CN115340130B - Large-batch continuous preparation method and equipment for nano metal oxide-amino acid molecular functional material - Google Patents
Large-batch continuous preparation method and equipment for nano metal oxide-amino acid molecular functional material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 40
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000001413 amino acids Chemical class 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001291 vacuum drying Methods 0.000 claims abstract description 16
- 239000012296 anti-solvent Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000008204 material by function Substances 0.000 claims abstract description 4
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 52
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- LCQLHJZYVOQKHU-VKHMYHEASA-N carglumic acid Chemical compound NC(=O)N[C@H](C(O)=O)CCC(O)=O LCQLHJZYVOQKHU-VKHMYHEASA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008827 biological function Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 26
- 238000003860 storage Methods 0.000 description 26
- 229910052725 zinc Inorganic materials 0.000 description 26
- 238000000703 high-speed centrifugation Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 230000002792 vascular Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229960003180 glutathione Drugs 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 206010006187 Breast cancer Diseases 0.000 description 3
- 208000026310 Breast neoplasm Diseases 0.000 description 3
- 108010024636 Glutathione Proteins 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 210000002919 epithelial cell Anatomy 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 210000004881 tumor cell Anatomy 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000001575 pathological effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical group OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention provides a method for continuously preparing nano metal oxide-amino acid molecular functional materials in a large batch, which comprises the following steps: adding the metal salt solution and the alkali solution into a reaction tank by a syringe pump according to a specific feeding speed and a specific molar ratio for mixed reaction, and injecting an amino acid molecule solution at the end of the reaction to generate nano metal oxide-amino acid molecule dispersion; the nanometer metal oxide-amino acid molecular functional material is obtained after antisolvent precipitation, high-speed centrifugal separation, solvent cleaning and vacuum drying. The nano metal oxide-amino acid molecular functional material prepared by the method has uniform size, breaks through the bottleneck of batch preparation of metal oxide nano particles below 20nm at present, has simple and stable process, and can realize continuous preparation. The synthesized nano material has good dispersibility and stability in deionized water, is endowed with corresponding physical and chemical properties or biological functions, and has wide application prospect in the biological field.
Description
Technical Field
The invention relates to the field of metal oxide preparation, in particular to a method and equipment for continuously preparing multifunctional composite materials in large batches by connecting nano metal oxide with amino acid molecules.
Background
The nano metal oxide is a novel multifunctional inorganic semiconductor nano material and has better thermal stability and chemical stability. The nano material has large surface area and high surface activity, and is widely applied to various fields of optics, gas sensitivity, catalysis, biological medicine and the like. In addition, the nano metal oxide has higher biocompatibility, low toxicity to organisms and simultaneously has antibacterial property, so that the nano metal oxide has wide prospect in the biological field.
Although metal oxides are widely used in many research fields, pure nano-metal oxides have limited use and suitability in practical biological applications. Therefore, how to develop and utilize the nano metal oxide material and further widen the application of the nano metal oxide material on organisms is a considerable problem. Studies have shown that: selectively attaching amino acid molecules with different functions to the nanoparticles will confer a richer variety of properties and possibilities to the nano-metal oxide, such as improving organism function, treating cancer, vascular regulation, pathological defenses, etc. However, the related technology of realizing the combination of amino acid molecules and nano metal oxides in batch has not yet realized breakthrough. In addition, although many methods for synthesizing nano metal oxides are currently available, high yield and uniform small scale are difficult to achieve, and the size effect of nano metal oxides determines the application area of nano metal oxides. The method for preparing the nano metal oxide smaller than 20nm in large batch still is not favorable for large-scale application and industrialization. In conclusion, the synthesis method for developing the material system which has the advantages of simple process, small and uniform scale and good dispersibility, and can continuously prepare and produce a large number of nano metal oxide-amino acid molecules has wide application prospect.
