CN106432594A - Light- heat-magnetism multi-responsive microgel and preparation method thereof - Google Patents

Light- heat-magnetism multi-responsive microgel and preparation method thereof Download PDF

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CN106432594A
CN106432594A CN201610863954.4A CN201610863954A CN106432594A CN 106432594 A CN106432594 A CN 106432594A CN 201610863954 A CN201610863954 A CN 201610863954A CN 106432594 A CN106432594 A CN 106432594A
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pda
microgel
particle
solution
pnipam
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CN106432594B (en
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吴仁安
戴玲凤
苏云飞
席光辉
王泽锋
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WENZHOU BIOMEDICAL MATERIALS AND ENGINEERING RESEARCH INSTITUTE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K2201/01—Magnetic additives
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

The invention discloses light-heat-magnetism multi-responsive microgel and a preparation method thereof. The microgel adopts a core-core membrane-core shell structure, taking magnetic Fe3O4 as a core, PDA (polydopamine) with photothermal performance as a core membrane and thermosensitive hydrogel PNIPAm (poly(N-isopropylacrylamide)) as a core shell layer. The microgel has wide application prospect in the biomedical field, such as nuclear magnetic imaging, thermothermal and photoacustic imaging and photothermal therapy, besides, supporting of drugs on the core shell or a protective layer can be used for target-controllable drug release, and specific functional groups modified on the surface can be used for separation of related protein and the like.

Description

Pyromagnetic multiple response microgel of a kind of light and preparation method thereof
Technical field
The present invention relates to a kind of pyromagnetic multiple response microgel extremely preparation method of light, belong to material and biologic applications field.
Background technology
At present, environmental sensitivity（As the change such as temperature sensor, light, electric field, magnetic field, stress, p H value）Polymer gel Have become as the focus of current research as new function material.Microgel is generally referred to as yardstick in 10 nm to several microns models The polymer gel of the crosslinking in enclosing, can be swelling in a solvent, and structure can be maintained will not to dissolve.With bulk hydrogel phase Than microgel not only has good biocompatibility and because its size is less, and the response speed of envirment factor is more to external world Hurry up.Different microgels have different using values to the response signal of environmental stimuluses, further according to monosomy confrontation gel Modify and compound, form the important research direction that multiple response multi-functional microgel gel has become as this field.
In recent years about the preparation of composite microgel, performance and in catalysis, medicine controlled releasing, sensor, immobilized enzyme, cell The research report of the aspects such as culture, temperature-sensitive switch film is swift and violent to be increased.Other functions composition and microgel are attached to one be combined In system, the new material prepared can be made to assume multiple performance, give full play to the synergism between different materials.For example, Mei By Au and Ag nanometer particle load in Temperature-Sensitive Microgel PNIPAm, nanoparticle is evenly distributed on Y et al. with independent individual In microgel network, form composite microgel.This composite microgel can adjust it by changing the swellbility of gel shell Catalysis activity to paranitrophenol, and nanoparticle is difficult to from polymer network removing it is easy to recycling.For another example Have and study the vanadium dioxide of different size size, pattern（VO2）Nano-particles filled, in PNIPAm network structure, imparts Temperature-Sensitive Microgel light sensitive characteristic, and explore this composite microgel further in efficient Thermochromic smart window field.
At present multiple response microgel is also confined to Lazer's property, such as Thermo-sensitive pH sensitivity, Thermo-sensitive heliosensitivity, temperature sensitive Property magnetic responsiveness.
By retrieval, the multiple response that there is presently no by simple synthetic method formation optical and thermal-magnetic susceptibility is multi-functional micro- Gel.
Content of the invention
The invention aims to overcoming the shortcoming and defect that prior art exists, and provide a kind of light pyromagnetic multiple response Microgel, it has light, thermal and magnetic multiple response performance simultaneously.
Another object of the present invention is to provide a kind of preparation method of light pyromagnetic multiple response microgel, the method is simple Easy to operate, it is easy to industrial applications.
