CN104289727A - Method for preparing nano-silver by taking modified chitosan as reducing agent - Google Patents
Method for preparing nano-silver by taking modified chitosan as reducing agent Download PDFInfo
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- CN104289727A CN104289727A CN201410565387.5A CN201410565387A CN104289727A CN 104289727 A CN104289727 A CN 104289727A CN 201410565387 A CN201410565387 A CN 201410565387A CN 104289727 A CN104289727 A CN 104289727A
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- chitosan
- reducing agent
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- nano silver
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 239000012031 Tollens' reagent Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 150000004676 glycans Chemical class 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 108010054033 Chitin deacetylase Proteins 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a method for preparing nano-silver by taking modified chitosan as a reducing agent. The method includes: dissolving chitosan in a 3% acetic acid solution with the bath ratio of 1:50, performing ultrasound treatment for 1-12h, then adding 2-10g/L of sodium periodate, performing photophobic reaction at the temperature of 40-80 DEG C for 10-60min, repeatedly cleaning with deionized water, and performing centrifuging and drying for standby application; then mixing chitosan liquid modified by 0.01-100g/L of sodium periodate with 0.01-100g/L of Tollens' reagent, performing ultrasound treatment at the temperature of 20-80 DEG C for 1-10h to obtain nano-silver colloidal solution, repeatedly cleaning with ethyl alcohol and deionized water, and performing centrifuging and drying treatment to obtain nano-silver. By taking chitosan modified with the sodium periodate as the reducing agent and a stabilizer, the method has the advantages of simple technology, mild reaction, greenness, environment friendliness and the like.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly a kind of take modification of chitosan as the method that Nano Silver prepared by reducing agent.
Background technology
Nano Silver has excellent conductivity of heat, electric conductivity, surface-active and catalytic performance, has huge using value in optics, catalysis, microelectronics, bio-sensing, the field such as antibacterial.The preparation of traditional Nano Silver is divided into Physical and chemical method.Physical requires higher to instrument and equipment, and producing cost is expensive.Chemical method many employings hydrazine hydrate, formaldehyde, polyalcohol, organic amine etc. make reducing agent, although these reducing agents have high activity, to bad environmental, and obtained Nano Silver easily agglomeration occurs.
In recent years, green, environmental protection, efficient and cheap method is adopted to prepare the focus that Nano Silver becomes research gradually.The green reducing agent adopted at present mainly comprises: vitamin, natrium citricum, pyrogallol, hydroquinones, Tea Polyphenols, glucose, fructose, sucrose, plant and pericarp extract, microorganism etc.
Chitin is a kind of natural organic high-molecular polysaccharide, is distributed widely in the cell membrane of the crust of nature Crustaceans (shrimp, crab, insect), fungi and plant.Account for second in reserves natural organic high-molecular material on earth, be only second to cellulose.Shitosan is the product after chitin deacetylase base, is a kind of linear macromolecule.Chinese invention patent CN201310555491.1 adopts nano wire fibroin, chitosan in situ reduction silver nitrate to prepare Nano Silver.Chinese invention patent CN201310434034.7 adopts shitosan (Mr=60000-120000) to make reducing agent, a small amount of natrium citricum used as stabilizers, and prepare particle diameter at below 5nm, monodispersity is good, and the nano silver colloidal sol of environmental protection.Chinese invention patent CN201410049491.9 provides a kind of method preparing stabilized nanoscale silver, wherein uses the micella of amphipathic chitosan graft polycaprolactone or derivatives thereof copolymer as stabilizing agent.Above-mentioned document mostly uses shitosan as stabilizing agent or uses modified shitosan as reducing agent.
Selective oxidation refers to the oxidation suppressing other position hydroxyl while certain ad-hoc location hydroxyl of oxidation of polysaccharides, and effectively can suppress the degraded of polysaccharide in oxidation reaction process.After sodium metaperiodate selective oxidation polysaccharide, can by C
2, C
3hydroxyl oxygen on position changes into aldehyde radical, and the functional modification for polysaccharide provides reactivity point, and active aldehyde radical can be utilized to carry out functional modification to polysaccharide, can generate numerous functional polysaccharide derivative, has greatly expanded the range of application of polysaccharide.Have no at present with sodium metaperiodate selective oxidation shitosan as the report of Nano Silver prepared by reducing agent and stabilizing agent.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, aiming to provide a kind of take modification of chitosan as the method that Nano Silver prepared by reducing agent.
