CN106270548A - Utilize method of sericin green syt nanometer silver in situ and products thereof - Google Patents
Utilize method of sericin green syt nanometer silver in situ and products thereof Download PDFInfo
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- CN106270548A CN106270548A CN201610804581.3A CN201610804581A CN106270548A CN 106270548 A CN106270548 A CN 106270548A CN 201610804581 A CN201610804581 A CN 201610804581A CN 106270548 A CN106270548 A CN 106270548A
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention discloses method and the application thereof utilizing sericin green syt sericin nanometer silver in situ, then its preparation method reacts prepared to solution yellowly for adding silver nitrate solution in sericin solution under the conditions of natural lighting, the method utilizes the phenolic hydroxyl group of tyrosine to have reproducibility, silver ion can be reduced in the solution, fabricated in situ sericin nanometer silver under conditions of illumination;It is simple to operate, mild condition, environmental protection;The sericin nanometer silver prepared has good dispersibility and stability;Staphylococcus aureus is had preferable bactericidal action, and cytotoxicity is low, there is good biocompatibility.Therefore, the sericin nanometer silver utilizing this method to synthesize has broad application prospects.
Description
Technical field
The invention belongs to technical field of biological material, particularly relate to sericin green syt sericin-nanometer silver in situ
Method, further relates to utilize product that the method prepares and products thereof.
Background technology
Nanotechnology is one of study hotspot in recent years.Nano material is because of its skin effect, small-size effect and macroscopic view
Quantum tunneling effect is with a wide range of applications in optics, electronics and field of biology.Nanometer silver is as one widely people
The nano material known, is respectively provided with good inhibitory activity to gram negative bacteria, gram positive bacteria, fungus and virus, is giving birth to
The fields such as thing medical science such as repair in trauma are widely used.The most nanometer silver products application is in clinical medicine, as received
Rice silver hydrogel, nanometer silver wound plaster, nano silver spray etc..
Nanometer silver is mainly synthesized by method chemically and physically, and these method general steps are loaded down with trivial details, and condition is harsh, and easily
Introduce poisonous and harmful reagent.Nanometer silver is easily oxidised in atmosphere and assembles, thus loses antibacterial activity, and these shortcomings make
Nano silver material is subject to certain restrictions in practice.Organic or inorganic material is utilized to prepare nano silver composite material,
Although the stability of nanometer silver can be increased, but usual method is complicated, relatively costly, and it is attended by asking of biocompatibility
Topic.Prepare nano silver composite material by green syt, in order to for biomedical sector, increasingly paid close attention to by people.
Sericin is glued by the middle division of silkgland emiocytosis of silkworm, a kind of natural macromolecular being wrapped around fibroin fiber top layer
Property albumen, fibroin is played protection and the effect that is adhered.Sericin contains 18 kinds of natural amino acids, and wherein 8 kinds is that human body is necessary
Aminoacid, the also glycine of high-load, serine, alanine and tyrosine.Sericin has multiple good biology
Activity, such as non-oxidizability, antibiotic property, anti-crosslinking, promotes the function such as cell proliferation and differentiation, and sericin is hydrophilic, has
Good biological reactable and biological degradability, therefore of increased attention in regenerative medicine field.Sericin is normal
Prepare various support by copolymerization, crosslinking or with other polymer mixed, thus improve properties of materials and make it preferably adapt to
Biomedical various demand, such as promoting epidermization etc..In addition to other biological Material cladding, people have also attempted using pure silk glue
Albumen prepares biological support, such as two-dimensional films, three-dimensional sponge support etc..Sericin is soluble in hot water, and the sericin of low concentration is when room temperature
In solution state, it is gel state during high concentration.Sericin powder dissolved state prepared by Different Extraction Method has certain difference, total
For, the sericin of low-molecular-weight is more soluble.But, the current and undisclosed report utilizing sericin to prepare nano silver material
Road.
Summary of the invention
In view of this, an object of the present invention is that offer utilizes sericin green syt sericin-nanometer silver in situ
Method, the method meet green prepare the environmentally acceptable solvent system of nanometer silver, the reducing agent of eco-friendly and
Three key elements of stabilizer;The two of the purpose of the present invention are to provide and utilize sericin green syt sericin-nanometer silver in situ
The product that method prepares, prepared product has preferable dispersibility and stability, has staphylococcus aureus well
Bactericidal action, and cytotoxicity is low.
