CN108047501A - Preparation method of nanogold-cellulose nano complex - Google Patents
Preparation method of nanogold-cellulose nano complex Download PDFInfo
- Publication number
- CN108047501A CN108047501A CN201711273751.0A CN201711273751A CN108047501A CN 108047501 A CN108047501 A CN 108047501A CN 201711273751 A CN201711273751 A CN 201711273751A CN 108047501 A CN108047501 A CN 108047501A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- nanogold
- nano complex
- gold
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 114
- 239000001913 cellulose Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052737 gold Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000004964 aerogel Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010276 construction Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 210000001525 retina Anatomy 0.000 claims abstract description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 19
- ZHLKXBJTJHRTTE-UHFFFAOYSA-N Chlorobenside Chemical compound C1=CC(Cl)=CC=C1CSC1=CC=C(Cl)C=C1 ZHLKXBJTJHRTTE-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000002045 lasting effect Effects 0.000 claims description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000006484 Paeonia officinalis Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- 229910020252 KAuCl4 Inorganic materials 0.000 claims description 2
- -1 N-methylmorpholine-N oxide monohydrates Chemical class 0.000 claims description 2
- 244000170916 Paeonia officinalis Species 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000004627 regenerated cellulose Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000006855 networking Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 abstract 1
- 229940005991 chloric acid Drugs 0.000 abstract 1
- 239000011664 nicotinic acid Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 46
- 239000000835 fiber Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- 238000002296 dynamic light scattering Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 241001189861 Candidatus Goldbacteria Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Chemical class 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000008112 carboxymethyl-cellulose Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003584 thiosemicarbazones Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/23—
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a preparation method of a nano gold-cellulose nano complex, which realizes the in-situ preparation of the nano gold-cellulose nano complex by utilizing the redox reaction between chloric acid or salt of gold and NMMO and through the physical and chemical combination action between the surface of generated nano gold particles and regenerated cellulose molecules. The preparation process is simple and easy to implement, the operation is convenient, the preparation technology is controllable, no pollution is caused, and the cost is low. The prepared nanogold-cellulose nano complex has high purity, uniform size and good dispersibility, can be used for preparing aerogel nano materials for catalysis and adsorption, or can be used as a support material to efficiently load living cells, and forms a sensitive electrochemical sensing network through nanogold networking, so that the nanogold-cellulose nano complex can be used as a biochemical sensing matrix and a tissue engineering support material for the construction and sensing of artificial tissues such as bionic retina and the like.
Description
Technical field
The present invention relates to a kind of nano complex material preparation method, more particularly to a kind of nano Au particle-cellulose is received
The preparation method of rice complex.
Background technology
In recent years, nano material opens new application approach, the different nanometer of a variety of compositions, structure in bioanalysis
Particle is widely used in electricity, optics and the micro sensing of biomolecule identification.In a variety of materials, biocompatibility is received
Rice corpuscles is optimal selection, has been used for constructing avirulent bionical interface using as timbering material.Gold is on nano-level
Most stable of noble metal, and with preferable electric conductivity, it is often more important that nanogold provides a unique chemism table
Face so that it is easy to combine with other chemical groups.There is certain bio-toxicity, but it is same when nanogold is used alone
Just have excellent biocompatibility after the natural polymers such as cellulose are compound, the nano complex of formation is as novel hybride
Material has a wide range of applications in biochemical sensitive and the fields such as tissue engineering bracket, it has also become the research hotspot of people.
