CN104889419A - Biological synthesis method for spherical silver nanoparticle - Google Patents
Biological synthesis method for spherical silver nanoparticle Download PDFInfo
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- CN104889419A CN104889419A CN201510255581.8A CN201510255581A CN104889419A CN 104889419 A CN104889419 A CN 104889419A CN 201510255581 A CN201510255581 A CN 201510255581A CN 104889419 A CN104889419 A CN 104889419A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000001308 synthesis method Methods 0.000 title claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 title abstract description 6
- 239000004332 silver Substances 0.000 title abstract description 6
- 239000002105 nanoparticle Substances 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 51
- 241000522190 Desmodium Species 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 235000004936 Bromus mango Nutrition 0.000 claims abstract description 11
- 235000014826 Mangifera indica Nutrition 0.000 claims abstract description 11
- 235000009184 Spondias indica Nutrition 0.000 claims abstract description 11
- 239000000284 extract Substances 0.000 claims description 59
- 240000002044 Rhizophora apiculata Species 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 7
- 240000007228 Mangifera indica Species 0.000 claims 1
- 241001093152 Mangifera Species 0.000 abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000000170 cell membrane Anatomy 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001408 fungistatic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 240000005020 Acaciella glauca Species 0.000 description 1
- 235000005976 Citrus sinensis Nutrition 0.000 description 1
- 240000002319 Citrus sinensis Species 0.000 description 1
- 235000011511 Diospyros Nutrition 0.000 description 1
- 244000236655 Diospyros kaki Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 241000896292 Odontothrips loti Species 0.000 description 1
- 240000003793 Rhizophora mangle Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- -1 chromocor compound Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 230000005622 photoelectricity Effects 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
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- 230000029663 wound healing Effects 0.000 description 1
Abstract
The invention discloses a biological synthesis method for a spherical silver nanoparticle. The biological synthesis method includes the steps: preparing mango peel extracting solution; preparing desmodium extracting solution; performing mixture reaction: mixing the mango peel extracting solution, the desmodium extracting solution and 0.5mM silver nitrate solution accounting for 9-10 times of the weight of the mango peel extracting solution and the desmodium extracting solution, adjusting a pH (potential of hydrogen) value of the silver nitrate solution to be 8.0, and reacting the solution for 12-15min at the temperature of 50-55 DEG C. According to the synthesis method, low temperature is needed, the pH is neutral, and the prepared silver nanoparticle is fine in dispersing performance, minimal in particle size, extremely narrow in distribution range, excellent in antibacterial effect and spherical or approximately spherical.
Description
Technical field
The present invention relates to a kind of biological synthesis method of Nano Silver, especially use mangrove bark extract and Herba Lysimachiae extract synthesizing nano-silver.
Background technology
Nano silver particles has unique physicochemical properties, is widely used in the aspects such as catalysis, photoelectricity, optics, bioscience and pharmacy.Therefore, the preparation method studying Nano Silver has great importance.At present, nano silver particles can pass through the method preparations such as physics (steam-condensation method, ball-milling method, sputtering method, discharging explosion method), chemistry (liquid phase reactor method, gas-phase reaction method, template synthesis method), photocatalysis and biology.Compared with physical chemistry method, bioanalysis is because having efficient, quick, stable, simple, environmental friendliness, the plurality of advantages such as nontoxic and cheap and being paid close attention to by numerous researcher.Biological preparation nano silver particles mainly refers to utilize biological organism as reducing agent and protective agent, by the Ag+ in AgNO3 solution is reduced into Ag0, generates nano silver particles.
Pericarp extract is adopted to prepare nano silver particles not only fast efficient, can also twice laid, be conducive to environmental protection, leaves of plants and seed resource enrich, there is extremely strong power of regeneration, utilize the extract of pericarp, leaves of plants and seed etc. to prepare nano silver particles great potential.With microbial ratio, although it is more quick to adopt pericarp and plant to prepare silver particles, little about its research at present.Prior art discloses with the successfully obtained nano silver particles such as air-dry banana skin, persimmon leaf, redwood leaf, sweet orange peel.The pattern of nano silver particles and particle diameter directly affect its antibacterial and photo-catalysis capability, and the nano silver particles preparing pattern and size tunable has great meaning to its application.Adopt different biomaterials may affect the pattern of the nano silver particles of preparation.Although bioanalysis still accurately can not control the particle diameter of prepared nano silver particles at present, more about research in this respect, the factor affecting particle diameter mainly contains pH value, biomaterial amount, temperature and reaction time.Research finds, along with pH value raises, the silver particles particle diameter prepared is less.Increase the amount of extract, there will be the result that particle diameter increases and reduction two kinds is contrary.Along with reaction temperature raises, the nano silver particles particle diameter of generation is less.