For realizing first purpose of the present invention, the technical scheme is that with Fe3O4Have for magnetic core introducing The poly-dopamine of photothermy is nuclear membrane, constitutes Fe3O4@PDA particle, introduces and has the PNIPAM of Thermo-sensitive and be Nucleocapsid, forms Fe3O4Fe in PNIPAM network structure for the@PDA particle dispersion package3O4@PDA@PNIPAm is micro- Gel, this Fe3O4@PDA@PNIPAm microgel has optical and thermal-magnetic multiple response characteristic.
Setting is described Fe further3O4Particle diameter be 10 nm ~ 30 nm.
Setting is Fe further3O4The overall particle diameter of@PDA particle is in 10 nm ~ 50 nm.
Setting is Fe further3O4The reaction molar ratio range of@PDA and NIPAm is 5:1~10:1, gained Fe3O4@PDA@ The particle diameter of PNIPAm microgel is in 500 nm ~ 1500 nm.
Setting is Fe further3O4The saturation magnetization of@PDA@PNIPAm microgel is 20.54 ~ 45.348（emu/g）、 Photo-thermal conversion efficiency is 8.5% ~ 13.1%, swelling ratio is 12 ~ 25.5.
Realize second goal of the invention of the present invention, its technical scheme is a kind of preparation side of light pyromagnetic multiple response microgel Method, comprises the following steps：
（1）Fe is prepared using coprecipitation3O4, by controlling Fe3+/ Fe2+Molar ratio 1:1~2:1, obtain particle diameter in 10 nm The Fe of ~ 30 nm3O4；
（2）Fe is aggregated in by solution oxide3O4Surface aggregate one strata dopamine, constitutes Fe3O4@PDA particle, poly-dopamine Thickness as core mould is 2 nm ~ 15 nm, Fe3O4The overall particle diameter of@PDA particle is in 10 nm ~ 50 nm；
（3）With N-isopropylacrylamide as monomer, N,N methylene bis acrylamide is cross-linking agent, by Fe3O4@PDA particle with Mixing, and with Ammonium persulfate. as initiator, may be polymerized reaction, the mol ratio of monomer and cross-linking agent is 10:1~5:1, Fe3O4The reaction molar ratio range of@PDA and NIPAm is 5:1~10:1, obtain Fe3O4The particle diameter of@PDA@PNIPAm microgel is 500 nm~1500 nm.
Setting is described step further（1）Mix under ultrasonic all with copperas solution for liquor ferri trichloridi Even, ferric chloride is 1 with the molar ratio of ferrous sulfate:1~2:1, above-mentioned mixed solution is slowly dropped to 2 mol/L NaOH solution in, mechanical agitation 60 min at 80 DEG C, stop heating after continue stirring 60 min, the phosphate being 6.4 with pH It is 6.4 that buffer solution is washed till pH by Magnetic Isolation, obtains Fe3O4Magnetic nano-particle.
Using dynamic light scattering（DLS）To obtained Fe3O4The particle diameter of magnetic nano-particle and monodispersity are characterized Detection.Using transmission electron microscope（TEM）To Fe3O4The pattern further characterization of magnetic nano-particle.Using vibrating example magnetic Strong meter（VSM）Under room temperature, sample is carried out with magnetic measurement, synthesized Fe3O4@PDA can be retained in microgel and have good Good magnetic.
Setting is described step further（2）Take above-mentioned Fe3O4Magnetic nano-particle, is configured to 100 mL 0.03 mol/L Solution, ultrasonic 15 min, add poly-dopamine, the concentration ratio scope of poly-dopamine is 1 ~ 3 mg/L, and mixed solution is in frozen water In bath, Quick mechanical stirs 1 h ~ 5 h, by Magnetic Isolation and be washed till solution and become neutral, obtains Fe3O4@PDA particle, ultra-pure water Dispersion is standby.
Using transmission electron microscope to Fe3O4The pattern further characterization of@PDA magnetic nano-particle.Using vibrating example Gaussmeter（VSM）Under room temperature, magnetic measurement is carried out to sample.Using uv-visible absorption spectra（UV-Vis）Detection is in near-infrared The spectral absorption situation in area.Detect its light thermal property using 808 nm near infrared lasers and digital temperature monitor, obtained Fe3O4@PDA particle has concurrently and is magnetic and light thermal property.