Cellulose is a kind of biodegradable and nontoxic poly- as a kind of natural polysaccharides with unique molecular structure
Object is closed, can hydridization directly be carried out by own ether oxygen chain, hydroxyl isoreactivity group and nanogold, without using any connection agent
Hybrid material is can be formed directly in, is the catalytic activity of effective screen nano gold, prepares nanogold-fibre of high-biocompatibility
The plain nano complex of dimension provides great convenience.However, since cellulose is easily reunited due to intermolecular hydrogen bonding acts on, it is long
The feasible method for preparing nanogold-cellulose nano complex is lacked since phase always.For example, 2008, ShingoYokota
It is fine using the low polymerization degree being grafted by thiosemicarbazones being dissolved in N-methylmorpholine-N oxides (NMMO) Deng once trial
Dimension element carries out direct combination with nano Au particle, but since nano Au particle occurs to reunite and can not again disperse and fail
(Angew.Chem.,2008,120:10014~10017).At the same time, nanogold-cellulose composite material is ground in recent years
Study carefully and be subject to people's extensive concern, and certain progress is achieved in terms of the preparation approachs such as chemical synthesis, physical deposition.Such as：
2003, Junhui He etc. used the nanoaperture of porous cellulosic fiber that gold etc. has been prepared in situ as nanometer reaction vessel
The hybrid material of nano-noble metal and cellulose；2006, RamaRanjanBhattacharjee etc. passed through polystyrolsulfon acid
Nanogold of the surface with poly- ethylene methacrylic ether is connected into the aggregation of bigger by sodium and carboxymethyl cellulose salt；2008, Cai
Jie etc. prepares the regenerated fiber hydrogel with nano-pore structure using alkali/urea aqueous solvent, can be used as silver,
The reducing agent and carrier of the noble metals such as gold, platinum；Taiji Zhang etc. use bacteria cellulose nanofiber as biological mould
Using poly- Ethylenimine as reducing agent and crosslinking agent, a kind of novel nano gold-bacteria cellulose is prepared for by one-step method for plate
Nano-fiber composite material；2011, EdmondLam etc. was received by the carboxylation nanocrystalline cellulose surface deposition coated in PDDA
Meter Jin is prepared for a kind of hybrid material with preferable catalytic capability；Chinese invention patent ZL201110209029.7 uses nanometer
Noble metal colloidal sol is noble metal source, realizes nano-noble metal in regenerated cellulose film capable of being industrialized by irreversible diffusion process
Nano-noble metal-cellulose hybrid membrane of high surface enrichment is prepared in the self assembly on surface.
In conclusion the preparation of nanogold-cellulose composite material is mainly based on method of chemical treatment at present, with fiber
Cellulosic material is template and reactor, reduces gold compound using strong reductants such as Boratex, amine, obtained composite material has one
Fixed photoelectricity and catalytic performance.But for the preparation of nanogold-cellulose nano complex, it is necessary to realize that cellulose exists
Scattered and its on nano Au particle surface the assembling of its molecules in solution level coats.However, use the fibre under the conditions of water phase
Dimension cellulosic material can not prepare the nanogold with micro/nano-scale structure-cellulose nano complex for template and carrier, we
Need to find more suitably synthetic method and process route.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, solve nanogold and cellulosic molecule in cellulose solution
Controlled Complex Problem in situ, provides a kind of preparation method of nanogold-cellulose nano complex suitable for industrialized production.
