CN102499260A - Application of copper nanomaterial with copper/carbon-core/shell structure in antibiosis - Google Patents

Application of copper nanomaterial with copper/carbon-core/shell structure in antibiosis Download PDF

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CN102499260A
CN102499260A CN2011103084772A CN201110308477A CN102499260A CN 102499260 A CN102499260 A CN 102499260A CN 2011103084772 A CN2011103084772 A CN 2011103084772A CN 201110308477 A CN201110308477 A CN 201110308477A CN 102499260 A CN102499260 A CN 102499260A
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copper
core
carbon
shell structure
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CN102499260B (en
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李维凤
连崑
王小鹏
牛晓峰
吴清林
齐亚冬
陈天宁
陈花玲
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Suzhou Jie Jie nano antibacterial coating technology Co., Ltd.
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Xian Jiaotong University
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Abstract

The invention discloses an application of a copper nanomaterial with a copper/carbon-core/shell structure in antibiosis, and especially in bacteriostasis and/or sterilization for fungi or bacteria. The nanomaterial with the copper/carbon-core/shell structure has stable material performance, is harmless to human body, is environment-friendly and ecology-friendly, and is an antibiotic material with a broad spectrum. Because of the function characteristics and the special sterilization mechanism of the copper nanomaterial, drug resistance is difficult to generate by various bacteria, and the advantage is incomparable to other biochemical antibiotic medicine.

Description

Have of the application of the copper nano material of copper/carbon-core/shell structure at antibiosis
Technical field
The invention belongs to the anti-biotic material technical field, be specifically related to have copper/carbon-the copper nano material of core/shell structure is in the application of antibiosis.
Background technology
The copper nano particles of copper/carbon-core/shell structure is to be template with the vegetable fiber, and metal copper ion is a raw material, (the Patent Application No. that connects the Kon professor: PCT/US07/61862) novel nano granular materials that is prepared from through the carbonizing reduction method of heating.Existing copper nano particles material is compared following property on this copper/carbon-nuclear/core-shell nanoparticles material and the market: (1) has the film formed shell structure of reticulated carbon of property, and it not only can protect nanometer copper nuclear to avoid the excessive erosion of external environment but also can let the characteristic present of nanometer copper come out; (2) copper nano particles of this core/shell structure is very stable in surroundings, can keep the form of metallic copper for a long time; (3) in oxidation environment, generate the nano particle equilibrium system of copper=cuprous oxide, do not form copper oxide; (4) nano particle that in oxidation environment, generates copper=cuprous oxide converts metallic copper again to when running into reducing condition, and keeps original nuclear/core-shell nanoparticles structure; (5) prepared material is to exist with the form that nano copper particle is embedded in the porous carbon black matrix equably; Its physical size scope can according to the actual process needs the hundreds of nanometer to several millimeters in addition decimeter between change (can give full play to the advantage of nano material, can avoid nano-particle material again) usually because the too little unmanageable shortcoming of size; (6) this copper nano particles material does not dissolve medium-term and long-term immersion of the aqueous solution of pH value 1-11, does not have tangible copper ion to ooze out in the solution; (7) netted carbon shell structure has kept functional groups such as original hydroxyl of cellulose and carbonyl, and prepared nano particle all has good dispersiveness and intersolubility in polar solvent (like water) and non-polar organic solutions (like oil).
Summary of the invention
The object of the present invention is to provide to have copper/carbon-the copper nano material of core/shell structure is in the application of antibiosis, can be applicable to aspects such as antibiosis, anticorrosion and sterilization.
For achieving the above object, this is that the technical scheme that adopts is:
The application of antibacterial and/or sterilization with nano material of copper/carbon-core/shell structure.
The application of the antibacterial and/or sterilization of described nano material with copper/carbon-core/shell structure is characterized in that: be the antibacterial and/or sterilization to fungi or bacterium.
The application of the antibacterial and/or sterilization of described nano material with copper/carbon-core/shell structure, it is characterized in that: described fungi is Bipolaris fungi (Bipolar mildew fungi), bipolaris fungi (Helminthosporium fungi), fungus Trichoderma (Trichoderma fungi), white-rot fungi (White rot fungi) or blue stain fungi (Blue stain fungus).
The application of the antibacterial and/or sterilization of described nano material with copper/carbon-core/shell structure, it is characterized in that: described bacterium is Escherichia coli (Escherichia coli), gold-coloured staphylococci (Staphylococcus aureus) or Candida albicans (Candida albicans).
