CN103329893A - Preparation of silver/fullerene nanocomposite and application of silver/fullerene nanocomposite as antibacterial agent - Google Patents
Preparation of silver/fullerene nanocomposite and application of silver/fullerene nanocomposite as antibacterial agent Download PDFInfo
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- CN103329893A CN103329893A CN2013102567708A CN201310256770A CN103329893A CN 103329893 A CN103329893 A CN 103329893A CN 2013102567708 A CN2013102567708 A CN 2013102567708A CN 201310256770 A CN201310256770 A CN 201310256770A CN 103329893 A CN103329893 A CN 103329893A
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- fullerene
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- malonate derivative
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 76
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 39
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 12
- 239000004332 silver Substances 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000967 suction filtration Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012065 filter cake Substances 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- -1 C60 malonate derivative Chemical class 0.000 claims abstract description 13
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- 239000000463 material Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 32
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003378 silver Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- FNJVDWXUKLTFFL-UHFFFAOYSA-N diethyl 2-bromopropanedioate Chemical compound CCOC(=O)C(Br)C(=O)OCC FNJVDWXUKLTFFL-UHFFFAOYSA-N 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 229910001961 silver nitrate Inorganic materials 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 14
- 239000002609 medium Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 235000015097 nutrients Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000011081 inoculation Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000006142 Luria-Bertani Agar Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003937 drug carrier Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000713772 Human immunodeficiency virus 1 Species 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- 241000192130 Leuconostoc mesenteroides Species 0.000 description 1
- 241000228153 Penicillium citrinum Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000191963 Staphylococcus epidermidis Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940086056 activeoxy Drugs 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical compound N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 208000002672 hepatitis B Diseases 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to preparation of a silver/fullerene nanocomposite and an application of the silver/fullerene nanocomposite as an antibacterial agent. Reuniting among nano silver particles can be effectively avoided. The method comprises the following steps of: dissolving fullerene into a solvent A, adding a reducing agent, carrying out agitation under nitrogen protection, adding diethyl bromomalonate, processing by a silica chromatographic column, carrying out suction filtration, removing the solvent A in the filtrate, and drying in vacuum to obtain dibasic C60 malonate derivative to dissolve into the solvent A; adding the reducing agent, carrying out hydrolysis reaction under nitrogen protection, removing the solvent A, dispersing concentrated hydrochloric acid, and diluting by ultra-pure water; carrying out suction filtration, ultrasonically dispersing a filter cake by a solvent B; carrying out suction filtration, removing the solvent B, and drying in vacuum; adding the prepared dibasic C60 malonate derivative aqueous suspension to a silver nitrate solution, ultrasonically mixing, and adding a solvent C to react; and centrifuging and washing solids to a neutral state, and drying in vacuum to obtain the silver/fullerene nanocomposite. The silver/fullerene nanocomposite is good in stability, not easy to reunite, high in antimicrobial activity, small in biological thrill, safe and efficient, and can be recycled.
Description
Technical field
The present invention relates to chemistry, particularly a kind of preparation of Yin ∕ fullerene nano composite material and as the application of antibacterial agent.
Background technology
As the discovery of the third allotrope fullerene family of carbon, it is one of most important breakthrough of natural science development history in last century.Three people such as Kroto also win Nobel chemistry Prize in 1996 because of the work of their initiative in fullerene research.The spherical molecule that fullerene is made up of 60 carbon atoms comprises 12 five-membered rings and 20 hexatomic rings, and diameter is 0.71nm.Fullerene is with its particular structure and extremely people's attention of character, and over past ten years, almost the scientist of all famous universities of the whole world and research institute has carried out the research relevant with fullerene.It has become the common problem of being concerned about of current physics, chemistry, material and life science person.The important scientific meaning of fullerene molecule is chosen as 1991 " star molecule " by the U.S. " Science " magazine.