For achieving the above object, the present invention provides following technical scheme:
1, the method utilizing sericin green syt sericin-nanometer silver in situ, specifically comprises the following steps that in sericin solution
Add silver nitrate solution, then react under the conditions of natural lighting to solution yellowly, prepare sericin-nanometer silver.
The present invention utilizes native protein sericin to have good biocompatibility and biodegradability, with sericin is
Biological template, utilizes the reproducibility that its tyrosine has, and can prepare sericin-nano silver composite material in situ.
Preferably, described sericin solution concentration is 2~16mg/ml.
Preferably, described sericin solution is prepared by following methods: after Bombyx bombycis is shredded 120 DEG C, under the conditions of 0.1Mpa
Managing at least 30min, solid-liquid separation collects solution, then lyophilization, adds the hot water dissolving that temperature is more than 60 DEG C and prepares.
It is furthermore preferred that described solid-liquid separation is for first to wring out silkworm silk, solution utilizes filtered through gauze.
It is furthermore preferred that described lyophilization is by the freezing under the conditions of-80 DEG C of sericin solution, it is subsequently placed in freezer dryer
In be dried at least 24h.
Preferably, described silver nitrate solution concentration is 2~16mg/ml.
Preferably, the time of described reaction is 24~36h.
2, the method utilizing sericin green syt sericin-nanometer silver in situ prepares sericin-nanometer silver.
The beneficial effects of the present invention is: the invention discloses and utilize sericin green syt sericin-nanometer silver in situ
Method, utilize the phenolic hydroxyl group of tyrosine to have reproducibility, can reduce silver ion in the solution, therefore add in sericin solution
Entering silver nitrate, then under the conditions of natural lighting, reaction prepares.The method is simple to operate, mild condition, environmental protection;Prepare
Nanometer silver has good dispersibility and stability, has good bactericidal action, and cytotoxicity to staphylococcus aureus
Low, there is good biocompatibility, prepared sericin-nanometer silver has good application prospect.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below:
Fig. 1 is sericin-nanometer silver preparation flow figure and result;A represents sericin-nanometer silver preparation flow figure;B represents UV-
Vis detects nanometer silver.
Fig. 2 is the impact that sericin-nanometer silver is generated by silver nitrate concentration;A represents the different silver nitrate concentration of UV-vis detection
Sericin-the nanometer silver prepared;B represents the impact on tyrosine endogenous fluorescence of the fluoroscopic examination silver nitrate concentration.
Fig. 3 is sericin/silver nitrate kinetics detection;A represents the UV-Vis of tyrosine in differential responses time sericin
Absorption spectrum;B represents the endogenous fluorescence spectrum of tyrosine in differential responses time sericin.
Fig. 4 is the form of nanometer silver in sericin-nanometer silver;A represents the TEM morphology observation of nanometer silver;B represents nanometer silver granuel
Footpath size is analyzed;C represents that the high-resolution of single nanometer silver is observed;D represents the diffracting spectrum of single nanometer silver.
Fig. 5 is sericin-nanometer silver composition detection result;A represents generation and the degree of crystallinity of XRD detection sericin-nanometer silver;B
Represent the generation of FT-IR detection sericin-nanometer silver.
Fig. 6 be nanometer silver Detection of Stability and illumination necessity experiment (A represents Detection of Stability result, and a is just to have reacted
Sericin-the nanometer silver of rear preparation;B is that the sericin-nanometer silver prepared places result after 50 days under light illumination;C is prepare
Sericin-nanometer silver place 50 days under dark condition after result;B represents that sericin mixes with silver nitrate and is placed on dark condition 50 days
Rear illumination detection nanometer silver is with the growing amount situation of change of light application time.
Fig. 7 is the sericin-nanometer silver bacteriostatic experiment to staphylococcus aureus;A represents that sericin-nanometer silver is minimum antibacterial dense
Degree;B represents sericin-nanometer silver minimum bactericidal concentration detection.
