CN102674312B - Water soluble fullerene and preparation method thereof - Google Patents
Water soluble fullerene and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of water soluble fullerene, which comprises the following steps: step 1, strongly mixing fullerene powder with water soluble molecules capable of generating stable action with the fullerene by using a mixer to form a mixture; step 2, dissolving the mixture into water for fully agitating; step 3, filtering an obtained filtrate for more times by using a filter, i.e. water soluble fullerene solution; and step 4, heating to evaporate solvent water and then vacuum-drying to obtain the powdery solid water soluble fullerene. The invention also relates to the water soluble fullerene prepared by the preparation method. The preparation method has the advantages of greenness, environment friendliness, safety and high efficiency and is suitable for mass production.
Description
Technical field
The water-soluble fullerene that the present invention relates to a kind of novel water-soluble fullerene preparation method and prepare by this preparation method, refers in particular to a kind of water-soluble fullerene with physiologically actives such as Green Tea Extract oxidations and preparation method thereof.
Background technology
Since within 1985, being found, soccerballene is just because its special physics and chemistry performance receives much attention.The richest C of output wherein
60, C
70two kinds of fullerene molecules and derivative thereof, mixture, inclusion compound, be found to have the physiologically actives such as excellent anti-oxidant activity, germ resistance and cancer resistance especially.1992, the Charles N.McEwen of E.I.Du Pont Company found that soccerballene has superpower elimination free radical character, has proposed first thus the concept that soccerballene can be used as " free radical sponge ".After this, the applied research of removing free radical around soccerballene extensively launches, and the researchist of Japan more successfully introduces soccerballene in makeup, has made and has had the skin care product of the special efficacies such as Green Tea Extract and approved.But through years of researches, it is found that soccerballene based compound, when application process, should guarantee the physiologically active that it is excellent, guarantee that again its satisfactory stability is very difficult.In existing report, address this problem the two kinds of methods (Biomedicine & Pharmacotherapy 59 (2005) 351-358) that mainly contain: 1) chemical modification method, utilizes chemical reaction outside soccerballene, to modify hydroxyl or carboxyl; 2) the coated method of water-soluble polymer, utilizes the water-soluble molecules such as polyoxyethylene glycol (PEG), polyvinylpyrrolidone (PVP), cyclodextrin that fullerene molecule is wrapped to form to water-soluble compound).Based on above-mentioned two kinds of methods, prepare in the relevant report of water-soluble fullerene at present, the processing condition that adopt are all very complicated, relate to a large amount of organic even uses to organism harmful reagent.The more important thing is that existing study (L.Xiao et al./Bioorg.Med.Chem.Lett.16 (2006) 1590-1595) points out, when water-soluble fullerene disperses the particle diameter of formation to be less than 100nm in water, can increase the bio-toxicity of water-soluble fullerene.And the particle diameter that makes water-soluble fullerene molecule in traditional method is conventionally less, thereby make practical application bring potential safety hazard.Therefore seek the preparation method of green high-efficient, guarantee that it is that soccerballene needs the urgent problem solving in actual applications that gained water-soluble fullerene molecule has rational size simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of both environmental protections, safe and efficient, is suitable for again the water-soluble fullerene preparation method of batch production and the water-soluble fullerene preparing by this method.
Solving the technical scheme that technical problem of the present invention adopts is: a kind of preparation method of water-soluble fullerene is provided, and it comprises the steps:
Step 1, fullerene powder and the water-soluble molecules that can produce stabilization with soccerballene are carried out to powerful mixing with mixer form mixture;
Step 2, then fully stir described mixture is soluble in water;
Step 3, with the filtrate that strainer multiple times of filtration obtains, be water-soluble fullerene solution;
Step 4, heating evaporation fall aqueous solvent, and then vacuum-drying obtains the water-soluble fullerene of pulverulent solids.
In preparation method of the present invention, described soccerballene comprises empty fullerene or embed fullerene.Preferably, described soccerballene is C
60or C
70.
