CN113735099B - Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups - Google Patents
Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups Download PDFInfo
- Publication number
- CN113735099B CN113735099B CN202110996351.2A CN202110996351A CN113735099B CN 113735099 B CN113735099 B CN 113735099B CN 202110996351 A CN202110996351 A CN 202110996351A CN 113735099 B CN113735099 B CN 113735099B
- Authority
- CN
- China
- Prior art keywords
- fullerene
- stock solution
- electron transfer
- water
- surface hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011550 stock solution Substances 0.000 title claims abstract description 65
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 40
- 230000027756 respiratory electron transport chain Effects 0.000 title claims abstract description 40
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000000502 dialysis Methods 0.000 claims abstract description 31
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 230000006641 stabilisation Effects 0.000 claims description 23
- 238000011105 stabilization Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 4
- 239000002537 cosmetic Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 231100000086 high toxicity Toxicity 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000033444 hydroxylation Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007760 free radical scavenging Effects 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000008176 lyophilized powder Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002292 Radical scavenging effect Effects 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 fullerenes alcohols Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- ATLMFJTZZPOKLC-UHFFFAOYSA-N C70 fullerene Chemical compound C12=C(C3=C4C5=C67)C8=C9C%10=C%11C%12=C%13C(C%14=C%15C%16=%17)=C%18C%19=C%20C%21=C%22C%23=C%24C%21=C%21C(C=%25%26)=C%20C%18=C%12C%26=C%10C8=C4C=%25C%21=C5C%24=C6C(C4=C56)=C%23C5=C5C%22=C%19C%14=C5C=%17C6=C5C6=C4C7=C3C1=C6C1=C5C%16=C3C%15=C%13C%11=C4C9=C2C1=C34 ATLMFJTZZPOKLC-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a preparation method of fullerene/water stock solution with synergistic stability of an electron transfer compound and surface hydroxyl. The method selects the nitrogen-containing polar organic solvent capable of forming the electron transfer complex with the fullerene, and is assisted with the processes of hydroxylation reaction, dialysis and the like to obtain the water-soluble fullerene with high water solubility, stability and good pi conjugation characteristics, thereby breaking through the prior two-phase preparation process of fullerene/water stock solution, avoiding the use of strong alkali and benzene series high-toxicity organic solvents and improving the biocompatibility of the stock solution. The fullerene/water stock solution obtained by the method has excellent antioxidation effect, and can be applied to the fields of cosmetics, biological medicines and the like.
Description
Technical Field
The invention relates to a preparation method of fullerene/water stock solution with synergistic stability of an electron transfer compound and surface hydroxyl, belonging to the technical field of fullerene materials.
Background
The fullerene has perfect molecular structure and rich physicochemical properties, has a large number of double bonds on the surface, has strong free radical removal performance, and has very wide application prospects in the fields of cosmetics, biological medicines, superconductivity, organic solar cells, nonlinear optical materials, artificial light synthesis and the like.
As a nonpolar molecule, fullerenes themselves have a strong hydrophobicity, have a very low solubility in polar solvents, in particular water, limiting their practical application, and are particularly apparent in the cosmetic and biomedical fields. In order to improve the water solubility of the fullerene, chemical modification is needed to obtain the fullerene/water stock solution. One common strategy is to hydroxylate the surface of fullerenes to obtain hydroxylated fullerenes, also known as fullerenes alcohols.
In order to obtain sufficient water solubility and colloid stability of the fullerene, a certain number of surface hydroxyl groups are required, so that the inherent pi conjugated system of the fullerene is inevitably destroyed. On the premise of ensuring water solubility and stability, the method ensures that the fullerene maintains pi conjugated structure to the maximum extent, which is a great difficulty in the field.