Setting is described step further（3）Fe3O4The preparation of@PDA@PNIPAm microgel：Take 50 mL above-mentioned Fe3O4@PDA nano-particle solution, adds N-isopropylacrylamide monomer, N,N methylene bis acrylamide cross-linking agent aqueous solution, Fe3O4@PDA particle is 5 with the reaction molar ratio range of NIPAM:1~10:1, the mol ratio of monomer and cross-linking agent is 10:1~5:1, It is passed through nitrogen stirring at low speed and removes oxygen, be heated to 70 DEG C and constant temperature keeps 30 min, add 0.45 mmol/L Ammonium persulfate. molten Liquid initiated polymerization, 70 DEG C of reaction constant temperature keeps logical nitrogen 6 h, naturally cools to room temperature, is washed till neutrality by Magnetic Isolation. Using dynamic light scattering, the dispersibility of obtained sample under different temperatures and particle diameter are characterized.Using transmission electron microscopy Mirror further characterizes to the pattern of material.Using vibrating specimen magnetometer（VSM）Under room temperature, magnetic measurement is carried out to sample.Use 808 nm laser and digital temperature monitor detect its light thermal property, confirm this Fe3O4@PDA@PNIPAm microgel have light- Thermo-magnetic multiple response characteristic.
The microgel of the present invention is with a wide range of applications in biomedical sector, for example NMR (Nuclear Magnetic Resonance) imaging, photo-thermal and light Acoustic imaging, photo-thermal therapy, in addition on nucleocapsid or in protective layer, carrying medicament can be additionally used in the controlled drug release of targeting, and Can be used for associated protein separation etc. in surface modification specific function group.
With reference to specification drawings and specific embodiments, the present invention is described further.
Brief description
Fe in Fig. 1 embodiment 13O4The transmission electron microscope picture of@PDA@PNIPAm, in Fig. 1, top right plot is that single microgel amplifies Figure；
Fig. 2 Fe3O4The room temperature B-H loop of@PDA@PNIPAm；
Fig. 3 Fe in the presence of Magnet3O4@PDA@PNIPAm microgel separates out from solution；
Fig. 4 Fe3O4The ultraviolet-visible absorption spectroscopy of@PDA@PNIPAm；
Fig. 5 Fe3O4The photo-thermal effect figure of@PDA@PNIPAm.
Specific embodiment
Below by embodiment, the present invention is specifically described, is served only for the present invention is further described, no It is understood that for limiting the scope of the present invention, the technician in this field can be according to the content of foregoing invention to the present invention Make some nonessential improvement and adjust.
Embodiment 1：
a）Preparation Fe3O4Magnetic nano-particle solution：The ferric chloride of 20 mL 0.8 mol/L（FeCl3）Solution and 10 mL The ferrous sulfate of 0.8 mol/L（FeSO4）Solution is in ultrasonic lower mix homogeneously.Above-mentioned mixed solution is slowly dropped to 200 mL In the NaOH solution of 2 mol/L, mechanical agitation 60 min at 80 DEG C, continues stirring 60 min after stopping heating.It is 6.4 with pH It is 6.4 that PBS solution is washed till pH by Magnetic Isolation, and it is standby to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4Magnetic nano-particle solution 100 mL, surpasses Sound 15 min, adds 200 mg DA Quick mechanical in ice-water bath to stir 3 h, removes reactant liquor by centrifugation, Magnetic Isolation is simultaneously It is washed till solution and become neutral standby.
c）" Punica granatum L. shape " Fe3O4The preparation method of@PDA@PNIPAm microgel:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticle Sub- solution, adds 100 mL 12.4 mmol/L NIPAM monomer, 1.4 mmol/L BIS cross-linking agent aqueous solutions, logical nitrogen low speed Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, adds 0.45 mmol/L APS initiated polymerization, reaction 70 DEG C of constant temperature keeps logical nitrogen 6 h, naturally cools to room temperature.Neutrality is washed till by Magnetic Isolation, lyophilizing is standby.