In preparation method of the present invention, described water-soluble molecules is selected from Polyvinylpyrolidone (PVP), polyoxyethylene glycol, starch and derivative thereof, methylol/propyl cellulose, polyacrylamide, polyacrylic acid, gum arabic, polyvinyl alcohol or POLYPROPYLENE GLYCOL a kind of.Preferably, described water-soluble molecules is Polyvinylpyrolidone (PVP).More preferably, the molecular-weight average of described Polyvinylpyrolidone (PVP) is 5000-1500000.
In preparation method of the present invention, the mass ratio of soccerballene and Polyvinylpyrolidone (PVP) is for being less than 1: 70.Preferably, the mass ratio of soccerballene and Polyvinylpyrolidone (PVP) is 1: 80-1: 100.
In preparation method of the present invention, when utilizing mixer to carry out powerful mixing, coordinate suitable cooling provision not oxidized to guarantee fullerene powder.
In preparation method of the present invention, the powerful mixing time should be 12-96 hour.
In preparation method of the present invention, the water temperature in step 2 is 20-40 ℃.
In preparation method of the present invention, the churning time in step 2 is 2-12 hour.
In preparation method of the present invention, the filter pore size in step 3 is 0.7-1.0 μ m.Preferably, described filter pore size is 0.8 μ m.
Solving another technical scheme that technical problem of the present invention adopts is: provide a kind of according to the water-soluble fullerene preparing according to above-mentioned preparation method.
With other prior art comparison, the present invention has the following advantages:
1, in preparation method's provided by the invention whole process, do not use any organic reagent, so do not have dissolvent residual problem in product.Guarantee the safety in utilization of product, also saved the needed complex process of follow-up removal residual solvent simultaneously.Whole technological process is simple, the equipment less energy-consumption adopting, high production capacity, and there is not the discharge of any pollutent in whole production process simultaneously, is therefore a kind of environmental protection, safely and effectively production technique.
2,, in preparation method provided by the invention, between water-soluble molecules and soccerballene, by the abundant combination of physical mixed method, make the peripheral coated a large amount of water-soluble molecules of soccerballene, and then realize soccerballene deliquescent raising in water.But the molecular structure of soccerballene does not change, stability and the physicochemical property of fullerene molecule carbon cage itself have been kept.
3, preparation method provided by the invention, be applicable to multiplely can produce interact soccerballene is carried out to coated water-soluble polymer with soccerballene, so universality be strong, is easy to apply.
4, preparation method provided by the invention, related whole technological process may be summarized to be: (1), powder batch mixing---dissolves and---filters---evaporating solvent---dry---pulverizing---sterilizing---packing; Or; (2), powder batch mixing------------demarcate concentration---sterilizing---packing, be highly susceptible to amplifying production in filtration in dissolving by constant volume.
5, the water-soluble fullerene of preparing in preparation method provided by the invention is compared and is had larger particle diameter with conventional solvent mediated method gained water-soluble fullerene of the same type, the inventive method residual, therefore safer in the application meeting of biomedical sector without any organic reagent in preparation process simultaneously.
6, preparation method provided by the invention, in production process, unrealized effectively compound soccerballene and water-soluble molecules, can realize recycling by solvent-extracted method.
7, method provided by the invention, resulting water-soluble fullerene is excellent performance aspect removal free radical, therefore in cosmetic industry, biomedical sector, has significant application value.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 a is the transmission electron microscope photo figure of the water-soluble fullerene of the embodiment of the present invention one gained.
Fig. 1 b is the dynamic light scattering size distribution plot of the water-soluble fullerene of the embodiment of the present invention one gained.
Fig. 2 a is the transmission electron microscope photo figure of the water-soluble fullerene of the embodiment of the present invention two gained.
Fig. 2 b is the dynamic light scattering size distribution plot of the water-soluble fullerene of the embodiment of the present invention two gained.
Fig. 3 a is the comparison diagram of the uv-absorbing spectrogram of the prepared water-soluble fullerene of the embodiment of the present invention one and conventional solvent mediated method gained water-soluble fullerene.
