CN102674312A - Water soluble fullerene and preparation method thereof - Google Patents
Water soluble fullerene and preparation method thereof Download PDFInfo
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- CN102674312A CN102674312A CN2012101261230A CN201210126123A CN102674312A CN 102674312 A CN102674312 A CN 102674312A CN 2012101261230 A CN2012101261230 A CN 2012101261230A CN 201210126123 A CN201210126123 A CN 201210126123A CN 102674312 A CN102674312 A CN 102674312A
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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 present invention relates to a kind of novel water-soluble fullerene preparation method and the water-soluble fullerene for preparing with this preparation method, refer in particular to a kind of water-soluble fullerene and preparation method thereof with physiologically actives such as Green Tea Extract oxidations.
Background technology
Since coming to light in 1985, soccerballene just receives much attention because of its special physics and chemical property.The richest C of output wherein
60, C
70Two kinds of fullerene molecules and verivate thereof, mixture, inclusion compound, physiologically actives such as especially having excellent antioxidant activity, bacterinertness and anti-carcinogenic property comes to light.1992, the Charles N.McEwen of E.I.Du Pont Company found that soccerballene has superpower elimination radical character, has proposed the notion that soccerballene can be used as " radical sponge " thus first.After this, the applied research of removing radical around soccerballene extensively launches, and the researchist of Japan more successfully introduces soccerballene in the makeup, has processed the skin care item that special efficacies such as Green Tea Extract are arranged and is approved.But through years of researches, it is found that the soccerballene based compound when application process, should guarantee the physiologically active that it is excellent, guarantee that again its satisfactory stability property 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, promptly utilize chemical reaction outside soccerballene, to modify hydroxyl or carboxyl; 2) water-soluble polymer coats method, promptly utilizes water-soluble molecules such as polyoxyethylene glycol (PEG), Vinylpyrrolidone polymer (PVP), Schardinger dextrins that fullerene molecule is wrapped to form water-soluble compound).Prepare in the relevant report of water-soluble fullerene based on above-mentioned two kinds of methods at present, the processing condition that adopted are all very complicated, relate to a large amount of organic even to the use of organism harmful reagent.The more important thing is that existing research (L.Xiao et al./Bioorg.Med.Chem.Lett.16 (2006) 1590-1595) points out, the particle diameter that in water, disperses formation when water-soluble fullerene can increase the bio-toxicity of water-soluble fullerene during less than 100nm.And the particle diameter that makes the water-soluble fullerene molecule in the traditional method is less usually, thereby makes practical application bring potential safety hazard.Therefore seek the preparation method of green high-efficient, guarantee that simultaneously it is that soccerballene needs the urgent problem that solves in practical application that gained water-soluble fullerene molecule has rational size.
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 water-soluble fullerene preparation method who produces in batches and the water-soluble fullerene for preparing with this method again.
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, with fullerene powder with can carry out powerful mixing with mixer with the water-soluble molecules that soccerballene produces stabilization and form mixture;
Step 2, fully stir said mixture is soluble in water then;
Step 3, the filtrating that obtains with the strainer multiple times of filtration are water-soluble fullerene solution;
Step 4, heating evaporation fall aqueous solvent, and vacuum-drying then obtains the water-soluble fullerene of pulverulent solids.
In preparation method of the present invention, said soccerballene comprises empty fullerene or embed fullerene.Preferably, said soccerballene is C
60Or C
70
In preparation method of the present invention, said water-soluble molecules is selected from PVP K120, polyoxyethylene glycol, starch and verivate thereof, methylol/propyl cellulose, SEPIGEL 305, ROHM, gum arabic, Z 150PH or POLYPROPYLENE GLYCOL a kind of.Preferably, said water-soluble molecules is a PVP K120.More preferably, the molecular-weight average of said PVP K120 is 5000-1500000.
In preparation method of the present invention, the mass ratio of soccerballene and PVP K120 is less than 1: 70.Preferably, the mass ratio of soccerballene and PVP K120 is 1: 80-1: 100.
In preparation method of the present invention, when utilizing mixer to carry out powerful mixing, cooperate 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 the step 2 is 20-40 ℃.
In preparation method of the present invention, the churning time in the step 2 is 2-12 hour.
In preparation method of the present invention, the filter pore size in the step 3 is 0.7-1.0 μ m.Preferably, said 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 for preparing according to above-mentioned preparation method.