By characterizing, the Fe of this embodiment synthesis3O4Particle diameter between 10 ~ 15 nm, saturation magnetization intensity（Ms）For 39.245（emu/g）, coercivity close to 0, shows superparamagnetism, and solution places after 96 h still no obvious sediment, illustrates In solution, dispersion stabilization is preferable.Fe3O4Although in 10 nm, composite nanoparticle is still for the coating layer thickness of PDA in@PDA Show stronger magnetic, saturation magnetization（Ms）For 28.158（emu/g）, this is because PDA is nonmagnetic.? 6.6 W cm−2Irradiate 500 s under the laser of 808 nm, record Fe3O4The photothermal conversion efficiency of@PDA is 10.1%, higher than Fe3O4 （About 5.7%）.Fe3O4The transmission electron microscope picture of@PDA@PNIPAm is shown in Fig. 1, and upper right corner illustration is partial enlarged drawing it can be seen that tiny Fe3O4@PDA granule, Fe as can be seen from Figure3O4@PDA is uniformly wrapped in microgel, and whole microgel assumes " Punica granatum L. Shape ", particle diameter is between 500 nm ~ 700 nm（Desiccation）, hydration radius is in 1100 nm ~ 1200 nm.Due to having wrapped up PDA And microgel, after being combined, saturation magnetization is reduced to 20.54（emu/g）, such as Fig. 2, but still can easily utilize external magnetic field It is separated from solution, after withdrawing magnetic field, and is soon distributed in solution, be very beneficial for reusing, such as scheme 3.By ultraviolet-visible absorption spectroscopy（Fig. 4）It can be clearly seen that composite microgel has absworption peak at the nm of near infrared region 808, With Fe3O4@PDA compares, due to the stop of nucleocapsid, Fe3O4@PDA@PNIPAm microgel photo-thermal conversion efficiency be down to 8.5%, PDA, Fe3O4@PDA、Fe3O4Fig. 5 is shown in the contrast of@PDA@PNIPAm photothermal conversion.Due to Fe3O4@PDA is interspersed in the grid of microgel, Fe3O4The swelling ratio of@PDA PNIPAm microgel is 12.22, and less than the PNIPAm not being combined, ginseng is shown in Table 1.
Table 1 Fe3O4@The swelling ratio of PDA@PNIPAM
Project PNIPAm Fe3O4@PDA@PNIPAm
Dh 25（nm） 907.8 1200.3
Dh 60（nm） 278.2 521.2
α 34.64 12.22
Embodiment 2：
a）Preparation Fe3O4Magnetic nano-particle solution：The ferric chloride of 20 mL 0.8 mol/L（FeCl3）Solution and 10 mL1.2 The ferrous sulfate of mol/L（FeSO4）Solution is in ultrasonic lower mix homogeneously.Above-mentioned mixed solution is slowly dropped to 200 mL 2 In the NaOH solution of mol/L, mechanical agitation 60 min at 80 DEG C, continues stirring 60 min after stopping heating.It is 6.4 with pH It is 6.4 that PBS solution is washed till pH by Magnetic Isolation, and it is standby to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4Magnetic nano-particle solution 100 mL, surpasses Sound 15 min, adds 200 mg DA Quick mechanical in ice-water bath to stir 3 h, removes reactant liquor by centrifugation, Magnetic Isolation is simultaneously It is washed till solution and become neutral standby.
c）" Punica granatum L. shape " Fe3O4The preparation method of@PDA@PNIPAM microgel:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticle Sub- solution, adds 100 mL 12.4 mmol/L NIPAM monomer, 1.4 mmol/L BIS cross-linking agent aqueous solutions, logical nitrogen low speed Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, adds 0.45 mmol/L APS initiated polymerization, reaction 70 DEG C of constant temperature keeps logical nitrogen 6 h, naturally cools to room temperature.Neutrality is washed till by Magnetic Isolation, lyophilizing is standby.
Compared with Example 1, embodiment 2 changes the mol ratio of reacted constituent, product Fe3O4Particle diameter increases, particle diameter distribution In 35 nm ~ 41 nm, saturation magnetization intensity is 66.31（emu/g）, there is ferromagnetism.In b, c operating condition identical situation Under, Fe3O4@PDA、Fe3O4The particle diameter of@PDA@PNIPAm also increased, and increases respectively to 50 ~ 60 nm, 1300 ~ 1500nm, Saturation magnetization intensity is increased to 54.239 respectively（emu/g）With 48.954（emu/g）.Further, since Fe3O4The particle diameter of particle diameter increases Plus, specific surface area reduces, Fe3O4@The light thermal efficiency of PDA slightly reduces, and Fe3O4@PDA@PNIPAm is reduced to 7.8 %, thus It can be seen that entering into the Fe of microgel network3O4@PDA amount can directly affect the light thermal efficiency.