Compared with prior art, the present invention has following beneficial technical effects:
Nano material with copper/carbon-core/shell structure is water insoluble, does not in use almost have the copper ion stripping, and the not diffusion everywhere with flowing of water can be medium-term and long-term not showy at air, has self-repair function, and the antibacterial effect phase is long; Harmless when routine is used, environmental friendliness, ecological friendly, be easy to control, low price, the broad-spectrum antiseptic material of contact killing type.
Cyclic oxidation-reduction reaction with nano material peculiar " copper-cuprous oxide-copper " of copper/carbon-core/shell structure can relate to continuous electron exchange.The exchange reaction of these electronics can produce the growth of microbial cell and disturb just, and then draws up, and destroys the growth of cell, plays antibiotic and effect sterilization.Because the functional characteristic of this copper metal nanoparticle and the special mechanism of sterilization thereof, this just makes that various mushrooms are difficult to it is developed immunity to drugs, and this advantage is that other biochemical type of antimicrobial institute is incomparable.
Compare with traditional anti-biotic material-Nano Silver, copper has 0 valency, 1 valency and three kinds of states of divalent, and the electronic switch process is arranged in course of reaction twice, has the antibiosis that is superior to silver, anticorrosion and the function of sterilizing, and has bigger price advantage.
Nano material with copper/carbon-core/shell structure not only can be processed formulations such as solvent, gel, also can sneak into plastic products, coating; Composite, toothpaste, textile, leather and fur products;, antifouling in the different products such as bamboo and wood products as antibiotic, mildew-resistant, anticorrosive additive.
Description of drawings
Fig. 1 is that the copper nano particles with copper/carbon-core/shell structure carries out continuous 4 times and repeats heating differential analysis figure from 40 ℃ to 500 ℃ under condition of nitrogen gas;
Fig. 2 is the heating differential analysis result of copper nano particles under excess oxygen with copper/carbon-core/shell structure;
Fig. 3-a~Fig. 3-b is with the anti-Bipolaris of nano material that contains variable concentrations (0.15%, 0.3%) copper/carbon-core/shell structure/observed result of 72,240 hours of bipolaris fungi experiment;
Fig. 4-a~Fig. 4-b is the contrast (40 *) that Bipolaris/bipolaris fungi is not containing/containing nano material cultivation displaing micro picture of culture experiment after 720 hours of copper/carbon-core/shell structure;
Fig. 5 is the antibiotic cultivation results of the copper nano particles of copper/carbon-core/shell structure to fungus Trichoderma;
Fig. 6 is the antibiotic cultivation results of the copper nano particles of copper/carbon-core/shell structure to white-rot fungi;
Fig. 7 is the antibiotic cultivation results of the copper nano particles of copper/carbon-core/shell structure to the blue stain fungi.
Embodiment
Below in conjunction with concrete embodiment and accompanying drawing the present invention is done further detailed description, said is to explanation of the present invention rather than qualification.
The nano particle of described copper/carbon-core/shell structure is the (Patent Application No. that connects the Kon professor: the PCT/US07/61862) nano particle of the copper/carbon-core/shell structure of preparation.Its major parameter is following:
1) nano particle of copper/carbon-core/shell structure, the percentage by weight of copper are 25%, and remaining is the porous carbon black;
2) nano particle all is the compound that inlays equably in the porous carbon black, and used copper nano particles material is of a size of average diameter at 15 microns the porous charcoal black-materials of inlaying a plurality of copper nano particles.Used dusty material is placed in the aqueous solution after ultrasonic agitation placed 24 hours, with the laser diffraction particle calculating instrument upper solution is detected, the result shows not have the nano particle existence that dissociates.
3) copper nano particles both can distribute and polarizable medium (like aqueous solvent etc.) equably, also can distribute equably with polarizable medium (like oil-based solvent, latex, materials such as plastics) in.
And the nano particle of prepared copper/carbon-core/shell structure carried out following stability test:
1) stability experiment of the nano particle of copper/carbon-core/shell structure in solution:
With the nano particle of the copper/carbon-core/shell structure of preparation is that (acid and alkaline solution adds sulfuric acid (H with deionized water respectively for 1,4,5,6,7,8,9 and 11 solution at pH respectively 2SO 4) or sodium hydroxide (NaOH) preparing solution form) in carried out 60 days immersion test by a definite date.Because the concentration of electrical conductivity and copper ion is directly proportional, in experiment, detect the change in concentration of copper ion in the solution with the variation of electrical conductivity.If copper ion is stripping from nano particle, the electrical conductivity of solution can correspondingly increase.The result shows the immersion of passing through 60 days, and the electrical conductivity of solution does not have marked change, explains that nano copper particle does not have the tendency of dissolving in pH is 1,4,5,6,7,8,9 and 11 solution.