Fig. 8 is the cell after 3T3 cell cultivates 12h in the culture medium that with the addition of variable concentrations sericin-nanometer silver solution
Activity determination.
Fig. 9 is the cell after 3T3 cell cultivates 12h in the culture medium that with the addition of variable concentrations sericin-nanometer silver solution
Morphologic observation.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.In embodiment unreceipted specifically
The experimental technique of condition, generally according to normal condition or according to the condition proposed by manufacturer.
Embodiment 1
The method utilizing sericin green syt nanometer silver in situ, preparation flow is as shown in A in Fig. 1, specific as follows:
1) extraction of sericin: take 10g Bombyx bombycis and be cut into fractionlet, is that 1:30 is placed in high-pressure sterilizing pot, 120 by bath raio
DEG C, process 30min under the conditions of 0.1Mpa, then silkworm silk is wrung out, collects filtrate by filtered through gauze and i.e. obtain sericin extracting solution;
2) preparation of sericin powder: by step 1) the sericin extracting solution for preparing under the conditions of-80 DEG C freezing 2 hours, then
It is placed in freezer dryer and is dried 24h, obtain sericin powder;
3) preparation of sericin solution: by step 2) the sericin powder for preparing adds the hot water of more than 60 DEG C by 0.1% (wt)
Weight is molten, prepares sericin solution;
4) preparation of sericin-nanometer silver: to step 3) the sericin solution for preparing adds the silver nitrate of 4mg/mL, prepare silk
Glue-silver nitrate solution, reacts 24 hours under the conditions of then sericin-silver nitrate solution is placed in natural lighting, it was observed that reactant liquor
Gradually become yellow by colourless, prepare sericin-nanometer silver.
Sericin-nanometer silver UV-vis the testing result prepared is as shown in B in Fig. 1.
Embodiment 2
The method utilizing sericin green syt nanometer silver in situ, preparation flow is as shown in A in Fig. 1, specific as follows:
1) extraction of sericin: take 10g Bombyx bombycis and be cut into fractionlet, is that 1:30 is placed in high-pressure sterilizing pot, 120 by bath raio
DEG C, process 30min under the conditions of 0.1Mpa, then silkworm silk is wrung out, collects filtrate by filtered through gauze and i.e. obtain sericin extracting solution;
2) preparation of sericin powder: by step 1) the sericin extracting solution for preparing under the conditions of-80 DEG C freezing 2 hours, then
It is placed in freezer dryer and is dried 24h, obtain sericin powder;
3) preparation of sericin solution: by step 2) the sericin powder for preparing adds the hot water of more than 60 DEG C by 0.1% (wt)
Middle heavy molten, prepare sericin solution;
4) preparation of sericin-nanometer silver: to step 3) the sericin solution for preparing adds the silver nitrate of 8mg/mL, prepare silk
Glue-silver nitrate solution, reacts 24 hours under the conditions of then sericin-silver nitrate solution is placed in natural lighting, it was observed that reactant liquor
Gradually become yellow by colourless, prepare sericin-nanometer silver.
Sericin-nanometer silver UV-vis the testing result prepared is as shown in B in Fig. 1.
Embodiment 3
The method utilizing sericin green syt nanometer silver in situ, preparation flow is as shown in A in Fig. 1, specific as follows:
1) extraction of sericin: take 10g Bombyx bombycis and be cut into fractionlet, is that 1:30 is placed in high-pressure sterilizing pot, 120 by bath raio
DEG C, process 30min under the conditions of 0.1Mpa, then silkworm silk is wrung out, collects filtrate by filtered through gauze and i.e. obtain sericin extracting solution;
2) preparation of sericin powder: by step 1) the sericin extracting solution for preparing under the conditions of-80 DEG C freezing 2 hours, then
It is placed in freezer dryer and is dried 24h, obtain sericin powder;
3) preparation of sericin solution: by step 2) the sericin powder for preparing adds the hot water of more than 60 DEG C by 0.1% (wt)
Middle heavy molten, prepare sericin solution;
4) preparation of sericin-nanometer silver: to step 3) the sericin solution for preparing adds the silver nitrate of 16mg/mL, prepare
Sericin-silver nitrate solution, reacts 36 hours under the conditions of then sericin-silver nitrate solution is placed in natural lighting, it was observed that reaction
Liquid is gradually become yellow by colourless, prepares sericin-nanometer silver.