Embodiment 3
a）Preparation Fe3O4Magnetic nano-particle solution：The ferric chloride of 20 mL 0.8 mol/L（FeCl3）Solution and 10 mL The ferrous sulfate of 0.8 mol/L（FeSO4）Solution is in ultrasonic lower mix homogeneously.Above-mentioned mixed solution is slowly dropped to 200 mL In the NaOH solution of 2 mol/L, mechanical agitation 60 min at 80 DEG C, continues stirring 60 min after stopping heating.It is 6.4 with pH It is 6.4 that PBS solution is washed till pH by Magnetic Isolation, and it is standby to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4Magnetic nano-particle solution 100 mL, surpasses Sound 15 min, adds 200 mg DA Quick mechanical in ice-water bath to stir 5 h, removes reactant liquor by centrifugation, Magnetic Isolation is simultaneously It is washed till solution and become neutral standby.
c）" Punica granatum L. shape " Fe3O4The preparation method of@PDA@PNIPAm microgel:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticle Sub- solution, adds 100 mL 12.4 mmol/L NIPAM monomer, 1.4 mmol/L BIS cross-linking agent aqueous solutions, logical nitrogen low speed Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, adds 0.45 mmol/L APS initiated polymerization, reaction 70 DEG C of constant temperature keeps logical nitrogen 6 h, naturally cools to room temperature.Neutrality is washed till by Magnetic Isolation, lyophilizing is standby.
Compared with Example 1, change the sedimentation time of PDA, PDA thickness increases to 15 nm ~ 20 nm, Fe3O4@PDA Particle size range be 30 nm ~ 40 nm.Because the thickness of PDA increased nearly 2 times, Fe3O4@PDA surface PDA coating layer thickness increases Plus, saturation magnetization is reduced to 15.20（emu/g）, but photo-thermal conversion efficiency brings up to 13.1%.Therefore, it can according to difference Function stress demand, suitably adjust Fe3O4Particle diameter and PDA coating layer thickness, take into account magnetic and photothermal conversion efficiency.
Embodiment 4
a）Preparation Fe3O4Magnetic nano-particle solution：The ferric chloride of 20 mL 0.8 mol/L（FeCl3）Solution and 10 mL The ferrous sulfate of 0.8 mol/L（FeSO4）Solution is in ultrasonic lower mix homogeneously.Above-mentioned mixed solution is slowly dropped to 200 mL In the NaOH solution of 2 mol/L, mechanical agitation 60 min at 80 DEG C, continues stirring 60 min after stopping heating.It is 6.4 with pH It is 6.4 that PBS solution is washed till pH by Magnetic Isolation, and it is standby to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4Magnetic nano-particle solution 100 mL, surpasses Sound 15 min, adds 200 mg DA Quick mechanical in ice-water bath to stir 3 h, removes reactant liquor by centrifugation, Magnetic Isolation is simultaneously It is washed till solution and become neutral standby.
c）" Punica granatum L. shape " Fe3O4The preparation method of@PDA@PNIPAm microgel:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticle Sub- solution, adds 100 mL 12.4 mmol/L NIPAm monomer, 2 mmol/L BIS cross-linking agent aqueous solutions, and logical nitrogen low speed stirs Mix removing oxygen, be heated to 70 DEG C and constant temperature keeps 30 min, add 0.45 mmol/L APS initiated polymerization, reaction is permanent 70 DEG C of temperature keeps logical nitrogen 6 h, naturally cools to room temperature.Neutrality is washed till by Magnetic Isolation, lyophilizing is standby.
Compared with Example 1, embodiment changes the consumption of cross-linking agent in microgel, and the consumption increasing cross-linking agent can change Become the degree of cross linking of microgel, that is, the aperture of microgel network structure changes.Work as Fe3O4@PDA particle diameter is less, in Fe3O4@ In the case of PDA and NIPAm constant rate, enter microgel network Fe3O4@PDA can increase, and shows the light of composite microgel The thermal efficiency brings up to 10.7%.