2) heat endurance of the nano particle of copper/carbon-core/shell structure
The nano particle of metal/carbon-core/shell structure has extraordinary heat endurance.Nano particle with copper/carbon-core/shell structure is an example, it has been carried out continuous 4 times repeat heating differential analysis from 40 ℃ to 500 ℃ under condition of nitrogen gas.Its result shows (Fig. 1) under anoxia condition, and the nano particle of copper/carbon-core/shell structure below 500 ℃ all is being stable (not reacting the peak occurs).When heating (aerobic environment) at air conditions, the heating differential analysis result shows that the nano particle of (Fig. 2) copper/carbon-core/shell structure all is being stable below 280 ℃.
Antibacterial action with copper nano material of copper/carbon-core/shell structure
With respect to traditional anti-biotic material-Nano Silver, copper has 0 valency, 1 valency and three kinds of states of divalent, and the electronic switch process is arranged in course of reaction twice, should have the antibiosis that is superior to silver, anticorrosion and the function of sterilizing in theory, and have bigger price advantage.But because existing nano copper particle is extremely unstable in environment, can all be oxidized to divalent copper (copper oxide or Kocide SD) in the short time, then lose its effect basically.It is documented to show with experimental result that in the compound of copper, 1 valency copper (cuprous oxide) has the strongest antibiosis, anticorrosion, sterilization and the effect of sterilizing.
The nano particle of copper/carbon-core/shell structure owing to its unique shell structure, can keep the chemical state of metallic copper for a long time in common environment.Under oxidizing condition, nano copper particle can form the equilibrium system of copper-cuprous oxide (1 valency copper), can not generate cupric.When running into reducing environment (many bacterial growths can produce reducing environment), the cuprous oxide in copper-cuprous oxide system can reduce again becomes zerovalent copper.Cyclic oxidation-the reduction reaction of the nano particle of this copper/carbon-core/shell structure peculiar " copper-cuprous oxide-copper " can relate to continuous electron exchange.The exchange reaction of these electronics can produce the growth of microbial cell and disturb just, and then draws up, and destroys the growth of cell, plays antibiotic and effect sterilization.Add because cuprous oxide is water insoluble, avoided the dissolving of nano copper particle in water, not only prevented the pollution of copper ion, also guaranteed the durability of copper nano particles environment.
The broad-spectrum antibacterial action of the nano material of copper/carbon-core/shell structure
1) anti-Bipolaris/bipolaris fungi
The medium (the copper nano particles compounds of 3.9 gram potato dextrose agar powder+100 ml distilled waters+different proportions) that is respectively 0.15%, 0.3% and 0 (control group) with the nano material mass percent concentration of cupric/carbon-core/shell structure carries out the cultivation of Bipolaris and two types of fungies of bipolaris fungi.After inoculation, put into temperature and be 30 ℃ insulating box and cultivate.Sample was put into aseptic laminar flow case and is detected also film recording in the time of 24,72,144 and 240 hours.
Cultivation results shown in Fig. 3-a (0.15%w), Fig. 3-b (0.3%w) (left side is the bipolaris fungi for Bipolaris fungi, right side among the figure); In containing the nano-particle complex particle of copper/carbon of the 0.15%w-core/shell structure medium of (weight ratio of cupric is about 8/10000ths); Size with colony growth is estimated, and Bipolaris/bipolaris fungi growth speed is compared obvious decline with control group; And nano-particle complex particle (weight ratio of cupric is about 16/10000ths) Bipolaris/bipolaris fungi growth speed that contains copper/carbon-core/shell structure of 0.3%w is zero.
Pass through microscopic; When the content that Bipolaris/bipolaris fungi is inoculated in the cupric nano-particle complex reaches the medium of 0.3%w, after 204 hours, there is not the generation of mycoderm at the edge in inoculation district; The mycelia drying shrinkage of the bacterium colony of implanting during inoculation; The metabolism of bacterium colony stops, and does not have conidium to generate, and bacterium colony is in dead state.