Disclosure of Invention
The invention aims to provide a large-batch continuous preparation technology of nano metal oxide-amino acid molecular functional materials, aiming at the defects of the prior art, so as to realize large-batch pipelined preparation of nano metal oxide-amino acid molecular composite materials with the particle size smaller than 20nm, uniform size, good stability and good dispersibility.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a method for continuously preparing nano metal oxide-amino acid molecular functional materials in large batch comprises the following steps:
(1) Injecting the salt solution and the alkali solution into the reaction tank at a specific speed by using a syringe pump respectively, mixing, and carrying out heat preservation and stirring reaction. And after cooling, injecting the amino acid molecule solution into a reaction tank to obtain nano metal oxide particle dispersion liquid with the amino acid molecules attached to the surface. Wherein the injection speed of the salt solution and the alkali solution is respectively 80-3000 ml/h, and the mol ratio of the added amino acid molecules to the salt is not less than 0.025;
(2) Adding an antisolvent into the product obtained in the step (1), performing solid-liquid separation through high-speed centrifugation, washing with a cleaning solution for multiple times, redispersing, performing high-speed centrifugation, and performing vacuum drying to obtain the nano metal oxide-amino acid molecular functional material.
Further, when the nano metal oxide is nano zinc oxide, the molar ratio of the salt to the alkali injected into the reaction tank in the step (1) is 0.25-0.75.
Further, when the nano metal oxide is nano ferroferric oxide, the molar ratio of the salt to the alkali injected into the reaction tank in the step (1) is 0.14-0.16.
Further, when the nano metal oxide is nano copper oxide, the molar ratio of the salt to the alkali injected into the reaction tank in the step (1) is 0.375-0.7.
Further, the molecular species of the amino acid in the step (1) is selected from one of gamma-aminobutyric acid, N-carbamylglutamic acid and glutathione.
Further, the high-speed centrifugal rotating speed in the step (2) is not lower than 8000rpm, the cleaning liquid is deionized water, and the vacuum drying temperature is 50-100 ℃.
According to one embodiment of the method, the nano zinc oxide-amino acid molecular functional material can be continuously prepared in batches. In this embodiment, the solvent of the salt solution in the step (1) is dimethyl sulfoxide, the salt is zinc acetate dihydrate, the solvent of the alkali solution is ethanol, and the alkali is tetramethyl ammonium hydroxide. The antisolvent in the step (2) is one of heptane and n-hexane. The injection speed ratio of the salt solution to the alkali solution in the step (1) is 3:2, the molar ratio of the salt to the alkali is 0.25-0.75, and the molar ratio of the amino acid molecules to the theoretical yield of the nano metal oxide is 0.025-0.07.
According to one embodiment of the method, the nano ferroferric oxide-amino acid molecular functional material can be continuously prepared in batches. In this embodiment, the solvent of the salt solution in the step (1) is deionized water, the salt is a mixture of ferric chloride hexahydrate and ferrous chloride tetrahydrate, the solvent of the alkaline solution is deionized water, and the alkaline is sodium hydroxide. The antisolvent in the step (2) is deionized water. The injection speed ratio of the salt solution to the alkali solution in the step (1) is 3:2, the molar ratio of the salt to the alkali is 0.14-0.16, the molar ratio of the iron ions to the ferrous ions is 2, and the molar ratio of the amino acid molecules to the theoretical yield of the nano metal oxide is 0.03-0.045. The reaction temperature of the reaction tank in the step (1) is 80 ℃, and nitrogen is blown in.
According to one embodiment of the method, the nano copper oxide-amino acid molecular functional material can be continuously prepared in batches. In this embodiment, the antisolvent in step (2) is deionized water. The injection speed ratio of the salt solution to the alkali solution in the step (1) is 20:3, the molar ratio of the salt to the alkali is 0.375-0.7, and the molar ratio of the amino acid molecules to the theoretical yield of the nano metal oxide is 0.025-0.03. And (3) adding glacial acetic acid into the salt solution in the step (1), wherein the volume ratio of the glacial acetic acid to the salt solution solvent is 1:300, and the temperature of the reaction tank is 105-110 ℃.
In addition, the equipment is characterized in that a salt solution storage tank is connected with a reaction tank through a salt solution injection pump, an alkali solution storage tank is connected with the reaction tank through an alkali solution injection pump, an amino acid molecule solution storage tank is connected with the reaction tank through an amino acid molecule solution injection pump, the reaction tank is connected with a mixing tank through a pipeline, an antisolvent storage tank is connected with the mixing tank through an antisolvent injection pump, the mixing tank is connected with a high-speed centrifuge through a pipeline, the high-speed centrifuge is connected with an ultrasonic cleaning tank through a bi-directional inlet and outlet pipeline, the cleaning solution storage tank is connected with the ultrasonic cleaning tank through the cleaning solution injection pump, the high-speed centrifuge is connected with a vacuum drying box through a conveying track, and the vacuum drying box is connected with a product collecting device through the conveying track.