Fig. 3 b is the comparison diagram of the dynamic light scattering size distribution plot of the prepared water-soluble fullerene of the embodiment of the present invention one and conventional solvent mediated method gained water-soluble fullerene.
Fig. 4 a is the transmission electron microscope picture of the prepared water-soluble fullerene of conventional solvent mediated method.
Fig. 4 b is the transmission electron microscope picture of the water-soluble fullerene of embodiments of the invention one gained.
The C that Fig. 5 a, 5b, 5c are different concns
60-PVP mixture is removed the ESR spectrogram of hydroxyl radical free radical.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.Described method is ordinary method if no special instructions.Described reactant all can obtain from open commercial sources if no special instructions.
Embodiment mono-:
By 4.8g polyvinylpyrrolidone (PVP), 55mg C
60(C
60shared mass percent is 1.14%) with mixer (mixer can be and is all applicable to the apparatus that solid material mixes), mix and be placed in ball mill, the abundant ball milling that adds wherein zirconia ball or agate ball to carry out 12 hours mixes, wherein, when utilizing mixer to carry out powerful mixing, coordinate suitable cooling provision, preferred cycle cooling water system, not oxidized to guarantee fullerene powder.
Subsequently mixture is dissolved in 400ml water, and fully stirs 2 hours, with strainer, the mixing solutions that stirs is filtered afterwards, gained transparent yellow brown filtrate is water-soluble fullerene solution; By the throw out of filtering, be to fail to carry out completely compound soccerballene residuum substantially, undercompounding soccerballene and polyvinylpyrrolidone reclaim dry.
Then, heating water-soluble fullerene solution, with solvent evaporated water, then carries out low pressure with Freeze Drying Equipment at low temperatures and is dried, and obtains the water-soluble fullerene of pulverulent solids.Fail to carry out compound C60 with PVP, utilize toluene to extract, C60-toluene solution after extraction is after Rotary Evaporators solvent evaporated, in vacuum drier, be dried to powder, the heavily about 4.1mg of dried C60 powder, carry out compound C60 with PVP and be about 50.9mg, calculate actual PVP-C
60c in mixture
60shared mass percent is 1.03%, the about 200nm of mixture grain size.With reference to accompanying drawing, Fig. 1 a is the PVP-C of the present embodiment one gained
60the transmission electron microscope photo figure of mixture, Fig. 1 b is the PVP-C of the present embodiment one gained
60the dynamic light scattering size distribution plot of mixture.
Embodiment bis-:
Concrete grammar is with embodiment mono-, and difference is C
60shared percentage composition is increased to 1.56%, and mixing time is 48 hours.Under this condition, obtain actual PVP-C
60c in mixture
60percentage is 1.01%, the about 200nm of mixture grain size.Fig. 2 a and Fig. 2 b are respectively the PVP-C of the present embodiment two gained
60the transmission electron microscope photo figure of mixture and dynamic light scattering size distribution plot.
Embodiment tri-:
By after gained water-soluble fullerene solution solvent evaporated in embodiment mono-or enforcement two, be placed in freezer compartment of refrigerator sample is fully freezed, be then placed in Freeze Drying Equipment and carry out abundant low pressure drying treatment, obtain PVP-C
60composite powder, about 4.7g weighs.Can draw white PVP powder and black C
60powder forms sundown powder after compound, and solution is brown color.Also further illustrate PVP and C
60really formed uniform mixture.
The sample of the method gained and conventional solvent mediated method gained sample are contrasted.
Tradition is dissolved mediated method (reference: L.Xiao et al./Bioorg.Med.Chem.Lett.16 (2006) 1590-1595): 4.8g PVP is dissolved in 100ml ethanol or chloroform, by 55mg C
60be dissolved in 60ml toluene, then under the state stirring, both mixed, rear continuation is stirred and is spent the night, and finds that there is and fail to carry out compound C with PVP in process
60powder deposition is in beaker bottom.By after the solution solvent evaporated on beaker upper strata, add 100ml water fully to stir mixture is dissolved completely, subsequently the solution stirring is added to heat extraction residual ethanol or chloroform, finally add water to 400ml.