Another difficulty in the field of fullerol preparation is the cumbersome and harsh manufacturing processes, and the need for strong acids or bases. The current mainstream technology takes a strong base preparation route as a main material, and in the preparation process, the original fullerene is required to be dissolved in a benzene solvent in advance and then reacts with an aqueous solution containing strong base such as sodium hydroxide and hydrogen peroxide; in order to allow the reaction to proceed smoothly, a phase transfer catalyst such as tetrabutylammonium hydroxide is also added. This route of preparation has a number of drawbacks including: benzene organic solvent residues are easy to bring cytotoxicity; the use of strong base is easy to damage equipment and the surrounding environment; the reaction is carried out at the interface of two phases, which is inefficient and difficult to expand production; the obtained product is easy to contain sodium ions and tetrabutylammonium ions, which is unfavorable for subsequent application.
Therefore, the development of the preparation method of the fullerene/water stock solution, which is environment-friendly, safe and efficient, can keep the pi conjugated structure of the fullerene to the maximum extent and has excellent water solubility and stability, has important significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of a fullerene/water stock solution with a synergistic stability of an electron transfer compound and surface hydroxyl. The method selects the nitrogen-containing polar organic solvent capable of forming the electron transfer complex with the fullerene, and is assisted with the processes of hydroxylation reaction, dialysis and the like to obtain the water-soluble fullerene with high water solubility, stability and good pi conjugation characteristics, thereby breaking through the prior two-phase preparation process of fullerene/water stock solution, avoiding the use of strong alkali and benzene series high-toxicity organic solvents and improving the biocompatibility of the stock solution. The fullerene/water stock solution obtained by the method has excellent antioxidation effect, and can be applied to the fields of cosmetics, biological medicines and the like.
The technical scheme of the invention is as follows:
a preparation method of an electron transfer compound and surface hydroxyl synergistically stabilized fullerene/water stock solution comprises the following steps:
(1) Fully dissolving fullerene in a nitrogen-containing polar organic solvent or a mixed solvent of the nitrogen-containing polar organic solvent and water to obtain fullerene/organic solvent mother liquor;
(2) Adding an oxidant into the fullerene/organic solvent mother liquor prepared in the step (1) to enable the fullerene to have hydroxylation reaction; and then, obtaining the fullerene/water stock solution with the synergistic stability of the electron transfer compound and the surface hydroxyl through dialysis treatment.
According to a preferred embodiment of the present invention, the fullerene of step (1) is C 60 Or C 70 One or a mixture of two of them; preferably C 60 。
According to the invention, preferably, the nitrogen-containing polar organic solvent in the step (1) is one or a mixture of more than two of pyridine, imidazole, pyrimidine, pyrazole or azomethyl pyrrolidone; preferably, nitrogen methyl pyrrolidone.
According to the invention, in the mixed solvent of the nitrogen-containing polar organic solvent and water in the step (1), the water accounts for 1-30% by volume, preferably 10-20% by volume.
According to a preferred embodiment of the present invention, the concentration of fullerene in the fullerene/organic solvent mother liquor in the step (1) is 0.1 to 1.0 milligrams per milliliter.
According to the invention, the oxidant in the step (2) is hydrogen peroxide aqueous solution, and the mass fraction is 10-30%.
According to the invention, the volume ratio of the hydrogen peroxide aqueous solution to the fullerene/organic solvent mother solution in the step (2) is preferably 1:50-1:5, and is preferably 1:20-1:5.
According to the present invention, preferably, the hydroxylation reaction of step (2) is carried out under stirring.
According to the invention, the temperature of the hydroxylation reaction in step (2) is preferably 10-60 degrees celsius, preferably 25-60 degrees celsius.
According to the invention, the hydroxylation reaction in step (2) takes 24 to 168 hours, preferably 70 to 150 hours.
According to a preferred embodiment of the invention, the dialysis membrane has a molecular weight cut-off of 100 to 1000 daltons, preferably 100 to 500 daltons, during the dialysis treatment of step (2). Dialysis treatment was employed to remove excess nitrogen-containing polar organic solvent.
According to the invention, the dialysis treatment in the step (2) is performed by using a dialysis bag, and the volume ratio of deionized water outside the dialysis bag to liquid in the dialysis bag is 20:1-80:1; the replacement interval of the deionized water outside the dialysis bag is 12-48 hours, and the replacement times of the deionized water are 3-8 times.
According to the invention, preferably, the dialysis treatment in step (2) may further comprise a dilution step.
