CN103329893B - 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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- CN103329893B CN103329893B CN201310256770.8A CN201310256770A CN103329893B CN 103329893 B CN103329893 B CN 103329893B CN 201310256770 A CN201310256770 A CN 201310256770A CN 103329893 B CN103329893 B CN 103329893B
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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 14
- 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 17
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 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
- 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 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-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
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 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
- 239000007788 liquid Substances 0.000 description 13
- 239000002609 medium Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
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- 235000015097 nutrients Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
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- 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
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- 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
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- 241000191967 Staphylococcus aureus Species 0.000 description 1
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- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical compound N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 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
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- 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 Development of Natural Science 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 comprised of 60 carbon atoms, comprises 12 five-membered rings and 20 hexatomic rings, and diameter is 0.71nm.Fullerene is with its unique structure and extremely people's attention of character, and nearly ten years, almost the scientist of all famous universities in 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 " star molecule " of 1991 by U.S.'s < < Science > > magazine.
Because silver has efficiently, wide, the warm tolerance of safety, fungicidal spectrum, have no drug resistance and the 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 starts to enter daily life, has been widely used in now health care and food hygiene field.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, as black-koji mould, Candida albicans, saccharomycete, palpus trichomyces and penicillium citrinum; (c) virus, as hepatitis B, HIV-1 and syncytial virus etc.
The sterilization mechanism of Nano Silver exists three kinds; comprise: (1) nano-Ag particles can discharge silver ion; silver ion can enter in cell by penetration cell wall; react with the functional group of the sulfur-bearings such as the coloured glaze base existing in protein in microbial body, 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 that bacterium is dead; (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 that bacterium is dead; (3) nano-Ag particles itself can adsorb and at bacteria cell wall surface enrichment, cause somatic cells cracking.But Nano Silver is easy to occur agglomeration in the aqueous solution, bactericidal effect is weakened 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
For above-mentioned situation, for overcoming the defect of prior art, the present invention's object is just to provide a kind of preparation of silver-colored ∕ fullerene nano composite material and as the application of antibacterial agent, can effectively avoid the reunion between nano-Ag particles, be beneficial to by porous ceramics filter membrane and dam, realize recycling, and as pharmaceutical carrier, realize the application problem in antibacterial agent.
The technical scheme that the present invention solves is, silver-colored ∕ fullerene nano composite material is by chemical bond-linking, to connect nano-Ag particles 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 go back original reagent 240-360mg, nitrogen protection, stirs after 0.5-1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.16-0.24mL; under nitrogen protection, with 200-300r/min, continue to stir 4-6h, cross silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed solvent orange 2 A, at 20-60 ℃ of vacuum drying 24-56h, obtains two replacement C
60malonate 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 sodium borohydride;
2) by two replacement C
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; at 75-85 ℃, stir and be hydrolyzed after reaction 10-12h; remove solvent orange 2 A; adding mass fraction is that 38% concentrated hydrochloric acid 10-24mL disperses; add again ultra-pure water 30-50mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the solvent B of 40-60mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is except desolventizing B, and vacuum drying 24-56h at 20-60 ℃, obtains two replacement C
60malonate derivative;
Described solvent B is methyl alcohol, ethanol, a kind of in acetone;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 50-100 mL dropwise joins in the liquor argenti nitratis ophthalmicus 12-25 mL that concentration is 10 mmol/L, after ultrasonic mixing 30-60min, obtain mixed liquor, again mixed liquor is transferred in 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, at the centrifugal 10-15 min of 10000-12000 r/min, obtain solids, solids uses 20-30 mL water washing 3-5 time to neutral at every turn, vacuum drying 24-56h at 20-60 ℃, get Yin ∕ fullerene nano composite material;
Described solvent C is sodium hydroxide solution or potassium hydroxide solvent.
Gai Yin ∕ fullerene nano composite material, as pharmaceutical carrier, is effective to prepare antibacterial agent.