Like Fig. 4-a (normal cultured; As contrast), the micro-view contrast (40 *) shown in Fig. 4-b (nano material of 0.3% bronze medal/carbon-core/shell structure); The metabolism of mycelia of (left figure) Bipolaris/bipolaris fungi and conidium is normal in the control sample; The conidium growth is vigorous, makes bacterium colony constantly grow up; When cupric nano material compound is 0.3%w (right figure), the mycelia drying shrinkage does not have visible conidium, and bacterium colony is in dead state.
The nano-particle complex that above result shows copper/carbon-core/shell structure has the obvious suppression effect to Bipolaris/bipolaris fungi (0.1%w) when the low concentration; (0.3%w) demonstrates effective sterilizing function when concentration reaches certain value.
2) ability of anti-fungus Trichoderma:
The nano-particle complex weight percent concentration of using cupric/carbon-core/shell structure is the culture experiment that the medium (the copper nano particles compounds of 3.9 gram potato dextrose agar powder+100 ml distilled waters+different proportions) of 0.03% and 0 (control group) carries out fungus Trichoderma; After inoculation, put into temperature and be 30 ℃ insulating box and cultivate.Sample was put into aseptic laminar flow case and is detected also film recording in the time of 24,48 and 72 hours.
The result is as shown in Figure 5: the fungus Trichoderma growth of control group is normal, and bacterium colony increases rapidly; And when the nano copper composition particle that contains 0.03%w in medium when (weight ratio of cupric is about 5/10000ths), the growth that fungus Trichoderma is given birth to stops, and whole bacterium colony is in dead state.Therefore visible, even when concentration is 0.03%w, life has good sterilization functions to the copper nano particles compound to fungus Trichoderma.
3) ability of anti-white-rot fungi
Using the cupric percentage by weight is that the nano-particle complex particle of copper/carbon-core/shell structure of 7/10000ths has carried out the wood corrosion experiment of whiterot fungi, and concrete the installation by american wood protects the AWPAE0 standard test method of association (AWPA) to carry out.Sample is the southern pine of the U.S., after the copper nano particles composite is handled, sample on average contain 7/10000ths copper nano particles composite.
Experimental result is as shown in Figure 6, and the sample of control group (right figure) white-rot fungi after 600 hours has covered whole specimen surface.Then do not receive the invasion and attack of white-rot fungi fully through sample (left figure) surface that the copper nano particles composite was handled.Experimental result shows that the nano-particle complex that contains the copper/carbon-core/shell structure of 7/10000ths bronze medals has effective sterilization antisepsis to white-rot fungi.
4) ability of anti-blue stain fungi:
The nano-particle complex particle that is respectively copper/carbon-core/shell structure of 0.01%, 0.05%, 0.1%, 0.25% and 0.5% with the cupric percentage by weight carries out the culture experiment (the copper nano particles compounds of 3.9 gram potato dextrose agar powder+100 ml distilled waters+different proportions) of blue stain fungi.
Show that through 25 days experimental results (Fig. 7) the blue stain fungi growth is unaffected basically when the content of copper nano particles composite is 0 to 0.1%w; But when the content of copper nano particles composite reaches 0.25%w; The blue stain fungi growth receives obvious suppression; The bacterium colony size obviously diminishes, and shows that the nano-particle complex of the copper/carbon-core/shell structure that contains 7/10000ths bronze medals has effective sterilization antisepsis to white-rot fungi.
5) ability of Chinese People's Anti-Japanese Military and Political College enterobacteria, gold-coloured staphylococci and Candida albicans:
The nano-particle complex of cupric/carbon-core/shell structure is that the sample of dry weight 5/1000ths has carried out the experiment of Chinese People's Anti-Japanese Military and Political College enterobacteria, staphylococcus aureus and Candida albicans in the disease prevention and control center, Shaanxi Province according to " disposable use amenities sanitary standard ".The neutralizer approval test adopts the suspension method approval test, and to staphylococcus aureus (ATCC6538) effect 1min, test temperature is 20 ± 2 ℃, and relative moisture is 50%.Quantitative disinfecting test is the suspension method test.Test temperature is 20 ± 2 ℃, and relative moisture is 50%.The test triplicate.
Experimental result shows that this sample has good bactericidal effect.The PBS solution that contains 3.0% Tween-80+0.3% lecithin can neutralize to 0.5% sample that contains nano copper particle fully, and this neutralizer product does not all have influence to staphylococcus aureus (ATCC6538), Candida albicans (ATCC10231), and result of the test is seen table 1.