According to the invention, the mass concentration of the fullerene in the fullerene/water stock solution obtained in the step (2) is preferably 0.2-1.5 mg/ml.
The invention has the technical characteristics and beneficial effects that:
1. the preparation process of the method does not adopt benzene reagent with high toxicity to dissolve fullerene, but selects nitrogen-containing polar organic solvent with relatively low toxicity, the preparation process is green, and finally the obtained fullerene/water stock solution has low cytotoxicity and high biocompatibility because the fullerene/water stock solution does not contain benzene organic solvent.
2. The hydroxylation reaction is a homogeneous reaction, overcomes the defect of low efficiency of the prior two-phase reaction, and is convenient for expanding production; the preparation process does not need to add a phase transfer catalyst, avoids the introduction of impurity ions, improves the purity of the product and further simplifies the preparation process.
3. The preparation process of the method avoids the use of strong alkali, is environment-friendly, and the final product does not contain metal ions, thereby avoiding the restriction of excessive metal ions on subsequent application.
4. The preparation method is simple, green, environment-friendly, safe and efficient, and is beneficial to industrial production. In the fullerene/water stock solution obtained by the method, a small amount of nitrogen-containing polar organic solvent forms an electron transfer compound with the fullerene, and the surface of the fullerene is subjected to hydroxylation reaction; the two effects cooperate to ensure that a smaller amount of hydroxyl groups are grafted on the surface of the fullerene to have very high water solubility and dispersion stability, and the original pi conjugated structure is reserved to the greatest extent, so that the fullerene has strong free radical scavenging effect and antioxidation activity. The nitrogen-containing polar organic solvents with specific types and amounts are combined with proper oxidation conditions to realize the excellent effects of the invention, namely, the invention has very high water solubility and dispersion stability, and compared with the prior fullerols, the invention furthest maintains the original pi conjugated structure, thereby showing strong free radical scavenging effect and antioxidation activity.
Drawings
FIG. 1 shows fullerene C in example 1 of the present invention 60 UV-visible absorption spectra before (Curve I) and after (Curve II) hydroxylation of the mother liquor of N-methylpyrrolidone.
FIG. 2 shows fullerene C obtained in example 1 of the present invention 60 Photographs of the water stock.
FIG. 3 shows fullerene C at different concentrations in the test example 60 Electron spin resonance test result diagram of the water stock solution for removing hydroxyl radical; wherein, figure b is an enlarged view of the second peak in figure a; panel c is the hydroxyl radical scavenging rate plotted according to panel b.
FIG. 4 shows fullerene C obtained in example 1 of the present invention 60 And (3) freeze-drying the water stock solution to obtain a thermogravimetric analysis curve of the freeze-dried powder.
FIG. 5 shows fullerene C obtained in example 1 of the present invention 60 Freeze-drying the water stock solution to obtain freeze-dried powder (curve I) and original fullerene C 60 Is shown (curve II).
FIG. 6 is a graph showing the appearance of the dispersion in the dialysis process bag of comparative example 1 according to the present invention compared with the appearance of the solution in the bag of example 1.
FIG. 7 is an infrared spectrum of a lyophilized powder obtained by lyophilizing the fullerene/water stock solution obtained in comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, and apparatus, unless otherwise specified, are all commercially available.
Example 1
A preparation method of an electron transfer compound and surface hydroxyl synergistically stabilized fullerene/water stock solution comprises the following steps:
weighing 500 mg of Fullerene C 60 Dissolved in 500 ml of azomethineStirring to C in the polyvinylpyrrolidone 60 Completely dissolved. 200 ml of the fullerene/azomethyl pyrrolidone mother solution is taken, 20 ml of hydrogen peroxide with the mass concentration of 30% is added, and the mixture is stirred and reacted for 6 days at 25 ℃. The product was transferred to a dialysis bag having a molecular weight cut-off of 100 daltons, and the deionized water was used outside the dialysis bag in an amount of 8000mL, and dialyzed against deionized water for one week, with water changed every 24 hours. After the dialysis is finished, the solution in the bag is transferred out and diluted to 400 milliliters by deionized water to obtain fullerene C 60 Water stock solution.