The invention has the beneficial effects that:
(1) Realizing the precise control of the particle size of the nano metal oxide. Through comprehensive investigation of molecular dynamics and reaction dynamics, continuous improvement and promotion of molecular collision on a microscopic scale are realized, and optimal feeding speeds and molar ratios of a metal salt solution and an alkali solution in a reaction tank are found out, so that the particle size of the nano metal oxide is controlled below 20nm, and the dimension is uniform under microscopic characterization.
(2) The problem of quality degradation after the batch amplification is solved. By adjusting the feeding mode, the feeding proportion and the speed, the influence of the amplification factors on the material property is reduced, and the fine control of the size can be realized at the same time even under the condition of larger reaction quantity.
(3) Can realize the preparation of various metal oxide materials. The invention can simultaneously realize the synthesis of several different nano metal oxides, including zinc oxide, ferroferric oxide and copper oxide, and can be further extended to other metal oxide materials. In addition, a plurality of metal salt solutions can be added simultaneously, so that the composite preparation of a plurality of metal oxides is realized, and the method has rich operability.
(4) The one-step method compounding of the amino acid and the nano metal oxide is successfully realized. Amino acid molecules are added at the end of the reaction of the metal oxide, and the combination of the amino acid and the metal oxide is realized by a one-step method, so that the nano metal oxide-amino acid molecular material with good dispersibility and small size is prepared in a large scale, has excellent dispersibility, can be kept dispersed in solvents such as water for a long time, and can be directly applied to the fields of biomedical use, cosmetics, textile additives and the like.
(5) The preparation and production method disclosed by the invention has the advantages of high automation degree, reduced manpower, improved production efficiency and simplicity and convenience. All links adopt the existing mature equipment, the manufacturing difficulty is low, and the design and purchasing cost can be saved.
Drawings
The technical scheme and the invention content of the embodiment of the invention can be better illustrated and shown by the following drawings. The drawings that are involved in the description of the embodiments will be briefly described as follows. Wherein:
FIG. 1 is a schematic diagram of a nano metal oxide-amino acid molecular functional material. Wherein, 1 is a salt solution storage tank, 2 is an alkali solution storage tank, 3 is a salt solution injection pump, 4 is an alkali solution injection pump, 5 is a reaction tank, 6 is an amino acid molecule solution storage tank, 7 is an amino acid molecule solution injection pump, 8 is a mixing tank, 9 is an antisolvent storage tank, 10 is an antisolvent injection pump, 11 is a high-speed centrifuge, 12 is a cleaning solution storage tank, 13 is a cleaning solution injection pump, 14 is an ultrasonic cleaning tank, 15 is a vacuum drying box, and 16 is a product collecting device.
Fig. 2 is a transmission electron microscope image of nano zinc oxide prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of nano zinc oxide prepared in example 1 of the present invention.
FIG. 4 is a thermogravimetric curve of the nano zinc oxide-GABA material prepared in example 1 of the present invention.
FIG. 5 is a thermogravimetric curve of the nano zinc oxide-NCG material prepared in example 2 of the present invention.
FIG. 6 is a photograph of a sterilization test of the nano zinc oxide-GABA material prepared in example 1 of the present invention.
FIG. 7 shows the results of tumor treatment and vascular stability test of the nano zinc oxide-GABA material prepared in example 1 of the present invention.
Detailed Description
In order to make the above objects, features and advantages of the present invention more comprehensible, embodiments accompanied with specific examples of the present invention are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but those skilled in the art will be able to make similar changes and modifications without departing from the spirit of the invention and will be able to fall within the scope of the invention, therefore the invention is not limited to the specific embodiments disclosed below.
Example 1
Preparing a nano zinc oxide-amino acid molecule (ZnO-GABA) functional material:
(1) The alkali solution storage tank was charged with tetramethylammonium hydroxide (C) at a concentration of 0.914mol/L and a volume of 105ml 4 H 13 NO) solution, wherein the solvent is a mixed solvent of ethanol and water (volume ratio is 2:1); the salt solution storage tank is filled with the salt solution with the concentration of 0.478moL/L, 150mL zinc acetate ((CH) 3 COO) 2 Zn) solution, the solvent is dimethyl sulfoxide. Injecting the salt solution into the reaction tank at the speed of 120ml/h, injecting the alkali solution into the reaction tank at the speed of 80ml/h, and carrying out heat preservation and stirring for 21h. After cooling, 50mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.1mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours, so as to obtain nano zinc oxide dispersion liquid with amino acid molecules attached to the surface.
(2) And (3) adding heptane with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation through high-speed centrifugation at 8000rpm, washing with water for multiple times, redispersing, performing high-speed centrifugal separation at 11000rpm, and performing vacuum drying at 80 ℃ to obtain the nano zinc oxide-amino acid molecular functional material.
Fig. 1 shows an apparatus used in this embodiment. The obtained nano zinc oxide-amino acid molecular functional material is named as ZnO-GABA, the microscopic morphology of the nano zinc oxide-amino acid molecular functional material is shown in figure 2, the nano zinc oxide-amino acid molecular functional material can be seen under a transmission electron microscope, the size of the nano zinc oxide-amino acid molecular functional material is between 12 and 20nm, and the nano zinc oxide-amino acid molecular functional material maintains high uniformity. FIG. 3 is an X-ray diffraction curve of ZnO-GABA, and a comparison standard spectrum can find that the ZnO-GABA has a standard ZnO characteristic peak, and the ZnO-GABA has good crystallinity. FIG. 4 is a graph of thermal weight loss of ZnO-GABA, from which the weight fraction of amino acids in the material can be calculated. The first step of weight loss (-112.31 ℃) belongs to the removal of crystal water and adsorbed water, and the weight loss rate at the stage is 1.320%; the second stage (112.31-401.24 ℃) belongs to the removal of amino and carboxyl, and the weight loss rate of the second stage is 2.563%; the third stage (401.24-DEG C) belongs to complete thermal oxygen degradation of the remainder, and the weight loss rate of the stage is 0.5818%. Thus, GABA carried on the nano zinc oxide was calculated to be 318. Mu. Mol/g.
FIG. 6 shows the results of the sterilization performance test of ZnO-GABA prepared in this example, the bacteria to be tested were Staphylococcus aureus, no additives were added to the blank culture dish, and nano zinc oxide-GABA was added to the test culture dish. By comparison, it is easy to find that the colony in the experimental group added with nano zinc oxide-GABA after 8 hours of culture is obviously reduced compared with the blank group; and the sterilization capability is obviously enhanced along with the increase of the concentration of the composite material.
FIG. 7 is a graph showing tumor treatment and vascular stability test of ZnO-GABA prepared in this example. Two cells were co-cultured, where HUVEC was vascular epithelial cells and MCF7 was breast cancer cells. The ordinate in the figure shows the ratio of the number of vascular epithelial cells to the number of breast cancer cells (HUVEC/MCF 7), and the abscissa shows the culture time, and the higher the ratio means the stronger the ability to destroy tumor cells and promote vascular stability. Meaning of symbols on the figure: wherein "Con" is a blank group, "GABA" is a free gamma-aminobutyric acid treatment group of 10. Mu.M, "ZnO" is a nano zinc oxide treatment group of 10. Mu.M, "nNO10" is a ZnO-GABA treatment group of 10. Mu.M, "nNO5" is a ZnO-GABA treatment group of 5. Mu.M, "nNO3" is a ZnO-GABA treatment group of 3. Mu.M, "nNO1" is a ZnO-GABA treatment group of 1. Mu.M, and "nNO0.1" is a ZnO-GABA treatment group of 0.1. Mu.M. In fig. 7, it can be seen that the ratio of the number of vascular epithelial cells to the number of breast cancer cells is gradually increased along with the increase of the concentration of ZnO-GABA, and is significantly higher than that of gamma-aminobutyric acid and nano zinc oxide, so that the composite functional material has excellent capabilities of inactivating tumor cells and promoting vascular stabilization.
Example 2
Preparing a nano zinc oxide-amino acid molecule (ZnO-NCG) functional material:
(1) The alkali solution storage tank was charged with tetramethylammonium hydroxide (C) at a concentration of 0.914mol/L and a volume of 105ml 4 H 13 NO) solution, wherein the solvent is a mixed solvent of ethanol and water (volume ratio is 2:1); a salt solution storage tank was charged with zinc acetate ((CH) at a concentration of 0.478mol/L and a volume of 150mL 3 COO) 2 Zn) solution, the solvent is dimethyl sulfoxide. Injecting the salt solution into the reaction tank at the speed of 120ml/h, injecting the alkali solution into the reaction tank at the speed of 80ml/h, and carrying out heat preservation and stirring for 21h. After cooling, 50mL of N-carbamylglutamic acid (NCG) solution with the concentration of 0.1mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours, so as to obtain nano zinc oxide dispersion liquid with amino acid molecules attached to the surface.
