CN110465674A - A kind of preparation method of magnetic bi-layer gold nano grain - Google Patents

A kind of preparation method of magnetic bi-layer gold nano grain Download PDF

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CN110465674A
CN110465674A CN201910914637.4A CN201910914637A CN110465674A CN 110465674 A CN110465674 A CN 110465674A CN 201910914637 A CN201910914637 A CN 201910914637A CN 110465674 A CN110465674 A CN 110465674A
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magnetic
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layer gold
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李秋瑾
赵芷芪
陈霖娜
张健飞
巩继贤
李政
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Tianjin Polytechnic University
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    • A61K49/1824Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles
    • A61K49/1827Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle
    • A61K49/183Nuclear magnetic resonance [NMR] contrast preparations; Magnetic resonance imaging [MRI] contrast preparations characterised by a special physical form, e.g. emulsions, microcapsules, liposomes particles, e.g. uncoated or non-functionalised microparticles or nanoparticles coated or functionalised microparticles or nanoparticles coated or functionalised nanoparticles having a (super)(para)magnetic core, being a solid MRI-active material, e.g. magnetite, or composed of a plurality of MRI-active, organic agents, e.g. Gd-chelates, or nuclei, e.g. Eu3+, encapsulated or entrapped in the core of the coated or functionalised nanoparticle having a (super)(para)magnetic core coated or functionalised with an inorganic material or being composed of an inorganic material entrapping the MRI-active nucleus, e.g. silica core doped with a MRI-active nucleus
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    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
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Abstract

The present invention relates to a kind of preparation methods of magnetic bi-layer gold nano grain, belong to field of compound material.Method includes the following steps: preparing magnetic nanometer particles using certain density four water frerrous chloride, Iron trichloride hexahydrate, glucan and sodium hydroxide, and dopamine is added to generate magnetic core-shell plasma nano gap nanoparticle, finally with reagents such as gold chloride, hydroxylamine hydrochloride and cetyl trimethylammonium bromides, magnetic bi-layer gold nano grain is prepared.Magnetic bi-layer gold nano grain prepared by the present invention is because having good magnetic responsiveness, biocompatibility, the characteristics such as unique plasma resonance, therefore have important application prospect in the fields such as biotechnology, biosensor and biomedicine, magnetic resonance imaging and catalysis.