The UV-visible absorption spectra of the fullerene/azamethylpyrrolidone mother liquor before (I) and after (II) hydroxylation are shown in FIG. 1. To ensure smooth testing, fullerene/azamethylpyrrolidone mother liquor or fullerene C 60 The aqueous stock was diluted to a concentration of 0.1 milligrams per milliliter. As can be seen from the figure, fullerene C 60 The characteristic absorption peak near 328 nm disappears after reaction, indicating fullerene C 60 Is partially destroyed, thereby strongly proving successful progress of the hydroxylation reaction.
The obtained fullerene C 60 A photograph of the/water stock solution is shown in fig. 2; from the figure, the bottom of the stock solution is free of any solid residues, which indicates that the stock solution has good solubility and stability.
The obtained fullerene C 60 Freeze-drying the water stock solution to obtain freeze-dried powder, and performing thermogravimetric analysis, wherein the thermogravimetric analysis curve is shown in figure 4. As can be seen from the figure, there is only a slight weight loss before 150 degrees of powder, indicating that the powder contains very little water of crystallization.
The obtained fullerene C 60 Freeze-drying the water stock solution to obtain freeze-dried powder, mixing the above freeze-dried powder (I) with original fullerene C 60 (II) IR spectrum test was conducted and the test results are shown in FIG. 5. Wherein is derived from fullerene C 60 Is marked with an asterisk. Characteristic peaks from solvent molecules are marked with triangles. Characteristic absorption peaks from hydroxyl groups are marked by circles, original fullerene C 60 The signal here is derived from the trace moisture contained.
The obtained fullerene C 60 Water stock solutionFreeze-drying to obtain freeze-dried powder, wherein the number ratio of carbon atoms to nitrogen atoms is 25.98 and the number ratio of carbon atoms to oxygen atoms is 4.31 according to the test result of the X-ray photoelectron spectroscopy of the freeze-dried powder. Wherein the nitrogen is derived from a small amount of fullerene C 60 A nitrogen-containing polar organic solvent that forms an electron transfer complex.
Example 2
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: replacing the nitrogen methyl pyrrolidone with pyridine; other steps and conditions were consistent with example 1.
Example 3
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: replacing the nitrogen methyl pyrrolidone with imidazole; other steps and conditions were consistent with example 1.
Example 4
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: replacing the nitrogen methyl pyrrolidone with pyrimidine; other steps and conditions were consistent with example 1.
Example 5
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: replacing the nitrogen methyl pyrrolidone with pyrazole; other steps and conditions were consistent with example 1.
Example 6
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: fullerene C 60 The amount of (2) was 375 mg and the concentration of fullerene in the fullerene/azamethylpyrrolidone mother liquor was 0.75 mg/ml; other steps and conditions were consistent with example 1.
Example 7
Preparation method of fullerene/water stock solution with synergistic stability of electron transfer compound and surface hydroxylThe process is as described in example 1, except that: fullerene C 60 The amount of (2) was 250 mg, and the concentration of fullerene in the fullerene/azamethylpyrrolidone mother liquor was 0.5 mg/ml; other steps and conditions were consistent with example 1.
Example 8
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: fullerene C 60 The amount of (2) was 125 mg, and the concentration of fullerene in the fullerene/azamethylpyrrolidone mother liquor was 0.25 mg/ml; other steps and conditions were consistent with example 1.
Example 9
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the solvent nitrogen methyl pyrrolidone is replaced by nitrogen methyl pyrrolidone/water mixed solution (volume ratio is 5:1); other steps and conditions were consistent with example 1.
Example 10
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: fullerene C 60 Substituted by fullerenes C 70 The method comprises the steps of carrying out a first treatment on the surface of the Other steps and conditions were consistent with example 1.
Example 11
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: fullerene C 60 Replaced by fullerene C with the weight ratio of 1:1 60 Fullerene C 70 A mixture; other steps and conditions were consistent with example 1.
Example 12
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the dosage of the hydrogen peroxide with the mass concentration of 30 percent is 40 milliliters; other steps and conditions were consistent with example 1.