Prior art discloses a kind of method that mangrove bark prepares nano silver particles.Mangrove bark, as the processing byproduct produced in mango industrialization processing, is generally abandoned, and has both caused the huge waste of resource, again contaminated environment.According to the study, containing a large amount of chromocor compound, polyphenolic substance and polysaccharide in mangrove bark, be all good reducing agent.Experimental study using food industry leftover bits and pieces mangrove bark as reducing agent and dispersant, the dispersed well Nano Silver of synthesis.Research shows, pH value is 11, the addition of mangrove bark extract is 0.1mL, liquor argenti nitratis ophthalmicus concentration is 0.5mM, reaction condition is 80 DEG C, during water-bath 15min, the particle diameter characterizing the Nano Silver of synthesis through ultraviolet-visible spectrophotometry and TEM is minimum, is 7nm(± 23%).But the method reaction temperature is high, and PH is high, in a large amount of suitability for industrialized production, observable index is higher.
The present invention aims to provide a kind of biological synthesis method of Nano Silver, utilizes mangrove bark and desmodium, and at a lower temperature, can produce particle diameter little, narrow distribution range, form is in the nano silver particles compared with regular spherical.
Prior art is all that a kind of plant material of single use extracts, the present inventor attempts with two kinds or two or more plant extraction liquids, under finding mangrove bark extract and Herba Lysimachiae extract acting in conjunction, certain synergy can be reached, remarkable Optimal reaction conditions.Specifically, be reduce reaction temperature, allow PH partial neutral, reduce the diameter of nano silver particles.
In order to realize above-mentioned object, present invention employs following technical scheme:
A biological synthesis method for Nano Silver, its step is as follows:
(1) mangrove bark extract is prepared;
(2) desmodium extract is prepared;
(3) hybrid reaction:
Get mangrove bark extract, desmodium extract, mix with the liquor argenti nitratis ophthalmicus of the 0.5mM of 9-10 times of weight, regulate the pH value of liquor argenti nitratis ophthalmicus to be 8.0,50-55 DEG C of reaction 12-15min.
As preferably, step (1) is: take fresh mango skin, and amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
As preferably, step (2) is: get dry medicinal material desmodium, and amount of water is 8 times of desmodium weight, extracts 3-4 h through 85-90 DEG C of water-bath, filters, obtains desmodium extract;
As preferably, step (3) is: get 1 times of weight mangrove bark extract, and 0.15-0.2 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of the 0.5mM of 9-10 times of weight, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,50 DEG C and reacts 12-15min.
Usefulness of the present invention is:
1. the present invention adopts mangrove bark as raw materials for production, and mangrove bark is generally abandoned, and has both caused the huge waste of resource, again contaminated environment, utilizes the present invention to turn waste into wealth.
2. synthetic method of the present invention have efficiently, quick, stable, simple, environmental friendliness, nontoxic and cheap advantage
3. synthetic method of the present invention needs temperature low, and pH partial neutral, prepares dispersive property good, and particle diameter is minimum, and distribution is extremely narrow, the extraordinary nano silver particles of fungistatic effect.
Summary of the invention
The object of this invention is to provide a kind of biological synthesis method of Nano Silver, utilize mangrove bark extract and Herba Lysimachiae extract, can at a lower temperature, the reaction environment of partial neutral is little, produces particle diameter about 6nm, the nano silver particles of narrow distribution range.
Nano silver particles has stronger antibacterial ability, is widely used in clinical medicine, as operation and wound healing etc., following potential for aspects such as anti-inflammatory, antitumor, gynaecology and regenerative medicines.At present, the antifungal mechanism of nano silver particles is still not fully aware of, and possible mechanism can be divided into: the meeting soluble in water of (1) nano silver particles changes into silver ion, kills pathogen; (2) nano silver particles is accumulated outward in a large number at bacterial cell membrane, can change the permeability of cell membrane, cause bacterial death; (3) nano silver particles has less particle diameter and large specific area, and therefore, nano silver particles can destroy cell membrane easily, enters in cell, in cytoplasm, changes into silver ion, damages born of the same parents' inner structure.
