CN107555418A - Amino fullerene and preparation method thereof - Google Patents
Amino fullerene and preparation method thereof Download PDFInfo
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- CN107555418A CN107555418A CN201610514134.4A CN201610514134A CN107555418A CN 107555418 A CN107555418 A CN 107555418A CN 201610514134 A CN201610514134 A CN 201610514134A CN 107555418 A CN107555418 A CN 107555418A
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Abstract
The present invention proposes amino fullerene and preparation method thereof.This method includes：By solid fullerene and Amine Solutions hybrid reaction, to obtain the amino fullerene.This method directly prepares amino fullerene using solid-liquid reaction, and the amino fullerene of acquisition has at least one of following advantages：Good water solubility, particle diameter are small, yield is higher, are easily enlarged production scale, suitable for biologic medical field.
Description
Technical field
The present invention relates to Material Field.In particular it relates to the preparation of fullerene derivate, more particularly to ammonia
Base fullerene and preparation method thereof.
Background technology
The elementide with enclosed construction that fullerene is made up of different number of carbon atom.Fullerene is due to stable
Property it is good, intensity is high, specific surface area is big the advantages that, all table in the application of biological medicine, energy storage, storage hydrogen, catalysis etc.
Reveal excellent performance.But fullerene body can only be dissolved in part organic solvent, water can not be dissolved in, therefore can not directly answer
For biosystem.Therefore, it is necessary to carry out modification to fullerene, water miscible fullerene derivate is prepared to meet to give birth to
The demand of thing medical applications.
However, water miscible fullerene derivate and preparation method thereof still has much room for improvement at present.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.
The present invention is the following discovery based on inventor and completed：
The method for preparing amino fullerene at present, generally existing is difficult to be prepared on a large scale, purge process very complicated, peace
Total stability is poor, the problems such as being difficult to meet biological medicine demand.Inventor passes through further investigation and many experiments are found, this
Mainly there are two major classes mainly due to the method for preparing water-soluble fullerenes derivates at present：By polymer to fullerene molecule
Coated；Or water soluble group such as amino, carboxyl are bonded on Fullerene Carbon cage by chemical reaction.Polymer bag
The potential danger that method does not only exist fullerene leakage is covered, and the particle after cladding is larger it is difficult to be phagocytized by cells.And chemical bond
Needing in organic solvent to be reacted fullerene dissolving with fado, the solubility of fullerene in organic solvent is limited, because
This is difficult to scale of mass production, and later-period purification process is cumbersome.In water-soluble fullerenes derivates, the polyhydroxy of Fullerol
The integrality of carbon cage can be destroyed, causes it to remove free radical effect and has declined compared with body, and Fullerol is not suitable for further
Derivatization, limit its other application in biomedical sector.The preparation process of carboxylic acid fullerene derivate is cumbersome, bonding
Carboxylic acid quantity it is few, water-soluble poor.And amino fullerene good water solubility and surface is positively charged, it is adapted to cell phagocytosis.And
And compared with carboxylic acid, the reactivity of organic amine and fullerene is high, selects different types of organic amine to prepare with not
The amino fullerene derivate of same purposes.Amino in amino fullerene derivate can also further with biomolecule such as
Bonding reaction occurs for DNA, amino acid, so as to further enrich its application in biomedical sector.
In view of this, invention provides a kind of method that solid-liquid reaction prepares water soluble amino fullerene.This method
Directly reacted using the fullerene of solid with Amine Solutions, can conveniently by regulation reaction temperature or reaction time,
Control the amino quantity in the amino fullerene obtained.This method has at least one of following advantages：The amino fowler of acquisition
Alkene good water solubility, particle diameter are small, yield is higher, are easily enlarged production scale, suitable for biologic medical field.
In one aspect of the invention, the present invention proposes a kind of method for preparing amino fullerene.According to the implementation of the present invention
Example, this method include：By solid fullerene and Amine Solutions hybrid reaction, to obtain the amino fullerene.The party
Method directly prepares amino fullerene using solid-liquid reaction, and the amino fullerene of acquisition has at least one of following advantages：It is water-soluble
Property is good, particle diameter is small, yield is higher, is easily enlarged production scale, suitable for biologic medical field.