The present invention is achieved by the following technical solutions：
A kind of preparation method of nanogold-cellulose nano complex, implements according to the following steps：
S1, cellulose solution is prepared：
At 90~100 DEG C, by cellulose dissolution in N-methylmorpholine-N oxide monohydrates (NMMOH2O in),
When persistently stirring 2~24 is small, until cellulose is completely dissolved, the two mass ratio is cellulose:NMMO·H2O=1:9~49；
The cellulose includes alpha-cellulose, microcrystalline cellulose, wood pulp cellulose, cotton pulp cellulose, straw pulp fiber
Element, bacteria cellulose etc.；Since alpha-cellulose degree of polymerization range of choice is big, bacteria cellulose good biocompatibility, preferably
Alpha-cellulose and bacteria cellulose；
A certain amount of dimethyl sulfoxide (DMSO) (DMSO) is added in into cellulose solution, is stirred and evenly mixed after being cooled to 70~80 DEG C,
Cellulose solution is obtained, 20~35 DEG C are cooled under lasting stirring；DMSO and NMMOH2O has good compatibility, and
It is miscible with water as a kind of good polar solvent of biocompatibility, is conducive to cellulosic molecule from its solution to water phase ring
The regeneration in border；
DMSO:The NMMOH of cellulose2Mass ratio=1~8 of O solution:4；
Preferably, above-mentioned steps carry out under inert gas shielding, it is preferred that carry out under nitrogen protection；
S2, the chloracid or salting liquid for preparing gold：
At 20~35 DEG C, the chloracid of a certain amount of gold or salt are dissolved in the DMSO solvents of certain volume, obtained yellow
The chloracid or salting liquid of the transparent gold of color；
The chloracid or salt of the gold include gold chloride (HAuCl4), potassium chloroaurate (KAuCl4), sodium chloraurate
(NaAuCl4), chlorauride (AuCl3) etc., preferably using gold chloride (HAuCl4)；
Preferably, golden chloracid or salt:Mass ratio=1~3 of DMSO:1000；
S3, nanogold-cellulose nano complex is prepared：
At 20~35 DEG C, the cellulose solution of preparation is added to the chloracid or salt of the lower gold of 500~2500rpm stirrings
In solution, persistently stir 2~12 it is small when after, yellow solution becomes dark red suspension, by suspension centrifuge removal liquid phase in
Peony precipitation is scattered in DMSO or deionized water, is used for ease of preserving, obtained most by unreacted chemical substance again
Final product is the liquid phase dispersion liquid for nanogold-cellulose nano complex that nanometer gold surface is coated with cellulose；
Preferably, peony precipitation is scattered in the DMSO or deionization with the chloracid of gold or the quality such as salting liquid again
In water；
Due to mixing speed directly affect nanogold generation size and cellulosic molecule nanometer gold surface cladding
Situation need to carry out under suitable high-speed stirred, it is preferred that by the cellulose solution of preparation be added to mixing speed for 1000~
Under 2000rpm in golden chloracid or salting liquid；
Preferably, mass ratio=1~2 of cellulose solution and DMSO in the chloracid or salting liquid of gold:10；
Preferably, when disperseing again, deionized water substitution DMSO solvents is selected, nanometer gold surface is obtained and is coated with fiber
The aqueous dispersion liquid of nanogold-cellulose nano complex of element；
Further, the airsetting glue material of nanogold-cellulose nano complex can be obtained by the processing such as centrifuging, drying
Material.
The method of the present invention is using the redox reaction occurred between the chloracid of gold or salt and NMMO, passes through generation
Nano Au particle surface is acted on the intermolecular physics of regenerated cellulose, chemical bond, realizes that nanogold-cellulose nanometer is answered
Fit is prepared in situ, and passes through the chloracid of gold or the regulation and control of salt and cellulose ratios, solves nanogold-cellulose nanometer
The physical property control technique problem such as surface potential of complex.
Nanogold-cellulose nano complex the average grain diameter prepared using the method for the present invention is 22~27nm, has table
The adjustable feature of face potential, Zeta gesture are about -28~5mV, the mass ratio of nanogold and cellulose in the nano complex of generation
About 1~9:10, while the hydrogen bond action based on cellulose cladding interlayer is, it can be achieved that nanogold-cellulose nano complex
Self assembly.Preparation process of the present invention is simple and practicable, easy to operate, technology of preparing is controllable, pollution-free, at low cost.Prepared receives
Meter Jin-cellulose nano complex purity height, size uniformity, good dispersion, the aeroge that can prepare to be catalyzed, adsorb are received
Rice material is used as timbering material high-efficient carrier active somatic cell, and passes through nanogold networking and form sensitive electrochemical sensing
Network, so as to be used for the construction and biography of the artificial organs such as bionical retina as biochemical sensitive matrix and tissue engineering bracket material
Sense.