(2) And (3) adding heptane with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation through high-speed centrifugation at 8000rpm, washing with water for multiple times, redispersing, performing high-speed centrifugal separation at 11000rpm, and performing vacuum drying at 80 ℃ to obtain the nano zinc oxide-amino acid molecular functional material.
The obtained nano zinc oxide-amino acid molecular functional material is named ZnO-NCG, and the size is between 10 and 18nm and high uniformity is maintained through observation by a transmission electron microscope. FIG. 5 shows the thermal weight loss curve of ZnO-NCG, and it was found that the NCG supported on nano zinc oxide was 357.5. Mu. Mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 3
Preparing a nano zinc oxide-amino acid molecule (ZnO-GABA) functional material:
(1) The alkali solution storage tank was charged with tetramethylammonium hydroxide (C) at a concentration of 0.9mol/L and a volume of 160ml 4 H 13 NO) solution, wherein the solvent is a mixed solvent of ethanol and water (volume ratio is 2:1); a salt solution storage tank was charged with zinc acetate ((CH) at a concentration of 0.478mol/L and a volume of 200mL 3 COO) 2 Zn) solution, the solvent is dimethyl sulfoxide. Injecting salt solution into the reaction tank at the speed of 150ml/h, injecting alkali solution into the reaction tank at the speed of 100ml/h, and carrying out heat preservation and stirring reaction for 21h. After cooling, 100mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.024mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours, so as to obtain nano zinc oxide dispersion liquid with amino acid molecules attached to the surface.
(2) Adding n-hexane with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for multiple times, redispersing, performing high-speed centrifugation at 11000rpm, and vacuum drying at 80 ℃ to obtain the nano zinc oxide-amino acid molecular functional material.
The obtained nano zinc oxide-amino acid molecular functional material is named ZnO-GABA, and has the size of 12-19 nm and high uniformity after being observed by a transmission electron microscope. GABA supported on the nano zinc oxide was 153.4. Mu. Mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 4
Preparing a nano zinc oxide-amino acid molecule (ZnO-GABA) functional material:
(1) Filling the alkali solution storage tank with concentrationTetramethyl ammonium hydroxide (C) in a volume of 4300ml at 0.806mol/L 4 H 13 NO) solution, wherein the solvent is a mixed solvent of ethanol and water (volume ratio is 2:1); a salt solution storage tank was charged with zinc acetate ((CH) at a concentration of 0.52mol/L and a volume of 4000mL 3 COO) 2 Zn) solution, the solvent is dimethyl sulfoxide. Injecting salt solution into the reaction tank at a speed of 3000ml/h, injecting alkali solution into the reaction tank at a speed of 2000ml/h, and reacting for 20h under heat preservation and stirring. After cooling, 2000mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.052mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours to obtain nano zinc oxide dispersion liquid with amino acid molecules attached to the surface.
(2) Adding n-hexane with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for multiple times, redispersing, performing high-speed centrifugation at 11000rpm, and vacuum drying at 80 ℃ to obtain the nano zinc oxide-amino acid molecular functional material.
The obtained nano zinc oxide-amino acid molecular functional material is named ZnO-GABA, and the size of the nano zinc oxide-amino acid molecular functional material is between 12 and 20nm and keeps high uniformity through observation by a transmission electron microscope. GABA supported on the nano zinc oxide was 304.7. Mu. Mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 5
Preparing a nano copper oxide-amino acid molecule (CuO-GABA) functional material:
(1) Filling sodium hydroxide solution with the concentration of 6.6mol/L and the volume of 350ml into an alkali solution storage tank, wherein the solvent is deionized water; a salt solution storage tank is filled with a copper acetate monohydrate solution with the concentration of 0.52mol/L and the volume of 3100mL, and the solvent is deionized water. The salt solution was injected into the reaction tank at a rate of 2000ml/h, the alkali solution was injected into the reaction tank at a rate of 300ml/h, and the reaction was stirred at 105℃for 2 hours. After cooling, 2015mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.02mol/L is injected into the reaction tank, and stirred for 3 hours to obtain nano copper oxide dispersion with amino acid molecules attached to the surface.