Example 13
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the dosage of the hydrogen peroxide with the mass concentration of 30 percent is 10 milliliters; other steps and conditions were consistent with example 1.
Example 14
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the reaction temperature is 40 ℃; other steps and conditions were consistent with example 1.
Example 15
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the reaction temperature is 60 ℃; other steps and conditions were consistent with example 1.
Example 16
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the reaction time is 5 days; other steps and conditions were consistent with example 1.
Example 17
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the reaction time is 3 days; other steps and conditions were consistent with example 1.
Example 18
A method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups, as described in example 1, except that: the molecular weight cut-off of the dialysis bag is 500 daltons; other steps and conditions were consistent with example 1.
Comparative example 1
A preparation method of fullerene/water stock solution comprises the following steps:
weighing 500 mg of Fullerene C 60 Dissolved in 500 ml of nitrogen methyl pyrrolidone and stirred to C 60 Completely dissolved. 200 ml of the fullerene/azomethyl pyrrolidone mother solution is taken and directly transferred to a molecular cut-offIn a dialysis bag of 100 daltons, the deionized water was used outside the dialysis bag in an amount of 8000mL, and dialyzed with deionized water for one week, with water changed every 24 hours. After the dialysis is finished, the solution in the bag is transferred out and diluted to 400 milliliters by deionized water.
In comparison with examples 1-18, in the comparative example, the hydroxylation reagent hydrogen peroxide was not used in the preparation of the fullerene crude liquid.
A comparison of the appearance of the dispersion in the bag with the solution in the bag of example 1 during dialysis is shown in fig. 6; as can be seen from the figure, the dispersion obtained in comparative example 1 was cloudy in appearance; after the dialysis is finished, layering occurs in the dispersion liquid placing process, and the stability is poor, which indicates that the use of the hydroxylation reagent hydrogen peroxide is beneficial to obtaining fullerene/water stock solution with good stability.
The infrared spectrum of the lyophilized powder obtained by lyophilizing the fullerene/water stock solution obtained in comparative example 1 is shown in fig. 7. From the figure, it can be seen that the lyophilized powder still retains the original fullerene C 60 Characteristic absorption peaks (asterisks) of (a) indicate fullerene C 60 No significant hydroxylation occurred.
Test examples
For fullerene C prepared in example 1 60 Diluting the water stock solution to obtain fullerene C with fullerene concentration of 1.6ppm, 8.0ppm, 16ppm and 80ppm 60 The water stock solution is subjected to electron spin resonance test for removing hydroxyl free radicals (the electron spin resonance test condition is that the concentration of the free radical trapping agent DMPO is 0.2 mol/liter, the concentration of hydrogen peroxide is 10 millimoles/liter, and FeSO is carried out) 4 ·7H 2 O concentration of 0.25 mmole/liter) while being free of fullerene C 60 The test results are shown in FIG. 3. FIG. b is an enlarged view of the second peak in FIG. a, with the left peak from top to bottom, fullerene C 60 The concentration (ppm) of (a) is: 0. 1.6, 8.0, 16, 80. Panel c is the hydroxyl radical scavenging rate plotted according to panel b. As can be seen from the figure, fullerene C 60 The water stock solution has strong capability of scavenging hydroxyl free radicals, and the free radical scavenging rate continuously rises with the increase of the concentration.
Claims (10)
1. A preparation method of an electron transfer compound and surface hydroxyl synergistically stabilized fullerene/water stock solution comprises the following steps:
(1) Fully dissolving fullerene in a nitrogen-containing polar organic solvent or a mixed solvent of the nitrogen-containing polar organic solvent and water to obtain fullerene/organic solvent mother liquor; the concentration of the fullerene in the fullerene/organic solvent mother solution is 0.1-1.0 milligram per milliliter;
the nitrogen-containing polar organic solvent is one or a mixture of more than two of pyridine, imidazole, pyrimidine, pyrazole or azomethyl pyrrolidone;
(2) Adding an oxidant into the fullerene/organic solvent mother liquor prepared in the step (1) to enable the fullerene to have hydroxylation reaction; then, the fullerene/water stock solution with the synergistic stability of the electron transfer compound and the surface hydroxyl is obtained after dialysis treatment;
the oxidant is hydrogen peroxide aqueous solution, and the mass fraction is 10-30%; the volume ratio of the hydrogen peroxide aqueous solution to the fullerene/organic solvent mother solution is 1:50-1:5; the temperature of the hydroxylation reaction is 10-60 ℃; the hydroxylation reaction time is 24-168 hours.