Description of the drawings
Fig. 1 is transmission electron microscope photo (the Electronic Speculum model JEOL JEM of 1 nanogold of embodiment-cellulose nano complex
1200EX, electron energy 120keV), nano complex average grain diameter is about 22nm；
Fig. 2 is Zeta gesture distribution map (the dynamic light scattering model of 1 nanogold of embodiment-cellulose nano complex
Malvern ZetasizerNano-ZS), Zeta gesture is about -28.0mV；
Fig. 3 is transmission electron microscope photo (the Electronic Speculum model JEOL JEM of 2 nanogold of embodiment-cellulose nano complex
1200EX, electron energy 120keV), nano complex average grain diameter is about 27nm；
Fig. 4 is Zeta gesture distribution map (the dynamic light scattering model of 2 nanogold of embodiment-cellulose nano complex
Malvern ZetasizerNano-ZS), Zeta gesture is about -25.1mV；
Fig. 5 is transmission electron microscope photo (the Electronic Speculum model JEOL JEM of 3 nanogold of embodiment-cellulose nano complex
1200EX, electron energy 120keV), nano complex average grain diameter is about 25nm；
Fig. 6 is Zeta gesture distribution map (the dynamic light scattering model of 3 nanogold of embodiment-cellulose nano complex
Malvern ZetasizerNano-ZS), Zeta gesture is about 5.0mV；
Fig. 7 is the centrifugation of the liquid phase dispersion liquid of 1 nanogold of embodiment-cellulose nano complex through drying process
The aerogel material stereoscan photograph (Electronic Speculum model JEOL IT 300, electron energy 15keV) of acquisition；
Fig. 8 is the centrifugation of the liquid phase dispersion liquid of 2 nanogold of embodiment-cellulose nano complex through drying process
The aerogel material stereoscan photograph (Electronic Speculum model JEOL IT 300, electron energy 15keV) of acquisition；
Fig. 9 is the centrifugation of the liquid phase dispersion liquid of 3 nanogold of embodiment-cellulose nano complex through drying process
The aerogel material stereoscan photograph (Electronic Speculum model JEOL IT 300, electron energy 15keV) of acquisition.
Specific embodiment
The invention will be further described by the following examples, but protection domain is not restricted by the embodiments.This
It is outer that it is to be understood that after present disclosure has been read, those skilled in the art can make various modifications or changes to the present invention,
Such equivalent forms equally fall within the appended claims limited range of the present invention.
Embodiment 1
At 90 DEG C, 2g alpha-celluloses are added to 98g NMMOH2In O, persistently stir 2 it is small when after cellulose it is complete
Dissolving is cooled to addition 25g DMSO, constant temperature in 80 DEG C of backward cellulose solutions and stirs and evenly mixs, it is molten to obtain flaxen cellulose
Liquid is cooled to 35 DEG C under lasting stirring；At 35 DEG C, by the gold chloride (HAuCl of 3.75g4) be dissolved in 1250g DMSO solvents, it obtains
Obtain the chlorauric acid solution of yellow transparent；At 35 DEG C, 125g cellulose solutions are added rapidly to the gold chloride under 1000rpm stirrings
In solution, 2 it is small when after, generate dark red suspension, be scattered in again in 1250g DMSO after suspension is centrifuged, obtain nanometer
The DMSO dispersion liquids of gold-cellulose nano complex, the mass ratio of nanogold and cellulose is about in the nano complex of generation
9:10.Nanogold-cellulose nano complex is can be seen that because there is cellulose clad on surface from its transmission electron microscope photo, point
It is preferable to dissipate property；It is tested through dynamic light scattering, Zeta gesture is about -28.0mV.Nanogold-fibre is obtained by centrifugation, drying process
The aerogel material of the plain nano complex of dimension.