(2) Adding deionized water with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for many times, redispersing, performing high-speed centrifugation at 11000rpm, and performing vacuum drying at 50 ℃ to obtain the nano copper oxide-amino acid molecular functional material.
The obtained nano zinc oxide-amino acid molecular functional material is named as CuO-GABA, and the size of the nano zinc oxide-amino acid molecular functional material is between 10 and 17nm and keeps high uniformity through observation by a transmission electron microscope. GABA supported on the nano copper oxide was 127.2. Mu. Mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 6
Preparing a nano copper oxide-amino acid molecule (CuO-glutathione) functional material:
(1) Filling sodium hydroxide solution with the concentration of 8mol/L and the volume of 400ml into an alkali solution storage tank, wherein the solvent is deionized water; a salt solution storage tank was charged with a copper acetate monohydrate aqueous solution having a concentration of 0.2mol/L and a volume of 600mL, and 2mL of glacial acetic acid was added. The salt solution is injected into the reaction tank at the speed of 1000ml/h, the alkali solution is injected into the reaction tank at the speed of 150ml/h, and the reaction is stirred for 3h at 110 ℃. After cooling, 37mL of glutathione solution with the concentration of 0.1mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours to obtain nano copper oxide dispersion liquid with the surface attached with amino acid molecules.
(2) Adding deionized water with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for many times, redispersing, performing high-speed centrifugation at 11000rpm, and vacuum drying at 80 ℃ to obtain the nano copper oxide-amino acid molecular functional material.
The obtained nano copper oxide-amino acid molecular functional material is named as CuO-glutathione, and the size of the nano copper oxide-amino acid molecular functional material is between 11 and 18nm and keeps high uniformity through observation by a transmission electron microscope. The glutathione loaded on the nano copper oxide is 143.9 mu mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 7
Preparation of nano-tetraoxideIron-amino acid molecule (Fe 3 O 4 -GABA) functional material:
(1) Filling sodium hydroxide solution with the concentration of 1.15mol/L and the volume of 500ml into an alkali solution storage tank, wherein the solvent is deionized water; a salt solution storage tank is filled with ferric chloride hexahydrate solution with the concentration of 1mol/L and the volume of 40mL and ferrous chloride tetrahydrate solution with the concentration of 1mol/L and the volume of 20mL, and the solvent is deionized water. Injecting the alkaline solution into a reaction tank at the temperature of 80 ℃ with nitrogen bubbling at the speed of 200ml/h, injecting the salt solution into a reaction tank at the temperature of 80 ℃ with nitrogen bubbling at the speed of 300ml/h, and stirring for reaction for 3h. After cooling, 36mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.1mol/L is injected into the reaction tank, and the mixture is stirred for 3 hours to obtain nano ferroferric oxide dispersion liquid with amino acid molecules attached to the surface.
(2) Adding deionized water with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for many times, redispersing, performing high-speed centrifugation at 11000rpm, and vacuum drying at 80 ℃ to obtain the nano ferroferric oxide-amino acid molecular functional material.
The obtained nano ferroferric oxide-amino acid molecular functional material is named as Fe 3 O 4 GABA, observed by transmission electron microscopy, has a size between 11 and 18nm and maintains a high degree of uniformity. Gamma-aminobutyric acid loaded on nano ferroferric oxide is 192 mu mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Example 8
Preparation of nano ferroferric oxide-amino acid molecules (Fe 3 O 4 -GABA) functional material:
(1) Filling sodium hydroxide solution with the concentration of 1.5mol/L and the volume of 2000ml into an alkali solution storage tank, wherein the solvent is deionized water; a salt solution storage tank is filled with ferric chloride hexahydrate solution with the concentration of 1.2mol/L and the volume of 200mL, and ferrous chloride tetrahydrate solution with the volume of 1mol/L and the volume of 120mL, wherein the solvent is deionized water. The alkaline solution is injected into a reaction tank with nitrogen bubbling at the temperature of 80 ℃ at the speed of 420ml/h, the salt solution is injected into the reaction tank with nitrogen bubbling at the temperature of 80 ℃ at the speed of 630ml/h, and the reaction is carried out for 5h with stirring at the temperature. After cooling, 180mL of gamma-aminobutyric acid (GABA) solution with the concentration of 0.1mol/L is injected into the reaction tank, and stirring is carried out for 4 hours, thus obtaining nano ferroferric oxide dispersion liquid with amino acid molecules attached to the surface.