Table 1 neutralizer approval test result
Figure BDA0000098163730000081
In test temperature is under 20 ± 2 ℃ of conditions, and submitted sample contains 0.5% mass action 1min of nano copper particle, and the average bactericidal rate of staphylococcus aureus (ATCC6538) is reached more than 90%; In test temperature is under 20 ± 2 ℃ of conditions, and submitted sample contains 0.5% mass action 1min of nano copper particle, and the average bactericidal rate of Escherichia coli (8099) is reached more than 90%; In test temperature is under 20 ± 2 ℃ of conditions, and submitted sample contains 0.5% mass action 1min of nano copper particle, and the average bactericidal rate of Candida albicans (ATCC10231) is reached more than 90%.The result sees table 2, table 3, table 4.
Table 2 copper core-shell nano particle is to the bactericidal effect of staphylococcus aureus
Figure BDA0000098163730000082
Annotate: the average clump count of positive controls is 3.95 * 10 4Cfu/mL; The negative control group asepsis growth
Table 3 copper core-shell nano particle is to colibacillary bactericidal effect
Figure BDA0000098163730000083
Annotate: the average clump count of positive controls is 4.35 * 10 4Cfu/mL; The negative control group asepsis growth
Table 4 copper core-shell nano particle is to the oidiomycetic bactericidal effect of white
Figure BDA0000098163730000092
Annotate: the average clump count of positive controls is 5.01 * 10 4Cfu/mL; The negative control group asepsis growth
The safety of the nano material of copper/carbon-core/shell structure
1) nanometer copper is to the stimulation test of skin:
The nano-particle complex of copper/carbon-core/shell structure is carried out zoopery to the effect of stimulation of skin: during experiment, get 10 of healthy regular grade NZws, be divided into three groups, A group working concentration is the nano copper particle compound of 2% weight ratio; B group working concentration is the nano copper particle compound of 5% weight ratio; The C group uses the carboxymethyl cellulose-based matter that does not contain nanometer copper as the blank group.
Tame rabbit back is lost hair or feathers with hair remover, and the depilation area is 150cm 2, treat to clean up with warm water after 2~3 minutes, till visible bright and clean skin.Whether the inspection skin of unhairing is because of the unhairing damaged after 24 hours, and compromised skin is unfit to do the irritant test of intact skin.Clean gauze is immersed in to take out behind the different solution applies at the rabbit back, divide cage to feed, remove gauze after 24 hours and use the distilled water flush away, observation topical application of drug position, unhairing district has or not symptoms such as erythema and oedema in 1,24,48, in the 72h.The rabbit skin of handling with 2% and 5% your nano copper particle compound in observation period does not see that ANOMALOUS VARIATIONS is arranged, and show is not swollen to smear the back of being tried thing, festers reactions such as inflammation necrosis.
This experiment shows that the kind concentration of working as the nano copper particle compound below 5%, does not have toxicity and excitant to skin.
2) nanometer copper is tested the sensitization of skin:
Sensitization of skin experiment is the nano copper particle compound and 2 with 2% and 5% weight ratio, and 4-dinitrochlorobenzene (DNCB) (positive control) is scattered in and carries out on one's body the SD rat in the excipient of 5%w sodium carboxymethylcellulose.
Preceding 1 day of experiment to the mouse left side with hair remover processings of losing hair or feathers, preceding 1 day of sensitization is carried out cropping to the right side, and then loses hair or feathers.Get each one milliliter of excipient, positive drug, 2% and 5% nano copper particle complex formulation during sensitization respectively and be applied to above depilation place of respectively organizing cavy left side skin, bandage fixing then; Remove the drug combination warm water cleaning behind the 6h, observe in 1h and 24h time point, and give a mark according to " guideline "; 7th, repeated in 14 days with quadrat method administration and observation; The 28th day in the right side administration excites, observe and same marking (experiment amounts to about 28 days of fate).
During sensitization, the guinea pig skin of vehicle control group was not met quick reaction; The nano copper particle compound is tried the individual animal skin of drug group and is seen that a little erythema is arranged; Positive drug treated animal skin is seen has slight oedema.After exciting, the vehicle control group with tried drug group and seen have a little erythema except that guinea pig skin out of the ordinary, all do not see other abnormal responses; Positive drug treated animal skin sees that obvious oedema and edematous erythema are arranged, and has skin to decrease appearance mostly.
The sensitization of skin experimental result shows: vehicle control group and nano copper particle compound are tried drug group allergy incidence of 24h and 48h after sensitization and are zero; Positive drug group allergy incidence of 24h and 48h after sensitization is 100%.The nano copper particle compound does not have sensitization below 5% weight ratio concentration.
