CN110270682A - A kind of nano material and its manufacturing method - Google Patents

A kind of nano material and its manufacturing method Download PDF

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Publication number
CN110270682A
CN110270682A CN201810211451.8A CN201810211451A CN110270682A CN 110270682 A CN110270682 A CN 110270682A CN 201810211451 A CN201810211451 A CN 201810211451A CN 110270682 A CN110270682 A CN 110270682A
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layer
ligand
functional group
protective layers
multiple protective
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李吉光
徐一舟
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14Treatment of metallic powder
    • B22F1/145Chemical treatment, e.g. passivation or decarburisation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01DMEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D5/00Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable
    • G01D5/26Mechanical means for transferring the output of a sensing member; Means for converting the output of a sensing member to another variable where the form or nature of the sensing member does not constrain the means for converting; Transducers not specially adapted for a specific variable characterised by optical transfer means, i.e. using infrared, visible, or ultraviolet light

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Pharmacology & Pharmacy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a kind of stable nanometer particle materials and similar system and its manufacturing method.This method includes forming stabilized protection course, and external connection functional group is reserved on layer using modes such as crosslinkings in multilayer covering, interlayer connection, layer on nanoparticle.

Description

A kind of nano material and its manufacturing method
Technical field
The present invention relates to a kind of nano material and its manufacturing method more particularly to it is a kind of for stable nano material or Similar system and its manufacturing method.
Background technique
Diameter has high electron density, dielectric property in nanogold particle, nano gold spherical, nanometer gold bar of 1~100nm etc. And catalytic action, it can be in conjunction with a variety of large biological molecules, and its bioactivity is not influenced.Be widely used in life medicine (including Oncotherapy, medical imaging, medicine quickly detect), can be used for infrared detector, effectively insulating energy-saving coatings etc. etc., Application prospect is extensive.
A major issue in the application of nanogold is stability.It is too long between when left, solution environmental changes, Whens temperature change etc., nano Au particle is easy to be lost protective layer, surfactant etc., then loses the characteristic of nanoparticle. Therefore, the stability for improving nano Au particle is necessary to large-scale application nano Au particle.
The present invention provides a kind of stable nano Au particle materials and similar system and its manufacturing method.
Summary of the invention
The present invention relates to a kind of stable nano Au particle materials and similar system and its manufacturing method.This method is included in Using modes such as crosslinkings in multilayer covering, interlayer connection, layer on nano Au particle, stabilized protection course is formed, and reserve on layer External connection functional group.
In one embodiment of the invention, a kind of structure of nano material with stabilized protection course is provided.The structure is adopted Replace the surfactant in former nano material with new double shielding layer structure, improves the stability of nanoparticle and reservation Protective layer activity.
A kind of method of nano material of the manufacture with stabilized protection course is provided in another embodiment of the present invention.The party Method includes generating initial nanoparticle, certain concentration, temperature, etc. under the conditions ofs the new ligand of multilayer is added, generate to stablize and protect Sheath.
Invention embodiment
A specific embodiment of the invention explained below, it should be pointed out that in the specific descriptions process of these embodiments In, in order to carry out brief and concise description, this specification can not all features to actual embodiment make in detail Description.It is to be understood that during the actual implementation of any one embodiment, as in any one engineering item During mesh or design object, in order to realize the objectives of developer, in order to meet, system is relevant or business phase The limitation of pass can usually make various specific decisions, and this also can be from a kind of embodiment to another embodiment Between change.Although moreover, it is to be understood that the effort gone out done in this development process may be it is complicated and It is interminable, however for those skilled in the art relevant to present disclosure, it is disclosed in the disclosure Technology contents on the basis of some designs for carrying out, the changes such as manufacture or production are conventional technology, should not It is insufficient to be interpreted as content of this disclosure.
Nano Au particle can be prepared various different grains in which can be convenient by gold chloride by modes such as reduction method, crystal seed methods The nano Au particle of diameter.But in gold nanoparticle forming process, the surfactant stability on gold particle surface is poor, again Such as the surfactants such as CTAB have bio-toxicity, when nanoparticle is applied to the fields such as medicine, need to remove such table Face activating agent.But nano Au particle can decompose the characteristic for losing nanoparticle after only removing surfactant.So needing It is modified that surface is carried out to nano particle.