Tradition dissolving mediated method is compared with method of the present invention (as the method for embodiment mono-), method of the present invention has following clear superiority: one, environmental protection more in the technological process of the inventive method, both without the use of organic reagent, again without the discharge of any pollutent; Two, the particle size of the inventive method products therefrom obviously increases compared with the particle size of conventional solvent mediated method products therefrom, and particle size prepared by method of the present invention is completely controlled, can significantly improve the security of products therefrom biologic applications.As shown in the figure, Fig. 3 a and Fig. 3 b are respectively uv-absorbing spectrogram and the dynamic light scattering size distribution plot of two kinds of method gained samples.Known from Fig. 3 a, two kinds of method gained PVP-C
60the ultraviolet-visible absorption spectroscopy of mixture does not have notable difference, and PVP-C
60mixture has obvious C at 340nm place
60absorption peak, illustrate that both are really evenly compound.From Fig. 3 b and Fig. 4 a and Fig. 4 b (Fig. 4 a is conventional solvent mediated method, and Fig. 4 b is the inventive method), can learn that two kinds of methods but have marked difference on grain size distributes: the PVP-C that the inventive method is prepared
60the particle diameter of mixture (about 200nm) will be far longer than conventional solvent mediated method gained PVP-C
60the particle diameter of mixture (about 60nm), larger particle diameter, by the biological safety of gained mixture is improved, is conducive to PVP-C more
60mixture is in the application of biological association area.
By embodiment mono-gained liquid sample stirring and refluxing 48 hours in the temperature range of 130-200 ℃, have no sample property and change, carry out ultraviolet and dynamic light scattering and characterize and find that it absorbs and any variation does not all occur particle diameter.Embodiment mono-gained sample is dissolved after 20 days again and carries out uv-absorbing and dynamic light scattering sign-20 ℃ of placements, have no considerable change.The PVP-C that known the inventive method is prepared
60mixture has good thermostability.
Get embodiment mono-gained liquid sample 10ml and mix with 20ml toluene, stratification after ultrasonic 48 hours, upper toluene solution carries out mass spectral characteristi and has no C
60(molecular weight 720) peak value occurs; Lower aqueous solution carries out ultraviolet and dynamic light scattering characterizes, and UV, visible light absorbs spectrogram and size distribution has no considerable change.Toluene solvant is changed and is ethanol or DMF, carry out same Experimental Ultrasonic, find too, prepared water-soluble fullerene can stable existence, PVP and C
60can't be separated because of the effect of other solvent.Illustrate that the preparation-obtained water-soluble fullerene of the inventive method has good solvent stability, can stable existence in most of solvents.Get embodiment mono-gained solid sample and carry out above same test, find to have the stability identical with liquid sample.
For adopting the resulting C of the inventive method
60-PVP mixture, adopts spin trapping method (ESR) to measure free radical removal effect.Concrete operations are: for hydrogen peroxide, react the free radical producing with ferrous ion, utilize DMPO (5，5-dimethyl-1-pyrroline-N-oxide compound) as spin trapping agent, detect the signal of the product D MPO-OH of DMPO and hydroxyl radical reaction generation.
In actual test: the concentration of ferrous sulfate is 0.4mmol/L, and the pH value that the mass concentration of hydrogen peroxide is 5%, PBS is 7.4, C
60the concentration of-PVP is 15mmol/L, and the concentration of DMPO is 0.4mol/L, respectively gets after above five kinds of solution, 50 μ L mix and tests.As Fig. 5 a, 5b, 5c are depicted as the C of different concns
60-PVP mixture is removed the ESR spectrogram of hydroxyl radical free radical: Fig. 5 a is blank test, in DMPO-OH test system, does not add C
60-PVP mixture; Fig. 5 b adds C in DMPO-OH test system
60-PVP mixture, and its ultimate density is 300 μ mol/L; Fig. 5 c adds C in DMPO-OH test system
60-PVP mixture, and its ultimate density is 3000 μ mol/L.From Fig. 5 a, Fig. 5 b, Fig. 5 c, can learn, along with C
60the increase of-PVP complex concentration, the performance of removing hydroxyl radical free radical also strengthens thereupon.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (11)
1. a preparation method for water-soluble fullerene, is characterized in that, it comprises the steps:
Step 1, fullerene powder and Polyvinylpyrolidone (PVP) are carried out after powerful mixing to ball milling again with mixer be mixed to form mixture; While utilizing mixer to carry out powerful mixing, coordinate cooling provision not oxidized to guarantee fullerene powder;
Step 2, then fully stir described mixture is soluble in water;
Step 3, with the filtrate that strainer multiple times of filtration obtains, be water-soluble fullerene solution;
Step 4, heating evaporation fall aqueous solvent, and then vacuum-drying obtains the water-soluble fullerene of pulverulent solids.