Claims (9)

1. a kind of pyromagnetic multiple response microgel of light it is characterised in that：With Fe3O4For magnetic core and introduce there is photothermy Poly-dopamine is nuclear membrane, constitutes Fe3O4@PDA particle, the PNIPAM that introducing has Thermo-sensitive is nucleocapsid, is formed Fe3O4Fe in PNIPAM network structure for the@PDA particle dispersion package3O4@PDA@PNIPAm microgel, should Fe3O4@PDA@PNIPAm microgel has optical and thermal-magnetic multiple response characteristic.
2. a kind of pyromagnetic multiple response microgel of light according to claim 1 it is characterised in that：Described Fe3O4Particle diameter be 10 nm~30 nm.
3. a kind of pyromagnetic multiple response microgel of light according to claim 1 it is characterised in that：Fe3O4The entirety of@PDA particle Particle diameter is in 10 nm ~ 50 nm.
4. a kind of pyromagnetic multiple response microgel of light according to claim 1 it is characterised in that：Fe3O4@PDA and NIPAm's Reaction molar ratio range is 5:1~10:1, gained Fe3O4The particle diameter of@PDA@PNIPAm microgel is in 500 nm ~ 1500 nm.
5. a kind of pyromagnetic multiple response microgel of light according to claim 1 it is characterised in that：Fe3O4@PDA@PNIPAm is micro- The saturation magnetization of gel is 20.54 ~ 45.35（emu/g）, photo-thermal conversion efficiency be 8.5% ~ 13.1%, swelling ratio be 12 ~ 25.5.
6. a kind of preparation method of the pyromagnetic multiple response microgel of light is it is characterised in that comprise the following steps：
Fe is prepared using coprecipitation3O4, by controlling Fe3+/ Fe2+Molar ratio 1:1~2:1, obtain particle diameter in 10 nm ~ 30 The Fe of nm3O4；
Fe is aggregated in by solution oxide3O4Surface aggregate one strata dopamine, constitutes Fe3O4@PDA particle, poly-dopamine conduct The thickness of core mould is 2 nm ~ 15 nm, Fe3O4The overall particle diameter of@PDA particle is in 10 nm ~ 50 nm；
With N-isopropylacrylamide as monomer, N,N methylene bis acrylamide is cross-linking agent, by Fe3O4@PDA particle mixes therewith Close, and with Ammonium persulfate. as initiator, may be polymerized reaction, the mol ratio of monomer and cross-linking agent is 10:1~5:1, Fe3O4@ The reaction molar ratio range of PDA and NIPAm is 5:1~10:1, obtain Fe3O4The particle diameter of@PDA@PNIPAm microgel 500 nm ~ 1500 nm.
7. a kind of pyromagnetic multiple response microgel of light according to claim 6 preparation method it is characterised in that：Described step Suddenly（1）Mix homogeneously under ultrasonic with copperas solution for liquor ferri trichloridi, the mol ratio of ferric chloride and ferrous sulfate Example scope is 1:1~2:1, above-mentioned mixed solution is slowly dropped in the NaOH solution of 2 mol/L, mechanical agitation 60 at 80 DEG C Min, continues stirring 60 min after stopping heating, the phosphate buffered solution being 6.4 with pH is washed till pH by Magnetic Isolation and is 6.4, obtain Fe3O4Magnetic nano-particle.
8. a kind of pyromagnetic multiple response microgel of light according to claim 7 preparation method it is characterised in that：Described step （2）Take above-mentioned Fe3O4Magnetic nano-particle, is configured to 100 mL 0.03 mol/L solution, ultrasonic 15 min, adds poly- DOPA Amine, the concentration ratio scope of poly-dopamine is 1 ~ 3 mg/L, and mixed solution Quick mechanical in ice-water bath stirs 1 h ~ 5 h, leads to Cross Magnetic Isolation and be washed till solution one-tenth neutrality, obtain Fe3O4@PDA particle, ultra-pure water dispersion is standby.