2. The method for preparing a fullerene/water stock solution with synergistically stabilized electron transfer complex and surface hydroxyl groups according to claim 1, wherein the fullerene in step (1) is C 60 Or C 70 One or a mixture of both.
3. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein the nitrogen-containing polar organic solvent in step (1) is nitrogen methyl pyrrolidone.
4. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein the volume percentage of water in the mixed solvent of the nitrogen-containing polar organic solvent and water in the step (1) is 1-30%.
5. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein in the step (2), the volume ratio of the hydrogen peroxide aqueous solution to the fullerene/organic solvent mother solution is 1:20-1:5.
6. The method of preparing a synergistically stable fullerene/water stock solution of an electron transfer complex and a surface hydroxyl group according to claim 1, wherein in step (2), one or more of the following conditions are included:
i. the hydroxylation reaction is carried out under stirring conditions;
ii. The temperature of the hydroxylation reaction is 25-60 ℃;
and iii, the hydroxylation reaction time is 70-150 hours.
7. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein the molecular weight cut-off of the dialysis membrane is 100-1000 dalton, preferably 100-500 dalton, during the dialysis treatment in step (2).
8. The method for preparing the fullerene/water stock solution with the synergistic stabilization of the electron transfer compound and the surface hydroxyl group according to claim 1, wherein the dialysis treatment in the step (2) is performed by using a dialysis bag, and the volume ratio of deionized water outside the dialysis bag to liquid in the dialysis bag is 20:1-80:1; the replacement interval of the deionized water outside the dialysis bag is 12-48 hours, and the replacement times of the deionized water are 3-8 times.
9. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein the step (2) may further comprise a dilution step after the dialysis treatment.
10. The method for preparing a fullerene/water stock solution with synergistic stabilization of electron transfer complex and surface hydroxyl groups according to claim 1, wherein the mass concentration of fullerene in the fullerene/water stock solution obtained in the step (2) is 0.2-1.5 mg/ml.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110996351.2A CN113735099B (en) | 2021-08-27 | 2021-08-27 | Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110996351.2A CN113735099B (en) | 2021-08-27 | 2021-08-27 | Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113735099A CN113735099A (en) | 2021-12-03 |
CN113735099B true CN113735099B (en) | 2023-11-07 |
Family
ID=78733436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110996351.2A Active CN113735099B (en) | 2021-08-27 | 2021-08-27 | Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113735099B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115350284B (en) * | 2022-08-10 | 2023-10-27 | 山东大学 | Tryptophan-modified fullerene nanomaterial, preparation method thereof and application thereof in field of nerve repair |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007176899A (en) * | 2005-12-28 | 2007-07-12 | Vitamin C60 Bioresearch Kk | Hydroxylated fullerene, method for producing the same, antioxidation composition and composition for external application |
CN101239026A (en) * | 2007-12-25 | 2008-08-13 | 中国科学院上海应用物理研究所 | Application of fullerol in beauty treatment skin care products |
CN102583303A (en) * | 2012-02-24 | 2012-07-18 | 中国科学院化学研究所 | Method for preparing high water solubility fullerol |
CN105541635A (en) * | 2016-02-22 | 2016-05-04 | 陈铭 | Fullerol poly-nitrate and preparation method thereof |
CN107556166A (en) * | 2016-06-30 | 2018-01-09 | 中国科学院化学研究所 | Polyhydroxylated fullerene and preparation method thereof |
WO2018113684A1 (en) * | 2016-12-19 | 2018-06-28 | 北京福纳康生物技术有限公司 | Use of fullerene structure in preparation of drug for treating leukemia |
-