Description

A kind of preparation method of magnetic bi-layer gold nano grain
Technical field
The present invention relates to a kind of preparation methods of magnetic bi-layer gold nano grain, belong to field of compound material.
Background technique
Multi-functional in order to realize single nanostructure, people conduct extensive research core-shell nano.Its In, gold nano grain has many advantages, such as that chemical stability is high, reactivity is low, good biocompatibility, be using noble metal as The core material of core-shell nano and the ideal material of shell material.Meanwhile passing through covalent bond and amine or Mercaptofunctional on the surface of golden shell Group is combined the functionalization that may be implemented for golden shell.Magnetic nano-particle (Fe of the gold as shell material cladding3O4It NPs) can be with The performance of the magnetic property of ferroso-ferric oxide and golden shell is combined, as one for biotechnology and biomedical applications Suitable platform.
For the magnetic bi-layer gold nano grain that this patent is related to because having good magnetic responsiveness, biocompatibility is unique Plasma resonance, and protecting so that core material improves from aoxidizing and corroding the chemistry of structure by outer bilayer golden shell Stability, therefore have important application in the fields such as biotechnology, biosensor and biomedicine, magnetic resonance imaging and catalysis Prospect.
Summary of the invention
The present invention improves in above method thinking, prepares the magnetic bi-layer gold nano grain with excellent performance; Use certain density four water frerrous chloride (FeCl2·4H2O), Iron trichloride hexahydrate (FeCl3·6H2O), glucan (Dextran) and sodium hydroxide (NaOH) prepares magnetic nanometer particles (Fe3O4- Dextran), and be added dopamine (PDA) with Magnetic core-shell plasma nano gap nanoparticle is generated, gold chloride (HAuCl is finally used4), hydroxylamine hydrochloride (NH2OH·HCl) And the reagents such as cetyl trimethylammonium bromide (CTAB), prepare magnetic bi-layer gold nano grain.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of magnetic bi-layer gold nano grain, comprising the following steps:
(1) magnetic nanometer particles (Fe3O4- Dextran) synthesis: four water frerrous chloride (FeCl2·4H2O), six water chlorine Change iron (FeCl3·6H2O it) is dissolved in deionized water, under agitation gradually by mixed solution with glucan (Dextran) Sodium hydroxide (NaOH) is added and stirs 2h, the black precipitate occurred is collected with magnet, is then washed with deionized 5 times;
(2) magnetic core-shell plasma nano gap nanoparticle: magnetic nanometer particles are dispersed in bicine buffering In solution, dopamine (PDA) is then added to reach the thickness of required dopamine, after stirring 8h, by product centrifugal purification;
(3) magnetic core-shell plasma nano gap nanoparticle the preparation of Single Magnetic gold particle: is added to 10mL Deionized water in, isometric gold chloride (HAuCl is added after stirring4) and hydroxylamine hydrochloride (NH2OH·HCl);
(4) preparation of magnetic bi-layer gold nano grain: 5,5 '-two thiobis (2- are added in the Single Magnetic gold particle of preparation Nitrobenzoic acid) (DTNB) and stir 3 hours, be centrifuged to 1mL.Sequentially add cetyl trimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), silver nitrate (AgNO3), ascorbic acid (L-AA) and NaOH solution, by mixture temperature After educating 2 hours, HAuCl is added4Solution simultaneously heats.
FeCl described in above-mentioned steps (1)2·4H2O and FeCl3·6H2The molar ratio of O mixing is 1: 1-1: 5.
The dosage of the Dextran of addition described in above-mentioned steps (1) is 0.1-0.5g.
The concentration that NaOH is added described in above-mentioned steps (1) is 1-10mol/L.
Fe described in above-mentioned steps (1)3O4The dosage of glucan nanoparticle is 10-100 μ L.
The volume of bicine buffer solution described in above-mentioned steps (2) is 10-20mL.
The concentration that PDA is added described in above-mentioned steps (2) is 0.01-0.2mg/mL.
The dosage that magnetic core-shell plasma nano gap nanoparticle is added described in above-mentioned steps (3) is 0.1-1mL.
The mixing time in magnetic core-shell plasma nano gap nanoparticle described in above-mentioned steps (3) is 1- 10min。
Isometric HAuCl described in above-mentioned steps (3)4And NH2The volume of OHHCl is 1-10mL.
The HAuCl of addition described in above-mentioned steps (3)4Concentration be 2.5mmol/L, NH2The concentration of OHHCl is The concentration of 0.2mol/L, DTNB are 1-10mmol/L, volume 0.1-10mL.
The concentration of the CTAB of addition described in above-mentioned steps (4) be 50-200mmol/L, volume 0.1-10mL, PVP's Mass percent is 1-10%, volume 1-10mL, AgNO3Concentration be 1-10mmol/L, volume 0.1-10mL, L-AA's Concentration is 100-500mmol/L, and the concentration of volume 0.1-10mL, NaOH are 100-500mmol/L, volume 0.1-10mL, HAuCl4Concentration be 1-10mmol/L, volume 0.1-10mL, the temperature of heating is 80-150 DEG C, heating time 10- 30min。
Superiority of the invention:
A kind of synthetic method of magnetic bi-layer gold nano grain, it is total in biotechnology, biosensor and biomedicine, magnetic There is important application in the fields such as vibration imaging and catalysis.Fe3O4The superparamagnetic characteristic of core material can be used for exterior guiding or as magnetic resonance at As developer in (MRI).In recent years, the magnetic nanoparticle of gold cladding is a kind of ideal complex for combining nucleocapsid advantage System has unique medical applications potentiality.
Detailed description of the invention
The following drawings is only intended to schematically illustrate the present invention and explain, however it is not limited to the scope of the present invention.Wherein:
Fig. 1 is the result photo of the embodiment of the present invention 1;
Fig. 2 is the result photo of the embodiment of the present invention 2;
Fig. 3 is the result photo of the embodiment of the present invention 3.
Specific embodiment
The present invention is described with specific embodiment with reference to the accompanying drawing.Unless stated otherwise, skill used in the present invention Art means are method known in those skilled in the art.In addition, embodiment be interpreted as it is illustrative, rather than limit this The range of invention, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, not Under the premise of spirit and scope of the present invention, in these embodiments material component and dosage carry out various changes or Change also belongs to protection scope of the present invention.
Embodiment 1:
The magnetic bi-layer gold nano grain of preparation is placed under transmission electron microscope and is observed, obtains TEM's as shown in Figure 1 Photo can be seen that the magnetic bi-layer gold nano grain after drying occurs comparing by the magnetism of itself institute's band from image Apparent agglomeration.
Embodiment 2:
The magnetic bi-layer gold nano grain of preparation is placed in energy disperse spectroscopy (EDS) and is tested.It is tied as shown in Figure 2 Fruit, there are mainly three types of the components of the magnetic bi-layer gold nano grain of preparation, respectively gold, silver and iron, corresponding quality Percentage is respectively 84.11%, 14.23% and 1.66%.
Embodiment 3:
The Raman detection of hand-held is put into after the magnetic bi-layer gold nano grain prepared drop is dried on silicon wafer It is tested in instrument.It obtains as shown in Figure 3 as a result, the characteristic peak for the magnetic bi-layer gold nano grain prepared is located at 1331cm-1 Near, there is stronger Raman signal and good signal-to-noise ratio.