2. method according to claim 1, is characterized in that: described soccerballene comprises empty fullerene or embed fullerene.
3. method according to claim 2, is characterized in that: described soccerballene is C
60or C
70.
4. method according to claim 1, is characterized in that: the molecular-weight average of described Polyvinylpyrolidone (PVP) is 5000-1500000.
5. method according to claim 4, is characterized in that: the mass ratio of described soccerballene and Polyvinylpyrolidone (PVP) is for being less than 1:70.
6. method according to claim 5, is characterized in that: the mass ratio of described soccerballene and Polyvinylpyrolidone (PVP) is 1:80-1:100.
7. method according to claim 1, is characterized in that: the powerful mixing time should be 12-96 hour.
8. method according to claim 7, is characterized in that: in step 2, water temperature is 20-40 ℃.
9. method according to claim 1, is characterized in that: in step 2, churning time is 2-12 hour.
10. method according to claim 1, is characterized in that: in step 3, described filter pore size is 0.7-1.0 μ m.
11. methods according to claim 10, is characterized in that: in step 3, described filter pore size is 0.8 μ m.
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| CN103072966A (en) * | 2012-12-18 | 2013-05-01 | 深圳市通产丽星股份有限公司 | Apparatus for preparing water-soluble fullerene |
| CN105085937B (en) * | 2015-07-20 | 2018-03-30 | 深圳市华星光电技术有限公司 | Fullerene/PEDOT:The preparation method of PSS mixed solutions and there is fullerene/PEDOT:The preparation method of the substrate of PSS composite transparent conductive films |
| CN105125580B (en) * | 2015-07-30 | 2017-01-11 | 北京大学深圳研究院 | Fullerene-macromolecule composite and preparation method thereof |
| CN105482341A (en) * | 2016-01-29 | 2016-04-13 | 吴现成 | Preparation method for carbon fullerene water-soluble solids |
| CN107814375B (en) * | 2016-09-13 | 2020-05-22 | 中国科学院化学研究所 | Fullerene water-soluble modifier and preparation method thereof |
| WO2018064963A1 (en) * | 2016-10-08 | 2018-04-12 | 北京福纳康生物技术有限公司 | Use of fullerene structure in preparation of medicament for treating tumor |
| CN107411983B (en) * | 2017-09-12 | 2020-10-20 | 北京福纳康生物技术有限公司 | Water-soluble fullerene external composition |
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| CN108904302B (en) * | 2018-08-02 | 2021-01-29 | 北京福纳康生物技术有限公司 | Water-soluble fullerene external composition |
| CN108852870A (en) * | 2018-09-04 | 2018-11-23 | 广东科玮生物技术股份有限公司 | A kind of anti-radiation sun screen and preparation method thereof |
| CN110063909A (en) * | 2019-05-10 | 2019-07-30 | 刘银忠 | A kind of water-soluble fullerene preparation and preparation method thereof |
| CN111374824A (en) * | 2020-04-24 | 2020-07-07 | 上海紫河生物科技有限公司 | Manufacturing process of antibacterial paper diaper for children |
| CN112941906B (en) * | 2021-03-03 | 2022-12-06 | 厦门福纳新材料科技有限公司 | Fullerene composite fiber fabric and preparation method thereof |
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