2021
- 2021-08-27 CN CN202110996351.2A patent/CN113735099B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007176899A (en) * | 2005-12-28 | 2007-07-12 | Vitamin C60 Bioresearch Kk | Hydroxylated fullerene, method for producing the same, antioxidation composition and composition for external application |
CN101239026A (en) * | 2007-12-25 | 2008-08-13 | 中国科学院上海应用物理研究所 | Application of fullerol in beauty treatment skin care products |
CN102583303A (en) * | 2012-02-24 | 2012-07-18 | 中国科学院化学研究所 | Method for preparing high water solubility fullerol |
CN105541635A (en) * | 2016-02-22 | 2016-05-04 | 陈铭 | Fullerol poly-nitrate and preparation method thereof |
CN107556166A (en) * | 2016-06-30 | 2018-01-09 | 中国科学院化学研究所 | Polyhydroxylated fullerene and preparation method thereof |
WO2018113684A1 (en) * | 2016-12-19 | 2018-06-28 | 北京福纳康生物技术有限公司 | Use of fullerene structure in preparation of drug for treating leukemia |
Non-Patent Citations (1)
Title |
---|
朱道本等.《有机固体》.上海科学技术出版社,1999,第244-245页. * |
Also Published As
Publication number | Publication date |
---|---|
CN113735099A (en) | 2021-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20190001307A1 (en) | Novel composite of iron compound and graphene oxide | |
CN113735099B (en) | Preparation method of electron transfer compound and fullerene/water stock solution with synergistic stability of surface hydroxyl groups | |
Zhang et al. | Synthesis and solvent enhanced relaxation property of water-soluble endohedral metallofullerenols | |
DE19637433B4 (en) | Metal-encapsulated fullerene compound and process for its manufacture | |
CN111359589A (en) | Chitosan/bacterial cellulose composite aerogel adsorbent and preparation method and application thereof | |
CN107879335B (en) | Preparation method of nitrogen-doped graphene quantum dot material | |
CN111012915A (en) | Carbon dot with tumor targeting function, preparation method and application | |
US20240122178A1 (en) | Caffeic acid-based composite material and preparation method thereof | |
AU2020104156A4 (en) | A nano-capsule type polydopamine drug material and method for preparing the same | |
CN111840574A (en) | Preparation and application of 5-aminolevulinic acid-camptothecin small-molecule prodrug | |
Zhou et al. | Modulated covalent organic frameworks with higher specific surface area for the ultrasensitive detection of polybrominated biphenyls | |
CN110078055B (en) | Porphyrin-metal complex functionalized carbon nanotube composite material with controllable layer thickness and preparation method and application thereof | |
CN113897625B (en) | Composite catalyst and preparation method thereof | |
CN103553021A (en) | Water-soluble poly gamma cyclodextrin-C60 supermolecule clathrate compound as well as preparation method thereof | |
CN112409228A (en) | Preparation method of chiral sulfur and nitrogen co-doped graphene quantum dot | |
JPH0748302A (en) | Method for synthesizing fullerol | |
CN106810462B (en) | A kind of preparation method of the more azepine bridge soluble derivatives of fullerene | |
CN108394927A (en) | A kind of preparation method of the nano cupric oxide of morphology controllable | |
CN112574146A (en) | Preparation method of butenolide compound composite nanocrystal | |
CN108517006B (en) | Polypeptide material for improving dispersibility of carbon nano tube in water under normal temperature and pressure condition and application thereof | |
JP2008222585A (en) | beta-1,3-GLUCAN/CARBORANE COMPLEX | |
CN115710283A (en) | Compound, preparation method and application thereof, and preparation method of near-infrared-IIa fluorescence imaging contrast agent | |
CN112023044A (en) | Near-infrared light and pH dual-response oleic acid derivative nano drug-loaded material and preparation method and application thereof | |
CN108467407B (en) | Method for enhancing proton conductivity of two-dimensional layered rare earth organic phosphonate | |
CN109331189B (en) | Preparation method of paramagnetic gadolinium-based metal fullerol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |