CN109223828A - A kind of amino fullerene is preparing application and anti-biotic material in anti-biotic material - Google Patents
A kind of amino fullerene is preparing application and anti-biotic material in anti-biotic material Download PDFInfo
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Abstract
The invention discloses a kind of amino fullerenes to prepare application and anti-biotic material in anti-biotic material.The amino fullerene used in the application includes the fullerene derivate for having organic amine compound group in fullerene raw material surface chemical bonding, is as fullerene and organic amine compound through made from nucleophilic addition.Amino fullerene used in the present invention have it is good it is water-soluble, partial size is small, good dispersion, is not susceptible to reunite, and surface is positively charged, is easy to be adsorbed on phage surface, is easy to thallus phagocytosis, has the effect of good removing free radical；Just there is good antibacterial effect in low concentration simultaneously, do not need by it is photodynamic under the conditions of can achieve the effect that effectively to sterilize, it can kill or inhibit gram-positive bacteria, Gram-negative bacteria or fungi, bacterium is killed or inhibited to alternative, there is no toxicity to cell, can be used for preparing anti-biotic material.
Description
Technical field
The present invention relates to antimicrobial technology field, in particular to a kind of amino fullerene prepare the application in anti-biotic material and
Anti-biotic material.
Background technique
Antibacterial agent refers to can make certain micro-organisms (bacterium, fungi, saccharomycete, algae and virus etc.) within a certain period of time
Growth or breeding are maintained at necessary chemical substance below horizontal, with antibacterial and bactericidal property.Currently, antibacterial on the market
Agent type is more, but there is larger toxic side effect mostly.Therefore, strong, the safe and non-toxic antibacterial agent of exploitation antibiotic property has become
The research hotspot of various countries scientific worker.
Fullerene is the most stable of antioxidant found so far, itself to cell without any toxicity.Fullerene
The research of water slurry and fullerene derivate in terms of antibacterial properties focuses primarily upon its phototoxicity, i.e., under the excitation of light,
Fullerene can generate singlet oxygen to realize antibacterial action.Phototoxic effect can be by intensity of illumination, light application time, temperature etc.
Several factors are adjusted, so that the antibacterial action of fullerene is adjustable in a certain range.
But problem is, does not have selectivity for the injury of cell due to singlet oxygen in phototoxicity antibacterial, so that this
Kind method not only generates damage to microbial cell, but also can also generate certain damage to normal human body cell.Therefore, base
A series of kill microorganism of property of can choose is developed in fullerene molecule while not having any toxic side effect to normal cell
Antibacterial agent will be with important clinical meaning and social value.
Summary of the invention
In order to solve the problems, such as fullerene can only antibacterial under illumination condition and its do not have selectively antibacterial, the present invention
It provides a kind of amino fullerene and is preparing the application in anti-biotic material, amino fullerene used is not needed can by light power
To achieve the effect that effective antibacterial, i.e., amino fullerene used has effects that dark toxicity antibacterial, while amino fullerene used
Can also selective antibiotic, there is no toxic side effect to normal cell.Meanwhile the present invention also provides a kind of anti-biotic materials.
In order to realize goal of the invention, the present invention provides following technical schemes:
The present invention provides a kind of amino fullerenes to prepare the application in anti-biotic material, wherein the amino fullerene packet
Include the fullerene derivate for having organic amine compound group in fullerene raw material surface chemical bonding.
In another embodiment, the fullerene raw material includes having general formula C for above-mentioned application2nEmpty fullerene,
Wherein, 30≤n≤60, optional fullerene raw material are fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene
C84At least one of；Further alternative, the fullerene raw material is fullerene C70。
In another embodiment, the organic amine compound group is organic amine compound and richness for above-mentioned application
Strangle the incomplete organic amine compound after losing any a part when alkene raw material surface is chemically bonded comprising: rouge
Fat aminated compounds group, alcamine compound group, amides compound group, alicyclic ring amine compound group, aromatic amine
At least one of class compound group, naphthalene system aminated compounds group；Optionally, the organic amine compound group includes
Monomethyl amine group, dimethylamine group, trimethylamine group, monoethyl amine group, diethylamino group, triethylamine group, ethylenediamine group,
One propylamine group, dipropyl amine groups, tripropyl amine (TPA) group, isopropylamine group, diisopropylamine group, 1,2- dimethyl propylene amine groups,
Propane diamine group, cyclopropylamine group, n-butylamine group, di-n-butylamine group, different determines amine groups, sec-butylamine at 2- propylene amine groups
Group, butanediamine group, tert-butylamine group, di-iso-butylmanice group, hexylamine group, 2 ethyl hexylamine group, hexamethylene diamine group, three
Octylame group, 1,10- certain herbaceous plants with big flowers diamine groups, certain herbaceous plants with big flowers amine groups, lauryl amine group, cetylamine group, octadecylamine group, distearyl amido
Group, 1,5- dimethylhexylamine group, monoethanolamine group, diethanolamine group, triethanolamine group, 3- propyl alcohol amine groups, one
Isopropanolamine group, diisopropanol amine groups, triisopropanolamine group, n,N-dimethylacetamide group, N, N- diethyl second
Alcohol amine groups, carbonylamino group, acetamide group, propionamide group, butyramide group, isobutyramide group, acrylamido
Group, polyacrylamide group, caprolactam group, dimethylformamide group, dimethylacetamide amine groups, triethylenediamine
Group, diethylenetriamines group, hexa group, hexamethylene imine group, triethylenediamine group, ring second
Alkene imine group, morpholine group, piperazine group, cyclohexylamine group, aniline group, diphenylamino group, benzidine group, adjacent benzene two
Amine groups, m-phenylene diamine (MPD) group, p-phenylenediamine group, o-methyl-benzene amine groups, m-toluidine group, open-chain crown ether base
Group, 2,3- dimethylaniline group, 2,4- dimethylaniline group, 2,5- dimethylaniline group, 2,6- accelerine base
Group, 3,4- dimethylaniline group, 3,5- dimethylaniline group, 2,4,6- trimethylbenzene amine groups, o ethyl aniline group,
N- butylaniline group, 2,6- diethylbenzene amine groups, formanilide group, to butylaniline group, monoacetylaniline base
Group, 3- methoxybenzene amine groups, o-chloraniline group, m-chloroaniline group, parachloroanilinum group, O-ethoxyl amine groups,
M-oxethyl aniline group, p-ethoxyaniline group, methylphenylamine group, 2,3- dichloroaniline group, 2,4- dichloro-benzenes
Amine groups, 2,6-DCA group, 3,4-DCA group, 3,5- dichloroaniline group, 2,5- dichloroaniline group, N-
Ethyl aniline group, N, N- diethylbenzene amine groups, n,N-Dimethylaniline group, o-bromoaniline group, m-bromoaniline group,
Para-bromoaniline group, 2,4,5- trichloroaniline groups, 2,4,6- trichloroaniline groups, 2,4- dibromo aniline group, 2,5- dibromo
Aniline group, 2,6- dibromo aniline group, adjacent fluoroaniline group, m-fluoroaniline group, para-fluoroaniline group, 2,4- difluoroaniline
Group, 3,4- difluoroaniline group, 2,3,4- trifluoromethyl aniline groups, ortho-nitrophenyl amine groups, m-nitro amine groups, to nitro
Aniline group, 2,4- dinitroaniline group, the chloro- 4- fluoroaniline group of 3-, to nitro-p-toluidine group, naphthalidine group,
2- naphthylamines group, 1-Naphthylamine-5-sulfonic group, Kerafyrm acid groups, week vertical acid groups, tobias acid group, J acid groups, R acid groups, H acid
Group, K acid groups, phthalimide-based group, taurine group, naphthylenediamine group, ethylene bis stearamide group, poly- second
At least one of alkene imine group, hydroxyamine groups；Further alternative, the organic amine compound group includes ethylenediamine
At least one of group, propane diamine group, butanediamine group；It is further alternative, the organic amine compound group packet
Include at least one of 1,3- propane diamine group, Putriscine group.
In another embodiment, the amino fullerene includes: for above-mentioned application At least one of, its letter respectively later
Referred to as C70(EDA)8、C70(PDA)6、C70(DAB)2。
The present invention also provides a kind of anti-biotic materials comprising: amino fullerene and other acceptable auxiliary materials, wherein institute
Stating amino fullerene includes the fullerene derivate for having organic amine compound group in fullerene raw material surface chemical bonding.
Above-mentioned application or anti-biotic material in another embodiment, the preparation method of the amino fullerene include: by
Fullerene raw material and organic amine compound mixing, are made amino fullerene through nucleophilic addition.
In another embodiment, the organic amine compound includes fatty amines for above-mentioned application or anti-biotic material
Close object, alcamine compound, amides compound, alicyclic ring aminated compounds, aromatic amine compounds, in naphthalene system aminated compounds
At least one；Optionally, the organic amine compound includes monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, three
Ethamine, ethylenediamine (EDA), a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamine, propane diamine,
2- allylamine, n-butylamine, di-n-butylamine, different determines amine, sec-butylamine, butanediamine, tert-butylamine, di-iso-butylmanice, hexylamine, 2- at cyclopropylamine
Ethylhexylamine, hexamethylene diamine, trioctylamine, 1,10- certain herbaceous plants with big flowers diamines, certain herbaceous plants with big flowers amine, lauryl amine, cetylamine, octadecylamine, distearyl amine, 1,5- bis-
Tuaminoheptane, monoethanolamine, diethanol amine, triethanolamine, 3- Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), three isopropanols
Amine, n,N-dimethylacetamide, N, N- diethyl ethylene diamine, formamide, acetamide, propionamide, butyramide, isobutyramide, third
Acrylamide, polyacrylamide, caprolactam, dimethylformamide, dimethyl acetamide, triethylenediamine, diethylidene three
Amine, hexa, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine, cyclohexylamine, aniline, two
Aniline, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, open-chain crown ether, 2,3-
Dimethylaniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- dimethylaniline, 3,4- dimethylaniline, 3,5- bis-
Methylaniline, 2, it is 4,6- trimethylanilines, o ethyl aniline, N- butylaniline, 2,6- diethylaniline, formanilide, right
Butylaniline, monoacetylaniline, 3- aminoanisole, o-chloraniline, m-chloroaniline, parachloroanilinum, O-ethoxyl amine, second
Oxygroup aniline, p-ethoxyaniline, methylphenylamine, 2,3- dichloroaniline, 2,4- dichloroaniline, 2,6-DCA, 3,4-
Dichloroaniline, 3,5- dichloroaniline, 2,5- dichloroaniline, N-ethylaniline, N, N- diethylaniline, n,N-Dimethylaniline,
O-bromoaniline, m-bromoaniline, para-bromoaniline, 2,4,5- trichloroanilines, 2,4,6- trichloroanilines, 2,4- dibromo aniline, 2,5- bis-
Bromaniline, 2,6- dibromo aniline, adjacent fluoroaniline, m-fluoroaniline, para-fluoroaniline, 2,4- difluoroaniline, 3,4- difluoroaniline, 2,3,
The chloro- 4- fluoroaniline of 4- trifluoromethyl aniline, ortho-nitraniline, meta nitro aniline, paranitroanilinum, 2,4- dinitroaniline, 3-, to nitre
Base para-totuidine, naphthalidine, 2- naphthylamines, 1-Naphthylamine-5-sulfonic, Kerafyrm acid, week vertical acid, tobias acid, J acid, R acid, H acid, K acid, adjacent benzene two
At least one of carboximide, taurine, naphthylenediamine, ethylene bis stearamide, polyethyleneimine, azanol；It is further optional
, the organic amine compound includes at least one of ethylenediamine, propane diamine and butanediamine；It is further alternative, it is described
Organic amine compound includes at least one of 1,3- propane diamine (PDA), Putriscine (DAB).
Above-mentioned application or anti-biotic material in another embodiment, are mixed by fullerene raw material and organic amine compound
First by the fullerene stock dispersion in aromatic hydrocarbon organic solvent before closing, optionally, the aromatic hydrocarbon organic solvent includes
At least one of toluene, dimethylbenzene, ortho-xylene.
In another embodiment, condition or heating is stirred at room temperature in the necleophilic reaction for above-mentioned application or anti-biotic material
It is carried out under the conditions of being stirred at reflux, the stirring rate can be 1000~3000rpm/min.
In another embodiment, the reaction time of the necleophilic reaction is 2~24 small for above-mentioned application or anti-biotic material
When；Optionally, above-mentioned mixed solution is stirred at room temperature 24 hours in the reaction, or reacts 8 under heating stirring counterflow condition
Hour.
Above-mentioned application or anti-biotic material in another embodiment, necleophilic reaction obtain amino fullerene after further include mentioning
Pure step:
The amino fullerene that nucleophilic addition obtains is dried, dissolves the remaining solid after drying with ultrapure water,
Optionally, if any insoluble matter, a small amount of dilute acid soln dissolution is added；Adjust the pH value of solution obtained above to faintly acid, thoroughly
Analysis, less than 1 μ s/cm, obtains final product to conductivity.
In above-mentioned purification step, the pH value is 4~6.
Above-mentioned application or anti-biotic material in another embodiment, the fullerene raw material and organic amine compound
Molar ratio is 1: 1~100；Optionally, the molar ratio of the fullerene raw material and organic amine compound is 1: 1~50；Into one
Step is optional, and the molar ratio of the fullerene raw material and organic amine compound is 1: 1~30.
In another embodiment, the product further progress after the dialysis filters for above-mentioned application or anti-biotic material,
Freeze-drying.
In another embodiment, the dilute acid soln is inorganic acid solution for above-mentioned application or anti-biotic material；Optionally,
The diluted acid includes at least one of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid；
In another embodiment, the concentration of the dilute acid soln is 0.05~3mmol/ for above-mentioned application or anti-biotic material
L；Optionally, the concentration of the dilute acid soln is 0.5~1.5mmol/L.
Above-mentioned application or anti-biotic material in another embodiment, it is described dialysis use molecular cut off for 3500 it is saturating
Analyse bag.
In another embodiment, the dialysis is not less than 18.2M Ω using conductivity for above-mentioned application or anti-biotic material
The ultrapure water of cm is dialysed.
In another embodiment, the auxiliary material includes preservative, diluent, excipient, filling to above-mentioned anti-biotic material
Agent, adhesive, wetting agent, sorbefacient, surfactant, disintegrating agent, lubricant, rate of release regulator, flavouring agent, sweet tea
At least one of taste agent；Optionally, wetting agent includes magnesium stearate, superfine silica gel powder, polyethylene glycols, and sorbefacient can be
At least one of poly- sorb rouge, lecithin, surfactant include poloxamer, fatty acid sorbitan, poly- sorb rouge, disintegration
Agent includes starch, sodium carboxymethyl starch, hydroxypropul starch, low-substituted hydroxypropyl cellulose, croscarmellose sodium, low takes
For at least one of sodium carboxymethylcellulose and alginic acid, adhesive includes polyvinylpyrrolidone, hydroxypropyl cellulose, hydroxyl
At least one of third methylcellulose, starch slurry, gelatin and sodium alginate, filler include lactose, pregelatinized starch, crystallite fibre
Tie up element, calcium carbonate, calcium monohydrogen phosphate, starch, glycine, sucrose, at least one of mannitol, lubricant include magnesium stearate,
At least one of calcium stearate, talcum powder, superfine silica gel powder, rate of release regulator include hydroxypropyl methyl cellulose, carboxylic first
At least one of base sodium cellulosate, ethyl cellulose, cellulose acetate, polyoxyethylene.
In another embodiment, the anti-biotic material includes external preparation, oral preparation or note to above-mentioned anti-biotic material
Penetrate at least one of preparation.
In another embodiment, the anti-biotic material includes anti-Gram-negative bacteria material, resists above-mentioned anti-biotic material
At least one of gram-positive bacteria material and anti-mycotic material, optionally, the anti-biotic material include anti-Escherichia coli material
At least one of material, anti-Staphylococcus aureus material, resisting pseudomonas aeruginosa material, anti-candida albicans material.
In another embodiment, the amino fullerene concentration is in 40 μm of ol/L, to big portion for above-mentioned anti-biotic material
Divide bacterial strain just to have apparent inhibiting effect, in 80 μm of ol/L, 90% or more is reached to the inhibiting effect of bacterial strain.
Compared with prior art, the invention has the following beneficial effects:
(1) amino fullerene produced by the present invention has good water solubility, and partial size is small, and yield is higher, good dispersion, no
Easily reunite, and gained amino fullerene surface is positively charged, be easy to be adsorbed on phage surface, is easy to thallus phagocytosis, tool
There is the good effect for removing free radical, good free radical capture rate can be obtained.
(2) amino fullerene produced by the present invention just has good antibacterial effect in low concentration, is not needing by light
It can achieve the effect that effectively to sterilize under conditions of power, that is, there is dark toxicity bactericidal effect, can kill or inhibit gram
Escherichia coli, staphylococcus aureus, P. aeruginosa can specifically be killed or be inhibited to positive bacteria, Gram-negative bacteria or fungi
Bacterium, alternative are killed or are inhibited bacterium, do not have toxicity to normal cell, so as to be used for antibacterial field.
(3) when the amino fullerene that the present invention uses passes through regulation and control reaction temperature or reaction in which can be convenient
Between, and then obtain different amino fullerene, the solid fullerene of selection includes empty fullerene, be easier to receive electronics and with
Organic amine compound carries out nucleophilic addition.
(4) in the method for preparing amino fullerene that the present invention uses, subsequent purification processing operation simplicity and refining effect
Good, dialysis can remove unreacted organic amine and excessive inorganic matter in acid condition, further dialyse, obtain higher
The water-soluble amido fullerene of purity, therefore gained amino fullerene only needs the purification processes such as simply to protonate, dialyse, then
It is dried to obtain final product, preparation flow simplifies, and shortens the production cycle.
Detailed description of the invention
Fig. 1 is the amino fullerene C according to embodiment 170(EDA)8Infrared absorption pattern.
Fig. 2 is the amino fullerene C according to embodiment 170(EDA)8Hydration partial size and Zeta potential.
Fig. 3 is the amino fullerene C according to embodiment 270(PDA)6Infrared absorption pattern.
Fig. 4 is the amino fullerene C according to embodiment 270(PDA)6Hydration partial size and Zeta potential.
Fig. 5 is the amino fullerene C according to embodiment 370(DAB)2Infrared absorption pattern.
Fig. 6 is the amino fullerene C according to embodiment 370(DAB)2Hydration partial size and Zeta potential.
Fig. 7 is the amino fullerene C of various concentration70(EDA)8Act on lower E. coli plate lab diagram.
Fig. 8 is the amino fullerene C of various concentration70(EDA)8Act on lower staphylococcus aureus plate lab diagram.
Fig. 9 is the amino fullerene C of various concentration70(EDA)8Act on lower pseudomonas aeruginosa plate lab diagram.
Figure 10 is the amino fullerene C of various concentration70(PDA)6Act on lower E. coli plate lab diagram.
Figure 11 is the amino fullerene C of various concentration70(PDA)6Act on lower staphylococcus aureus plate lab diagram.
Figure 12 is the amino fullerene C of various concentration70(DAB)2Act on lower E. coli plate lab diagram.
Figure 13 is the amino fullerene C of various concentration70(DAB)2Act on lower staphylococcus aureus plate lab diagram.
Figure 14 be under different conditions flow analysis chart (a be untreated cell as control group, b invades for bacterium
C is added after dye70(EDA)8Experimental group, c be bacterial invasion do not add C70(EDA)8Group)
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Embodiment 1: fullerene ethylenediamine C70(EDA)8Preparation, infrared spectroscopy detection and dynamic light scattering (DLS) survey
Examination
(1) fullerene ethylenediamine C70(EDA)8Preparation process
Fullerene ethylenediamine C70(EDA)8Structural formula
(a) 50mg (i.e. 0.0595mol) solid fullerene C is weighed with assay balance70(purity 99%, Xiamen good fortune are taken in the fresh
Material Science and Technology Ltd.) it is dissolved in the o-xylene solution of 25ml, ultrasonic disperse 30min, 50mL is measured (i.e. with graduated cylinder
0.75mol) ethylenediamine (analyzing pure, traditional Chinese medicines reagent), is added in the 100mL stuffed conical flask with magnetic stir bar, in room
Temperature is lower to use magnetic stirrer for 24 hours (revolving speed 1000r/min), uses the solvent mistake that volume is 1L, filter sizes are 200nm
Filter (Jin Teng company) filters reactant, obtains brown-red solution, and the ingredient of solution does not participate in the ethylenediamine of reaction mainly
And C70(EDA)8And solvent ortho-xylene；
(b) solution for obtaining (a) step is added in the round-bottomed flask of 250ml, then rotation is used under conditions of 60 DEG C
Evaporimeter (model: IKA RV10basic) is dry completely (revolving speed 80r/min) by filtrate rotary evaporation；It is added ultrapure water-soluble
Solution, if there is a small amount of insoluble matter, it is the dilute hydrochloric acid of lmol/L into round-bottomed flask that a little concentration, which is added, and oscillation flask makes in it
The object that is evaporated on wall is dissolved in dilute hydrochloric acid, obtains brownish red clear solution；
(c) solution for obtaining (b) step is neutralized using the NaOH aqueous solution that concentration is 10mol/L, and pH test paper is detected as
PH is 5 or so, and faintly acid is presented, to guarantee that excessive ethylenediamine, can be in subsequent dialysis step with the presence of chlorination salt form
Sufficiently remove；Solution after neutralization is fitted into the bag filter that molecular cut off is 3500 to be put into ultrapure water and dialyse, dialysis is to ultrapure
The conductivity of water is less than 1 μ s/cm.
(2) fullerene ethylenediamine C70(EDA)8Infrared spectroscopy detection
By above-mentioned brown-red solution drop on silver mirror, tested after natural drying with infrared spectroscopy (IR).As shown in Figure 1, sample
Infrared signature of the product in 3300nm or so absorbs (- NH2Stretching vibration absworption peak) prove that ethylenediamine is bonded to fullerene
Carbon cage, while also being proved in the variation that 800~1500nm infrared signature absorbs (stretching vibration peak of C-C and C=C on carbon cage)
Ethylenediamine has been bonded on carbon cage.
(3) fullerene ethylenediamine C70(EDA)8Dynamic light scattering test
15 μM/L is directly used in dynamic light scattering test, as shown in Fig. 2, it is hydrated partial size on 140nm or so and surface
It is positively charged, it is suitble to by thallus capture, phagocytosis.Sample freeze-drying is used for C, H, N element analysis (EA), at random in the sample
2 positions are selected, obtain two groups of data of 1# and 2#, and average, analysis the results are shown in Table 1, element percent mass ratio
62.02,4.31,13.765, it can determine that its chemical composition is C by the ratio of C, H, N70(EDA)8。
1 C of table70(EDA)8Elemental analysis result
Embodiment 2: fullerene propane diamine C70(PDA)6Preparation, infrared spectroscopy detection and dynamic light scattering test
(1) fullerene propane diamine C70(PDA)6Preparation process
Fullerene propane diamine C70(PDA)6Structural formula
(a) 50mg (i.e. 0.0595mol) solid fullerene C is weighed with assay balance70(purity 99%, Xiamen good fortune are taken in the fresh
Material Science and Technology Ltd.) it is dissolved in the o-xylene solution of 25ml, ultrasonic disperse 30min, 60mL propane diamine is measured with graduated cylinder
(i.e. 0.7mol) (analyzes pure, traditional Chinese medicines reagent), is added in the 100mL stuffed conical flask with magnetic stir bar, at room temperature
For 24 hours (revolving speed 1000r/min) using magnetic stirrer, using the solvent filter that volume is 1L, filter sizes are 200nm
(Jin Teng company) filters reactant, obtains brown-red solution, and the ingredient of solution does not participate in the propane diamine and C of reaction mainly70
(PDA)6And solvent ortho-xylene；
(b) solution for obtaining (a) step is added in the round-bottomed flask of 250ml, then rotation is used under conditions of 60 DEG C
Evaporimeter (model: IKA RV10basic) is dry completely (revolving speed 80r/min) by filtrate rotary evaporation；It is added ultrapure water-soluble
Solution, if there is a small amount of insoluble matter, it is the dilute hydrochloric acid of 1mol/L into round-bottomed flask that a little concentration, which is added, and oscillation flask makes in it
The object that is evaporated on wall is dissolved in dilute hydrochloric acid, obtains brownish red clear solution；
(c) solution for obtaining (b) step is neutralized using the NaOH aqueous solution that concentration is 10mol/L, and pH test paper is detected as
PH is 5 or so, and faintly acid is presented, to guarantee that excessive propane diamine, can be in subsequent dialysis step with the presence of chlorination salt form
Sufficiently remove；Solution after neutralization is fitted into the bag filter that molecular cut off is 3500 to be put into ultrapure water and dialyse, dialysis is to ultrapure
The conductivity of water is less than 1 μ s/cm.
(2) fullerene propane diamine C70(PDA)6Infrared spectroscopy detection
By above-mentioned brown-red solution drop on silver mirror, tested after natural drying with infrared spectroscopy (IR).As shown in figure 3, sample
Infrared signature of the product in 3300nm or so absorbs (- NH2Stretching vibration absworption peak) prove that propane diamine is bonded to fullerene
Carbon cage, while also being proved in the variation that 800~1500nm infrared signature absorbs (stretching vibration peak of C-C and C=C on carbon cage)
Propane diamine has been bonded on carbon cage.
(3) fullerene propane diamine C70(PDA)6Dynamic light scattering test
15 μM/L is directly used in dynamic light scattering test, as shown in figure 4, it is hydrated partial size on 140nm or so and surface
It is positively charged, it is suitble to by thallus capture, phagocytosis.Sample freeze-drying is used for C, H, N element analysis (EA), at random in the sample
2 positions are selected, obtain two groups of data of 1# and 2#, and average, analysis the results are shown in Table 1, element percent mass ratio 66.6,
4.94,11.03, it can determine that its chemical composition is C by the ratio of C, H, N70(PDA)6。
2 C of table70(PDA)6Elemental analysis result
Embodiment 3: fullerene butanediamine C70(DAB)2Preparation, infrared spectroscopy detection and dynamic light scattering test
(1) fullerene butanediamine C70(DAB)2Preparation process
Fullerene butanediamine C70(DAB)2Structural formula
(a) 50mg (i.e. 0.0595mol) solid fullerene C is weighed with assay balance70(purity 99%, Xiamen good fortune are taken in the fresh
Material Science and Technology Ltd.) it is dissolved in the o-xylene solution of 25ml, ultrasonic disperse 30min, 70mL butanediamine is measured with graduated cylinder
(i.e. 0.7mol) (analyzes pure, traditional Chinese medicines reagent), is added in the 100mL stuffed conical flask with magnetic stir bar, at room temperature
For 24 hours (revolving speed 1000r/min) using magnetic stirrer, using the solvent filter that volume is 1L, filter sizes are 200nm
(Jin Teng company) filters reactant, obtains brown-red solution, and the ingredient of solution does not participate in the butanediamine and C of reaction mainly70
(DAB)2And solvent ortho-xylene；
(b) solution for obtaining (a) step is added in the round-bottomed flask of 250ml, then rotation is used under conditions of 60 DEG C
Evaporimeter (model: IKA RV10basic) is dry completely (revolving speed 80r/min) by filtrate rotary evaporation；It is added ultrapure water-soluble
Solution, if there is a small amount of insoluble matter, it is the dilute hydrochloric acid of 1mol/L into round-bottomed flask that a little concentration, which is added, and oscillation flask makes in it
The object that is evaporated on wall is dissolved in dilute hydrochloric acid, obtains brownish red clear solution；
(c) solution for obtaining (b) step is neutralized using the NaOH aqueous solution that concentration is 10mol/L, and pH test paper is detected as
PH is 5 or so, and faintly acid is presented, to guarantee that excessive butanediamine, can be in subsequent dialysis step with the presence of chlorination salt form
Sufficiently remove；Solution after neutralization is fitted into the bag filter that molecular cut off is 3500 to be put into ultrapure water and dialyse, dialysis is to ultrapure
The conductivity of water is less than 1 μ s/cm.
(2) fullerene butanediamine C70(DAB)2Infrared spectroscopy detection
By above-mentioned brown-red solution drop on silver mirror, tested after natural drying with infrared spectroscopy (IR).As shown in figure 5, sample
Infrared signature of the product in 3300nm or so absorbs (- NH2Stretching vibration absworption peak) prove that propane diamine is bonded to fullerene
Carbon cage, while also being proved in the variation that 800~1500nm infrared signature absorbs (stretching vibration peak of C-C and C=C on carbon cage)
Propane diamine has been bonded on carbon cage.
(3) fullerene butanediamine C70(DAB)2Dynamic light scattering test
15 μM/L sample solution is directly used in dynamic light scattering test, as shown in fig. 6, it is hydrated partial size on the left side 140nm
Right and surface is positively charged, is suitble to by thallus capture, phagocytosis.Sample freeze-drying is used for C, H, N element analysis (EA), at random
2 positions are selected in the sample, obtain two groups of data of 1# and 2#, and average, and analysis the results are shown in Table 1, element quality percentage
Ratio 58.47,4.72,5.62 can determine that its chemical composition is C by the ratio of C, H, N70(DAB)2。
3 C of table70(DAB)2Elemental analysis result
Embodiment 4: fullerene ethylenediamine C70(EDA)8Bacteriostatic test plate
Strain selected by bacteriostatic experiment is Escherichia coli (Escherichia coli Top 10), Staphylococcus aureus
Bacterium (Staphylococcus aureus ATCC6538) and pseudomonas aeruginosa (Pseudomonas aeruginosa) (strain
From organic solid key lab of Institute of Chemistry, Academia Sinica), experimental method is mainly that gradient dilution plate is antibacterial
Method.Specific experiment operation is as follows:
(1) actication of culture: the Escherichia coli (4 DEG C of preservations) of 10 μ l is taken to be transferred to the fresh liquid Luria- of 10ml
In Bertani (LB) culture medium, the staphylococcus aureus of 10 μ l (4 DEG C preservation) be transferred to the fresh liquid of 10ml
In NutrientBroth (NB) culture medium, the pseudomonas aeruginosa of 10 μ l (4 DEG C preservation) be transferred to the fresh liquid of 10ml
In Luria-Bertani (LB) culture medium, 37 DEG C, 180r/min isothermal vibration culture 18h~for 24 hours.
(2) preparation of bacteria suspension: the bacteria suspension of shake culture is centrifuged, and supernatant is removed, with sterile PBS (phosphate-buffered
Liquid) cleaning twice after be resuspended, the absorbance value (OD value) of bacteria suspension is measured at 600nm by ultraviolet specrophotometer, according to
The OD value of measurement is diluted bacterium solution, and final concentration of 108CFU/ml。
(3) 6 1500 μ l sterile centrifugation tubes are taken, be separately added into 10 μ l concentration be 4000 μm of ol/L, 2000 μm of ol/L,
The C of 1000 μm of ol/L, 500 μm of ol/L, 250 μm of ol/L, 0 μm of ol/L70(EDA)8Then solution has diluted in addition step 2
Bacterium solution 100 μ l, 1 × PBS (phosphate buffered saline solution) 390 μ l, is placed in 37 DEG C of climatic chambers and reacts 30min.
(4) rubbing method prepares antibacterial plate: the agar powder that mass fraction is 14%, configuration battalion being added in liquid medium
Agar medium is supported, 121 DEG C of sterilizing 20min in autoclave are placed in；Taken out after slightly cooling, then in 50 DEG C of water-baths heat preservation to
With；On superclean bench, each culture dish first pours into 20mL culture medium, condensed water is dried up, after solidification, in solid culture base table
Face is added 100 μ l and dilutes 5 × 104Bacteria suspension again, then uniformly with the coating of sterilizing spreading rod, be with no liquid trickling on plate
Preferably, three repetitions of every group of experimental setup.
(5) culture and counting of bacterium colony: coated antibacterial plate is placed in 37 DEG C of constant temperature and humidity incubators, is not being had
Culture 16 under conditions of light~for 24 hours, it is placed under gel imager and records colonial morphology on plate, and count clump count.It can by Fig. 7
To find out, in C70(EDA)8When concentration is 40 μm of ol/L, most Escherichia coli can be killed, as seen from Figure 8, when dense
When degree is 40 μm of ol/L, most staphylococcus aureus can be killed under no light condition.As seen from Figure 9, C70
(EDA)8Also there is certain killing effect to pseudomonas aeruginosa under no light condition.
Embodiment 5: fullerene propane diamine C70(PDA)6Bacteriostatic test plate
Strain selected by bacteriostatic experiment is Escherichia coli (Escherichia coli Top 10), Staphylococcus aureus
(strain is from Institute of Chemistry, Academia Sinica's organic solid emphasis for bacterium (Staphylococcus aureus ATCC6538)
Laboratory), experimental method is mainly gradient dilution plate bacteriostatic method.Specific experiment operation is as follows:
(1) actication of culture: the Escherichia coli (4 DEG C of preservations) of 10 μ l is taken to be transferred to the fresh liquid Luria- of 10ml
In Bertani (LB) culture medium, the staphylococcus aureus of 10 μ l (4 DEG C preservation) be transferred to the fresh liquid Nutrient of 10ml
In Broth (NB) culture medium, 37 DEG C, 180r/min isothermal vibration culture 18h~for 24 hours.
(2) preparation of bacteria suspension: the bacteria suspension of shake culture is centrifuged, and supernatant is removed, with sterile PBS (phosphate-buffered
Liquid) cleaning twice after be resuspended, the absorbance value (OD value) of bacteria suspension is measured at 600nm by ultraviolet specrophotometer, according to
The OD value of measurement is diluted bacterium solution, and final concentration of 108CFU/ml。
(3) 6 1500 μ l sterile centrifugation tubes are taken, be separately added into 10 μ l concentration be 2000 μm of ol/L, 1000 μm of ol/L,
The C of 500 μm of ol/L, 250 μm of ol/L, 0 μm of ol/L70(PDA)6Solution, is then added the bacterium solution 100 μ l diluted in step 2, and 1
390 μ l of × PBS (phosphate buffered saline solution), is placed in 37 DEG C of climatic chambers and reacts 30min.
(4) rubbing method prepares antibacterial plate: the agar powder that mass fraction is 14%, configuration battalion being added in liquid medium
Agar medium is supported, 121 DEG C of sterilizing 20min in autoclave are placed in；Taken out after slightly cooling, then in 50 DEG C of water-baths heat preservation to
With；On superclean bench, each culture dish first pours into 20mL culture medium, condensed water is dried up, after solidification, in solid culture base table
Face is added 100 μ l and dilutes 5 × 104Bacteria suspension again, then uniformly with the coating of sterilizing spreading rod, be with no liquid trickling on plate
Preferably, three repetitions of every group of experimental setup.
(5) culture and counting of bacterium colony: coated antibacterial plate is placed in 37 DEG C of constant temperature and humidity incubators, is not being had
Culture 16 under conditions of light~for 24 hours, it is placed under gel imager and records colonial morphology on plate, and count clump count.By Figure 10
As can be seen that in C70(PDA)6When concentration is 20 μm of ol/L, most Escherichia coli can be killed under no light condition, by scheming
11 as can be seen that in C70(PDA)6When concentration is 10 μm of ol/L, most golden yellow grape can be killed under no light condition
Coccus.
Embodiment 6: fullerene butanediamine C70(DAB)2Bacteriostatic test plate
Strain selected by bacteriostatic experiment is Escherichia coli (Escherichia coli Top 10), Staphylococcus aureus
(strain is from Institute of Chemistry, Academia Sinica's organic solid emphasis for bacterium (Staphylococcus aureus ATCC6538)
Laboratory), experimental method is mainly gradient dilution plate bacteriostatic method.Specific experiment operation is as follows:
(1) actication of culture: the Escherichia coli (4 DEG C of preservations) of 10 μ l is taken to be transferred to the fresh liquid Luria- of 10ml
In Bertani (LB) culture medium, the staphylococcus aureus of 10 μ l (4 DEG C preservation) be transferred to the fresh liquid Nutrient of 10ml
In Broth (NB) culture medium, 37 DEG C, 180r/min isothermal vibration culture 18h~for 24 hours.
(2) preparation of bacteria suspension: the bacteria suspension of shake culture is centrifuged, and supernatant is removed, with sterile PBS (phosphate-buffered
Liquid) cleaning twice after be resuspended, the absorbance value (OD value) of bacteria suspension is measured at 600nm by ultraviolet specrophotometer, according to
The OD value of measurement is diluted bacterium solution, and final concentration of 108CFU/ml。
(3) 6 1500 μ l sterile centrifugation tubes are taken, be separately added into 10 μ l concentration be 2000 μm of ol/L, 1000 μm of ol/L,
The C of 500 μm of ol/L, 250 μm of ol/L, 0 μm of ol/L70(DAB)2Solution, is then added the bacterium solution 100 μ l diluted in step 2, and 1
390 μ l of × PBS (phosphate buffered saline solution), is placed in 37 DEG C of climatic chambers and reacts 30min.
(4) rubbing method prepares antibacterial plate: the agar powder that mass fraction is 14%, configuration battalion being added in liquid medium
Agar medium is supported, 121 DEG C of sterilizing 20min in autoclave are placed in；Taken out after slightly cooling, then in 50 DEG C of water-baths heat preservation to
With；On superclean bench, each culture dish first pours into 20mL culture medium, condensed water is dried up, after solidification, in solid culture base table
Face is added 100 μ l and dilutes 5 × 104Bacteria suspension again, then uniformly with the coating of sterilizing spreading rod, be with no liquid trickling on plate
Preferably, three repetitions of every group of experimental setup.
(5) culture and counting of bacterium colony: coated antibacterial plate is placed in 37 DEG C of constant temperature and humidity incubators, is not being had
Culture 16 under conditions of light~for 24 hours, it is placed under gel imager and records colonial morphology on plate, and count clump count.By Figure 12
As can be seen that in C70(DAB)2Concentration can kill most Escherichia coli when being 40 μm of ol/L under no light condition, by scheming
13 as can be seen that in C70(DAB)2Concentration can kill most Staphylococcus aureus when being 10 μm of ol/L under no light condition
Bacterium.
Embodiment 7: bacterial invasion cell experiment
Selected cell is horn cell (HEK-a cell), and specific implementation process is as follows:
(1) culture of HEK-a cell: 0.25% pancreatin (Coming T1320) of adherent HEK-a cell is digested,
And be resuspended with the DMEM culture medium (Corning-cellgro R10-013-CVR) containing 10% fetal calf serum, use blood counting chamber
10 are diluted to after counting5A/ml is added in 6 orifice plates, and every hole adds 2ml cell suspension, is placed in 37 DEG C of carbon dioxide and cultivated
Night.
(2) bacterial invasion cell preliminary experiment: Escherichia coli, the staphylococcus aureus, the false list of verdigris that 4 DEG C of refrigerators are saved
Born of the same parents bacterium and Candida albicans bacteria suspension take 10 μ to be forwarded in the fresh fluid nutrient medium of 10ml, and 37 DEG C, 180r/min isothermal vibration
Culture 18h~for 24 hours.The bacteria suspension of shake culture is taken out, supernatant is removed in centrifugation, with without dual anti-after cleaning twice with sterile PBS
Cell culture medium is resuspended, and the absorbance value (OD value) of bacteria suspension is measured at 600nm by ultraviolet specrophotometer, according to measurement
OD value bacterium solution is diluted, final concentration of 5*108CFU/ml.According to bacterium and cell proportion 1: 1,1: 4,1: 10,1: 50,
1: 100,1: 200,1: 400,1: 800 gradient dilution bacterial suspension；Remove cell culture fluid, the bacterial suspension that will have been diluted
It is added in 6 orifice plates, is incubated overnight in carbon dioxide incubator；The suspension in 6 orifice plates is removed, and gently adds sterile PBS,
Every hole 2ml after impregnating 10min, removes PBS, the configured colourless DMEM culture medium containing 10%CCK-8 is added, after being incubated for 1h
With the light absorption at microplate reader measurement 450nm, cell survival rate is calculated, according to the Cmin of complete cell death, is determined most
Suitable bacterium and mixing with cells ratio.The bacterium finally determined by test of many times and mixing with cells ratio are 5: 1.
(3) bacterium, cell, drug are incubated for experiment altogether: after bacterium activation, dilution, bacteria suspension 1ml is taken to be added in 6 orifice plates,
And by C70(EDA)8It is configured to 4mmol/l, 2mmol/l, with the cell culture fluid dilution 5 without dual anti-(penicillin and streptomysin)
It is added in 6 orifice plates after times, every hole adds 1ml, is placed in carbon dioxide incubator and is incubated overnight；Nothing is added along wall in suspension in removal
Bacterium PBS impregnates 10min, observes and records cellular morphology with microscope, removes PBS, in the pancreatin digestion 6 orifice plates without EDTA
Cell, cell culture fluid is added and gently blows and beats that cell suspension is made is stand-by.
(4) detection of Apoptosis: using AnnexinV/PI kit (triumphant base Annexin V/PI 488nm,
KGA108 double fluorescent staining) is carried out to cell.Concrete operations are as follows: cell suspension is centrifuged 5~10 minutes in room temperature 2000rpm, is received
Collect cell, primary with (4 DEG C) resuspension cells of 1 × PBS of pre-cooling, 2000rpm is centrifuged 5~10 minutes, washs cell；300 μ are added
1 × Binding Buffer suspension cell of L；It after the Annexin V-FITC mixing of 5 μ L is added, is protected from light, is incubated at room temperature 15 points
Clock；Add within 5 minutes before upper machine the PI dyeing of 5 μ L；Upper machine testing is carried out with flow cytometer after the completion of dyeing.
As shown in figure 14, a group is the cell do not crossed by bacterial invasion as control group, it can be seen that cell is most of
In lower left corner region, illustrate that cell is normal condition, there is no apoptosis.B, two groups of c are the cell crossed by bacterial invasion,
It wherein joined the C of 80 μm of ol in b group70- EDA, cell are mostly in non-apoptotic state, and c group does not add C70- EDA, at cell
In the upper left corner, illustrate that complete apoptosis is cell fragment.It can be seen that C70- EDA can protect carefully while killing bacterium
Born of the same parents are not by bacterial infestation, that is to say, that amino fowler enamine in the system that bacterium and cell coexist there is selectivity kill to have
The property of evil bacterium.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of amino fullerene is preparing the application in anti-biotic material, wherein the amino fullerene is included in fullerene raw material
Surface chemistry is bonded with the fullerene derivate of organic amine compound group.
2. a kind of anti-biotic material, comprising: amino fullerene and other acceptable auxiliary materials, wherein the amino fullerene is included in
Fullerene raw material surface is chemically bonded the fullerene derivate for having organic amine compound group.
3. application according to claim 1 or anti-biotic material as claimed in claim 2, it is characterised in that: the fullerene
Raw material includes having general formula C2nEmpty fullerene, wherein 30≤n≤60, optional fullerene raw material be fullerene C60, it is rich
Strangle alkene C70, fullerene C76, fullerene C78, fullerene C84At least one of；Further alternative, the fullerene raw material is
Fullerene C70。
4. application according to claim 1 or anti-biotic material as claimed in claim 2, it is characterised in that: the organic amine
Class compound group is endless after losing any a part when organic amine compound is chemically bonded with fullerene surface
Whole organic amine compound comprising: fat amine compound group, alcamine compound group, amides compound base
At least one of group, alicyclic ring amine compound group, aromatic amine compounds group, naphthalene system aminated compounds group；It is optional
, the organic amine compound group includes monomethyl amine group, dimethylamine group, trimethylamine group, monoethyl amine group, diethyl
It is amine groups, triethylamine group, ethylenediamine group, a propylamine group, dipropyl amine groups, tripropyl amine (TPA) group, isopropylamine group, two different
Propylamine group, 1,2- dimethyl propylene amine groups, propane diamine group, 2- propylene amine groups, cyclopropylamine group, n-butylamine group, two
N-butylamine group, it is different determine amine groups, sec-butylamine group, butanediamine group, tert-butylamine group, di-iso-butylmanice group, hexylamine group,
2 ethyl hexylamine group, hexamethylene diamine group, trioctylamine group, 1,10- certain herbaceous plants with big flowers diamine groups, certain herbaceous plants with big flowers amine groups, lauryl amine group, 16
Amine groups, octadecylamine group, distearyl amine group, 1,5- dimethylhexylamine group, monoethanolamine group, diethanolamine group,
Triethanolamine group, 3- propyl alcohol amine groups, monoisopropanolamine group, diisopropanol amine groups, triisopropanolamine group, N, N- bis-
Methyl vinyl amine groups, N, N- diethylaluminum ethoxide amine groups, carbonylamino group, acetamide group, propionamide group, amide-based small
Group, isobutyramide group, acrylamide group, polyacrylamide group, caprolactam group, dimethylformamide group, two
Methyl vinyl amine groups, triethylenediamine group, diethylenetriamines group, hexa group, hexa-methylene are sub-
Amine groups, triethylenediamine group, cyclic ethylene imine group, morpholine group, piperazine group, cyclohexylamine group, aniline group,
Diphenylamino group, benzidine group, o-phenylenediamine group, m-phenylene diamine (MPD) group, p-phenylenediamine group, o-methyl-benzene amine groups,
M-toluidine group, open-chain crown ether group, 2,3- dimethylaniline group, 2,4- dimethylaniline group, 2,5- diformazan
Base aniline group, 2,6- dimethylaniline group, 3,4- dimethylaniline group, 3,5- dimethylaniline group, 2,4,6- tri-
Methylaniline group, o ethyl aniline group, N- butylaniline group, 2,6- diethylbenzene amine groups, formanilide group,
To butylaniline group, monoacetylaniline group, 3- methoxybenzene amine groups, o-chloraniline group, m-chloroaniline group, to chlorine
Aniline group, O-ethoxyl amine groups, m-oxethyl aniline group, p-ethoxyaniline group, methylphenylamine group, 2,
3- dichloroaniline group, 2,4- dichloroaniline group, 2,6-DCA group, 3,4-DCA group, 3,5- dichloro-benzenes
Amine groups, 2,5- dichloroaniline group, N-ethylaniline group, N, N- diethylbenzene amine groups, n,N-Dimethylaniline group,
O-bromoaniline group, m-bromoaniline group, para-bromoaniline group, 2,4,5- trichloroaniline groups, 2,4,6- trichloroaniline groups,
2,4- dibromo aniline groups, 2,5- dibromo aniline group, 2,6- dibromo aniline group, adjacent fluoroaniline group, m-fluoroaniline group,
Para-fluoroaniline group, 2,4- difluoroaniline group, 3,4- difluoroaniline group, 2,3,4- trifluoromethyl aniline groups, ortho-nitraniline
Group, m-nitro amine groups, p-nitrophenyl amine groups, 2,4- dinitroaniline group, the chloro- 4- fluoroaniline group of 3-, to nitre
Base para-totuidine group, naphthalidine group, 2- naphthylamines group, 1-Naphthylamine-5-sulfonic group, Kerafyrm acid groups, week vertical acid groups, Tu Shi
Acid groups, J acid groups, R acid groups, H acid groups, K acid groups, phthalimide-based group, taurine group, naphthylenediamine base
At least one of group, ethylene bis stearamide group, polyethyleneimine amine groups, hydroxyamine groups；It is further alternative, it is described to have
Machine aminated compounds group includes at least one of ethylenediamine group, propane diamine group, butanediamine group；It is further optional
, the organic amine compound group includes at least one of 1,3- propane diamine group, Putriscine group.
5. application according to claim 1 or anti-biotic material as claimed in claim 2, it is characterised in that: the amino is rich
The preparation method for strangling alkene includes: to mix fullerene raw material and organic amine compound, and amino richness is made through nucleophilic addition
Strangle alkene.
6. anti-biotic material described in application according to claim 5 or claim 5, it is characterised in that:
The organic amine compound includes fat amine compound, alcamine compound, amides compound, alicyclic ring amine
Close at least one of object, aromatic amine compounds, naphthalene system aminated compounds；Optionally, the organic amine compound includes
It is monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, ethylenediamine (EDA), a propylamine, di-n-propylamine, tripropyl amine (TPA), different
Propylamine, 1,2- dimethyl propylamine, propane diamine, 2- allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, different determines amine, secondary at diisopropylamine
Butylamine, butanediamine, tert-butylamine, di-iso-butylmanice, hexylamine, 2 ethyl hexylamine, hexamethylene diamine, trioctylamine, 1,10- certain herbaceous plants with big flowers diamines, certain herbaceous plants with big flowers amine, ten
Diamines, cetylamine, octadecylamine, distearyl amine, 1,5- dimethylhexylamine, monoethanolamine, diethanol amine, triethanolamine, 3- propyl alcohol
Amine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, n,N-dimethylacetamide, N, N- diethyl ethylene diamine, formamide,
Acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide, caprolactam, dimethylformamide, diformazan
Yl acetamide, triethylenediamine, diethylenetriamines, hexa, hexamethylene imine, triethylenediamine, ring
Aziridine, morpholine, piperazine, cyclohexylamine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, adjacent first
Base aniline, m-toluidine, open-chain crown ether, 2,3- dimethylaniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,
6- dimethylaniline, 3,4- dimethylaniline, 3,5- dimethylaniline, 2,4,6- trimethylanilines, o ethyl aniline, N- butyl
Aniline, 2,6- diethylaniline, formanilide, to butylaniline, monoacetylaniline, 3- aminoanisole, o-chloraniline,
Chloroaniline, parachloroanilinum, O-ethoxyl amine, m-oxethyl aniline, p-ethoxyaniline, methylphenylamine, 2,3- dichloro-benzenes
Amine, 2,4- dichloroaniline, 2,6-DCA, 3,4-DCA, 3,5- dichloroaniline, 2,5- dichloroaniline, N- ethylo benzene
Amine, N, N- diethylaniline, n,N-Dimethylaniline, o-bromoaniline, m-bromoaniline, para-bromoaniline, 2,4,5- trichloroanilines, 2,
4,6- trichloroanilines, 2,4- dibromo aniline, 2,5- dibromo aniline, 2,6- dibromo aniline, adjacent fluoroaniline, m-fluoroaniline, to fluorobenzene
Amine, 2,4- difluoroaniline, 3,4- difluoroaniline, 2,3,4- trifluoromethyl anilines, ortho-nitraniline, meta nitro aniline, paranitroanilinum,
The chloro- 4- fluoroaniline of 2,4- dinitroanilines, 3-, to nitro-p-toluidine, naphthalidine, 2- naphthylamines, 1-Naphthylamine-5-sulfonic, Kerafyrm acid, week
Vertical acid, tobias acid, J acid, R acid, H acid, K acid, phthalimide, taurine, naphthylenediamine, ethylene bis stearamide, poly- second
At least one of alkene imines, azanol；Further alternative, the organic amine compound includes ethylenediamine, propane diamine and fourth
At least one of diamines；Further alternative, the organic amine compound includes 1,3- propane diamine (PDA), Isosorbide-5-Nitrae-fourth two
At least one of amine (DAB)；
Optionally, the amino fullerene includes C70(EDA)8、C70(PDA)6、C70(DAB)2At least one of, structural formula
Successively are as follows:
7. anti-biotic material described in application according to claim 5 or claim 5, it is characterised in that: the fullerene
The molar ratio of raw material and organic amine compound is 1: 1~100；Optionally, the fullerene raw material and organic amine compound
Molar ratio be 1: 1~50；It is further alternative, the molar ratio of the fullerene raw material and organic amine compound is 1: 1~
30。
8. anti-biotic material according to claim 2, it is characterised in that: the auxiliary material includes preservative, diluent, figuration
Agent, filler, adhesive, wetting agent, sorbefacient, surfactant, disintegrating agent, lubricant, rate of release regulator, perfume (or spice)
At least one of taste agent, sweetener；Optionally, wetting agent includes magnesium stearate, superfine silica gel powder, polyethylene glycols, absorbs and promotees
It can be at least one of poly- sorb rouge, lecithin into agent, surfactant includes poloxamer, fatty acid sorbitan, poly- mountain
Pears rouge, disintegrating agent include starch, sodium carboxymethyl starch, hydroxypropul starch, low-substituted hydroxypropyl cellulose, cross-linked carboxymethyl fiber
At least one of plain sodium, low substituted carboxymethyl sodium cellulosate and alginic acid, adhesive includes polyvinylpyrrolidone, hydroxypropyl
At least one of cellulose, hydroxypropyl methylcellulose, starch slurry, gelatin and sodium alginate, filler include lactose, pregelatinated shallow lake
At least one of powder, microcrystalline cellulose, calcium carbonate, calcium monohydrogen phosphate, starch, glycine, sucrose, mannitol, lubricant include
At least one of magnesium stearate, calcium stearate, talcum powder, superfine silica gel powder, rate of release regulator include hydroxypropyl methyl fibre
Tie up at least one of element, sodium carboxymethylcellulose, ethyl cellulose, cellulose acetate, polyoxyethylene.
9. application according to claim 1 or anti-biotic material as claimed in claim 2, it is characterised in that: the antibacterial material
Material includes at least one of external preparation, oral preparation or ejection preparation.
10. application according to claim 1 or anti-biotic material as claimed in claim 2, it is characterised in that: the antibacterial material
Material includes at least one of anti-Gram-negative bacteria material, resisting gram-positive bacteria material and anti-mycotic material, optionally, institute
Stating anti-biotic material includes anti-Escherichia coli material, anti-Staphylococcus aureus material, resisting pseudomonas aeruginosa material, anti-white thought
At least one of pearl bacterium material.
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| CN111265547A (en) * | 2020-02-26 | 2020-06-12 | 上海紫河生物科技有限公司 | Fullerene and fullerene derivative-containing disinfection spray and preparation method thereof |
| CN113519552A (en) * | 2021-07-28 | 2021-10-22 | 安徽江淮汽车集团股份有限公司 | Preparation method of antibacterial agent, thermoplastic resin composite material and preparation method thereof |
| CN114276272A (en) * | 2021-12-03 | 2022-04-05 | 江南大学 | Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide |
| CN115557601A (en) * | 2022-11-08 | 2023-01-03 | 成都理工大学 | Biomass microsphere, preparation method and application thereof, bioreactor and underground well |
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| CN111265547A (en) * | 2020-02-26 | 2020-06-12 | 上海紫河生物科技有限公司 | Fullerene and fullerene derivative-containing disinfection spray and preparation method thereof |
| CN113519552A (en) * | 2021-07-28 | 2021-10-22 | 安徽江淮汽车集团股份有限公司 | Preparation method of antibacterial agent, thermoplastic resin composite material and preparation method thereof |
| CN113519552B (en) * | 2021-07-28 | 2021-12-07 | 安徽江淮汽车集团股份有限公司 | Preparation method of antibacterial agent, thermoplastic resin composite material and preparation method thereof |
| CN114276272A (en) * | 2021-12-03 | 2022-04-05 | 江南大学 | Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide |
| CN115557601A (en) * | 2022-11-08 | 2023-01-03 | 成都理工大学 | Biomass microsphere, preparation method and application thereof, bioreactor and underground well |
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