Sericin-nanometer silver UV-vis the testing result prepared is as shown in B in Fig. 1.
The impact generated nanometer silver for research silver nitrate concentration, concentration is respectively 2mg/ml, 4mg/ml, 6mg/
The silver nitrate solution of ml, 8mg/ml, 12mg/ml and 16mg/ml prepares sericin-nanometer silver, then detects the generation feelings of nanometer silver
Condition, result is as shown in A in Fig. 2.Result shows, along with the increase of silver nitrate concentration, the growing amount of nanometer silver is gradually increased;Work as nitre
Acid silver concentration is more than 4mg/ml, and the increase of nanometer silver is not the most notable.Therefore, the silver nitrate of 4mg/ml can be with most sericin
Reaction generates nanometer silver.For being further characterized by the experimental result of UV-vis, utilize the endogenous fluorescence of tyrosine analyze 2mg/ml,
The impact that nanometer silver is generated by the silver nitrate of 4mg/ml, 6mg/ml, 8mg/ml, 12mg/ml and 16mg/ml, B in result such as Fig. 2
Shown in.Result shows, along with the increase of silver nitrate concentration, the endogenous fluorescence intensity of tyrosine is gradually reduced, and shows sericin solution
In tyrosine gradually aoxidized by silver nitrate;When silver nitrate concentration is more than 4mg/ml, and the endogenous fluorescence Strength Changes of tyrosine is not
The most obvious.Result shows, the silver nitrate of 4mg/ml can react generation nanometer silver with most sericin, this and the detection of UV-vis
Result is consistent.
For the kinetics of research sericin and silver nitrate, the detection response time be respectively 2h, 4h, 8h, 12h, 16h,
The change of 20h, 24h, 28h and 32h tyrosine photon absorbing intensity, result is as shown in Figure 3;Wherein in Fig. 3, A represents sericin/silver nitrate
Kinetics testing result, in Fig. 3, B represents the impact that nanometer silver generates by the response time, and interior illustration shows along with reaction
The carrying out of time, the change of sericin-silver nitrate mixed solution color in cuvette.Result shows, along with the increase in response time,
The photon absorbing intensity of tyrosine is gradually increased, and reaction is persistently carried out, and the growing amount of nanometer silver is gradually increased;Exceed between when reacted
24h, the photon absorbing intensity increase of tyrosine is no longer obvious, shows that the response time of 24h has been sufficient for most silk in system
Glue and silver nitrate reaction generate nanometer silver.
Followed by the form of nanometer silver in transmission electron microscope tem observation sericin-nano silver composite material, result is such as
Shown in Fig. 4.Wherein in Fig. 4, A represents the pattern utilizing tem observation nanometer silver;In Fig. 4, B represents nanometer silver size analysis;Figure
In 4, C represents that the high-resolution of single nanometer silver is observed;In Fig. 4, D represents the diffracting spectrum of single nanometer silver.Result shows, utilizes
Nano-Ag particles prepared by this method has good dispersibility, and the particle diameter of most of nanometer silvers is positioned at 4-20nm, median
For 12nm, the nanometer silver of generation has preferable degree of crystallinity and antibacterial activity.Then X-ray diffraction XRD and Fourier is utilized to become
Changing the generation of infrared spectrum FT-IR detection sericin-nanometer silver, result is as shown in Figure 5.Wherein in Fig. 5, A represents and utilizes XRD to detect
The generation of nanometer silver and degree of crystallinity, B represents the generation utilizing FT-IR detection nanometer silver.Result shows, profit success in this way
Ground in-situ preparation nanometer silver on sericin, and the nanometer silver generated has good degree of crystallinity, this observation knot with TEM before
The most basically identical.
Sericin-nanometer silver stability and illumination condition analysis on Necessity:
It is individually positioned in illumination and dark bar after utilizing sericin-nanometer silver that UV-Vis spectral detection just prepared, reaction
Part 50 sericin-nanometer silver all over the world, result is as shown in A in Fig. 6.Result shows, under the conditions of three kinds, and the absorption maximum light of tyrosine
Peak position and the absorption intensity of spectrum are basically identical, show that once sericin and silver nitrate fully react and generate nanometer silver, and nanometer silver is modern
After will can change the most again.This experiment demonstrates the nanometer silver utilizing this method to prepare and has the stability of height at normal temperatures.