The bacteriostasis of nano silver particles depends on many-sided factor: (1) pattern.The nano silver particles process Escherichia coli of identical table area, its bacteriostasis of different patterns has difference, and it is different that perhaps difformity can cause it to play useful effect surface area, affects bacteriostasis.(2) particle diameter.Silver particles particle diameter is less, and bacteriostasis is stronger.(3) preparation method.The bacteriostasis of the nano silver particles of Biological preparation is higher than the nano silver particles prepared by chemical method.
Nano silver particles mainly experiences generation, reunion, broken and 4 stages of dissolving in course of reaction, Biological preparation nano silver particles has efficiently, fast and stability high, thus generate and reunion completes and broken and course of dissolution is not obvious at short notice, reaction just reaches balance within a short period of time.The organic matters such as alcohols, ether, carboxylic acid, aliphatic and aromatic compound in plant and pericarp likely serve as reducing agent and protective agent in the reaction.
Detailed description of the invention
embodiment 1:
A biological synthesis method for Nano Silver, its step is as follows:
Prepare mangrove bark extract:
Take fresh mango skin, amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
Preparation desmodium extract:
Get dry medicinal material desmodium, amount of water is 8 times of desmodium weight, extracts 4 h obtain desmodium extract through 85 DEG C of water-baths, filters, for subsequent use;
Get 1 times of weight mangrove bark extract, 0.15 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of 10 times of weight 0.5mM, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,50 DEG C of reaction 12min.
embodiment 2:
A biological synthesis method for Nano Silver, its step is as follows:
Prepare mangrove bark extract:
Take fresh mango skin, amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
Preparation desmodium extract:
Get dry medicinal material desmodium, amount of water is 8 times of desmodium weight, extracts 3 h obtain desmodium extract through 90 DEG C of water-baths, filters, for subsequent use;
Get 1 times of weight mangrove bark extract, 0.2 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of 9 times of weight 0.5mM, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,55 DEG C of reaction 15min.
embodiment 3:
A biological synthesis method for Nano Silver, its step is as follows:
Prepare mangrove bark extract:
Take fresh mango skin, amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
Preparation desmodium extract:
Get dry medicinal material desmodium, amount of water is 8 times of desmodium weight, extracts 4 h obtain desmodium extract through 87 DEG C of water-baths, filters, for subsequent use;
Get 1 times of weight mangrove bark extract, 0.18 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of 10 times of weight 0.5mM, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,53 DEG C of reaction 14min.
embodiment 4:
A biological synthesis method for Nano Silver, its step is as follows:
Prepare mangrove bark extract:
Take fresh mango skin, amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
Preparation desmodium extract:
Get dry medicinal material desmodium, amount of water is 8 times of desmodium weight, extracts 3 h obtain desmodium extract through 89 DEG C of water-baths, filters, for subsequent use;
Get 1 times of weight mangrove bark extract, 0.16 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of 9 times of weight 0.5mM, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,51 DEG C of reaction 13min.
embodiment 5:
A biological synthesis method for Nano Silver, its step is as follows:
Prepare mangrove bark extract:
Take fresh mango skin, amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup;
Preparation desmodium extract:
Get dry medicinal material desmodium, amount of water is 8 times of desmodium weight, extracts 4 h obtain desmodium extract through 86 DEG C of water-baths, filters, for subsequent use;
Get 1 times of weight mangrove bark extract, 0.19 times of weight desmodium extract, mixes with the liquor argenti nitratis ophthalmicus of 10 times of weight 0.5mM, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,54 DEG C of reaction 12min.
embodiment 6:
The Nano silver solution obtained embodiment 1-5 carries out the sign of form.
Adopt UV-VIS spectrophotometry, the Nano silver solution synthesized under transmission electron microscope (TEM) characterizes different embodiment, result is as shown in table 1.
Table 1
embodiment 7 fungistatic effect is tested and assessed:
Odontothrips loti is adopted to carry out bacteriostatic test.Place the Oxford cup that diameter is 8mm, add the Nano silver solution of embodiment 1-5 synthesis.Put into 37 DEG C of incubators and cultivate 24h, use vernier caliper measurement antibacterial circle diameter.Compare with mangrove bark extract and desmodium extract mixture.Test result is shown in Table 2.
Table 2
Can significantly find out from upper table, Nano silver solution of the present invention has extraordinary fungistatic effect.
Especially the Nano silver solution of embodiment 2 is most preferred embodiment of the present invention.
The above; be only the present invention's preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (5)
1. a biological synthesis method for ball shaped nano silver particles, its step is as follows:
Prepare mangrove bark extract;
Preparation desmodium extract;
Hybrid reaction:
Get mangrove bark extract, desmodium extract, liquor argenti nitratis ophthalmicus mixes, 50-55 DEG C of reaction 12-15min.
