CN109530718B - Preparation method of flower-shaped gold nanowire composite nanoparticles - Google Patents

Preparation method of flower-shaped gold nanowire composite nanoparticles Download PDF

Info

Publication number
CN109530718B
CN109530718B CN201811490724.3A CN201811490724A CN109530718B CN 109530718 B CN109530718 B CN 109530718B CN 201811490724 A CN201811490724 A CN 201811490724A CN 109530718 B CN109530718 B CN 109530718B
Authority
CN
China
Prior art keywords
gold
nano
sio
flower
solution
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.)
Active
Application number
CN201811490724.3A
Other languages
Chinese (zh)
Other versions
CN109530718A (en
Inventor
刘振中
徐鑫磊
应佳蕾
陈虹宇
谭文军
马春新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Research Institute of Zhejiang University Taizhou
Original Assignee
Research Institute of Zhejiang University Taizhou
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Research Institute of Zhejiang University Taizhou filed Critical Research Institute of Zhejiang University Taizhou
Priority to CN201811490724.3A priority Critical patent/CN109530718B/en
Publication of CN109530718A publication Critical patent/CN109530718A/en
Application granted granted Critical
Publication of CN109530718B publication Critical patent/CN109530718B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a flower-shaped gold nano-meterThe preparation method of the linear composite nano particle uses the colloidal nano particle Au @ SiO 2 The gold nanowire growth process is regulated and controlled by controlling parameters such as ligand types, reaction proportion, reaction time and the like as a template, so that a series of flower-shaped structure gold nanowire composite materials with different appearances are obtained. The material structure comprises Au @ SiO 2 The core and the gold nanowires radiating outwards form a flower-shaped micro-nano structure. The method has the advantages of low cost, simple experimental operation, short product preparation period and good repeatability, can prepare uniform flower-shaped gold nanowire composite nanoparticles, and provides a feasible technical route for preparing gold nanocomposite through a macromolecular ligand.