According to an embodiment of the invention, the solid fullerene includes empty fullerene C2n、M@C2n、M2@C2n、
MA@C2n、M3N@C2n、M2C2@C2n、M2S@C2n、M2O@C2nAnd MxA3-xN@C2nAt least one of,
Wherein, M and A is independently selected from Sc, Y and lanthanide element, 30≤n≤60,0≤x≤3.Above-mentioned hollow fowler
Alkene or metal embed fullerene and can preferably be dissolved in Amine Solutions and be reacted with organic amine, so as to enter one
Step improves the yield and yield of this method.
According to an embodiment of the invention, the organic amine includes organic primary amine and organic secondary.Thus, it is possible to further carry
The yield and yield of high this method this method.
According to an embodiment of the invention, the organic amine includes ethylenediamine, propylamine, Propanolamine, p-phenylenediamine and diethanol amine
At least one of.Thus, it is possible to further improve the yield and yield of this method this method.
According to an embodiment of the invention, in the mixed solution of the solid fullerene and Amine Solutions, the solid fowler
The mass ratio of alkene and the organic amine is 1：(0.5~1.5).Make organic amine suitably excessive, be advantageous to make solid fowler alkene reaction
Completely, and avoid organic amine excessive excessive and cause material waste.
According to an embodiment of the invention, the volume ratio of hydrogen peroxide and the aqueous slkali described in the mixed solution is 7:
(1~4).Thus, it is possible to further improving this method carries out amidized efficiency and effect to fullerene.
According to an embodiment of the invention, the reaction is carried out under stirring or heating stirring counterflow condition, the reaction
Time be 5~36 hours.Thus, it is possible to further improve the yield and yield of this method this method, the ammonia of acquisition is controlled
The quantity of the amino of base fullerene surface modification.
According to an embodiment of the invention, this method further comprises：The mixed solution Jing Guo the reaction is purified
Processing.Because this method is carried out in aqueous, therefore simple subsequent filter is only needed, dialyse and waits purification processes, i.e.,
The dispersion liquid of amino fullerene in aqueous can be obtained, so as to simplify the preparation flow of this method, shortens the production cycle.
In another aspect of this invention, the present invention proposes a kind of method for preparing amino fullerene.According to the implementation of the present invention
Example, this method include：(a) Amine Solutions are mixed with solid fullerene, be stirred at room temperature or heating stirring counterflow condition under
Reacted, wherein, the organic amine include ethylenediamine, propylamine, Propanolamine, p-phenylenediamine and diethanol amine at least it
One；The solid fullerene includes empty fullerene C2n, metal fullerene M@C2n、M2@C2n、MA@C2n、
M3N@C2n、M2C2@C2n、M2S@C2n、M2O@C2nAnd MxA3-xN@C2nAt least one of, wherein, M and
A is independently selected from Sc, Y and lanthanide element, 30≤n≤60,0≤x≤3.(b) solution rotating for obtaining step (a)
Dry, the remaining solid after the Rotary drying is dissolved with acid solution, wherein, the acid solution is inorganic acid solution, described
The concentration of acid solution is 0.5~1.5mol/L.(c) pH value for the solution that regulating step (b) obtains is 4~6, is dialysed to described
The electrical conductivity of solution is less than 1 μ s/cm.(d) solution obtained using anion exchange resin process step (c), is dialysed to institute
The electrical conductivity for stating solution is less than 1 μ s/cm.This method directly prepares amino fullerene, the amino fowler of acquisition using solid-liquid reaction
Alkene has at least one of following advantages：Good water solubility, particle diameter are small, yield is higher, are easily enlarged production scale, are applied to
Biologic medical field.
In still another aspect of the invention, the present invention proposes a kind of amino fullerene.According to an embodiment of the invention, the ammonia
Base fullerene is prepared using foregoing method.Thus, the amino fullerene have synthesis simple, good water solubility,
Particle diameter is small, yield is higher, be easily enlarged production scale, suitable for biologic medical field the advantages that at least one of.
Brief description of the drawings
Fig. 1 shows the amino fullerene FTIR of according to embodiments of the present invention 1 and embodiment 2；
Fig. 2 shows the amino fullerene electron-beam probe analysis result of according to embodiments of the present invention 1 and embodiment 2；
Fig. 3 shows the amino fullerene hydration particle diameter (Fig. 3 a) and zeta of according to embodiments of the present invention 1 and embodiment 2
Current potential (Fig. 3 b)；And
Fig. 4 is the cytotoxicity result of the amino fullerene prepared using the HEK-a cell tests embodiment of the present invention 2.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein identical from beginning to end
Or similar label represents same or similar element or the element with same or like function.Retouched below with reference to accompanying drawing
The embodiment stated is exemplary, is only used for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of method for preparing amino fullerene.According to the implementation of the present invention
Example, this method is directly by solid fullerene and Amine Solutions hybrid reaction, to obtain amino fullerene.This method is direct
Amino fullerene is prepared using solid-liquid reaction, the amino fullerene of acquisition has at least one of following advantages：Good water solubility,
Particle diameter is small, yield is higher, is easily enlarged production scale, suitable for biologic medical field.
The concrete operations to this method are described in detail below.According to an embodiment of the invention, it is used in the method
Solid fullerene can include empty fullerene C2n、M@C2n、M2@C2n、MA@C2n、M3N@C2n、M2C2@C2n、
M2S@C2n、M2O@C2nAnd MxA3-xN@C2nAt least one of, wherein, M and A be independently selected from Sc,
Y and lanthanide element, 30≤n≤60,0≤x≤3.For example, according to a particular embodiment of the invention, solid fullerene can be with
For C70、C76、C78、C84Deng empty fullerene, or the embedded metal fullerene of embedded metal element M, for example,
Can be the M C that M is the metallic elements such as Y, Ho, Lu82, or the M that M is the elements such as Sc, Y, Lu3N@C80。
Above-mentioned empty fullerene or metal, which embed fullerene, to be reacted preferably in water-based system with Amine Solutions, and above-mentioned richness
Strangle alkene to be easier to receive electronics and electrophilic addition reaction occurs with Amine Solutions, so as to further improve the production of this method
Amount and yield.
According to an embodiment of the invention, liquid organic primary amine and organic secondary can be used as Amine Solutions, or adopted
By the use of the aqueous solution of SOLID ORGANIC amine as Amine Solutions, with solid fowler alkene reaction.For example, the specific reality according to the present invention
Example is applied, organic amine can include at least one of ethylenediamine, propylamine, Propanolamine, p-phenylenediamine and diethanol amine.Thus,
The yield and yield of this method this method can further be improved.In the mixed solution of solid fullerene and Amine Solutions,
The mass ratio of solid fullerene and organic amine can be 1：(0.5~1.5).For example, the mass ratio of solid fullerene and organic amine
Can be 1:0.9.In above-mentioned mixed solution, make organic amine suitably excessive, be advantageous to make solid fowler alkene reaction complete, and
Avoid organic amine excessive excessive and cause material waste.
According to an embodiment of the invention, the mixed solution containing solid fullerene and Amine Solutions can be stirred or
Person's heating stirring reflow treatment, the time of reaction can be 5~36 hours.Thus, it is possible to improve the efficiency and effect of reaction.
For example, according to a particular embodiment of the invention, can stir above-mentioned mixed solution at room temperature and react 24 hours, or
Reacted 8 hours under heating stirring counterflow condition.Wherein, the heating-up temperature of heating stirring backflow can be according to the boiling of organic amine
Depending on point, stir speed (S.S.) can be 1000rpm/min.Thus, it is possible to further improve the yield and yield of this method.
According to an embodiment of the invention, this method may further include：Purification processes are carried out to reacted mixed solution.
Specifically, according to an embodiment of the invention, above-mentioned purification processes can include：With acid solution in mixed solution after reaction
Amino fullerene carry out protonation processing, then adjust solution pH value be alkalescent, for example, solution can be adjusted
PH value is 4~6, is that weakly acidic solution carries out dialysis treatment to pH value then, to remove not reaction completely in solution
Organic amine and the impurity component such as acid.Then, using the anion-exchange column containing anion exchange resin to by dialysing
Solution handled, the amino fullerene of protonation is converted to the amino fullerene of bulk states.Then, then to bulk states
Amino fullerene carry out dialysis treatment, remove anion exchange procedures in may introduce impurity.Thus, it is possible to obtain pure
The higher amino fullerene water solution of degree.Because in the method, organic amine with fullerene is reacted under water-based system
, fullerene without being first dissolved in polar organic solvent in advance, and therefore, the purification processes carried out to solution after reaction also only need
The processing steps such as simple protonation, dialysis, anion exchange.According to an embodiment of the invention, employed in proposition processing
Reagent, instrument and processing method be not particularly limited, as long as the impurity in reacted mixed solution can be removed.