Next checking illumination is the essential condition that nanometer silver generates.Sericin is mixed with silver nitrate after being placed on dark condition lower 50 days
Illumination, the situation of change that under the different light application time of detection, nanometer silver generates respectively, result is as shown in B in Fig. 6.Interior illustration reacts
Along with the increase in response time, the change of sericin-nanometer silver mixed solution color.Result shows, along with the increase in response time,
The light absorption value of tyrosine is continuously increased, and shows constantly have silver nitrate to be reduced by tyrosine, and the color change of interior illustration also reflects
Nanometer silver increases constantly synthesis along with the response time.It is that sericin reduction silver nitrate generates nanometer silver that this result indicates illumination
Essential condition.
The bacteriostatic experiment of sericin-nanometer silver:
1, minimum inhibitory concentration experiment
The present invention carries out minimum inhibitory concentration detection (MIC) by equimultiple dilution method, so that it is determined that sericin-nanometer silver is to gold
The minimum inhibitory concentration of Staphylococcus aureus, method particularly includes:
1) single colony inoculation of depletion Staphylococcus aureus is in the 100mL LB fluid medium (pH 7.4) of sterilizing,
Rotating speed is 220rpm, temperature is cultivated 12 hours under the conditions of being 37 DEG C;
2) diluting antibacterial to concentration by LB culture medium is 2 × 105CFU/mL, is distributed in 12 test tubes, the first pipe
1.6mL, remaining every pipe 1mL;
3) in the first pipe, add sericin-nanometer silver that concentration is 4mg/mL that 0.4mL prepares, mix next pipe backward
The mixed solution of middle addition 1mL the first pipe, the like, control sericin-nanometer silver final concentration scope be 1.5625mg/L~
800mg/L, sets up the blank being not added with sericin-nanometer silver He being not added with antibacterial simultaneously;
4) bacterium solution is cultivated 24h in 37 DEG C, be observed visually without bacterial growth, detect OD simultaneously600Light absorption value no longer become
Sericin-nanometer silver the Cmin changed is MIC, and result is as shown in A in Fig. 7.Result shows, sericin and the nanometer silver of low concentration
Growth to staphylococcus aureus has little to no effect;When nanometer silver concentration is 25mg/L, bacterium solution becomes clarification, observes not
To the growth of antibacterial, and OD600Light absorption value be significantly reduced, and the matched group being not added with antibacterial remains basically stable, and shows sericin-receive
The minimum inhibitory concentration of meter Yin is 25mg/L.
2. minimum bactericidal concentration experiment
For further determining that the bactericidal action of sericin-nanometer silver solution, utilize the detection method of minimum bactericidal concentration (MIC)
The bactericidal effect of test sericin-nanometer silver.Concrete grammar is as follows:
1) take in the test tube of more than MIC concentration often pipe and take 100 μ L, coat on 2YT solid medium;
2) it is positioned over 37 DEG C of constant incubators and cultivates 24h, monoclonal number sericin-nanometer less than 5 in each flat board
Silver concentration is minimum bactericidal concentration, and result is as shown in B in Fig. 7.Result shows, along with the increase of nanometer silver concentration, in flat board
Staphylococcus aureus number significantly reduces, and does not observes the existence of bacterial clump when the concentration of nanometer silver is 100mg/L,
Show that the nanometer silver of 100mg/L kills staphylococcus aureus completely, so the minimum bactericidal concentration of sericin-nanometer silver is
100mg/L。
Sericin-nanometer silver cytotoxicity experiment
In order to determine the biocompatibility of sericin-nanometer silver, sericin-nanometer silver is carried out cytotoxicity experiment, selected carefully
Born of the same parents are mouse embryo fibroblasts (NIH/3T3), method particularly includes:
1) NIH/3T3 cell is incubated in the DMEM culture medium containing 10% (v/v) hyclone (FBS, Gibco),
Containing 5%CO2, 37 DEG C of incubators are cultivated;
2) collect and grow to the NIH/3T3 cell of 96% degree of converging, cultivate by 500/100 μ L/ hole, 96 porocytes that tile
In plate, containing 5%CO2, 37 DEG C of incubators continue cultivate 12h;
3) sericin-nanometer silver solution of sericin solution that mass fraction is 0.1% and variable concentrations is added to 96 orifice plates
In, control final concentration of 5mg/L, 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/ of nanometer silver
L.Containing 5%CO2, 37 DEG C of incubators continue to cultivate 12h;
4) according to the dosage addition CCK-8 reagent in 10 μ L/ holes in 96 orifice plates, containing 5%CO2, 37 DEG C of conditions continue training
Supporting 4h, measure the cell light absorption value in hole under 450nm wavelength, result is as shown in Figure 8.Result shows, sericin and low concentration
The growth of cell is had little to no effect by nanometer silver, and when the concentration of nanometer silver increases to 30mg/L, the growth to cell has bright
Aobvious inhibitory action.