Embodiment 2
Under 95 DEG C, argon gas protection, 10g straw pulp celluloses are added to 90g NMMOH2In O, when persistently stirring 20 is small
Cellulose is completely dissolved afterwards, is cooled to addition 50g DMSO, constant temperature in 80 DEG C of backward cellulose solutions and is stirred and evenly mixed, obtain yellowish
The cellulose solution of color is cooled to 25 DEG C under lasting stirring；At 25 DEG C, by the sodium chloraurate (NaAuCl of 2g4) it is dissolved in 1000g
In DMSO solvents, the sodium chloraurate solution of yellow transparent is obtained；At 25 DEG C, 150g cellulose solutions are added rapidly to
In the sodium chloraurate solution of the lower 1L of 2000rpm stirrings, 8 it is small when after, generation dark red suspension, after suspension is centrifuged again
It is scattered in 1000g deionized waters, obtains the water phase aqueous dispersions of nanogold-cellulose nano complex, the nanometer of generation is answered
The mass ratio of nanogold and cellulose is about 1 in zoarium:10.Nanogold-cellulose is can be seen that from its transmission electron microscope photo
Nano complex is because there is cellulose clad on surface, and dispersiveness is preferably；Tested through dynamic light scattering, Zeta gesture about-
25.1mV.The aerogel material of nanogold-cellulose nano complex is obtained by centrifugation, drying process.
Embodiment 3
Under 100 DEG C, nitrogen protection, 8g bacteria celluloses are added to 92g NMMOH2In O, when persistently stirring 24 is small
Cellulose is completely dissolved afterwards, is cooled to addition 200g DMSO, constant temperature in 70 DEG C of backward cellulose solutions and is stirred and evenly mixed, obtain light
The cellulose solution of yellow is cooled to 20 DEG C under lasting stirring；At 20 DEG C, by the chlorauride (AuCl of 1.5g3) it is dissolved in 1500g
In DMSO solvents, the chlorogold solution of yellow transparent is obtained；At 20 DEG C, 300g cellulose solutions are added rapidly to 1500rpm
In the lower chlorogold solution of stirring, 12 it is small when after, generation red suspension is scattered in 1500g again after suspension is centrifuged
In DMSO, obtain the DMSO dispersion liquids of nanogold-cellulose nano complex, in the nano complex of generation nanogold with it is fine
The mass ratio of dimension element is about 1.6:10.Nanogold-cellulose nano complex is can be seen that because of table from its transmission electron microscope photo
There is cellulose clad in face, and dispersiveness is preferably；It is tested through dynamic light scattering, Zeta gesture is about 5.0mV.By centrifuging, drying
Processing obtains the aerogel material of nanogold-cellulose nano complex.
Claims (10)
1. a kind of preparation method of nanogold-cellulose nano complex, implements according to the following steps：
S1, cellulose solution is prepared：
At 90~100 DEG C, by cellulose dissolution in N-methylmorpholine-N oxide monohydrates (NMMOH2O in), persistently stir
Mix 2~24 it is small when, until cellulose is completely dissolved, the two mass ratio is:Cellulose:NMMO·H2O=1:9~49；
A certain amount of dimethyl sulfoxide (DMSO) (DMSO) is added in into cellulose solution, stirs and evenly mixs, obtains after being cooled to 70~80 DEG C
Cellulose solution is cooled to 20~35 DEG C under lasting stirring, wherein, DMSO:The NMMOH of cellulose2The mass ratio of O solution=
1~8:4；
S2, the chloracid or salting liquid for preparing gold：
At 20~35 DEG C, the chloracid of a certain amount of gold or salt are dissolved in the DMSO solvents of certain volume, golden chloracid
Or salt:Mass ratio=1~3 of DMSO:1000；
S3, nanogold-cellulose nano complex is prepared：
At 20~35 DEG C, the S1 cellulose solutions prepared are added to the chloride of the gold that under 500~2500rpm stirrings prepared by S2
Acid or salting liquid in, persistently stir 2~12 it is small when after, yellow solution becomes dark red suspension, by suspension centrifuge remove
Peony precipitation is scattered in DMSO or deionized water, obtains nanometer gold surface by unreacted chemical substance in liquid phase again
It is coated with the aqueous dispersion liquid of nanogold-cellulose nano complex of cellulose, the chloracid or salt of cellulose solution and gold
Mass ratio=1~2 of solution:10.
2. the preparation method of a kind of nanogold-cellulose nano complex according to claim 1, which is characterized in that described
Cellulose be alpha-cellulose or bacteria cellulose.