Popular method can be attached on gold nano-material with the functional group containing sulfydryl, for example sulfhydrylation is poly- Ethylene glycol (Thiolated polyethylene glycol, HS-PEG), sulfydryl-DNA or other containing amido (NH2-) Some functional groups.It only can not achieve with these functional groups and good covering carried out to the surface of nanometer rods, and because do not have Have good locking mechanism, there is no assurance that these ligands can stay in gold surface, be cleaned multiple times or when and particle surface When having the ligand of stronger compatibility to occur, these ligand moleculars can fall off, and so as to cause stability decline, even result in and receive Rice corpuscles finally reunites and precipitates.
The present invention uses the ligand of multilayer, is attached in nanoparticle surface with locking protective layer.Of the invention one In a embodiment, first layer is attached directly to nanoparticle surface with covalent bond.The ligand of first layer includes at least two functions Group, the functional group of one of ligand is connected by covalent bond with particle surface, the functional group of another ligand can be with The functional group of the ligand of the second layer is connected, while the ligand of dentate can be crosslinked connection in same layer.
In one embodiment of the invention, first layer stabilized zone may include the ligand with multiple attachment points, can be with It is two-dimentional ligand or three-dimensional ligand.The former free binding site in part has been attached in nanoparticle surface on ligand.There are also parts Free binding site does not react, can be reacted with other ligands.Because having multiple binding sites and nanometer rods on the ligand Surface be connected, so from nanorod surfaces be detached from degree with regard to relatively low.
In one embodiment of the invention, there is one layer of first layer first layer ligand directly adhered in nanorod surfaces In there are two above functional group, the ligand of first layer can be attached to by reaction appropriate with the head functional group for guaranteeing ligand The ligand in face can be crosslinked mutually by organo-functional group on the first layer in nanometer rods.These interlockings can effectively reduce first layer Stabilized zone is from the probability of the disengaging above nanoparticle.It also include that unreacted functional group can be in ligand on first layer Other layers such as second layer reacts.
In one embodiment, may include in the ligand of first layer it is some containing nitrogen, sulphur, phosphorus, oxygen element atom Functional group.Such as some dendron shaped polymer molecules, polyamidoamine dendrimer poly (amidoamine) (PAMAM) etc..These molecules have tree-shaped structure, and can extend to more branches.With increasing for branch, divide Son can become bended.After multiple extension, there is the binding site of some amidos that can be attached to nanoparticle surface, have simultaneously Some unattached binding sites.
In one embodiment, these ligands can be two-dimensional, and two-dimentional ligand can also be some and contain amine simultaneously The ligand of base and the monomer of acrylate-functional groups, such as poly- (2- amidoethyl methacrylate-co- methacrylic acid Methyl esters etc..In one embodiment of the invention, two-dimentional ligand may include containing amido and acrylate-functional groups simultaneously Monomer ligand it is for example poly- (2- amidoethyl methacrylate-co- methyl methacrylate).In one embodiment In, these ligands can be it is three-dimensional, three-dimensional ligand may include it is some there are three or the above functional group while at least Liang Ge functional group can molecule in the same plane, such as protein, peptide or synthesis macromolecule etc..
Fig. 1 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, the two-dimentional or three-dimensional ligand that can also be introduced in second layer ligand.Second layer ligand It can combine in several ways on the first layer.In one embodiment of the invention, on second layer ligand and first layer Combination between functional group is by carbon-nitrogen covalent bond.Such as the covalent bond can be through the acrylate on the second layer What the free amino functional group in functional group and first layer was formed by Michael addition reaction (Michael Addition).? In one embodiment, the ligand comprising acrylate-functional groups can be the acrylate ended that molecular weight is 1000-20000 Polyethylene glycol acrylate-terminated polyethylene glycol, the ligand containing amidine functional group can be Molecular weight is the polyamidoamine dendrimer of 1000-100000, Polyamidoamine (PAMAM).In a reality It applies in example, the combination between second layer ligand and first layer is to pass through amido bond.Such as pass through the anti-of carboxylic acid and amidine functional group It answers.In one embodiment, ligand in the second layer may include that multiple free binding sites with stabilized zone are formed altogether The functional group of valence link.In one embodiment, these functional groups can be acrylate-functional groups and amidine functional group.At one In embodiment, second layer ligand may include multiple acrylate-functional groups, such as double pentaerythritol C5 methacrylate, the third oxidation Glycerol tri-acrylate or three (2- ethoxy) isocyanuric acids etc..These multi-functional ligands can in first layer stabilized zone Ligand link can also be connect with extrinsic ligand such as long-chain amine end groups ligand etc..
Fig. 2 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases by the second protective layer again outside first layer protective layer.
Fig. 3 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases the second protective layer, the second protective layer interior molecules again outside first layer protective layer Form cross-linked structure.
Fig. 4 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases the second protective layer, the second protective layer interior molecules again outside first layer protective layer Cross-linked structure, while second layer molecule also contact nanometer particle surface are formed, forms intersection construction with first layer.
A kind of method of nano material of the manufacture with stabilized protection course is provided in one embodiment of the invention.This method Including generating initial nanoparticle, certain concentration, temperature, etc. under the conditions ofs new surfactant is added, generate protective layer Deng.
In one embodiment of the invention, all these, which react (including increasing ligand layer, the reaction such as crosslinking), is all It is completed in water or aqueous solution.Reaction between different ligands can carry out at room temperature, for example, PEG layers can be with It is manufactured using following steps: the aqueous solution addition of the amido end ligand containing 0.00001 M to 0.5M being had into CTAB first In the gold nanorods solution of covering, to adhere to the stabilized zone that one layer of amido end ligand is formed on gold nanorods.It is small at one When after, by the acrylate-based aqueous solution of the multifunctional chiral ligand such as triglycerin containing 0.00001 M to 0.001 M It is added in solution, after solution is stirred 20 minutes, the second layer is connected together by Michael addition reaction with stabilized zone. Unreacted acrylate-functional groups can be used to be reacted with the ligand containing amido envelope functional group of long-chain or short chain. In one embodiment, short chain ligand can be 6-aminocaprolc acid.In one embodiment, it is poly- to can be amido end for long-chain Ligand Ethylene glycol.
In one embodiment, by the way that the long-chain or short chain that concentration is 0.00001M to 0.1 M are contained propylene The solution of acid esters end group ligand is added in nano-particle solution, can be by acrylate end groups ligand, such as acrylate end groups Polyethylene glycol is reacted with the ligand on the stabilized zone of nanometer rods, carbon-to-nitrogen covalent bond is formed, to be attached on stabilized zone.
The replacement process of protective layer can be detected by UV-Vis spectrum, attachment mew layer can spectrally form the peak LSPR Red shift or blue shift, so as to determine whether to complete the replacement of layer molecule.TEM can also be used to the steady of detection extra play It is qualitative.
In some embodiments, diameter of nano particles is between 2nm-10nm, in some embodiments, nanoparticle it is straight Diameter is between 10nm -30nm, in some embodiments, the diameter of nanoparticle between 30nm -200nm,.
In embodiments of the present invention, " nanoparticle " used herein can refer to comprising can be nanometer rods, nanosphere, nanometer The various shapes such as line, can be metal (such as Au, Ag, Pt, Pb), semiconductor material (such as CdSe, CdS, ZnS, TiO2, PbS etc.), magnetic material (such as Fe2O3 or Co nano particle) and composite material (such as FePt, CoPt).It receives Rice material surface can be attached with activating agent, stabilizer.In some embodiments, nanoparticle can be with multiple actives Or the gold nanorods of protective layer package.
" layer " being related in the present invention includes the material or component for having thickness formed on a surface, not generation The specific thickness or other geometry dimensions of these materials of table or component." nano material " being related in the present invention include In the material that scale is 1-1000nm, the specific scale or other geometry dimensions of these materials or component are not represented.
Unless otherwise defined, technical term or scientific term used in claims and specification should be this hair The ordinary meaning that personage in bright technical field with general technical ability is understood.Present patent application specification and power " first ", " second " used in sharp claim and similar word are not offered as any sequence, quantity or importance, and It is used only to distinguish different component parts.The similar word such as "one" or " one " is not offered as quantity limitation, but indicates There are at least one.The similar word such as " comprising " or "comprising" means to appear in the element before " comprising " or "comprising" Either object covers the element for appearing in " comprising " or "comprising" presented hereinafter or object and its equivalent element, it is not excluded that Other elements or object." connection " either the similar word such as " connected " is not limited to physics or mechanical connection, It is also not necessarily limited to direct or indirect connection.
Although the present invention is described in conjunction with the specific embodiments, it will be appreciated by those skilled in the art that right The present invention can make many modifications and variations.It is therefore contemplated that claims are intended to be covered on the present invention very All such modifications and modification in positive conception and scope.
Detailed description of the invention
The embodiment of the present invention is described in conjunction with the accompanying drawings, the present invention may be better understood, in the accompanying drawings:
Fig. 1 is the schematic diagram of one embodiment of nano material of the present invention, and around nanoparticle 1, new single layer first layer is protected Sheath 2 replaces original protective layer 0.
Fig. 2 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases by the second protective layer again outside first layer protective layer.
Fig. 3 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases the second protective layer, the second protective layer interior molecules again outside first layer protective layer Form cross-linked structure.
Fig. 4 is the schematic diagram of one embodiment of nano material of the present invention, around nanoparticle 1, new single layer first Layer protective layer 2 replaces original protective layer 0, increases the second protective layer, the second protective layer interior molecules again outside first layer protective layer Cross-linked structure, while second layer molecule also contact nanometer particle surface are formed, forms intersection construction with first layer.