Compare with other prior art, the present invention has the following advantages:
1, in preparing method's provided by the invention whole process, do not use any organic reagent, so do not have the dissolvent residual problem in the 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 of being adopted, high production capacity, and there is not discharge any pollutant in whole process of production simultaneously, is a kind of environmental protection, production technique safely and effectively therefore.
2, among the preparation method provided by the invention, fully combine through the physical mixed method between water-soluble molecules and the soccerballene, make peripheral coating of soccerballene go up a large amount of water-soluble molecules, and then realize soccerballene deliquescent raising in water.But the molecular structure of soccerballene does not change, and has kept the stability and the physicochemical property of fullerene molecule carbon cage itself.
3, preparation method provided by the invention be applicable to the multiple water-soluble polymer that can produce interact soccerballene is coated with soccerballene, so universality is 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, and---dissolving---is filtered---evaporating solvent---drying---pulverizing---sterilization---packing; Perhaps; (2), powder batch mixing------------demarcate concentration---sterilization---packing, be highly susceptible to amplifying and produce in filtration in dissolving by constant volume.
5, the water-soluble fullerene for preparing among the preparation method provided by the invention is compared with conventional solvent mediated method gained water-soluble fullerene of the same type has bigger particle diameter; The inventive method has no the residual of organic reagent in the preparation process simultaneously, and is therefore safer in the application meeting of biomedical sector.
6, preparation method provided by the invention, be unrealized in the production process effective compound soccerballene and water-soluble molecules can realize recycling through solvent-extracted method.
7, method provided by the invention, resulting water-soluble fullerene is excellent performance aspect the removal radical, therefore in cosmetic industry, biomedical sector, has significant application value.
Description of drawings
To combine accompanying drawing and embodiment that the present invention is described further below, in the accompanying drawing:
Fig. 1 a is the transmission electron microscope photo figure of the water-soluble fullerene of the embodiment of the invention one gained.
Fig. 1 b is the dynamic light scattering size distribution plot of the water-soluble fullerene of the embodiment of the invention one gained.
Fig. 2 a is the transmission electron microscope photo figure of the water-soluble fullerene of the embodiment of the invention two gained.
Fig. 2 b is the dynamic light scattering size distribution plot of the water-soluble fullerene of the embodiment of the invention two gained.
Fig. 3 a is the comparison diagram of the uv-absorbing spectrogram of prepared water-soluble fullerene of the embodiment of the 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 prepared water-soluble fullerene of the embodiment of the 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.
Fig. 5 a, 5b, 5c are the C of different concns
60-PVP mixture is removed the ESR spectrogram of hydroxyl radical free radical.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.Said method is ordinary method if no special instructions.Said reactant all can get from open commercial sources if no special instructions.
Embodiment one:
With 4.8g Vinylpyrrolidone polymer (PVP), 55mg C
60(C
60Shared mass percent is 1.14%) mix with mixer (mixer can be all be fit to solid materials carry out the blended apparatus) and be placed in the ball mill; To wherein adding the abundant ball mill mixing that zirconia ball or agate ball carried out 12 hours; Wherein, when utilizing mixer to carry out powerful mixing, cooperate suitable cooling provision; The preferred cycle cooling water system, not oxidized to guarantee fullerene powder.
Subsequently mixture is dissolved in the 400ml water, and fully stirred 2 hours, filter the mixing solutions that stirs with strainer the back, and gained transparent yellow brown filtrating is water-soluble fullerene solution; Basically carried out compound soccerballene residuum fully for failing by the throw out of filtering, undercompounding soccerballene and Vinylpyrrolidone polymer reclaim dry.
Then, heating water-soluble fullerene solution carries out the low pressure drying with Freeze Drying Equipment then at low temperatures with solvent evaporated water, obtains the water-soluble fullerene of pulverulent solids.Fail to carry out compound C60 with PVP; Utilize toluene to extract; After the C60-toluene solution process Rotary Evaporators solvent evaporated after the extraction, 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 the 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 present embodiment one gained
60The transmission electron microscope photo figure of mixture, Fig. 1 b are the PVP-C of present embodiment one gained
60The dynamic light scattering size distribution plot of mixture.
Embodiment two:
Concrete grammar is with embodiment one, and difference is C
60Shared percentage composition is increased to 1.56%, and mixing time is 48 hours.Obtain actual PVP-C under this condition
60C in the mixture
60Shared per-cent is 1.01%, the about 200nm of mixture grain size.Fig. 2 a and Fig. 2 b are respectively the PVP-C of present embodiment two gained
60The transmission electron microscope photo figure of mixture and dynamic light scattering size distribution plot.
Embodiment three:
With embodiment one or implement in two to place freezer compartment of refrigerator that sample is fully freezed after the gained water-soluble fullerene solution solvent evaporated, place Freeze Drying Equipment to carry out abundant low pressure drying treatment then, obtain PVP-C
60Composite powder, about 4.7g weighs.Can draw white PVP powder and black C
60Powder forms the sundown powder through compound back, and solution is pale brown look.Also further illustrate PVP and C
60Really formed uniform mixture.
The sample and the conventional solvent mediated method gained sample of this method gained are compared.
(reference: L.Xiao et al./Bioorg.Med.Chem.Lett.16 (2006) 1590-1595): 4.8g PVP is dissolved in 100ml ethanol or the chloroform tradition dissolving mediated method, with 55mg C
60Be dissolved in the 60ml toluene, under the state that stirs, both mixed then, the continued stirred overnight is found in the process to fail to carry out compound C with PVP
60Powder deposition is in beaker bottom.After the solution solvent evaporated with the beaker upper strata, adding 100ml water fully stirs and makes the mixture dissolving fully, subsequently the solution that stirs is added heat extraction residual ethanol or chloroform, adds water to 400ml at last.
Tradition dissolving mediated method is compared with method of the present invention (like the method for embodiment one); Method of the present invention has following clear superiority: one, environmental protection more in the technological process of the inventive method; Both do not had the use of organic reagent, do not had discharge any pollutant again; Two, the particle size of the inventive method products therefrom obviously increases than the particle size of conventional solvent mediated method products therefrom, and the particle size of method of the present invention preparation is controlled fully, can significantly improve the security of products therefrom biologic applications.As shown in the figure, Fig. 3 a and Fig. 3 b are respectively the uv-absorbing spectrogram and the dynamic light scattering size distribution plot of two kinds of method gained samples.From Fig. 3 a, can know two kinds of method gained PVP-C
60The ultraviolet-visible absorption spectroscopy of mixture does not have notable difference, and PVP-C
60Mixture has tangible C at the 340nm place
60Absorption peak, explain that both are evenly compound really.Can learn that from Fig. 3 b and Fig. 4 a and Fig. 4 b (Fig. 4 a is the conventional solvent mediated method, and Fig. 4 b is the inventive method) 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), bigger particle diameter will make the biological safety of gained mixture improve, and help PVP-C more
60Mixture is in the application of biological association area.
With embodiment one gained liquid sample stirring and refluxing 48 hours in 130-200 ℃ TR, do not see that the sample proterties changes, carry out ultraviolet and dynamic light scattering and characterize and find that it absorbs and any variation does not all take place particle diameter.With embodiment one gained sample-20 ℃ place 20 days after again dissolving carry out uv-absorbing and dynamic light scattering sign, do not see considerable change.But the PVP-C that the knowledge capital inventive method is prepared
60Mixture has good thermostability.
Get embodiment one gained liquid sample 10ml and mix with 20ml toluene, standing demix after ultrasonic 48 hours, upper toluene solution carry out mass spectral characteristi and do not see 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 is not seen considerable change.Toluene solvant changed be ethanol or DMF, carry out same ultrasonic experiment, find too, prepared water-soluble fullerene can stable existence, PVP and C
60Can't separate because of the effect of other solvent.Explain that the prepared water-soluble fullerene that obtains of the inventive method has good solvent stability, can stable existence in most of solvents.Get embodiment one 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 the radical removal effect.Concrete operations are: the radical for hydrogen peroxide and ferrous ion reaction generation, and utilize DMPO (5-N-oxide compound) as the spin trapping agent, detect the signal of the product D MPO-OH of DMPO and hydroxyl free radical reaction generation.