The present invention is achieved by following technical proposals:
Shitosan is dissolved in the acetic acid solution of 3%, bath raio 1:50, ultrasonic 1-12h, adds the sodium metaperiodate of 2-10g/L subsequently, at 40-80 DEG C, lucifuge reaction 10-60min, cleans repeatedly by deionized water, centrifugal, dry for standby; Then according to the volume ratio of 10:1-1:1, chitosan solution modified for 0.01-100g/L sodium metaperiodate is mixed with the silver ammino solution of 0.01-100g/L, ultrasonic 1-10h under the temperature conditions of 20 DEG C-80 DEG C, obtain nano-class silver colloidal solution, repeatedly clean by ethanol and deionized water, centrifugal, obtain Nano Silver after dry process.
Preferably, described silver ammino solution is the complex compound that nitrate or silver sulfate and ammoniacal liquor are formed.
Preferably, described centrifugal be with the centrifugal 5-20min of the rotating speed of 8000-12000r/min.
Preferably, described drying process refers to and drying box temperature is set in 40 DEG C, dry 1-24h under the environment of vacuum.
The present invention has following beneficial effect:
Adopt sodium metaperiodate by the saccharide residue C of shitosan
2and C
3position is oxidized to the aldehyde radical with reproducibility, can be Nano Silver by silver ion reduction, the hydroxyl simultaneously existed in shitosan, similar cancellated cage molecule can be formed by means of hydrogen bond or ionic bond, thus and silver ion coordination, prevent Nano Silver from reuniting, and then obtain stable Nano silver solution.The shitosan that the present invention adopts sodium metaperiodate modified as reducing agent and stabilizing agent, possess that technique is simple, reaction temperature and, the advantage such as environmental protection.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.
Embodiment 1:
2g shitosan is dissolved in 3% acetic acid solution of 100ml, ultrasonic 1h, adds the sodium metaperiodate of 2g/L subsequently, at 80 DEG C, lucifuge reaction 60min, cleans repeatedly by deionized water, centrifugal, dry for standby;
1g modification of chitosan is dissolved in 100ml deionized water, obtain the modification of chitosan aqueous solution of concentration 10g/L, mix with the silver ammino solution of 10ml concentration 10g/L, ultrasonic 1h under the temperature conditions of 80 DEG C, obtain nano-class silver colloidal solution, repeatedly clean by ethanol and deionized water, the centrifugal 10min of rotating speed of 9000r/min, under 40 DEG C of vacuum environments, dry 20h obtains Nano Silver.
Embodiment 2:
2g shitosan is dissolved in 3% acetic acid solution of 100ml, ultrasonic 5h, adds the sodium metaperiodate of 5g/L subsequently, at 60 DEG C, lucifuge reaction 30min, cleans repeatedly by deionized water, centrifugal, dry for standby;
1g modification of chitosan is dissolved in 50ml deionized water, obtain the modification of chitosan aqueous solution of concentration 20g/L, mix with the silver ammino solution of 10ml concentration 5g/L, ultrasonic 10h under the temperature conditions of 20 DEG C, obtain nano-class silver colloidal solution, repeatedly clean by ethanol and deionized water, the centrifugal 10min of rotating speed of 8000r/min, under 40 DEG C of vacuum environments, dry 24h obtains Nano Silver.
Embodiment 3:
2g shitosan is dissolved in 3% acetic acid solution of 100ml, ultrasonic 10h, adds the sodium metaperiodate of 10g/L subsequently, at 40 DEG C, lucifuge reaction 10min, cleans repeatedly by deionized water, centrifugal, dry for standby;
1g modification of chitosan is dissolved in 20ml deionized water, obtain the modification of chitosan aqueous solution of concentration 50g/L, mix with the silver ammino solution of 10ml concentration 50g/L, ultrasonic 4h under the temperature conditions of 40 DEG C, obtain nano-class silver colloidal solution, the centrifugal 15min of rotating speed of 10000r/min, under 40 DEG C of vacuum environments, dry 4h obtains Nano Silver.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (7)
1. be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that:
(1) shitosan is dissolved in the acetic acid solution of 3%, bath raio 1:50, ultrasonic 1-12h, add the sodium metaperiodate of 2-10g/L subsequently, and at 40-80 DEG C, lucifuge reaction 10-60min, cleans repeatedly by deionized water, centrifugal, dry for standby;
(2) according to certain volume ratio, by chitosan solution modified for certain density sodium metaperiodate, mix with certain density silver ammino solution, ultrasonic 1-10h under the temperature conditions of 20 DEG C-80 DEG C, obtain nano-class silver colloidal solution, repeatedly clean by ethanol and deionized water, centrifugal, obtain Nano Silver after dry process.
2. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, the volume ratio described in step 2 is 10:1-1:1.
3. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, the concentration of the modified chitosan solution described in step 2 is 0.01-100g/L.
4. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, the silver ammino solution described in step 2 is the complex compound that nitrate or silver sulfate and ammoniacal liquor are formed.
5. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, the concentration of silver ammino solution described in step 2 is 0.01-100g/L.
6. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, centrifugal described in step 2 is with the centrifugal 5-20min of the rotating speed of 8000-12000r/min.
7. according to claim 1 a kind of be the method that Nano Silver prepared by reducing agent with modification of chitosan, it is characterized in that, the drying process described in step 2 refers to and drying box temperature is set in 40 DEG C, dry 1-24h under the environment of vacuum.
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| CN201410565387.5A CN104289727B (en) | 2014-10-22 | 2014-10-22 | A kind of method preparing Nano Silver for reducing agent with modification of chitosan |
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| CN104289727B CN104289727B (en) | 2016-08-24 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815990A (en) * | 2015-04-20 | 2015-08-05 | 西安理工大学 | Method for preparing nanometer sliver colloid with liquid phase reduction method |
| CN105040436A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Finishing method of antibacterial cotton fabric |
| CN105040418A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Manufacture method of nano-gold antibacterial blended fabric |
| CN105040419A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Antibacterial cotton/cashmere/spun silk fabric |
| CN105131349A (en) * | 2015-08-22 | 2015-12-09 | 苏州正业昌智能科技有限公司 | Preparation method of graphene oxide-chitosan composite material |
| CN105442307A (en) * | 2015-12-16 | 2016-03-30 | 厦门大学 | Preparation method of nanosilver-supported antibiotic fibers |
| CN105478792A (en) * | 2015-12-05 | 2016-04-13 | 浙江大学 | Environment-friendly preparing method for modified chitosan-nano-silver sol |
| CN106215222A (en) * | 2016-07-07 | 2016-12-14 | 四川大学 | A kind of aoxidize oligochitosan crosslinked with collagen and method that in-situ preparation nanometer silver prepares antimicrobial form collagen |
| CN106513703A (en) * | 2016-11-22 | 2017-03-22 | 宁波工程学院 | Preparation method of chitosan Ag nano-composite film |
| CN109317692A (en) * | 2018-11-17 | 2019-02-12 | 璧典附 | One kind is using modified sugar as reducing agent and protectant nano silver and preparation method thereof |
| CN112371991A (en) * | 2020-09-09 | 2021-02-19 | 华南理工大学 | Succinylated chitosan coated monodisperse nano-silver particle and preparation method thereof |
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| CN105040436A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Finishing method of antibacterial cotton fabric |
| CN105040418A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Manufacture method of nano-gold antibacterial blended fabric |
| CN105040419A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Antibacterial cotton/cashmere/spun silk fabric |
| CN105131349A (en) * | 2015-08-22 | 2015-12-09 | 苏州正业昌智能科技有限公司 | Preparation method of graphene oxide-chitosan composite material |
| CN105478792A (en) * | 2015-12-05 | 2016-04-13 | 浙江大学 | Environment-friendly preparing method for modified chitosan-nano-silver sol |
| CN105442307A (en) * | 2015-12-16 | 2016-03-30 | 厦门大学 | Preparation method of nanosilver-supported antibiotic fibers |
| CN105442307B (en) * | 2015-12-16 | 2017-07-04 | 厦门大学 | A kind of preparation method of loading nano silvery anti-bacterial fibre |
| CN106215222B (en) * | 2016-07-07 | 2019-07-23 | 四川大学 | A method of oxidation chitosan oligosaccharide crosslinked with collagen and in-situ preparation nano silver preparation antibacterial Collagen Type VI |
| CN106215222A (en) * | 2016-07-07 | 2016-12-14 | 四川大学 | A kind of aoxidize oligochitosan crosslinked with collagen and method that in-situ preparation nanometer silver prepares antimicrobial form collagen |
| CN106513703A (en) * | 2016-11-22 | 2017-03-22 | 宁波工程学院 | Preparation method of chitosan Ag nano-composite film |
| CN106513703B (en) * | 2016-11-22 | 2018-05-15 | 宁波工程学院 | A kind of preparation method of chitosan Ag nano composite membranes |
| CN109317692A (en) * | 2018-11-17 | 2019-02-12 | 璧典附 | One kind is using modified sugar as reducing agent and protectant nano silver and preparation method thereof |
| CN112371991A (en) * | 2020-09-09 | 2021-02-19 | 华南理工大学 | Succinylated chitosan coated monodisperse nano-silver particle and preparation method thereof |
| CN114086405A (en) * | 2021-12-22 | 2022-02-25 | 中纺院（浙江）技术研究院有限公司 | Biological reducing agent and method for applying biological reducing agent to plant indigo dyed yarn |
| CN114086405B (en) * | 2021-12-22 | 2024-02-13 | 中纺院（浙江）技术研究院有限公司 | Biological reducing agent and method for applying biological reducing agent to plant indigo dyed yarns |
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