The present invention is by Nano Silver on fullerene area load, thereby obtain new fullerene nano composite material, this composite is effective to prepare antibacterial agent, carrier with fullerene as nano silver loaded, specifically by Nano Silver on fullerene area load, fullerene is as the carrier of nano silver loaded, can effectively avoid the reunion between nano-Ag particles, can be dammed by porous ceramics filter membrane, the antibacterial agent good stability that its product makes, nano-Ag particles is dispersed in fullerene surface, be difficult for reuniting, antibacterial activity is high, biostimulation is little, safe and efficient, and be convenient to recycling.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is elaborated.
The present invention in the specific implementation, can be provided by following examples.
Embodiment 1
The present invention, in concrete enforcement, can be realized by following steps:
1) fullerene 50mg is dissolved in the toluene of 50mL; add and go back original reagent sodium hydride 300mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.2mL; under nitrogen protection, with 200-300r/min, continue to stir 5h, cross 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, obtains two replacement C
60malonate derivative 55mg;
2) by two replacement C
60malonate derivative 50mg is dissolved in the toluene of 30mL; add and go back original reagent sodium hydride 180mg; nitrogen protection; at 80 ℃, stir and be hydrolyzed after reaction 10h; remove toluene; adding mass fraction is that 38% concentrated hydrochloric acid 20mL disperses; add again ultra-pure water 40mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the methyl alcohol of 50mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed methyl alcohol, and vacuum drying 30h at 50 ℃ obtains two replacement C
60malonate derivative 45mg;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 50mL dropwise joins in the liquor argenti nitratis ophthalmicus 12mL that concentration is 10 mmol/L, after ultrasonic mixing 30min, obtain mixed liquor, again mixed liquor is transferred in 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, with centrifuge, at the centrifugal 10min of 12000 r/min, obtain solids, solids uses 20mL water washing 5 times to neutral at every turn, vacuum drying 26h at 50 ℃, get Yin ∕ fullerene nano composite material 15mg.
Embodiment 2
The present invention, at embodiment, also can be realized by following steps:
1) fullerene 40mg is dissolved in the toluene of 40mL; add sodium borohydride 240mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.16mL; under nitrogen protection, with 200-300r/min, continue to stir 5h, cross silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed solvent orange 2 A, at 20 ℃ of vacuum drying 56h, obtains two replacement C
60malonate derivative;
2) by two replacement C
60malonate derivative 40mg is dissolved in the toluene of 24mL, adds sodium borohydride 144mg, nitrogen protection; at 75 ℃, stir and be hydrolyzed after reaction 12h, remove toluene, adding mass fraction is that 38% concentrated hydrochloric acid 16mL disperses; add again ultra-pure water 30mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the ethanol of 40mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed ethanol, and vacuum drying 48h at 40 ℃ obtains two replacement C
60malonate derivative;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 56mL dropwise joins in the liquor argenti nitratis ophthalmicus 14mL that concentration is 10 mmol/L, after ultrasonic mixing 45min, obtain mixed liquor, mixed liquor is transferred in the water of 65 ℃, under the stirring of 400r/min, dropwise adding concentration is the sodium hydroxide solution 20mL reaction 13min of 4mol/L again, at the centrifugal 12min of 10000r/min, obtain solids, solids uses 25mL water washing 3 times to neutral at every turn, vacuum drying 56h at 20 ℃, get Yin ∕ fullerene nano composite material.
Embodiment 3
The present invention, in concrete enforcement, also can be implemented by following steps:
1) fullerene 60mg is dissolved in the toluene of 60mL; add citric acid or lithium aluminium hydride 360mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.24mL; under nitrogen protection, with 200-300r/min, continue to stir 6h, cross 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, obtains two replacement C
60malonate derivative 62 mg;
2) by two replacement C
60malonate derivative 60mg is dissolved in the toluene of 36mL; add citric acid or lithium aluminium hydride 216mg; nitrogen protection; at 85 ℃, stir and be hydrolyzed after reaction 10h; remove toluene; adding mass fraction is that 38% concentrated hydrochloric acid 24mL disperses; add again ultra-pure water 50mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the acetone of 60mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed acetone, and vacuum drying 24h at 60 ℃ obtains two replacement C
60malonate derivative;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 100 mL dropwise join in liquor argenti nitratis ophthalmicus 25 mL that concentration is 10 mmol/L, after ultrasonic mixing 60min, obtain mixed liquor, again mixed liquor is transferred in the water of 75 ℃, under the stirring of 350r/min, dropwise adding concentration is the sodium hydroxide solution 25mL of 4mol/L, reaction 15min, at the centrifugal 10min of 10000r/min, obtain solids, solids each with 30 mL water washing 4 times to neutrality, vacuum drying 24h at 60 ℃, get 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; In described step 1), going back original reagent is 240-300 mg or 301-360 mg; Two described replacement C
60malonate derivative is 40-50mg or 51-60mg; Described step 2) in, reductant is 144-170mg or 171-216mg; In step 3), two replace C
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 Yin ∕ fullerene nano composite material, and preparation method is simple, prepared good product quality, good stability, nano-Ag particles is dispersed in fullerene surface, is difficult for reuniting, and antibacterial activity is high, biostimulation is little, safe and efficient, and be convenient to reclaim prepared antibacterial agent good stability, and be proven 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 band electric weight.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 setting is set to 25 ℃, and measurement pattern is set to automatically, usings Z average statistics value as measurement result.Each horizontal condensation body is all prepared 3 parts, and every part of measurement once, is 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 setting 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 once, is got the mean value of three measured values as measurement result.The result recording 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, disperseing as seen homogeneous and diameter is that the silver nano-grain of 2-5nm is only attached on 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 5ml liquid nutrient medium.Using Escherichia coli as experimental strain, from the fresh LB medium at 37 ℃ of cultivation 12-16h, picking list colony inoculation is in LB liquid nutrient medium, be placed in constant-temperature shaking incubator, 37 ℃, 225rpm constant temperature culture is spent the night, while measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop cultivating; Get 6 50ml triangular flasks of crossing through autoclaving, add respectively liquid nutrient medium and the bacterium liquid 50 μ L of 10ml.Take fullerene carrier, nano grain of silver is contrast, sets each dosage group and is: 250 μ g/ml, 125 μ g/ml, 100 μ g/ml, 50 μ g/ml, 25 μ g/ml, take LB liquid nutrient medium as medium, and long-pending than adding liquid for the ratio of 1:1 in liquid and bacteria liquid.Separately establish blank group, every group in triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture, sampling per hour once, is measured absorbance at 600nm wavelength place with ultraviolet specrophotometer, the data of gained are made to 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 5ml liquid nutrient medium.Using Escherichia coli as experimental strain, from the fresh LB medium at 37 ℃ of cultivation 12-16h, picking list colony inoculation is in LB liquid nutrient medium, be placed in constant-temperature shaking incubator, 37 ℃, 225rpm constant temperature culture is spent the night, while measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop cultivating, with normal saline dilution l.0 * l0 extremely
6cFU/ml, standby; Choosing silver-colored ∕ fullerene nano composite material is experiment material, take fullerene carrier as contrast, 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, and the ratio that is 1:1 in experiment material and bacteria suspension volume ratio adds.Separately establish blank group, every group in triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture 16-18 hour, get 100 μ l for every group and coat on LB agar plate, and 37 ℃ of incubators are cultivated 24 hours, colony counting, every group of experiment is in 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 5ml liquid nutrient medium.Using Escherichia coli as experimental strain, from the fresh LB medium at 37 ℃ of cultivation 12-16h, picking list colony inoculation is in LB liquid nutrient medium, be placed in constant-temperature shaking culture incubator, 37 ℃, 225rpm constant temperature culture is spent the night, while measuring OD value to 0.5 with ultraviolet specrophotometer at 600nm wavelength place, stop cultivating, with normal saline dilution l.0 * l0 extremely
6cFU/ml, standby; Choosing silver-colored ∕ fullerene nano composite material is experiment material, take fullerene carrier as standard, 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 respectively the experiment material (fullerene carrier) of appropriate volume, initial bacteria suspension by aseptic manipulation, and the ratio that is 1:1 in experiment material (fullerene) and bacteria suspension volume ratio adds.Separately establish blank group, every group in triplicate; 225rpm, 37 ℃ of shaking table constant temperature culture 4 hours, get 100 μ l for every group and coat on LB agar plate, and 37 ℃ of incubators are cultivated 24 hours, colony counting, every group of experiment is in 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 will not enumerate.
By above-mentioned, can be found out, the invention provides a kind of new silver-colored ∕ fullerene nano composite material, its preparation method is usingd and as the application of antibacterial agent.The antibacterial agent good stability that the present invention makes, nano-Ag particles is dispersed in fullerene surface, is difficult for reuniting, and antibacterial activity is high, and biostimulation is little, 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 containing 1 * 10
6the Escherichia coli bacteria liquid of CFU/ml, shaking table is cultivated 4 hours, and sterilizing rate can reach 100%, and bactericidal effect is remarkable; The abundant oxy radical in fullerene derivate surface is as carboxyl, and the metal cation in can also adsorbed water, is conducive to 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. a preparation method for silver-colored ∕ fullerene nano composite material, is characterized in that, this silver ∕ fullerene nano composite material is by chemical bond-linking, to connect nano-Ag particles 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 go back original reagent 240-360mg, nitrogen protection, stirs after 0.5-1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.16-0.24mL; under nitrogen protection, with 200-300r/min, continue to stir 4-6h, cross silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed solvent orange 2 A, at 20-60 ℃ of vacuum drying 24-56h, obtains two replacement C
60malonate 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 sodium borohydride;
2) by two replacement C
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; at 75-85 ℃, stir and be hydrolyzed after reaction 10-12h; remove solvent orange 2 A; adding mass fraction is that 38% concentrated hydrochloric acid 10-24mL disperses; add again the dilution of 30-50mL ultra-pure water; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the solvent B of 40-60mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is except desolventizing B, and vacuum drying 24-56h at 20-60 ℃, obtains two replacement C
60malonate derivative;
Described solvent B is methyl alcohol, ethanol, a kind of in acetone;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 50-100 mL dropwise joins in the liquor argenti nitratis ophthalmicus 12-25 mL that concentration is 10 mmol/L, after ultrasonic mixing 30-60min, obtain mixed liquor, again mixed liquor is transferred in 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, at the centrifugal 10-15 min of 10000-12000 r/min, obtain solids, solids uses 20-30 mL water washing 3-5 time to neutral at every turn, vacuum drying 24-56h at 20-60 ℃, get Yin ∕ fullerene nano composite material;
Described solvent C is sodium hydroxide solution or potassium hydroxide solvent.
2. the preparation method of Yin ∕ fullerene nano composite material according to claim 1, is characterized in that, by following steps, is realized:
1) fullerene 50mg is dissolved in the toluene of 50mL; add and go back original reagent sodium hydride 300mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.2mL; under nitrogen protection, with 200-300r/min, continue to stir 5h, cross 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, obtains two replacement C
60malonate derivative 55mg;
2) by two replacement C
60malonate derivative 50mg is dissolved in the toluene of 30mL; add and go back original reagent sodium hydride 180mg; nitrogen protection; at 80 ℃, stir and be hydrolyzed after reaction 10h; remove toluene; adding mass fraction is that 38% concentrated hydrochloric acid 20mL disperses; add again ultra-pure water 40mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the methyl alcohol of 50mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed methyl alcohol, and vacuum drying 30h at 50 ℃ obtains two replacement C
60malonate derivative 45mg;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 50mL dropwise joins in the liquor argenti nitratis ophthalmicus 12mL that concentration is 10 mmol/L, after ultrasonic mixing 30min, obtain mixed liquor, again mixed liquor is transferred in 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, with centrifuge, at the centrifugal 10min of 12000 r/min, obtain solids, solids uses 20mL water washing 5 times to neutral at every turn, vacuum drying 26h at 50 ℃, get Yin ∕ fullerene nano composite material 15mg.
3. the preparation method of Yin ∕ fullerene nano composite material according to claim 1, is characterized in that, by following steps, is realized:
1) fullerene 40mg is dissolved in the toluene of 40mL; add sodium borohydride 240mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.16mL; under nitrogen protection, with 200-300r/min, continue to stir 5h, cross silica chromatographic column, with 0.22 μ m miillpore filter suction filtration; collect filtrate; rotary evaporation is removed solvent orange 2 A, at 20 ℃ of vacuum drying 56h, obtains two replacement C
60malonate derivative;
2) by two replacement C
60malonate derivative 40mg is dissolved in the toluene of 24mL, adds sodium borohydride 144mg, nitrogen protection; at 75 ℃, stir and be hydrolyzed after reaction 12h, remove toluene, adding mass fraction is that 38% concentrated hydrochloric acid 16mL disperses; add again ultra-pure water 30mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the ethanol of 40mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed ethanol, and vacuum drying 48h at 40 ℃ obtains two replacement C
60malonate derivative;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 56mL dropwise joins in the liquor argenti nitratis ophthalmicus 14mL that concentration is 10 mmol/L, after ultrasonic mixing 45min, obtain mixed liquor, mixed liquor is transferred in the water of 65 ℃, under the stirring of 400r/min, dropwise adding concentration is the sodium hydroxide solution 20mL reaction 13min of 4mol/L again, at the centrifugal 12min of 10000r/min, obtain solids, solids uses 25mL water washing 3 times to neutral at every turn, vacuum drying 56h at 20 ℃, get Yin ∕ fullerene nano composite material.
4. the preparation method of Yin ∕ fullerene nano composite material according to claim 1, is characterized in that, by following steps, is implemented:
1) fullerene 60mg is dissolved in the toluene of 60mL; add citric acid or lithium aluminium hydride 360mg, nitrogen protection, stirs after 1h with 200-300r/min under room temperature; add bromo diethyl malonate 0.24mL; under nitrogen protection, with 200-300r/min, continue to stir 6h, cross 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, obtains two replacement C
60malonate derivative 62 mg;
2) by two replacement C
60malonate derivative 60mg is dissolved in the toluene of 36mL; add citric acid or lithium aluminium hydride 216mg; nitrogen protection; at 85 ℃, stir and be hydrolyzed after reaction 10h; remove toluene; adding mass fraction is that 38% concentrated hydrochloric acid 24mL disperses; add again ultra-pure water 50mL dilution; with 0.22 μ m miillpore filter suction filtration, obtain filter cake, filter cake is placed to ultrasonic dispersion in the acetone of 60mL; with 0.22 μ m miillpore filter suction filtration, obtain filtrate again; rotary evaporation is removed acetone, and vacuum drying 24h at 60 ℃ obtains two replacement C
60malonate derivative;
3) by concentration, be that two of 0.25 mg/ml replaces C
60malonate derivative aqueous suspension 100 mL dropwise join in liquor argenti nitratis ophthalmicus 25 mL that concentration is 10 mmol/L, after ultrasonic mixing 60min, obtain mixed liquor, again mixed liquor is transferred in the water of 75 ℃, under the stirring of 350r/min, dropwise adding concentration is the sodium hydroxide solution 25mL of 4mol/L, reaction 15min, at the centrifugal 10min of 10000r/min, obtain solids, solids each with 30 mL water washing 4 times to neutrality, vacuum drying 24h at 60 ℃, get 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; In described step 1), going back original reagent is 240-300 mg or 301-360 mg; Described step 2) in, two replace C
60malonate derivative is 40-50mg or 51-60mg; Described step 2) in, reductant is 144-170mg or 171-216mg; In step 3), two replace C
60the malonate derivative aqueous solution is 50-75mL or 76-100mL; Described liquor argenti nitratis ophthalmicus is 12-19mL or 20-25mL; In described step 3), sodium hydroxide or potassium hydroxide solution are 12-19mL or 20-25mL.
6. the application of Yin ∕ fullerene nano composite material in preparing antibacterial agent described in any one in claim 1 or 2-5.
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