3. the preparation method of a kind of nanogold-cellulose nano complex according to claim 1, which is characterized in that described
Gold chloracid or salt include gold chloride (HAuCl4), potassium chloroaurate (KAuCl4), sodium chloraurate (NaAuCl4), chlorauride
(AuCl3)。
4. the preparation method of a kind of nanogold-cellulose nano complex according to claim 3, which is characterized in that described
Gold chloracid be gold chloride (HAuCl4)。
5. the preparation method of a kind of nanogold-cellulose nano complex according to claim 1, which is characterized in that S1 is walked
Suddenly carried out under inert gas shielding.
6. the preparation method of any one nanogold-cellulose nano complex according to claims 1 to 5, feature exist
In, in S3, by S1 prepare cellulose solution be added under high-speed stirred gold chloracid or salting liquid in, mixing speed is
1000~2000rpm.
7. the preparation method of any one nanogold-cellulose nano complex according to claims 1 to 5, feature exist
In in S3, dispersant selects DMSO or deionized water.
8. the preparation method of any one nanogold-cellulose nano complex according to claims 1 to 5, feature exist
In, S3 products are centrifuged, drying process obtain nanogold-cellulose nano complex aerogel material.
9. nanogold-cellulose nano complex prepared by any one method according to claims 1 to 5, feature exist
In nano complex average grain diameter is 22~27nm, and wherein the mass ratio of nanogold and cellulose is 1~9:10, there is surface
The adjustable feature of potential, Zeta gesture are -28~5mV.
10. nanogold-cellulose nano complex according to claim 9, which is characterized in that the complex is as biochemical
Sense construction and sensing of the matrix with tissue engineering bracket material for artificial organs such as bionical retinas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711273751.0A CN108047501B (en) | 2017-12-06 | 2017-12-06 | Preparation method of nanogold-cellulose nano complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711273751.0A CN108047501B (en) | 2017-12-06 | 2017-12-06 | Preparation method of nanogold-cellulose nano complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108047501A true CN108047501A (en) | 2018-05-18 |
| CN108047501B CN108047501B (en) | 2020-06-30 |
Family
ID=62121972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711273751.0A Active CN108047501B (en) | 2017-12-06 | 2017-12-06 | Preparation method of nanogold-cellulose nano complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108047501B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811664A (en) * | 2010-04-15 | 2010-08-25 | 北京林业大学 | Cellulose/silver nano composite material and preparation method thereof |
| CN102225470A (en) * | 2011-06-20 | 2011-10-26 | 江西农业大学 | Method for preparing gold nanoparticles based on environmentally-friendly chemical method |
| CN102352049A (en) * | 2011-07-25 | 2012-02-15 | 中国人民解放军国防科学技术大学 | Preparation method of noble metal nanoparticle-cellulose hybrid membrane |
| CN103131030A (en) * | 2013-03-14 | 2013-06-05 | 北京林业大学 | Cellulose/sliver/silver chloride composite material and preparation method thereof |
| CN103469542A (en) * | 2013-09-10 | 2013-12-25 | 中国纺织科学研究院 | Bacterial cellulose fiber containing nano-silver chloride particles and preparation method of fiber |
| CN105754136A (en) * | 2014-12-13 | 2016-07-13 | 广东轻工职业技术学院 | Antibacterial aerogel with cellulose loaded with nano silver and preparation method and application thereof |
| CN105970613A (en) * | 2016-06-24 | 2016-09-28 | 东华大学 | Method for preparing continuous cellulose/nano-metal aerogel fiber with catalytic performance from back-loaded nano-metal |
-
2017
- 2017-12-06 CN CN201711273751.0A patent/CN108047501B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811664A (en) * | 2010-04-15 | 2010-08-25 | 北京林业大学 | Cellulose/silver nano composite material and preparation method thereof |
| CN102225470A (en) * | 2011-06-20 | 2011-10-26 | 江西农业大学 | Method for preparing gold nanoparticles based on environmentally-friendly chemical method |