Claims (9)

1. a kind of nanometer material structure and its manufacturing method, including using in multilayer covering, interlayer connection, layer on nanoparticle The modes such as crosslinking form stabilized protection course, and external connection pipe energy unity chalaza is reserved on layer.
2. multiple protective layers as claimed in claim 1, the functional group of the dentate of first layer includes one or more mismatch Electronics.
3. multiple protective layers as claimed in claim 1, the functional group in the ligand of first layer includes sulfydryl, in amido, oxygroup One or a combination thereof, it can be including acrylate-functional groups or amine functional group or simultaneously including the two, can wrap Third functional group is included, and it is coplanar for having at least two in three functional groups.
4. the dentate of multiple protective layers as claimed in claim 1, first layer can be with one or more two-dimentional ligand or three Ligand is tieed up, may include one or more kinds of dendritics.
5. multiple protective layers as claimed in claim 1, the functional group in the ligand of the second layer includes sulfydryl, in amido, oxygroup One or a combination thereof, it can be including acrylate-functional groups or amine functional group or simultaneously including the two, can wrap Third functional group is included, and it is coplanar for having at least two in three functional groups.
6. the dentate of multiple protective layers as claimed in claim 1, the second layer can be with one or more two-dimentional ligand or three Ligand is tieed up, may include one or more kinds of dendritics.
7. multiple protective layers as claimed in claim 1, the second layer is by C-N, and C-C's or a combination thereof is covalently bonded to On one layer.
8. multiple protective layers as claimed in claim 1, are attached to particle surface for first layer and the second layer are attached to first layer On reaction complete in an aqueous medium at a certain temperature.
9. nanoparticle as claimed in claim 1 " can refer to comprising can be the various shapes such as nanometer rods, nanosphere, nano wire, can To be metal (such as Au, Ag, Pt, Pb), semiconductor material (such as CdSe, CdS, ZnS, TiO2, PbS), magnetism Material (such as Fe2O3 or Co nano particle) and composite material (such as FePt, CoPt).
CN201810211451.8A 2018-03-15 2018-03-15 A kind of nano material and its manufacturing method Pending CN110270682A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101679022A (en) * 2007-04-02 2010-03-24 爱默蕾大学 in vivo tumor targeting and spectroscopic detection with surface-enhanced raman nanoparticle tags
CN102526769A (en) * 2010-09-28 2012-07-04 谢达斌 Double-developer for CT and MRI simultaneously and preparation method thereof
US20150038578A1 (en) * 2011-05-16 2015-02-05 Babak NIKOOBAKHT Methods and apparatuses for surface functionalization and coating of nanocrystals
CN107737945A (en) * 2017-09-12 2018-02-27 南京邮电大学 A kind of synthetic method of composite Nano gold grain and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101679022A (en) * 2007-04-02 2010-03-24 爱默蕾大学 in vivo tumor targeting and spectroscopic detection with surface-enhanced raman nanoparticle tags
CN102526769A (en) * 2010-09-28 2012-07-04 谢达斌 Double-developer for CT and MRI simultaneously and preparation method thereof
US20150038578A1 (en) * 2011-05-16 2015-02-05 Babak NIKOOBAKHT Methods and apparatuses for surface functionalization and coating of nanocrystals
CN107737945A (en) * 2017-09-12 2018-02-27 南京邮电大学 A kind of synthetic method of composite Nano gold grain and application

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