Because silver has efficiently, safety, fungicidal spectrum extensively, warm tolerance, have no drug resistance and advantage such as high selectivity, for a long time, people just bring into use silverware and utensil to carry out disinfection, emergence and development along with nanosecond science and technology, Nano Silver begins to enter daily life, has been widely used in health care and food hygiene field now.There are some researches prove that silver nano material has inhibitory action to some organism activity: (a) bacterium, as Escherichia coli, staphylococcus aureus, Staphylococcus epidermidis, Leuconostoc mesenteroides, hay bacillus, term enterobacteria, pneumobacillus etc.; (b) fungi is as black-koji mould, Candida albicans, saccharomycete, palpus trichomyces and penicillium citrinum; (c) virus, as hepatitis B, HIV-1 and syncytial virus etc.
There are three kinds in the sterilization mechanism of Nano Silver, comprise: (1) nano-Ag particles can discharge silver ion, silver ion can enter in the cell by the penetration cell wall, react with the functional group of sulfur-bearings such as the coloured glaze base that exists in protein in the microbial body, the nucleic acid, amino, nitrogen, the activity of destructive enzyme and genetic material, thereby destroy the generation of ATP and the normal replication of DNA, cause bacterium death; (2) Nano Silver can produce the active oxy group of hyperoxia voltinism, as superoxide ion, hydrogen peroxide and hydroxyl free radical etc., with material in the bacterial body oxidation reaction that reacts, causes bacterium death; (3) nano-Ag particles itself can adsorb and at the bacteria cell wall surface enrichment, cause the somatic cells cracking.But Nano Silver is easy to take place agglomeration in the aqueous solution, makes bactericidal effect weaken greatly; Safety problem or perhaps recovery problem, after the bacterium in killing water body, nano particle will reclaim effectively exactly, so just can not cause new pollution.But have not yet to see the open report of this respect technology.
Summary of the invention
At above-mentioned situation, for overcoming the defective of prior art, the present invention's purpose just provides a kind of preparation of silver-colored ∕ fullerene nano composite material and as the application of antibacterial agent, can effectively avoid the reunion between the nano-Ag particles, be beneficial to by the porous ceramics filter membrane and dam, realize recycling, and as pharmaceutical carrier, be implemented in the application problem in the antibacterial agent.
The technical scheme that the present invention solves is, silver-colored ∕ fullerene nano composite material is to connect nano-Ag particles by chemical bond-linking on fullerene molecule, and the mass ratio of its Nano Silver and fullerene is 1-8 ︰ 1, and fullerene is C
60Fullerene, its preparation method is:
1) fullerene 40-60mg is dissolved in the solvent orange 2 A of 40-60mL; add and to go back original reagent 240-360mg, nitrogen protection, stir 0.5-1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.16-0.24mL; continue to stir 4-6h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation desolventizing A at 20-60 ℃ of vacuum drying 24-56h, gets two and replaces C
60The malonate derivative;
Described solvent orange 2 A is toluene, and going back original reagent is sodium hydride, citric acid, lithium aluminium hydride, a kind of in the sodium borohydride;
2) replace C with two
60Malonate derivative 40-60mg is dissolved in the solvent orange 2 A of 20-36mL; add and go back original reagent 144-216mg; nitrogen protection; after stirring the reaction 10-12h that is hydrolyzed under 75-85 ℃; desolventizing A; the adding mass fraction is 38% concentrated hydrochloric acid 10-24mL dispersion; add ultra-pure water 30-50mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion among the solvent B of 40-60mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation desolventizing B at 20-60 ℃ of following vacuum drying 24-56h, gets two and replaces C
60Malonate derivative;
Described solvent B is methyl alcohol, ethanol, a kind of in the acetone;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 50-100 mL dropwise joins among the liquor argenti nitratis ophthalmicus 12-25 mL that concentration is 10 mmol/L, behind the ultrasonic mixing 30-60min, get mixed liquor, again mixed liquor is transferred in the water-bath, water temperature is 65-75 ℃, under the stirring of 300-400r/min, the solvent C reaction 10-15min that dropwise adds 12-25mL, get solids at the centrifugal 10-15 min of 10000-12000 r/min, solids uses 20-30 mL water washing 3-5 time to neutral at every turn, at 20-60 ℃ of following vacuum drying 24-56h, namely De Yin ∕ fullerene nano composite material;
Described solvent C is sodium hydroxide solution or potassium hydroxide solvent.
Gai Yin ∕ fullerene nano composite material is effective to prepare antibacterial agent as pharmaceutical carrier.
The present invention is with Nano Silver on the fullerene area load, thereby obtain new fullerene nano composite material, this composite is effective to prepare antibacterial agent, support the carrier of Nano Silver with the fullerene conduct, specifically be with Nano Silver on the fullerene area load, fullerene is as the carrier that supports Nano Silver, can avoid the reunion between the nano-Ag particles effectively, can be dammed by the porous ceramics filter membrane, the antibacterial agent good stability that its product makes, nano-Ag particles is dispersed in the fullerene surface, be difficult for reuniting, the antibacterial activity height, biostimulation is little, safe and efficient, and be convenient to recycling.
Embodiment
Elaborate below in conjunction with the specific embodiment of the present invention of embodiment.
The present invention can be provided by following examples in the specific implementation.
Embodiment 1
The present invention can be realized by following steps in concrete enforcement:
1) fullerene 50mg is dissolved in the toluene of 50mL; add and to go back original reagent sodium hydride 300mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.2mL; continue to stir 5h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed toluene, at 50 ℃ of vacuum drying 35h, gets two and replaces C
60Malonate derivative 55mg;
2) replace C with two
60Malonate derivative 50mg is dissolved in the toluene of 30mL; add and go back original reagent sodium hydride 180mg; nitrogen protection; after stirring the reaction 10h that is hydrolyzed under 80 ℃; remove toluene; the adding mass fraction is 38% concentrated hydrochloric acid 20mL dispersion; add ultra-pure water 40mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the methyl alcohol of 50mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed methyl alcohol, at 50 ℃ of following vacuum drying 30h, gets two and replaces C
60Malonate derivative 45mg;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 50mL dropwise joins among the liquor argenti nitratis ophthalmicus 12mL that concentration is 10 mmol/L, behind the ultrasonic mixing 30min, get mixed liquor, again mixed liquor is transferred in the water-bath, water temperature is 70 ℃, under the stirring of 300r/min, dropwise adding concentration is the sodium hydroxide solution 12mL reaction 11min of 4mol/L, get solids with centrifuge at the centrifugal 10min of 12000 r/min, solids uses 20mL water washing 5 times to neutral at every turn, at 50 ℃ of following vacuum drying 26h, namely De Yin ∕ fullerene nano composite material 15mg.
Embodiment 2
The present invention also can be realized by following steps at embodiment:
1) fullerene 40mg is dissolved in the toluene of 40mL; add sodium borohydride 240mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.16mL; continue to stir 5h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation desolventizing A at 20 ℃ of vacuum drying 56h, gets two and replaces C
60The malonate derivative;
2) replace C with two
60Malonate derivative 40mg is dissolved in the toluene of 24mL, adds sodium borohydride 144mg, nitrogen protection; after stirring the reaction 12h that is hydrolyzed under 75 ℃, remove toluene, the adding mass fraction is 38% concentrated hydrochloric acid 16mL dispersion; add ultra-pure water 30mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the ethanol of 40mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed ethanol, at 40 ℃ of following vacuum drying 48h, gets two and replaces C
60Malonate derivative;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 56mL dropwise joins among the liquor argenti nitratis ophthalmicus 14mL that concentration is 10 mmol/L, behind the ultrasonic mixing 45min, get mixed liquor, mixed liquor is transferred in 65 ℃ the water, under the stirring of 400r/min, dropwise adding concentration is the sodium hydroxide solution 20mL reaction 13min of 4mol/L again, get solids at the centrifugal 12min of 10000r/min, solids uses 25mL water washing 3 times to neutral at every turn, at 20 ℃ of following vacuum drying 56h, namely Des Yin ∕ fullerene nano composite material.
Embodiment 3
The present invention also can be implemented by following steps in concrete enforcement:
1) fullerene 60mg is dissolved in the toluene of 60mL; add citric acid or lithium aluminium hydride 360mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.24mL; continue to stir 6h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed toluene, at 60 ℃ of vacuum drying 24h, gets two and replaces C
60Malonate derivative 62 mg;
2) replace C with two
60Malonate derivative 60mg is dissolved in the toluene of 36mL; add citric acid or lithium aluminium hydride 216mg; nitrogen protection; after stirring the reaction 10h that is hydrolyzed under 85 ℃; remove toluene; the adding mass fraction is 38% concentrated hydrochloric acid 24mL dispersion; add ultra-pure water 50mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the acetone of 60mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed acetone, at 60 ℃ of following vacuum drying 24h, gets two and replaces C
60Malonate derivative;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 100 mL dropwise join among liquor argenti nitratis ophthalmicus 25 mL that concentration is 10 mmol/L, behind the ultrasonic mixing 60min, get mixed liquor, again mixed liquor is transferred in 75 ℃ the water, under the stirring of 350r/min, dropwise adding concentration is the sodium hydroxide solution 25mL of 4mol/L, reaction 15min, get solids at the centrifugal 10min of 10000r/min, solids each with 30 mL water washings 4 times to neutrality, at 60 ℃ of following vacuum drying 24h, namely De Yin ∕ fullerene nano composite material.
In concrete enforcement, described fullerene also can be 40-50mg or 51-60mg; Described toluene is 40-50 mL or 51-60 mL; Going back original reagent in the described step 1) is 240-300 mg or 301-360 mg; Described two replace C
60The malonate derivative is 40-50mg or 51-60mg; Described step 2) reductant is 144-170mg or 171-216mg in; Two replace C in the step 3)
60The malonate derivative aqueous solution is 50-75mL or 76-100mL; Described liquor argenti nitratis ophthalmicus is 12-19mL or 20-25mL; Described sodium hydroxide or potassium hydroxide solution are 12-19mL or 20-25mL.
The present invention is a kind of new De Yin ∕ fullerene nano composite material, and the preparation method is simple, prepared good product quality, good stability, nano-Ag particles is dispersed in the fullerene surface, is difficult for reuniting the antibacterial activity height, biostimulation is little, safe and efficient, and be convenient to reclaim prepared antibacterial agent good stability, and obtained proof through test, interrelated data is as follows:
Test 1
Determining of the silver-colored particle size of silver ∕ fullerene nano composite material particle size and the load of surperficial institute and surface charging amount.Use Nano-ZS90 type laser particle size analyzer to measure, refractive index is set to 1.590, and absorption coefficient is set to 0.010, and temperature is set to 25 ℃, and measurement pattern is set to automatically, with Z average statistics value as measurement result.Each horizontal condensation body is all prepared 3 parts, and every part of measurement is once got the mean value of three measured values as measurement result.Dielectric constant is set to 79, and coefficient of viscosity is set to 0.8872, and temperature is set to 25 ℃, and measurement pattern is set to automatically.Each horizontal condensation body is all prepared 3 parts, and every part of measurement is once got the mean value of three measured values as measurement result.The result who records is that particle diameter is 50-300nm, and current potential is-27.5mV.Use the desk-top transmission electron microscope of LVEM5 to observe sign, as seen disperseing homogeneous and diameter is that the silver nano-grain of 2-5nm only is attached on the fullerene surface.
Test 2
Yin ∕ fullerene nano composite material is measured the minimal inhibitory concentration of the inhibition activity of bacterial growth.
Get the test tube of crossing once autoclaving, add the 5ml liquid nutrient medium.With Escherichia coli as experimental strain, picking list colony inoculation is in the LB liquid nutrient medium from the fresh LB medium of cultivating 12-16h at 37 ℃, place the constant-temperature shaking culture case, 37 ℃, the 225rpm constant temperature culture is spent the night, when measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop to cultivate; Get 6 50ml triangular flasks of crossing through autoclaving, add liquid nutrient medium and the bacterium liquid 50 μ L of 10ml respectively.Be contrast with fullerene carrier, nano grain of silver, set each dosage group and be: 250 μ g/ml, 125 μ g/ml, 100 μ g/ml, 50 μ g/ml, 25 μ g/ml are medium with the LB liquid nutrient medium, in soup and bacteria liquid is long-pending adds soup than the ratio for 1:1.Other establishes the blank group, every group of triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture, per hour sampling is once measured absorbance with ultraviolet specrophotometer at 600nm wavelength place, and the data of gained are made growth curve of bacteria figure; According to growth curve of bacteria, the minimal inhibitory concentration (MIC) of determining Yin ∕ fullerene nano composite material is 100 μ g/ml.
Test 3
Yin ∕ fullerene nano composite material is measured the minimal bactericidal concentration of the inhibition activity of bacterial growth.
Get the test tube of crossing once autoclaving, add the 5ml liquid nutrient medium.With Escherichia coli as experimental strain, picking list colony inoculation is in the LB liquid nutrient medium from the fresh LB medium of cultivating 12-16h at 37 ℃, place the constant-temperature shaking culture case, 37 ℃, the 225rpm constant temperature culture is spent the night, when measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop to cultivate, be diluted to l.0 * l0 with physiological saline
6CFU/ml, standby; Choosing silver-colored ∕ fullerene nano composite material is experiment material, is contrast with the fullerene carrier, is formulated as 100 μ g/ml, and abundant ultrasonic dispersion is standby; By two-fold dilution's method, set each dosage group and be: 200 μ g/ml, 175 μ g/ml, 150 μ g/ml, 125 μ g/ml, 100 μ g/ml, 75g μ g/ml, 50 μ g/ml.On superclean bench, the triangular flask that the autoclaving of learning from else's experience is crossed adds the experiment material of appropriate volume, initial bacteria suspension by aseptic manipulation, is the ratio adding of 1:1 in experiment material and bacteria suspension volume ratio.Other establishes the blank group, every group of triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture 16-18 hour are got 100 μ l for every group and are coated on the LB agar plate, and 37 ℃ of incubators were cultivated 24 hours, colony counting, every group of experiment triplicate.Measuring colibacillary minimal bactericidal concentration (MBC) is 150 μ g/ml.
Test 4
Yin ∕ fullerene nano composite material is measured the minimal bactericidal concentration of the inhibition activity of bacterial growth.
Get the test tube of crossing once autoclaving, add the 5ml liquid nutrient medium.With Escherichia coli as experimental strain, picking list colony inoculation is in the LB liquid nutrient medium from the fresh LB medium of cultivating 12-16h at 37 ℃, place the constant-temperature shaking culture incubator, 37 ℃, the 225rpm constant temperature culture is spent the night, when measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop to cultivate, be diluted to l.0 * l0 with physiological saline
6CFU/ml, standby; Choosing silver-colored ∕ fullerene nano composite material is experiment material, is standard with the fullerene carrier, is formulated as 150 μ g/ml, and abundant ultrasonic dispersion is standby; On superclean bench, the triangular flask that the autoclaving of learning from else's experience is crossed adds the experiment material (fullerene carrier) of appropriate volume, initial bacteria suspension respectively by aseptic manipulation, is the ratio adding of 1:1 in experiment material (fullerene) and bacteria suspension volume ratio.Other establishes the blank group, every group of triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture 4 hours are got 100 μ l for every group and are coated on the LB agar plate, and 37 ℃ of incubators were cultivated 24 hours, colony counting, every group of experiment triplicate.Calculate colibacillary sterilizing rate and can reach 100%, be effective to prepare antibacterial agent, open up the new purposes of Yin ∕ fullerene nano composite material.
When doing above-mentioned experiment, also adopt other bacteriums or fungi to do similar experiment, all obtained identical and similar result, the present invention's science of dividing into groups, method is reliable and stable, and other experimental results are enumerated no longer one by one.
By as can be seen above-mentioned, the invention provides a kind of new silver-colored ∕ fullerene nano composite material, its preparation method with and as the application of antibacterial agent.The antibacterial agent good stability that the present invention makes, nano-Ag particles is dispersed in the fullerene surface, is difficult for reuniting, the antibacterial activity height, biostimulation is little, and is safe and efficient, and is convenient to reclaim, and compared with prior art, has the useful technique effect of clear superiority:
1, Yin ∕ fullerene nano composite material antibacterial agent of the present invention is acted on contains 1 * 10
6The Escherichia coli bacteria liquid of CFU/ml, shaking table was cultivated 4 hours, and sterilizing rate can reach 100%, and bactericidal effect is remarkable; Oxy radical such as carboxyl that fullerene derivate surface is abundant, the metal cation in can also adsorbed water is conducive to the water body purifying.
2, Yin ∕ fullerene nano composite material antibacterial agent of the present invention can prevent the reunion of nano-silver ionic in the aqueous solution effectively, also can be dammed by porous ceramic film, recycles very conveniently, can not work the mischief to environment.
Claims (6)
1. the preparation method of a silver-colored ∕ fullerene nano composite material is characterized in that, this silver ∕ fullerene nano composite material is to connect nano-Ag particles by chemical bond-linking on fullerene molecule, and the mass ratio of its Nano Silver and fullerene is 1-8 ︰ 1, and fullerene is C
60Fullerene, its preparation method is:
1) fullerene 40-60mg is dissolved in the solvent orange 2 A of 40-60mL; add and to go back original reagent 240-360mg, nitrogen protection, stir 0.5-1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.16-0.24mL; continue to stir 4-6h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation desolventizing A at 20-60 ℃ of vacuum drying 24-56h, gets two and replaces C
60The malonate derivative;
Described solvent orange 2 A is toluene, and going back original reagent is sodium hydride, citric acid, lithium aluminium hydride, a kind of in the sodium borohydride;
2) replace C with two
60Malonate derivative 40-60mg is dissolved in the solvent orange 2 A of 20-36mL; add and go back original reagent 144-216mg; nitrogen protection; after stirring the reaction 10-12h that is hydrolyzed under 75-85 ℃; desolventizing A; the adding mass fraction is 38% concentrated hydrochloric acid 10-24mL dispersion; add the dilution of 30-50mL ultra-pure water again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion among the solvent B of 40-60mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation desolventizing B at 20-60 ℃ of following vacuum drying 24-56h, gets two and replaces C
60Malonate derivative;
Described solvent B is methyl alcohol, ethanol, a kind of in the acetone;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 50-100 mL dropwise joins among the liquor argenti nitratis ophthalmicus 12-25 mL that concentration is 10 mmol/L, behind the ultrasonic mixing 30-60min, get mixed liquor, again mixed liquor is transferred in the water-bath, water temperature is 65-75 ℃, under the stirring of 300-400r/min, the solvent C reaction 10-15min that dropwise adds 12-25mL, get solids at the centrifugal 10-15 min of 10000-12000 r/min, solids uses 20-30 mL water washing 3-5 time to neutral at every turn, at 20-60 ℃ of following vacuum drying 24-56h, namely De Yin ∕ fullerene nano composite material.
2. the preparation method of Yin ∕ fullerene nano composite material according to claim 1 is characterized in that, is realized by following steps:
1) fullerene 50mg is dissolved in the toluene of 50mL; add and to go back original reagent sodium hydride 300mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.2mL; continue to stir 5h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed toluene, at 50 ℃ of vacuum drying 35h, gets two and replaces C
60Malonate derivative 55mg;
2) replace C with two
60Malonate derivative 50mg is dissolved in the toluene of 30mL; add and go back original reagent sodium hydride 180mg; nitrogen protection; after stirring the reaction 10h that is hydrolyzed under 80 ℃; remove toluene; the adding mass fraction is 38% concentrated hydrochloric acid 20mL dispersion; add ultra-pure water 40mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the methyl alcohol of 50mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed methyl alcohol, at 50 ℃ of following vacuum drying 30h, gets two and replaces C
60Malonate derivative 45mg;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 50mL dropwise joins among the liquor argenti nitratis ophthalmicus 12mL that concentration is 10 mmol/L, behind the ultrasonic mixing 30min, get mixed liquor, again mixed liquor is transferred in the water-bath, water temperature is 70 ℃, under the stirring of 300r/min, dropwise adding concentration is the sodium hydroxide solution 12mL reaction 11min of 4mol/L, get solids with centrifuge at the centrifugal 10min of 12000 r/min, solids uses 20mL water washing 5 times to neutral at every turn, at 50 ℃ of following vacuum drying 26h, namely De Yin ∕ fullerene nano composite material 15mg.
3. the preparation method of Yin ∕ fullerene nano composite material according to claim 1 is characterized in that, is realized by following steps:
1) fullerene 40mg is dissolved in the toluene of 40mL; add sodium borohydride 240mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.16mL; continue to stir 5h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation desolventizing A at 20 ℃ of vacuum drying 56h, gets two and replaces C
60The malonate derivative;
2) replace C with two
60Malonate derivative 40mg is dissolved in the toluene of 24mL, adds sodium borohydride 144mg, nitrogen protection; after stirring the reaction 12h that is hydrolyzed under 75 ℃, remove toluene, the adding mass fraction is 38% concentrated hydrochloric acid 16mL dispersion; add ultra-pure water 30mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the ethanol of 40mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed ethanol, at 40 ℃ of following vacuum drying 48h, gets two and replaces C
60Malonate derivative;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 56mL dropwise joins among the liquor argenti nitratis ophthalmicus 14mL that concentration is 10 mmol/L, behind the ultrasonic mixing 45min, get mixed liquor, mixed liquor is transferred in 65 ℃ the water, under the stirring of 400r/min, dropwise adding concentration is the sodium hydroxide solution 20mL reaction 13min of 4mol/L again, get solids at the centrifugal 12min of 10000r/min, solids uses 25mL water washing 3 times to neutral at every turn, at 20 ℃ of following vacuum drying 56h, namely Des Yin ∕ fullerene nano composite material.
4. the preparation method of Yin ∕ fullerene nano composite material according to claim 1 is characterized in that, is implemented by following steps:
1) fullerene 60mg is dissolved in the toluene of 60mL; add citric acid or lithium aluminium hydride 360mg, nitrogen protection, stir 1h with 200-300r/min under the room temperature after; add bromo diethyl malonate 0.24mL; continue to stir 6h with 200-300r/min under the nitrogen protection, cross the silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed toluene, at 60 ℃ of vacuum drying 24h, gets two and replaces C
60Malonate derivative 62 mg;
2) replace C with two
60Malonate derivative 60mg is dissolved in the toluene of 36mL; add citric acid or lithium aluminium hydride 216mg; nitrogen protection; after stirring the reaction 10h that is hydrolyzed under 85 ℃; remove toluene; the adding mass fraction is 38% concentrated hydrochloric acid 24mL dispersion; add ultra-pure water 50mL dilution again; with 0.22 μ m miillpore filter suction filtration, get filter cake, filter cake is presented to ultrasonic dispersion in the acetone of 60mL; obtain filtrate with 0.22 μ m miillpore filter suction filtration again; rotary evaporation is removed acetone, at 60 ℃ of following vacuum drying 24h, gets two and replaces C
60Malonate derivative;
3) be that two of 0.25 mg/ml replaces C with concentration
60Malonate derivative aqueous suspension 100 mL dropwise join among liquor argenti nitratis ophthalmicus 25 mL that concentration is 10 mmol/L, behind the ultrasonic mixing 60min, get mixed liquor, again mixed liquor is transferred in 75 ℃ the water, under the stirring of 350r/min, dropwise adding concentration is the sodium hydroxide solution 25mL of 4mol/L, reaction 15min, get solids at the centrifugal 10min of 10000r/min, solids each with 30 mL water washings 4 times to neutrality, at 60 ℃ of following vacuum drying 24h, namely De Yin ∕ fullerene nano composite material.
5. the preparation method of Yin ∕ fullerene nano composite material according to claim 1 is characterized in that described fullerene also can be 40-50mg or 51-60mg; Described toluene is 40-50 mL or 51-60 mL; Going back original reagent in the described step 1) is 240-300 mg or 301-360 mg; Described two replace C
60The malonate derivative is 40-50mg or 51-60mg; Described step 2) reductant is 144-170mg or 171-216mg in; Two replace C in the step 3)
60The malonate derivative aqueous solution is 50-75mL or 76-100mL; Described liquor argenti nitratis ophthalmicus is 12-19mL or 20-25mL; Described sodium hydroxide or potassium hydroxide solution are 12-19mL or 20-25mL.
6. the application of the described Yin ∕ fullerene of each among claim 1 or 2-5 nano composite material in the preparation antibacterial agent.
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