| CN102352049A (en) * | 2011-07-25 | 2012-02-15 | 中国人民解放军国防科学技术大学 | Preparation method of noble metal nanoparticle-cellulose hybrid membrane |
| CN103131030A (en) * | 2013-03-14 | 2013-06-05 | 北京林业大学 | Cellulose/sliver/silver chloride composite material and preparation method thereof |
| CN103469542A (en) * | 2013-09-10 | 2013-12-25 | 中国纺织科学研究院 | Bacterial cellulose fiber containing nano-silver chloride particles and preparation method of fiber |
| CN105754136A (en) * | 2014-12-13 | 2016-07-13 | 广东轻工职业技术学院 | Antibacterial aerogel with cellulose loaded with nano silver and preparation method and application thereof |
| CN105970613A (en) * | 2016-06-24 | 2016-09-28 | 东华大学 | Method for preparing continuous cellulose/nano-metal aerogel fiber with catalytic performance from back-loaded nano-metal |
Non-Patent Citations (1)
| Title |
|---|
| ZHIMING LIU等: "Self-Assembly of Electrically Conducting Biopolymer Thin Films by Cellulose Regeneration in Gold Nanoparticle Aqueous Dispersions", 《CHEM. MATER.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108047501B (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hebeish et al. | Carboxymethyl cellulose for green synthesis and stabilization of silver nanoparticles | |
| Lokanathan et al. | Cellulose nanocrystal-mediated synthesis of silver nanoparticles: Role of sulfate groups in nucleation phenomena | |
| Shi et al. | Preparation of starch-based nanoparticles through high-pressure homogenization and miniemulsion cross-linking: Influence of various process parameters on particle size and stability | |
| Zheng et al. | In situ synthesis of silver nanoparticles dispersed or wrapped by a Cordyceps sinensis exopolysaccharide in water and their catalytic activity | |
| CN101703915B (en) | Preparation method of conducting polyaniline-lignosulfonic acid composite hollow sphere | |
| CN103588886B (en) | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
| CN104525966B (en) | A kind of xanthan gum-argentum nano composite material and preparation method thereof | |
| CN110026568B (en) | Method for synthesizing medicinal dendritic nano gold particles by mediation of polyhydroxy natural products | |
| CN1810422A (en) | Prepn process of nanometer silver sol | |
| CN106832437A (en) | A kind of preparation method of silver-carrying nano cellulose chitosan complex film | |
| Fujii et al. | Preparation of cellulose/silver composite particles having a recyclable catalytic property | |
| CN101786168A (en) | Method for preparing flower-like nanometer gold | |
| CN108411401B (en) | Nano-selenium composite fiber and preparation method thereof | |
| CN106495225B (en) | A kind of polysaccharide hydridization manganese dioxide nano particle and its preparation method and purposes for magnetic resonance development | |
| Cieśla et al. | Effect of different conditions of synthesis on properties of silver nanoparticles stabilized by nanocellulose from carrot pomace | |
| Dolinska et al. | Noble metal nanoparticles in pectin matrix. Preparation, film formation, property analysis, and application in electrocatalysis | |
| CN108047501A (en) | Preparation method of nanogold-cellulose nano complex | |
| CN108246215A (en) | A kind of ultra-thin-wall chitosan microcapsules and preparation method thereof | |
| CN105838013B (en) | One kind is based on methyl vinyl ether maleic acid copolymer and the sensitive composite Nano gels of chitosan pH and preparation method thereof | |
| CN107324286A (en) | A kind of method of stable dispersion metal oxide nanoparticles in aqueous phase | |
| CN107755689B (en) | Bimetal nano particles containing Pt-Au and preparation method thereof | |
| CN105033281A (en) | Simple and environment-friendly preparation method for gold nanoparticle solution | |
| CN110064752A (en) | A kind of preparation method of mesoporous metal platinum nanosphere | |
| CN106916757B (en) | Single cell bio-based high-hydrophobicity micron powder material and preparation method thereof | |
| Shi et al. | Regulation of the micromorphology and performance of cellulose hydrogels by silk nanofibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |