol mixed phase with extractant
The extractant can be selected from toluene, xylene and chlorobenzene, preferably toluene; and/or
The volume ratio of the extractant to the water-alcohol mixed phase is generally (8-5) to 1, and the extraction is carried out for 2-4 times.
7. The method of claim 1, wherein the rotary evaporation method comprises:
removing the solvent under reduced pressure with a rotary evaporator to obtain black viscous solid, wherein the temperature of the rotary evaporation is 50-100 deg.C, optionally 60-80 deg.C, and/or the rotation speed is 100-200 r/min
The mass ratio of the obtained black viscous solid to the liquid is about 0.5-1: 10.
8. The method of claim 1, wherein the crude product refining comprises:
and adding a certain amount of deionized water into the solid after rotary evaporation to completely dissolve the solid, adding a certain amount of absolute ethyl alcohol, adding deionized water and absolute ethyl alcohol according to the volume ratio of 1 (10-15), and oscillating to obtain brown sandy precipitate.
9. The method of claim 1, wherein the final filter drying comprises:
filtering the precipitate, washing the precipitate for 2-4 times by using absolute ethyl alcohol, and drying the precipitate under the following drying conditions: the temperature is 20-30 ℃, the time is 3-5 hours, and the obtained brown-black solid powder is the fullerene lysine derivative.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101302008A (en) * | 2008-06-30 | 2008-11-12 | 北京理工大学 | Solid phase synthesis method of single addition fullerene aminoacid derivate |
| CN102688225A (en) * | 2011-03-24 | 2012-09-26 | 中国人民解放军第二军医大学 | Fullerene lysine derivative and its preparation method and use in radiation protection |
| CN104478886A (en) * | 2014-12-30 | 2015-04-01 | 郑州大学 | Fullerene biaddition amino acid and synthetic method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101302008A (en) * | 2008-06-30 | 2008-11-12 | 北京理工大学 | Solid phase synthesis method of single addition fullerene aminoacid derivate |
| CN102688225A (en) * | 2011-03-24 | 2012-09-26 | 中国人民解放军第二军医大学 | Fullerene lysine derivative and its preparation method and use in radiation protection |
| CN104478886A (en) * | 2014-12-30 | 2015-04-01 | 郑州大学 | Fullerene biaddition amino acid and synthetic method thereof |
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