Observing the cellular morphology after variable concentrations nanometer silver processes the most under an optical microscope, result is as shown in Figure 9.Knot
Fruit display, sericin solution and low concentration nanometer silver solution process the form to cell and have little to no effect, when the concentration of nanometer silver
During for 35mg/L, it may be observed that have the situation of obvious cell rupture to occur.
It is last it should be noted that preferred embodiment above is only in order to illustrate technical scheme and unrestricted, to the greatest extent
The present invention is described in detail by pipe by above preferred embodiment, it is to be understood by those skilled in the art that can
In the form and details it is made various change, the model limited without departing from claims of the present invention
Enclose.
Claims (8)
1. the method utilizing sericin green syt sericin-nanometer silver in situ, it is characterised in that specifically comprise the following steps that to silk
Sol solution adds silver nitrate solution, then reacts under the conditions of natural lighting to solution yellowly, prepare sericin-nanometer silver.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 1, it is characterised in that:
Described sericin solution concentration is 2~16mg/ml.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 1, it is characterised in that:
Described sericin solution is prepared by following methods: after Bombyx bombycis is shredded 120 DEG C, process at least 30min, solid-liquid under the conditions of 0.1Mpa
Collect solution, then lyophilization after separation, add the temperature hot water dissolving higher than 60 DEG C and prepare.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 3, it is characterised in that:
Described solid-liquid separation is for first to wring out silkworm silk, and solution utilizes filtered through gauze.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 3, it is characterised in that:
Described lyophilization is by the freezing under the conditions of-80 DEG C of sericin solution, is subsequently placed in freezer dryer and is dried at least 24h.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 1, it is characterised in that:
Described silver nitrate solution concentration is 2~16mg/ml.
The method utilizing sericin green syt sericin-nanometer silver in situ the most according to claim 1, it is characterised in that:
The time of described reaction is 24~36h.
8. described in any one of claim 1~7, utilize the silk that the method for sericin green syt sericin-nanometer silver in situ prepares
Glue-nanometer silver.
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CN107088661A (en) * | 2017-05-11 | 2017-08-25 | 扬州大学 | A kind of synthetic method of Nano Silver |
CN108672718A (en) * | 2018-06-07 | 2018-10-19 | 武汉船用电力推进装置研究所(中国船舶重工集团公司第七二研究所) | A kind of preparation method of the spherical silver powder of high specific area and its silver powder obtained |
CN108746664A (en) * | 2018-09-10 | 2018-11-06 | 河南金渠银通金属材料有限公司 | A kind of high oil absorption rate photovoltaic silver powder and the preparation method and application thereof |
CN109794616A (en) * | 2019-01-15 | 2019-05-24 | 南通纺织丝绸产业技术研究院 | The preparation of the silver nanoclusters of sericin package and fluorescence probe |
CN113826643A (en) * | 2021-11-01 | 2021-12-24 | 烟台大学 | Silver-carrying hydroxyapatite particle with controllable silver ion spatial distribution and preparation method thereof |
CN113826643B (en) * | 2021-11-01 | 2022-07-05 | 烟台大学 | Silver-carrying hydroxyapatite particle with controllable silver ion spatial distribution and preparation method thereof |
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