Claims (12)

1. a kind of preparation method of magnetic bi-layer gold nanorods, comprising the following steps:
(1) magnetic nanometer particles (Fe3O4- Dextran) synthesis: four water frerrous chloride (FeCl2·4H2O), Iron trichloride hexahydrate (FeCl3·6H2O it) is dissolved in deionized water with glucan (Dextran), mixed solution is gradually added under agitation Sodium hydroxide (NaOH) simultaneously stirs 2h, and the black precipitate occurred is collected with magnet, is then washed with deionized 5 times;
(2) magnetic core-shell plasma nano gap nanoparticle: magnetic nanometer particles are dispersed in bicine buffer solution In, dopamine (PDA) is then added to reach the thickness of required dopamine, after stirring 8h, by product centrifugal purification;
(3) magnetic core-shell plasma nano gap nanoparticle the preparation of Single Magnetic gold particle: is added to going for 10mL Isometric gold chloride (HAuCl is added in ionized water, after stirring4) and hydroxylamine hydrochloride (NH2OH·HCl);
(4) preparation of magnetic bi-layer gold nano grain: 5,5 '-two thiobis (2- nitros are added in the Single Magnetic gold particle of preparation Benzoic acid) (DTNB) and stir 3 hours, be centrifuged to 1mL.It sequentially adds cetyl trimethylammonium bromide (CTAB), gather Vinylpyrrolidone (PVP), silver nitrate (AgNO3), ascorbic acid (L-AA) and NaOH solution, after mixture is incubated 2 hours, HAuCl is added4Solution simultaneously heats.
2. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (1) Described in FeCl2·4H2O and FeCl3·6H2The molar ratio of O mixing is 1: 1-1: 5.
3. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (1) Described in addition Dextran dosage be 0.1-0.5g.
4. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (1) Described in addition NaOH concentration be 1-10mol/L.
5. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (1) Described in Fe3O4The dosage of glucan nanoparticle is 10-100 μ L.
6. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (2) Described in bicine buffer solution volume be 10-20mL.
7. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (2) Described in addition PDA concentration be 0.01-0.2mg/mL.
8. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (3) Described in addition magnetic core-shell plasma nano gap nanoparticle dosage be 0.1-1mL.
9. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (3) Described in magnetic core-shell plasma nano gap nanoparticle mixing time be 1-10min.
10. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (3) Described in isometric HAuCl4And NH2The volume of OHHCl is 1-10mL.
11. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (3) Described in HAuCl4Concentration be 2.5mmol/L, NH2The concentration of OHHCl is 0.2mol/L, and the concentration of DTNB is 1- 10mmol/L, volume 0.1-10mL.
12. a kind of preparation method of magnetic bi-layer gold nanorods according to claim 1, which is characterized in that above-mentioned steps (4) Described in the concentration of CTAB be 50-200mmol/L, the mass percent of volume 0.1-10mL, PVP is 1-10%, volume For 1-10mL, AgNO3Concentration be 1-10mmol/L, the concentration of volume 0.1-10mL, L-AA is 100-500mmol/L, body Product is 0.1-10mL, and the concentration of NaOH is 100-500mmol/L, volume 0.1-10mL, HAuCl4Concentration be 1-10mmol/ L, volume 0.1-10mL, the temperature of heating are 80-150 DEG C, heating time 10-30min.
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CN102861921A (en) * 2011-07-08 2013-01-09 西南民族大学 Preparation method of core-shell magnetic/gold nano particles
US20130330280A1 (en) * 2007-07-16 2013-12-12 University Of Central Florida Research Foundation, Inc. Aqueous Method of Making Magnetic Iron Oxide Nanoparticles
CN105198003A (en) * 2015-08-17 2015-12-30 商丘师范学院 Method for preparing paramagnetic ferroferric oxide nano particles
CN107552806A (en) * 2016-06-30 2018-01-09 郑州科斗创客科技有限公司 A kind of preparation method with the size Fe3O4@Au core@shell structure nanorod controllable with dispersiveness that can be prepared on a large scale
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US20100228237A1 (en) * 2006-08-08 2010-09-09 Korea Research Institute of Bioscience and Biotecnology Gold nanocages containing magnetic nanoparticles
US20130330280A1 (en) * 2007-07-16 2013-12-12 University Of Central Florida Research Foundation, Inc. Aqueous Method of Making Magnetic Iron Oxide Nanoparticles
CN101773810A (en) * 2009-12-31 2010-07-14 厦门大学 Method for synthesizing gold-coated ferroferric oxide nano particles
CN102861921A (en) * 2011-07-08 2013-01-09 西南民族大学 Preparation method of core-shell magnetic/gold nano particles
CN105198003A (en) * 2015-08-17 2015-12-30 商丘师范学院 Method for preparing paramagnetic ferroferric oxide nano particles
CN107552806A (en) * 2016-06-30 2018-01-09 郑州科斗创客科技有限公司 A kind of preparation method with the size Fe3O4@Au core@shell structure nanorod controllable with dispersiveness that can be prepared on a large scale
CN110217828A (en) * 2019-07-02 2019-09-10 北华航天工业学院 A kind of Fe3O4Nanometer rods and preparation method thereof

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