9. a kind of pyromagnetic multiple response microgel of light according to claim 8 preparation method it is characterised in that：Described step Suddenly（3）Fe3O4The preparation of@PDA@PNIPAm microgel：Take the above-mentioned Fe of 50 mL3O4@PDA nano-particle solution, adds isopropyl Acrylamide monomer, N,N methylene bis acrylamide cross-linking agent aqueous solution, Fe3O4The reaction molar ratio range of@PDA and NIPAM For 5:1~10:1, the mol ratio of monomer and cross-linking agent is 10:1~5:1, it is passed through nitrogen stirring at low speed and removes oxygen, be heated to 70 DEG C And constant temperature keeps 30 min, add 0.45 mmol/L ammonium persulfate solution initiated polymerization, 70 DEG C of reaction constant temperature keeps logical nitrogen Gas 6 h, naturally cools to room temperature, is washed till neutrality by Magnetic Isolation.
CN201610863954.4A 2016-09-29 2016-09-29 A kind of photo-thermal magnetic multiple response microgel and preparation method thereof Expired - Fee Related CN106432594B (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107213137A (en) * 2017-06-21 2017-09-29 西南大学 Pegylation wraps up the preparation method of poly-dopamine drug loaded magnetic nano particle
CN108329442A (en) * 2018-02-09 2018-07-27 西北工业大学 A kind of CuO@PNIPAm temperature sensitive composite materials and preparation method
CN109295716A (en) * 2018-09-14 2019-02-01 晋江瑞碧科技有限公司 A kind of preparation method of magnetic, temperature collaboration stimuli responsive hydrogel
CN109730968A (en) * 2019-03-15 2019-05-10 深圳大学 Photosensitizer and preparation method thereof
CN111374960A (en) * 2018-12-29 2020-07-07 上海原子科兴药业有限公司 EGFR receptor targeted tumor diagnosis and treatment radioactive nanoparticle and preparation method thereof
CN111793171A (en) * 2020-07-22 2020-10-20 中国科学院地质与地球物理研究所 Platinum group element specific resin and preparation method and application thereof
CN112957313A (en) * 2021-02-07 2021-06-15 华中科技大学 Injectable adhesive temperature-sensitive gel system and application thereof
CN114100378A (en) * 2021-10-20 2022-03-01 山东大学 D-amino acid thermosensitive controlled-release nanoparticles with magnetic targeting-magnetic heating functions and application of nanoparticles to MBR membrane pollution
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CN115282942A (en) * 2022-09-01 2022-11-04 江苏大学 Preparation method of near-infrared response crescent imprinted microgel adsorbent
CN115433309A (en) * 2022-09-06 2022-12-06 郑州大学 Liquid composite interlayer material for energy-saving window and preparation method thereof
CN116038653A (en) * 2022-12-21 2023-05-02 深圳大学 Magnetic micro-robot with microalgae as template and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104672396A (en) * 2015-03-24 2015-06-03 哈尔滨工业大学 Preparation method and application of photo-thermal material Fe3O4/polydopamine/polyisopropyl acrylamide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104672396A (en) * 2015-03-24 2015-06-03 哈尔滨工业大学 Preparation method and application of photo-thermal material Fe3O4/polydopamine/polyisopropyl acrylamide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIANWEN TIAN,ETAL,: "Marrying Mussel Inspired Chemistry with SET-LRP: A Novel Strategy for Surface Functionalization of Carbon Nanotubes", 《JOURNAL OF POLYMER SCIENCE》 *
骆东升等: "超顺磁Fe3O4@PDA核-壳结构纳米粒子的制备及表征", 《功能高分子学报》 *

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CN108329442A (en) * 2018-02-09 2018-07-27 西北工业大学 A kind of CuO@PNIPAm temperature sensitive composite materials and preparation method
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CN111793171A (en) * 2020-07-22 2020-10-20 中国科学院地质与地球物理研究所 Platinum group element specific resin and preparation method and application thereof
CN112957313A (en) * 2021-02-07 2021-06-15 华中科技大学 Injectable adhesive temperature-sensitive gel system and application thereof
CN112957313B (en) * 2021-02-07 2022-09-23 华中科技大学 Injectable adhesive temperature-sensitive gel system and application thereof
CN114100378A (en) * 2021-10-20 2022-03-01 山东大学 D-amino acid thermosensitive controlled-release nanoparticles with magnetic targeting-magnetic heating functions and application of nanoparticles to MBR membrane pollution
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