For example, according to the specific implementation of the present invention, above-mentioned acid solution concentration can be 0.5~1.5mol/L, and selected acid can be with
For inorganic acid, such as hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid etc..Dialysis treatment can use cutoff for 3500 dialysis
Bag, dialysed using ultra-pure water of the electrical conductivity not less than 18.2M Ω cm, the electrical conductivity to solution is less than 1 μ s/cm.According to
Some embodiments of the present invention, first reacted solution can be centrifuged obtaining supernatant liquor, through solvent filter
After suction filtration, filtrate is evaporated using Rotary Evaporators, it can be 70 degrees Celsius that rotation, which is evaporated condition, rotating speed 80r/min.It is surplus
Remaining solid is the amino fullerene containing impurity.The remaining solid being evaporated using the inorganic acid solution dissolving of dilution and stirring,
The fullerene for being bonded with organic amine is completely dissolved in dilute acid soln, then dilute acid soln is filtered, retain filtrate.
Alkaline solution is added dropwise in filtrate, filtrate is adjusted to faintly acid (pH value is 4~6).Alkaline solution can be sodium hydroxide,
The aqueous solution of the alkali inorganic substances such as potassium hydroxide, sodium carbonate or sodium acid carbonate.Above-mentioned faintly acid filtrate is loaded into bag filter again,
It is put into dialyse in ultra-pure water and fully removes excessive inorganic matter and unreacted organic amine.By the solution after dialysis pass through equipped with it is cloudy from
The pillar of sub-exchange resin carries out anion exchange.Wherein, anion exchange resin can be oh type anion exchange resin,
For example, can be Ambersep 900 (OH).Thus, it is possible to be the amino of bulk states by the amino complete exchange of protonation,
Then filter again.Finally filtrate is dialysed, then obtains the aqueous solution of the amino fullerene by purification.Above-mentioned
In suction filtration or filter process, filter membrane of the aperture for 200nm can be used.
It is to sum up shown, this method have it is following at least one of a little：
1st, this method is simple to operate, and cost is cheap, beneficial to large-scale promotion application.
2nd, selected solid fullerene includes empty fullerene and embedded fullerene, is easier to receive electronics and send out with organic amine
Raw electrophilic addition reaction.
3rd, active strong, the product yield height of the ammoxidation that this method uses, can be by selecting the type of organic amine to regulate and control ammonia
The type of base fullerene.
4th, the easy to operate and refining effect of subsequent purification processing is good, and dialysis in acid condition can remove unreacted organic
Amine and excessive inorganic matter, then by anion exchange and further dialysis, obtain the water soluble amino fullerene of high-purity.
In another aspect of this invention, the present invention proposes a kind of method for preparing amino fullerene.According to the implementation of the present invention
Example, this method include：
(a) Amine Solutions are mixed with solid fullerene, be stirred at room temperature or heating stirring counterflow condition under reacted, its
In, organic amine includes at least one of ethylenediamine, propylamine, Propanolamine, p-phenylenediamine and diethanol amine；Solid fullerene bag
Include empty fullerene C2n, metal fullerene M@C2n、M2@C2n、MA@C2n、M3N@C2n、M2C2@C2n、
M2S@C2n、M2O@C2nAnd MxA3-xN@C2nAt least one of, wherein, M and A be independently selected from Sc,
Y and lanthanide element, 30≤n≤60,0≤x≤3.
(b) solution rotating for obtaining step (a) is dried, and the remaining solid after Rotary drying is dissolved with acid solution, wherein, acid is molten
Liquid is inorganic acid solution, and the concentration of acid solution is 0.5~1.5mol/L.
(c) pH value for the solution that regulating step (b) obtains is 4~6, and the electrical conductivity dialysed to solution is less than 1 μ s/cm.
(d) solution obtained using anion exchange resin process step (c), the electrical conductivity dialysed to institute's liquid are less than 1 μ s/cm.
This method have it is following at least one of a little：
1st, this method is simple to operate, and cost is cheap, beneficial to large-scale promotion application.
2nd, selected solid fullerene includes empty fullerene and embedded fullerene, is easier to receive electronics and send out with organic amine
Raw electrophilic addition reaction.
3rd, active strong, the product yield height of the ammoxidation that this method uses, can be by selecting the type of organic amine to regulate and control ammonia
The type of base fullerene.
4th, the easy to operate and refining effect of subsequent purification processing is good, and dialysis in acid condition can remove unreacted organic
Amine and excessive inorganic matter, then by anion exchange and further dialysis, obtain the water soluble amino fullerene of high-purity.
In still another aspect of the invention, the present invention proposes a kind of amino fullerene.According to an embodiment of the invention, the amino
Fullerene is prepared using foregoing method.Therefore, the amino fullerene has ammonia prepared by previously described method
Whole features and advantage, will not be repeated here possessed by base fullerene.Generally speaking, the amino fullerene has synthesis
Simply, good water solubility, particle diameter are small, yield is higher, be easily enlarged production scale, suitable for biologic medical field the advantages that
At least one.
The solution of the present invention is explained below in conjunction with embodiment.It will be appreciated by those skilled in the art that following implementation
Example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted particular technique or condition in embodiment,
Carried out according to the technology described by document in the art or condition or according to product description.Agents useful for same or instrument are not noted
Bright production firm person, being can be by the conventional products of acquisition purchased in market.
Embodiment 1：Prepare C60(EDA)9
(a) 50mL ethylenediamines (analyzing pure, traditional Chinese medicines reagent) are added into 100mL conical flask with cover, it is rich adds 50mg solids
Strangle alkene C60(purity：99%, Xiamen good fortune is taken in the fresh material Science and Technology Ltd.), magnetic stir bar is added, is stirred using magnetic force
Mix device stirring 24h (temperature：Room temperature, rotating speed：1000r/min), using solvent filter (volume：1L, filter sizes：
200nm, Jin Teng company) reactant is filtered after obtain brown-red solution.The composition of solution does not participate in the second of reaction mainly
Diamines and C60(EDA)9。
(b) solution for obtaining (a) step is added in 250ml round-bottomed flask, reuses Rotary Evaporators (model：IKA RV10
Basic) by filtrate Rotary drying (temperature completely：70 degrees Celsius, rotating speed：80r/min).By hydrochloric acid (concentration：1mol/L)
It is added in round-bottomed flask, vibration flask makes the thing that is evaporated on its inwall be dissolved in watery hydrochloric acid, obtains brownish red settled solution.
(c) solution for obtaining (b) step uses the NaOH aqueous solution (concentration：10mol/L) pH test paper is neutralized to be detected as
Faintly acid (pH is 5 or so), exists to ensure excessive ethylenediamine with chlorination salt form, can be in follow-up dialysis step
Fully remove.Solution, which is fitted into bag filter (cutoff 3500) and is put into ultra-pure water, after neutralizing dialyses, and dialyses to surpassing
The electrical conductivity of pure water is less than 1 μ s/cm.
(d) solution after (c) step is dialysed is flowed through equipped with anion exchange resin (Ambersep900 (OH), Yi Nuokai examination
Agent company) chromatographic column, be repeated 3 times.Solution after ion exchange is loaded into bag filter (cutoff 3500) to be put into
Dialysis dialysis to the electrical conductivity of ultra-pure water is less than 1 μ s/cm in ultra-pure water.Solution is in the brownish red clarified.
Brown-red solution is dripped on silver mirror, tested after natural drying for infrared spectrum (IR).As shown in figure 1, sample
(- NH is absorbed in 3300nm or so infrared signature2Stretching vibration absworption peak) prove that ethylenediamine is bonded to fullerene
Carbon cage, while also helped in the change of 800-1500nm infrared signatures absorption (C-C and C=C stretching vibration peak on carbon cage)
Card ethylenediamine has been bonded on carbon cage.Sample solution is dripped in being stained with the electron probe platform of carbonaceous conductive glue, after natural drying
(EPMA) is analyzed for electron-beam probe, shown in test result such as Fig. 2 (a), in the sample after anion exchange only
CN elements (H can not be detected) be present, the ethylenediamine for illustrating bonding is present with bulk form rather than with chlorination salt form.
Sample solution is directly used in dynamic light scattering (DLS) test, as shown in figure 3, its be hydrated particle diameter in 100nm or so and
Surface is positively charged, is adapted to by cell capture, phagocytosis.Sample is freeze-dried for CHN elementary analyses (EA), at random
2 positions are selected in the sample, and analysis result is shown in Table 1, by N：C ratio can determine that its chemical composition is C60(EDA)9。
By adjusting the reaction time of ethylenediamine and fullerene in (a) step, the quantity of the ethylenediamine of bonding can be regulated and controled, obtained
C60(EDA)n, n=5-9.
Table 1：C60(EDA)9Elementary analysis result
Embodiment 2：Prepare Gd@C82(EDA)8
Reaction condition and step with embodiment 1, except that, using 50mg metal fullerene Gd@C82Solid is (pure
Degree：99%, Xiamen good fortune is taken in the fresh material Science and Technology Ltd.) substitute C60.Final obtain contains Gd@C82(EDA)8Clarification
Dark brown solution.Composition detection is carried out to the product of acquisition using method of testing and condition in the same manner as in Example 1, such as
Shown in Fig. 1, infrared signature of the sample in 3300nm or so absorbs (- NH2Stretching vibration absworption peak) prove ethylenediamine quilt
The carbon cage of fullerene is bonded to, while (C-C and C=C stretching vibration on carbon cage is absorbed in 800-1500nm infrared signatures
Peak) change also prove ethylenediamine and be bonded on carbon cage.Sample solution is dripped in the electron probe platform for being stained with carbonaceous conductive glue
On, electron-beam probe analysis (EPMA) is used for after natural drying, shown in test result such as Fig. 2 (b), is handed over by anion
C, N, Gd element (H can not be detected) are only existed in sample after changing, illustrate bonding ethylenediamine be with bulk form and
It is not to exist with chlorination salt form.Sample solution is directly used in dynamic light scattering (DLS) test, as shown in figure 3, its
Be hydrated particle diameter 100nm or so and surface it is positively charged, be adapted to by cell capture, phagocytosis.Sample is freeze-dried for CHN
Elementary analysis (EA), select 2 positions in the sample at random, analysis result is shown in Table 2, by N：C ratio can determine it
Chemical composition is Gd@C82(EDA)8.By adjusting the reaction time of ethylenediamine and metal fullerene, bonding can be regulated and controled
The quantity of ethylenediamine, obtain Gd@C82(EDA) n, n=6-8.The inductively coupled plasma atomic emission spectrum such as use
(ICP-AES) Gd in test sample3+Ion concentration is (using concentrated nitric acid processing sample, by the Gd acidolysis in sample into Gd3+
Ion), it may be determined that sample concentration in solution.
Table 2：Gd@C82(EDA)8Elementary analysis result
Embodiment 3：Prepare Cm(EDA)9(m=70,76,78,84)
Reaction condition and step with embodiment 1, except that, using 50mg C70、C76、C78Or C84Solid is (pure
Degree：99%, Xiamen good fortune is taken in the fresh material Science and Technology Ltd.) substitute C60。
Embodiment 4：Prepare M@C82(EDA)8(M=Y, Ho, Lu)
Reaction condition and step with embodiment 1, except that, using 50mg Y@C82、Ho@C82Or Lu@C82
Solid (purity：99%, Xiamen good fortune is taken in the fresh material Science and Technology Ltd.) substitute C60。
Embodiment 5：Prepare M3N@C80(EDA)8(M=Sc, Y, Lu)
Reaction condition and step with embodiment 1, except that, using 50mg Sc3N@C80、Y3N@C80Or
Lu3N@C80Solid (purity：99%, Xiamen good fortune is taken in the fresh material Science and Technology Ltd.) substitute C60。
Cytotoxicity test
Use the Gd@C prepared in adult epidermal's horn cell (HEK-a) testing example 282(EDA)8Cytotoxicity：
Incubation passage is carried out to HEK-a cells using the DMEM culture mediums containing 15% calf serum, disappeared using trypsase
After changing cell, with 5*104The orifice plate of/mL cell densities kind 96 (using 6 holes as 1 experimental group), 200 μ L cells point are added per hole
Dispersion liquid, phosphate buffer solution (PBS) is added in the week hole that makes a circle and is incubated 24 hours in incubator；It is replaced by 90 μ L
Fresh culture, it is separately added into the Gd@C of 10 μ L PBS (- Control as a control group) and concentration for 800 μm of ol/L82(EDA)8
Solution, it is incubated 3 hours under the conditions of lucifuge, or in light intensity is 20mw/cm2Natural light under be incubated 0.5 hour and keep away again
Light is incubated 2.5 hours；200 μ L fresh cultures are replaced by be incubated 24 hours；It is replaced by the colourless culture mediums of 90 μ L and 10 μ L
CCK-8 (cytoactive detection agent), be incubated 120min to color become bright orange when, with ELIASA detect cytoactive.