2. the biological synthesis method of nano silver particles according to claim 1, is characterized in that:
Step (1) is: take fresh mango skin, and amount of water is that 2 times of mangrove bark weight are squeezed into juice, and filter, 4 DEG C save backup.
3. the biological synthesis method of nano silver particles according to claim 2, is characterized in that:
Step (2) is: get dry medicinal material desmodium, and amount of water is 8 times of desmodium weight, extracts 3-4 h through 85-90 DEG C of water-bath, filters, obtains desmodium extract.
4. the biological synthesis method of nano silver particles according to claim 3, is characterized in that:
Step (3) is: get mangrove bark extract, and desmodium extract mixes with the liquor argenti nitratis ophthalmicus of the 0.5mM of 9-10 times of weight, regulates the pH value of liquor argenti nitratis ophthalmicus to be 8.0,50-55 DEG C of reaction 12-15min.
5. the nano silver solution that the method described in claim 1-4 prepares.
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| CN106112008A (en) * | 2016-08-18 | 2016-11-16 | 安徽科技学院 | Utilize the method that Flos Osmanthi Fragrantis blade prepares nanometer silver |
| CN106223016A (en) * | 2016-07-27 | 2016-12-14 | 张冬财 | A kind of autumn and winter automotive trim antibacterial rabbit hair fabric |
| CN107088661A (en) * | 2017-05-11 | 2017-08-25 | 扬州大学 | A kind of synthetic method of Nano Silver |
| CN107309438A (en) * | 2017-07-14 | 2017-11-03 | 福建农林大学 | A kind of method that polysaccharide from Phyllanthus Emblica L prepares Nano Silver compound particle |
| CN109158613A (en) * | 2018-08-29 | 2019-01-08 | 扬州大学 | A method of utilizing sinigrin synthesizing nano-silver |
| CN109528768A (en) * | 2018-12-29 | 2019-03-29 | 鲁东大学 | A kind of nano antibacterial preparation and preparation method thereof for treating horse endometritis |
| CN109909513A (en) * | 2019-04-26 | 2019-06-21 | 中国科学院西双版纳热带植物园 | A kind of method and purposes with comospore Glochidion puberum biosynthesis nano silver particles |
| CN113070484A (en) * | 2021-03-10 | 2021-07-06 | 海南华创槟榔研究院 | Size-controllable spherical nano silver particles, preparation method and application |
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| CN105750562A (en) * | 2016-04-21 | 2016-07-13 | 太原理工大学 | Method for green synthesis of nanometer zero-valent iron suspension liquid with peels or seed kernels |
| CN106223016A (en) * | 2016-07-27 | 2016-12-14 | 张冬财 | A kind of autumn and winter automotive trim antibacterial rabbit hair fabric |
| CN106112008A (en) * | 2016-08-18 | 2016-11-16 | 安徽科技学院 | Utilize the method that Flos Osmanthi Fragrantis blade prepares nanometer silver |
| CN106112008B (en) * | 2016-08-18 | 2019-04-05 | 安徽科技学院 | The method for preparing nano silver using sweet osmanthus blade |
| CN107088661A (en) * | 2017-05-11 | 2017-08-25 | 扬州大学 | A kind of synthetic method of Nano Silver |
| CN107309438A (en) * | 2017-07-14 | 2017-11-03 | 福建农林大学 | A kind of method that polysaccharide from Phyllanthus Emblica L prepares Nano Silver compound particle |
| CN109158613A (en) * | 2018-08-29 | 2019-01-08 | 扬州大学 | A method of utilizing sinigrin synthesizing nano-silver |
| CN109528768A (en) * | 2018-12-29 | 2019-03-29 | 鲁东大学 | A kind of nano antibacterial preparation and preparation method thereof for treating horse endometritis |
| CN109528768B (en) * | 2018-12-29 | 2021-04-27 | 鲁东大学 | Nano bacteriostatic preparation for treating equine endometritis and preparation method thereof |
| CN109909513A (en) * | 2019-04-26 | 2019-06-21 | 中国科学院西双版纳热带植物园 | A kind of method and purposes with comospore Glochidion puberum biosynthesis nano silver particles |
| CN109909513B (en) * | 2019-04-26 | 2022-03-04 | 中国科学院西双版纳热带植物园 | Method for biologically synthesizing nano silver particles by using glochidion pubescens and application |
| CN113070484A (en) * | 2021-03-10 | 2021-07-06 | 海南华创槟榔研究院 | Size-controllable spherical nano silver particles, preparation method and application |
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