(2) Adding deionized water with the same volume into the product obtained in the step (1), mixing and precipitating, performing solid-liquid separation by high-speed centrifugation at 8000rpm, washing with water for many times, redispersing, performing high-speed centrifugation at 11000rpm, and vacuum drying at 100 ℃ to obtain the nano ferroferric oxide-amino acid molecular functional material.
The obtained nano copper oxide-amino acid molecular functional material is named as Fe 3 O 4 GABA, observed by transmission electron microscopy, has a size between 13 and 19nm and maintains a high degree of uniformity. Gamma-aminobutyric acid loaded on nano ferroferric oxide is 167.5 mu mol/g. The material has excellent dispersibility, can be dispersed in water for a long time, and has a bacteriostasis rate of more than 90% for various bacteria.
Claims (2)
1. A method for continuously preparing nano metal oxide-amino acid molecular functional materials in large batch is characterized by comprising the following steps:
(1) Respectively injecting a salt solution and an alkali solution into a reaction tank at a specific speed for mixing, and carrying out heat preservation and stirring reaction; after cooling, injecting the amino acid molecule solution into a reaction tank to obtain nano metal oxide particle dispersion liquid with the amino acid molecules attached to the surface; wherein the injection speed of the salt solution and the alkali solution is respectively 80-3000 ml/h, and the mol ratio of the added amino acid molecules to the salt is not less than 0.025; the amino acid molecular species is selected from one of gamma-aminobutyric acid, N-carbamylglutamic acid and glutathione; the mol ratio of the salt to the alkali injected into the reaction tank is 0.25-0.75; the solvent of the salt solution is dimethyl sulfoxide, the salt is zinc acetate, the solvent of the alkali solution is a mixed solvent of ethanol and water, and the alkali is tetramethyl ammonium hydroxide; wherein, the injection speed ratio of the salt solution to the alkali solution is 3:2, the mol ratio of the salt to the alkali is 0.25-0.75, and the mol ratio of the amino acid molecule to the salt is 0.025-0.07;
(2) Adding the anti-solvent with the same volume into the product obtained in the step (1), centrifugally washing, and vacuum drying to obtain the nano metal oxide-amino acid molecular functional material; the antisolvent is one of heptane and n-hexane; the nano metal oxide is nano zinc oxide.
2. The method according to claim 1, wherein the centrifugal speed in the step (2) is not lower than 8000rpm, the cleaning liquid is deionized water, and the vacuum drying temperature is 50-100 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101693011A (en) * | 2009-08-13 | 2010-04-14 | 苏州纳米技术与纳米仿生研究所 | Preparation method of magnetic medicine-carrying nano-particle |
| US20140262811A1 (en) * | 2013-03-12 | 2014-09-18 | Ut-Battelle, Llc | Controllable reductive method for synthesizing metal-containing particles |
| CN104140141A (en) * | 2014-07-30 | 2014-11-12 | 中国科学院新疆理化技术研究所 | Composite magnetic micro-nano particle decorated on surface of amino acid and preparation method and application thereof |
| CN109110796A (en) * | 2018-08-30 | 2019-01-01 | 湖北大学 | A kind of water dispersible oxide copper nanometer tube and its colloidal solution and preparation method |
| CN114394614A (en) * | 2021-12-14 | 2022-04-26 | 浙江臻纳科技有限公司 | Zinc oxide compound, preparation method and quantum dot light-emitting diode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101693011A (en) * | 2009-08-13 | 2010-04-14 | 苏州纳米技术与纳米仿生研究所 | Preparation method of magnetic medicine-carrying nano-particle |
| US20140262811A1 (en) * | 2013-03-12 | 2014-09-18 | Ut-Battelle, Llc | Controllable reductive method for synthesizing metal-containing particles |
| CN104140141A (en) * | 2014-07-30 | 2014-11-12 | 中国科学院新疆理化技术研究所 | Composite magnetic micro-nano particle decorated on surface of amino acid and preparation method and application thereof |
| CN109110796A (en) * | 2018-08-30 | 2019-01-01 | 湖北大学 | A kind of water dispersible oxide copper nanometer tube and its colloidal solution and preparation method |
| CN114394614A (en) * | 2021-12-14 | 2022-04-26 | 浙江臻纳科技有限公司 | Zinc oxide compound, preparation method and quantum dot light-emitting diode |
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