Cytoactive result is shown in Fig. 4, Gd@C82(EDA)8Sample does not show any cytotoxicity, and is lived compared with cellular control unit
Degree also increases, and illustrates there is good cytoprotection.
In the description of this specification, the description of reference term " one embodiment ", " another embodiment " etc. means to combine the reality
Specific features, structure, material or the feature for applying example description are contained at least one embodiment of the present invention.In this explanation
In book, identical embodiment or example are necessarily directed to the schematic representation of above-mentioned term.Moreover, description is specific
Feature, structure, material or feature can combine in an appropriate manner in any one or more embodiments or example.In addition,
In the case of not conflicting, those skilled in the art can by the different embodiments or example described in this specification with
And the feature of different embodiments or example is combined and combined.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment be it is exemplary,
It is not considered as limiting the invention, one of ordinary skill in the art within the scope of the invention can be to above-described embodiment
It is changed, changes, replacing and modification.
Claims (9)
- A kind of 1. method for preparing amino fullerene, it is characterised in that including：Solid fullerene is mixed with Amine Solutions Reaction, to obtain the amino fullerene.
- 2. according to the method for claim 1, it is characterised in that the solid fullerene includes empty fullerene C2n、 Metal fullerene M@C2n、M2@C2n、MA@C2n、M3N@C2n、M2C2@C2n、M2S@C2n、M2O@C2n And MxA3-xN@C2nAt least one of,Wherein, M and A is independently selected from Sc, Y and lanthanide element, 30≤n≤60,0≤x≤3.
- 3. according to the method for claim 1, it is characterised in that the organic amine includes organic primary amine and organic secondary.
- 4. according to the method for claim 3, it is characterised in that the organic amine include ethylenediamine, propylamine, Propanolamine, At least one of p-phenylenediamine and diethanol amine.
- 5. according to the method for claim 1, it is characterised in that in the mixing of the solid fullerene and Amine Solutions In solution, the mass ratio of the solid fullerene and the organic amine is 1：(0.5~1.5).
- 6. according to the method for claim 1, it is characterised in that the reaction is in stirring or heating stirring reflux condition Carried out under part, the time of the reaction is 5~36 hours.
- 7. according to the method for claim 1, it is characterised in that further comprise：To by the described mixed of the reaction Close solution and carry out purification processes.
- A kind of 8. method for preparing amino fullerene, it is characterised in that including：(a) Amine Solutions are mixed with solid fullerene, be stirred at room temperature or heating stirring counterflow condition under reacted,Wherein, the organic amine includes at least one of ethylenediamine, propylamine, Propanolamine, p-phenylenediamine and diethanol amine；The solid fullerene includes empty fullerene C2n, metal fullerene M@C2n、M2@C2n、MA@C2n、 M3N@C2n、M2C2@C2n、M2S@C2n、M2O@C2nAnd MxA3-xN@C2nAt least one of,Wherein, M and A is independently selected from Sc, Y and lanthanide element, 30≤n≤60,0≤x≤3.(b) solution rotating for obtaining step (a) is dried, and the remaining solid after the Rotary drying is dissolved with acid solution,Wherein, the acid solution is inorganic acid solution, and the concentration of the acid solution is 0.5~1.5mol/L.(c) pH value for the solution that regulating step (b) obtains is 4~6, and the electrical conductivity dialysed to the solution is less than 1 μ s/cm.(d) solution obtained using anion exchange resin process step (c), the electrical conductivity dialysed to the solution are less than 1μs/cm。
- 9. a kind of amino fullerene, it is characterised in that the amino fullerene is using described in any one of claim 1~8 Prepared by method.
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| CN109939732A (en) * | 2019-03-26 | 2019-06-28 | 中国科学院化学研究所 | Application of the semiconductor composite of fullerene derivate modification in formaldehyde degradation by photocatalytic oxidation process |
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| CN114433160A (en) * | 2021-12-22 | 2022-05-06 | 重庆工商大学 | Fullerene C60Process for preparing derivatized electrocatalysts |
| CN114433160B (en) * | 2021-12-22 | 2023-09-01 | 重庆工商大学 | Fullerene C 60 Process for preparing derivative electrocatalyst |
| CN115350284A (en) * | 2022-08-10 | 2022-11-18 | 山东大学 | Tryptophan-modified fullerene nano material, preparation method thereof and application thereof in nerve repair field |
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