In the actual test: the concentration of Presfersul is 0.4mmol/L, and the mass concentration of ydrogen peroxide 50 is 5%, and the pH value of PBS is 7.4, C
60The concentration of-PVP is 15mmol/L, and the concentration of DMPO is 0.4mol/L, respectively gets and tests after above five kinds of solution, 50 μ L mix.Be depicted as the C of different concns like Fig. 5 a, 5b, 5c
60-PVP mixture is removed the ESR spectrogram of hydroxyl radical free radical: Fig. 5 a is blank test, does not promptly add C in the DMPO-OH test system
60-PVP mixture; Fig. 5 b adds C in the DMPO-OH test system
60-PVP mixture, and its ultimate density is 300 μ mol/L; Fig. 5 c adds C in the 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 above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (14)
1. the preparation method of a water-soluble fullerene is characterized in that, it comprises the steps:
Step 1, with fullerene powder with can carry out powerful mixing with mixer with the water-soluble molecules that soccerballene produces stabilization and form mixture;
Step 2, fully stir said mixture is soluble in water then;
Step 3, the filtrating that obtains with the strainer multiple times of filtration are water-soluble fullerene solution;
Step 4, heating evaporation fall aqueous solvent, and vacuum-drying then obtains the water-soluble fullerene of pulverulent solids.
2. method according to claim 1 is characterized in that: said soccerballene comprises empty fullerene or embed fullerene.
3. method according to claim 2 is characterized in that: said soccerballene is C
60Or C
70
4. method according to claim 1 is characterized in that: said water-soluble molecules is selected from a kind of of PVP K120, polyoxyethylene glycol, starch and verivate thereof, methylol/propyl cellulose, SEPIGEL 305, ROHM, gum arabic, Z 150PH or POLYPROPYLENE GLYCOL.
5. method according to claim 4 is characterized in that: the molecular-weight average of said PVP K120 is 5000-1500000.
6. method according to claim 5 is characterized in that: the mass ratio of said soccerballene and PVP K120 is less than 1: 70.
7. method according to claim 6 is characterized in that: the mass ratio of said soccerballene and PVP K120 is 1: 80-1: 100.
8. method according to claim 1 is characterized in that: when utilizing mixer to carry out powerful mixing, cooperate cooling provision not oxidized to guarantee fullerene powder.
9. method according to claim 1 is characterized in that: the powerful mixing time should be 12-96 hour.
10. method according to claim 9 is characterized in that: in step 2, water temperature is 20-40 ℃.
11. method according to claim 1 is characterized in that: in step 2, churning time is 2-12 hour.
12. method according to claim 1 is characterized in that: in step 3, said filter pore size is 0.7-1.0 μ m.
13. method according to claim 12 is characterized in that: in step 3, said filter pore size is 0.8 μ m.
14. water-soluble fullerene for preparing according to any one described preparation method of claim 1-13.
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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 |
| CN105125580A (en) * | 2015-07-30 | 2015-12-09 | 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 |
| WO2017012162A1 (en) * | 2015-07-20 | 2017-01-26 | 深圳市华星光电技术有限公司 | Preparation method for fullerene/pedot:pss mixed solution and preparation method for substrate having fullerene/pedot:pss composite transparent conductive film |
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| CN107814375A (en) * | 2016-09-13 | 2018-03-20 | 中国科学院化学研究所 | Fullerene water dissolubility trim and preparation method thereof |
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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 |
| WO2017012162A1 (en) * | 2015-07-20 | 2017-01-26 | 深圳市华星光电技术有限公司 | Preparation method for fullerene/pedot:pss mixed solution and preparation method for substrate having fullerene/pedot:pss composite transparent conductive film |
| CN105125580A (en) * | 2015-07-30 | 2015-12-09 | 北京大学深圳研究院 | Fullerene-macromolecule composite and preparation method thereof |
| 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 |
| CN107814375A (en) * | 2016-09-13 | 2018-03-20 | 中国科学院化学研究所 | Fullerene water dissolubility trim 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 |
| CN107411983A (en) * | 2017-09-12 | 2017-12-01 | 北京福纳康生物技术有限公司 | A kind of water-soluble fullerene topical composition |
| CN108653084A (en) * | 2018-06-25 | 2018-10-16 | 广东科玮生物技术股份有限公司 | A kind of man's skin care compositions and its application containing growth factor |
| CN108653084B (en) * | 2018-06-25 | 2020-11-24 | 广东科玮生物技术股份有限公司 | Growth factor-containing skin care composition for men and application thereof |
| EP3848014A4 (en) * | 2018-08-02 | 2022-08-10 | Beijing Fullcan Biotechnology Co., Ltd | Water-soluble fullerene topical 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 |
| CN112941906A (en) * | 2021-03-03 | 2021-06-11 | 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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