Description

Preparation method of flower-shaped gold nanowire composite nanoparticles
Technical Field
The invention relates to a preparation method of flower-shaped gold nanowire composite nanoparticles, belonging to the technical field of nano materials.
Background
The gold nano material has unique physical and chemical properties, has potential application in the fields of drug delivery, catalysis, electrode modification, drug analysis and the like, and is widely concerned by researchers. Research shows that some characteristics of the gold nano material are closely related to the shape and the size of the gold nano material, so that the specific structure and the shape of the gold nano material can be effectively controlled to obtain new physical and chemical properties.
Compared with a zero-dimensional structure, the one-dimensional gold nanowire has the advantages of large length-diameter ratio, few lattice defects, high surface atomic number and the like. In recent years, a method for preparing gold nanowires by active surface growth using small molecule sulfhydryl ligands has been developed. Yang et al use aminated SiO 2 Provides a high-curvature surface, and successfully grows the radial gold nanowire composite nano-particles with high length-diameter ratio and flexibility on the surface. Similarly, Liz-Marz-n, etc. are also SiO 2 Preparing plasma metal dielectric nano particles with the length of 40-200nm of gold nano wires which are grown on the surfaces of colloid particles by radiation. Zhang et al firstly grow gold nanowires on the surface of polystyrene microspheres by a seed growth method, then remove the polystyrene microspheres with tetrahydrofuran to form high-grade cage-like gold nanowire vesicles, and provide sharp and high-density hot spots for SERS detection. The preparation of the radial nano-wire composite nano-particles is synthesized based on micromolecular sulfydryl ligands, but the preparation of the gold nano-wire composite structure with common appearance can only be generally prepared.
The preparation of the gold nanowires is rarely researched by adopting a high-molecular ligand. Polymers have been used in various fields such as science and technology and life as one of important materials. From the synthesis angle, if a macromolecular ligand is introduced into the synthesis of the gold nanoparticles, a novel functional nano composite material can be obtained.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel preparation method of flower-shaped gold nanowire composite nanoparticles.
In order to achieve the above object, the present invention provides a method for preparing flower-like gold nanowire composite nanoparticles, comprising the steps of:
(1) boiling a certain amount of chloroauric acid aqueous solution, then adding a proper amount of sodium citrate aqueous solution, and continuously heating, stirring and refluxing to react to obtain a nano gold ball solution;
(2) centrifugally concentrating the nano gold ball solution, transferring the nano gold ball solution into isopropanol solution under stirring, sequentially adding 11-mercaptoundecanoic acid ethanol solution, ethyl orthosilicate aqueous solution and concentrated ammonia water, reacting at room temperature, and centrifuging to obtain Au @ SiO 2 An aqueous solution of nanoparticles;
(3) in the above Au @ SiO 2 Adding 3-aminopropyl triethoxy silane into nano particle water solution, reacting at room temperature, centrifugally purifying with ethanol, and adding 3-5nm gold seed solutionAdsorbing at room temperature, and finally centrifuging to obtain Au @ SiO adsorbed with seeds 2 @ seeds composite nanoparticles, stored in ethanol for later use;
(4) taking a certain amount of Au @ SiO adsorbed with seeds 2 And (3) adding growth liquid containing micromolecule sulfhydryl ligand, polyvinylpyrrolidone, chloroauric acid and ascorbic acid into the @ seeds composite nanoparticles, reacting at room temperature, and centrifuging and washing to obtain the composite nanoparticles with the flower-shaped gold nanowires.
Further, the diameter of the gold nanospheres in the step (1) is 15-30 nm.
Further, the Au @ SiO in the step (2) 2 The diameter of the nano particles is 20-40 nm.
Further, the adsorption time in the step (3) is 2-6 h.
Further, the mercapto ligand in the step (4) is one or a mixture of two of 3-mercaptobenzoic acid, 4-hydroxythiophenol and 4-mercaptophenylacetic acid, and the reaction time is 0-15 min.
Further, the molecular weight of the polyvinyl pyrrole in the step (4) is 8000-60000.
Further, the molar ratio of the sulfhydryl ligand, the polyvinylpyrrolidone, the chloroauric acid and the ascorbic acid in the step (4) is 1:25:3:7-1:250:3: 7.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a novel preparation method, and on one hand, the colloid Au @ SiO with the core-shell structure is prepared by adopting the colloid nano particles with the core-shell structure as a template 2 Nanoparticles; on the other hand, the mixed ligand such as a macromolecular ligand and the like is used for changing the growth process, so that the composite nano particle with the adjustable flower-shaped gold nano wire size can be obtained.
The invention uses colloid nano particles Au @ SiO 2 The gold nanowire growth process is regulated and controlled by controlling parameters such as ligand types, reaction proportion, reaction time and the like as a template, so that a series of flower-shaped structure gold nanowire composite materials with different appearances are obtained. The material structure comprises Au @ SiO 2 The core and the gold nanowires radiating outwards form a flower-shaped micro-nano structure.
The method has the advantages of low cost, simple experimental operation, short product preparation period and good repeatability, can prepare uniform flower-shaped gold nanowire composite nanoparticles, and provides a feasible technical route for preparing gold nanocomposite through a macromolecular ligand.
The method has the advantages of simple reaction condition, simple equipment, short whole process flow, good product uniformity, good repeatability and good potential application prospect.
Drawings
FIG. 1 shows Au @ SiO prepared in example 1 of the present invention 2 SEM image of (d).
Fig. 2 is an SEM image of the flower-shaped gold nanowire composite nanoparticle prepared in embodiment 1 of the present invention.
Fig. 3 is an SEM image of the flower-shaped gold nanowire composite nanoparticle prepared in embodiment 2 of the present invention.
Fig. 4 is an SEM image of the flower-shaped gold nanowire composite nanoparticle prepared in embodiment 3 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
A preparation method of flower-shaped gold nanowire composite nanoparticles comprises the following steps:
(1) 10mg, 100mL of HAuCl 4 Heating and boiling the aqueous solution, then adding 3mL of 1 wt% sodium citrate aqueous solution, stirring at 600rpm, heating, refluxing and reacting for 30min to obtain a wine red solution, and naturally cooling to room temperature to obtain gold nanospheres;
(2) centrifuging and concentrating 3mL of nano gold ball solution at 4000g for 8min, removing supernatant, and dispersing in 500 mu L of deionized water; transferred to 2.5mL isopropanol solution under vigorous stirring, followed by the addition of 20 μ L of 2mM ethanol solution of 11-alkyl undecanoic acid; 600. mu.L of 9mM ethyl orthosilicate aqueous solution and finally 90. mu.L of concentrated ammonia water were added and reacted at room temperature for 12 hours. After the reaction is finished, centrifuging for 9min at 5200g to obtain Au @ SiO with a core-shell structure 2 Nanoparticles dispersed in 500 μ L deionized water. As can be seen from FIG. 1, the resulting nanoparticle rulerThe size is about 30nm, and the material has an obvious core-shell structure;
(3) au @ SiO at 500. mu.L 2 Adding 500 mu L of 1mM 3-aminopropyltriethoxysilane into the aqueous solution, and reacting for 1h at room temperature; centrifuging and purifying twice at 5200g for 9min, and storing in 500 μ L ethanol; then adding the gold seed solution into 500 mu L of gold seed solution, and adsorbing for 2h at room temperature to ensure that a layer of gold seeds is adsorbed on the surface of the gold seeds; finally, the mixture is centrifuged for 8min at 5200g to obtain Au @ SiO 2 @ seeds, stored in 1mL ethanol for use;
(4) taking 100 mu L of Au @ SiO 2 @ seeds solution, followed by addition of a growth medium containing 0.37mM of 4-mercaptophenylacetic acid, 72.5mM of polyvinylpyrrolidone, 1.13mM of chloroauric acid and 2.73mM of ascorbic acid, and reaction at room temperature for 15 min. Then centrifuged at 1000rpm for 4min and redispersed in water. As can be seen from fig. 2, the size of gold nanowires in the obtained flower-like gold nanocomposite nanoparticles was about 300 nm. The embodiment uses the 4-mercaptophenylacetic acid mixed ligand to prepare the composite nano-particle with longer gold nano-wire.
Example 2
A preparation method of flower-shaped gold nanowire composite nanoparticles comprises the following steps:
(1) 10mg, 100mL of HAuCl 4 Heating and boiling the aqueous solution, then adding 3mL of 1 wt% sodium citrate aqueous solution, stirring at 600rpm, heating, refluxing and reacting for 30min to obtain a wine red solution, and naturally cooling to room temperature to obtain gold nanospheres;
(2) centrifuging and concentrating 3mL of nano gold ball solution at 4000g for 8min, removing supernatant, and dispersing in 500 mu L of deionized water; transferred to 2.5mL of isopropanol solution with vigorous stirring, followed by the addition of 20. mu.L of 2mM ethanol solution of 11-mercaptoundecanoic acid; adding 600 mu L of 9mM ethyl orthosilicate aqueous solution, finally adding 90 mu L of concentrated ammonia water, and reacting for 12h at room temperature; after the reaction is finished, centrifuging for 9min at 5200g to obtain Au @ SiO with a core-shell structure 2 Nano particles dispersed in 500 microliter deionized water for storage;
(3) au @ SiO at 500. mu.L 2 Adding 500 mu L of 1mM 3-aminopropyltriethoxysilane into the aqueous solution, and reacting for 1h at room temperature; it is centrifuged and purified twice at 5200g for 9min,stored in 500 μ L ethanol; then adding the mixture into 500 mu L of gold seed solution, and adsorbing for 2h at room temperature; finally, the mixture is centrifuged for 8min at 5200g to obtain Au @ SiO 2 @ seeds, stored in 1mL ethanol for use;
(4) taking 100 mu L of Au @ SiO 2 @ seeds solution, followed by addition of a growth medium containing 0.37mM of 4-hydroxythiophenol, 72.5mM of polyvinylpyrrolidone, 1.13mM of chloroauric acid and 2.73mM of ascorbic acid, and reaction at room temperature for 15 min; the nanoparticles were centrifuged at 1000rpm for 4min and redispersed in water. As can be seen from fig. 3, the gold nanowires in the obtained flower-like gold nanocomposite nanoparticles have a size of about 150 nm. In the embodiment, the composite nano-particles with shorter flower-like gold nano-wires can be prepared by using the 4-hydroxythiophenol mixed ligand.
Example 3
A preparation method of an electrocatalyst gold-silver palladium-plated nanowire comprises the following steps:
(1) 10mg, 100mL of HAuCl 4 Heating and boiling the aqueous solution, then adding 3mL of 1 wt% sodium citrate aqueous solution, stirring at 600rpm, heating, refluxing and reacting for 30min to obtain a wine red solution, and naturally cooling to room temperature to obtain gold nanospheres;
(2) centrifuging and concentrating 9mL of nano gold ball solution at 4000g for 8min, removing supernatant, and dispersing in 1.5mL of deionized water again; transferred to 7.5mL of isopropanol solution with vigorous stirring, followed by the addition of 60. mu.L of 2mM ethanol solution of 11-mercaptoundecanoic acid. Then 600. mu.L of 27mM aqueous tetraethyl orthosilicate solution was added, and finally 270. mu.L of concentrated aqueous ammonia was added, and the reaction was carried out at room temperature for 12 hours. After the reaction is finished, centrifuging for 9min at 5200g to obtain Au @ SiO with a core-shell structure 2 Nanoparticles dispersed in 1.5mL deionized water;
(3) au @ SiO at 500. mu.L 2 To the aqueous solution, 500. mu.L of 1mM 3-aminopropyltriethoxysilane was added and the reaction was carried out at room temperature for 1 hour. Centrifuging and purifying twice at 5200g for 9min, and storing in 500 μ L ethanol; then adding the mixture into 500 mu L of gold seed solution, and adsorbing for 2h at room temperature; finally, the mixture is centrifuged for 8min at 5200g to obtain Au @ SiO 2 @ seeds, stored in 1mL ethanol for use;
(4) taking 300 mu L of Au @ SiO 2 @ seeds solution, howeverThen, a growth medium containing 0.37mM of 4-mercaptophenylacetic acid, 72.5mM of polyvinylpyrrolidone, 1.13mM of chloroauric acid and 2.73mM of ascorbic acid was added and reacted at room temperature for 15 min; then centrifuged at 1000rpm for 4min and redispersed in water. As can be seen from fig. 4, the gold nanowires in the obtained flower-like gold nanocomposite nanoparticles have a size of about 100 nm. The embodiment can prepare the flower-shaped gold nanowire composite nanoparticles with shorter length by regulating and controlling the concentration of the seeds.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (1)

1. A preparation method of flower-shaped gold nanowire composite nanoparticles comprises the following steps:
(1) 10mg, 100mL of HAuCl 4 Heating and boiling the aqueous solution, then adding 3mL of 1 wt% sodium citrate aqueous solution, stirring at 600rpm, heating, refluxing and reacting for 30min to obtain a wine red solution, and naturally cooling to room temperature to obtain gold nanospheres;
(2) centrifuging and concentrating 9mL of nano gold ball solution at 4000g for 8min, removing supernatant, and dispersing in 1.5mL of deionized water again; transferred to 7.5mL of isopropanol with vigorous stirring, followed by the addition of 60. mu.L of 2mM ethanol solution of 11-mercaptoundecanoic acid; then 600 mu L of 27mM ethyl orthosilicate water solution is added, and finally 270 mu L of strong ammonia water is added, and the mixture reacts for 12 hours at room temperature; after the reaction is finished, centrifuging for 9min at 5200g to obtain Au @ SiO with a core-shell structure 2 Nano particles dispersed in 1.5mL of deionized water;
(3) at 500. mu. LAu @ SiO 2 Adding 500 mu L of 1mM 3-aminopropyl triethoxysilane into the nano particle water solution, and reacting for 1h at room temperature; centrifuging and purifying twice at 5200g for 9min, and storing in 500 μ L ethanol; then adding the mixture into 500 mu L of gold seed solution with the particle size of 3-5nm, and adsorbing for 2h at room temperature; finally, the mixture is centrifuged for 8min at 5200g to obtain Au @ SiO 2 @ seeds, stored in 1mL of BAlcohol for later use;
(4) taking 300 mu L of Au @ SiO 2 @ seeds solution, followed by addition of a growth medium containing 0.37mM of 4-mercaptophenylacetic acid, 72.5mM of polyvinylpyrrolidone, 1.13mM of chloroauric acid and 2.73mM of ascorbic acid, and reaction at room temperature for 15 min; centrifuging the nanoparticles at 1000rpm for 4min, and redispersing in water; the length of the gold nano-wire in the obtained flower-shaped gold nano composite nano particle is 100 nm; the molecular weight of the polyvinylpyrrolidone is 8000-;
the diameter of the gold nanospheres in the step (1) is 15-30 nm; the Au @ SiO in the step (2) 2 The diameter of the nano particles is 20-40 nm.
CN201811490724.3A 2018-12-06 2018-12-06 Preparation method of flower-shaped gold nanowire composite nanoparticles Active CN109530718B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811490724.3A CN109530718B (en) 2018-12-06 2018-12-06 Preparation method of flower-shaped gold nanowire composite nanoparticles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811490724.3A CN109530718B (en) 2018-12-06 2018-12-06 Preparation method of flower-shaped gold nanowire composite nanoparticles