3) nano particle of copper/carbon-core/shell structure is to the influence of people's kidney blastocyte strain HEK-293 cells survival rate:
The toxicity test of nano copper particle compound is to measure cell viability through its influence to people's kidney blastocyte strain HEK-293 cells survival rate with mtt assay to estimate.In the control group, the survival rate was 100%, when the concentration of nano-Cu 5 × 10 -7 ~ 5 × 10 -2 mg / mL range, the cell viability at 95.47 ± 9.17% to 102.94 ± 4.43%, seen at this concentration range, Pei copper on human kidney cell line HEK-293 cell growth was not inhibited; when the nano Cu concentration of 5 × 10-1mg/mL, the cell viability dropped 67.05052 ± 14.4601%, the concentration of copper on HEK-293 cell growth inhibition.
Comprehensive above the analysis, the result shows to have copper/carbon-the nano material stable in properties of core/shell structure, and is harmless, environmental friendliness is ecological friendly, is a kind of broad-spectrum antiseptic material.Nano material with copper/carbon-core/shell structure not only can be processed formulations such as solvent, gel, also can sneak into plastic products, coating; Composite, toothpaste, textile, leather and fur products;, antifouling in the different products such as bamboo and wood products as antibiotic, mildew-resistant, anticorrosive additive.

Claims (4)

1. the application of antibacterial and/or sterilization that has the nano material of copper/carbon-core/shell structure.
2. the application of the antibacterial and/or sterilization of the nano material with copper/carbon-core/shell structure as claimed in claim 1 is characterized in that: be the antibacterial and/or sterilization to fungi or bacterium.
3. the application of the antibacterial and/or sterilization of the nano material with copper/carbon-core/shell structure as claimed in claim 2, it is characterized in that: described fungi is Bipolaris fungi (Bipolar mildew fungi), bipolaris fungi (Helminthosporium fungi), fungus Trichoderma (Trichoderma fungi), white-rot fungi (White rot fungi) or blue stain fungi (Blue stain fungus).
4. the application of the antibacterial and/or sterilization of the nano material with copper/carbon-core/shell structure as claimed in claim 2, it is characterized in that: described bacterium is Escherichia coli (Escherichia coli), gold-coloured staphylococci (Staphylococcus aureus) or Candida albicans (Candida albicans).
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CN108395680A (en) * 2017-09-22 2018-08-14 浙江中迪纺织新材料科技有限公司 A kind of tablecloth of the polyester antibacterial plastic concentrate based on nanometer Cu/C composite materials
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CN108653240A (en) * 2018-06-22 2018-10-16 苏州冠洁纳米抗菌涂料科技有限公司 The application of the composite nanoparticle of carbon and copper
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CN106277473A (en) * 2016-09-29 2017-01-04 西安交通大学苏州研究院 A kind of water purifying cup with antibacterial filter element
CN108395680A (en) * 2017-09-22 2018-08-14 浙江中迪纺织新材料科技有限公司 A kind of tablecloth of the polyester antibacterial plastic concentrate based on nanometer Cu/C composite materials
CN108410139A (en) * 2017-09-22 2018-08-17 浙江中迪纺织新材料科技有限公司 A kind of high molecular polymer antibacterial plastic concentrate and preparation method thereof based on nanometer Cu/C composite materials
CN108653240A (en) * 2018-06-22 2018-10-16 苏州冠洁纳米抗菌涂料科技有限公司 The application of the composite nanoparticle of carbon and copper
CN108653240B (en) * 2018-06-22 2021-03-02 苏州冠洁纳米材料科技有限公司 Application of composite nano-particle of carbon and copper
EP3811934A4 (en) * 2018-06-22 2022-06-08 Suzhou Guanjie Nano Materials Technology Co., Ltd. Use of composite nanoparticle of carbon and copper
CN112341712A (en) * 2019-08-09 2021-02-09 安徽银源环保科技有限公司 Copper-carbon antibacterial water delivery pipe, microbead copper-carbon antibacterial water delivery pipe and preparation method thereof
CN112522861A (en) * 2020-10-12 2021-03-19 苏州冠洁纳米材料科技有限公司 Application of composite nano particles of carbon and copper in melt-blown non-woven material
CN112356368A (en) * 2020-10-14 2021-02-12 上海那博新材料科技有限公司 Production process of nano-copper latex pillow
CN113068714A (en) * 2021-04-01 2021-07-06 联科华技术有限公司 Monoatomic copper preparation capable of replacing traditional agricultural copper preparation and preparation method thereof

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