Publications (2)

Publication Number Publication Date
CN109530718A CN109530718A (en) 2019-03-29
CN109530718B true CN109530718B (en) 2022-09-13

Family

ID=65853099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811490724.3A Active CN109530718B (en) 2018-12-06 2018-12-06 Preparation method of flower-shaped gold nanowire composite nanoparticles

Country Status (1)

Country Link
CN (1) CN109530718B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110227815B (en) * 2019-06-11 2021-04-27 东南大学 Preparation method of water-dispersible gold nanowire
CN110711610B (en) * 2019-10-17 2021-10-29 桂林理工大学 Preparation method of super-hydrophobic/super-hydrophilic mixed pattern microarray dendritic gold chip
CN112501651B (en) * 2020-12-03 2022-07-29 南京工业大学 Substrate-based gold nanowire and preparation method and application thereof
CN112705724A (en) * 2020-12-07 2021-04-27 南京工业大学 Adjustable gold nanostructure and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19734974A1 (en) * 1997-08-13 1999-02-25 Hoechst Ag Production of supported catalyst for vinyl acetate production
US10332657B2 (en) * 2011-09-23 2019-06-25 Nanyang Technological University Methods for forming gold nanowires on a substrate and gold nanowires formed thereof
CN104971366A (en) * 2014-04-03 2015-10-14 中国科学院理化技术研究所 Biodegradable magnetic nano gold shell microsphere as well as preparation method and application thereof
CN105174272B (en) * 2015-09-24 2017-10-24 上海大学 Au@SiO2Composite mesoporous nano material and preparation method thereof

Also Published As

Publication number Publication date
CN109530718A (en) 2019-03-29

Similar Documents

Publication Publication Date Title
CN109530718B (en) Preparation method of flower-shaped gold nanowire composite nanoparticles
CN101559951B (en) Method for preparing nanoscale silica hollow microspheres
CN103056384B (en) Preparation method of precious metal and magnetic nano particles
Wang et al. Effective octadecylamine system for nanocrystal synthesis
US9415442B2 (en) Stable oxide encapsulated metal clusters and nanoparticles
KR101304325B1 (en) Method for fabricating silica-coated Au nanorods and nanohybrization of silica-coated Au nanorods and silica nanoballs
CN104174865B (en) Carbon parcel polyhedron Nano silver grain and the preparation method of controlled self assembly thereof
Hu et al. Magnetic nanoparticle sorbents
CN108031475B (en) Preparation method of gold-loaded ferric oxide nano photocatalyst
CN112516956A (en) Preparation method and application of magnetic composite nano material
US10143988B2 (en) Method for synthesizing non-spherical nanostructures
CN106141171B (en) Hud typed superstructure nano material, its preparation method and application
CN114425055B (en) Silica supported multi-metal nano-particle, preparation method and antibacterial application thereof
Imura et al. Highly stable silica-coated gold nanoflowers supported on alumina
CN111423878A (en) Fluorescent magnetic composite nano-particles, preparation method thereof and biological probe prepared from fluorescent magnetic composite nano-particles
CN104439276A (en) Method for fast preparing hollow porous silicon dioxide/silver nanoparticle composite and product
CN108187739B (en) Raisin bread type gold-silicon dioxide nano catalyst and preparation and application thereof
CN102000833A (en) Submicron Au particles and preparation method thereof
CN113871119A (en) Magnetotactic nano motor and preparation method thereof
CN110078031B (en) Te nanowire three-dimensional aerogel, and preparation method and application thereof
CN109502594B (en) Silicon oxide nanotube with asymmetric internal and external surface properties and preparation method and application thereof
Wang et al. Preparation of Fe 3 O 4@ Au nano-composites by self-assembly technique for immobilization of glucose oxidase
Nasseri et al. Interfacial control of the synthesis of cellulose nanocrystal gold nanoshells
CN112191860B (en) Chemical synthesis method for continuously adjusting surface roughness of gold nanoparticles
CN112876807B (en) Fe2O3Preparation method of Ag/phenolic resin sandwich structure nano disc

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