CN104497235A - Temperature responsive fluorescent carbon nanoparticle hybrid microgel and preparation method thereof - Google Patents
Temperature responsive fluorescent carbon nanoparticle hybrid microgel and preparation method thereof Download PDFInfo
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- CN104497235A CN104497235A CN201410762873.6A CN201410762873A CN104497235A CN 104497235 A CN104497235 A CN 104497235A CN 201410762873 A CN201410762873 A CN 201410762873A CN 104497235 A CN104497235 A CN 104497235A
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Abstract
The invention relates to a temperature responsive fluorescent carbon nanoparticle hybrid microgel and a preparation method thereof. The method comprises the following steps: (1) weighing a proper amount of fluorescent carbon nanoparticles, preparing a fluorescent carbon nanoparticle solution by using dichloromethane, adding an acyl chloride monomer, reacting for 10 hours at room temperature, removing a reaction solvent, adding and spin-drying; (2) weighing the obtained double-bond fluorescent carbon nanoparticles and dispersing and dissolving in the fluorescent carbon nanoparticles; and transferring into a reaction container, introducing nitrogen to discharge air, adding a crosslinking agent, sodium dodecyl sulfate and refined N-isopropylacrylamide and stirring; introducing nitrogen, heating, and when the reaction liquid flows back, weighing an initiator and adding the initiator into a three-necked flask; (3) continuously introducing nitrogen and stirring; carrying out reflux react for 5-16 hours at 50-90 DEG C, and then stopping reaction; and (4) cooling to room temperature, filtering, and taking the filtrate and carrying out dialysis for 48 hours. The product prepared by the method is non-toxic, has a very good temperature response by fluorescence and has a good application prospect in drug controlled release, temperature sensing and the like.
Description
Technical field
The present invention relates to chemical technology field, fluorescent carbon nano particle hybrid microgel of particularly a kind of temperature response and preparation method thereof.
Technical background
Microgel (microgel) is the polymeric colloid particle that molecule inner height is cross-linked, and its internal structure is typical tridimensional network.The nano microgel of usual preparation is all the high dispersing system swollen in colloidal form in certain solvent, and this system is referred to as nano-hydrogel dispersion system.Microgel (hydrogel) a kind ofly can save large quantity of moisture and significantly swelling hydrophilic gel.Because of general containing hydrophilic group in structure, as-CONH
2,-COOH ,-SO
3h etc.The water reaching the own weight several times of polymer to hundreds of times can be saved in most microgel reticulated void.Because microgel is with a large amount of functional groups, these microgels have environment (as pH, temperature) stimuli responsive performance usually, and namely its volume can be grown up along with the change of environment or reduce.Because of various features such as micro-gel surface absorption property are strong, specific surface area large, functional diversity, gel particle size are controlled, structure composition can design, it is made to have potential using value widely in various fields such as medicine transmission, civil construction, food fresh keeping, fire-fighting, sewage disposals.But existing responsiveness microgel only has volume response usually, namely during environmental change, just its volume responds to environmental change, this greatly limits the practical application of microgel.Therefore, utilize novel material novel method to design the responsiveness microgel that preparation is novel, can be applied to a lot of field better, the responsiveness microgel of development of new also becomes one of the focus direction in research hydrogel field.
Summary of the invention
Fluorescent carbon nano particle hybrid microgel that the invention provides a kind of temperature response and preparation method thereof, the fluorescence of obtained fluorescent carbon nano particle hybrid microgel has good temperature-responsive, in medicine controlled releasing, temperature sensing, organizational project etc., have good application prospect.
Technical scheme of the present invention is: a kind of preparation method of fluorescent carbon nano particle hybrid microgel of temperature response, comprises the following steps:
(1) take appropriate fluorescent carbon nano particle, dissolve with methylene dichloride, be mixed with the fluorescent carbon particle solution that concentration is 0.5-10mg/mL, add acyl chloride monomer, at room temperature react 10h, removing reaction solvent, add water, be then spin-dried for, obtain double bond fluorescent carbon nano particle;
(2) take double bond fluorescent carbon nano particle, add dispersing and dissolving in 100mL distilled water; And transferred in the there-necked flask that agitator, reflux condensing tube and thermometer are housed; Open agitator, and even logical nitrogen, the air in complete amount discharge container and solution, adds linking agent, sodium laurylsulfonate (SDS), refining NIPA; Stir, and continue logical nitrogen, the air in complete amount discharge container and solution, heating, question response liquid takes initiator and is added in there-necked flask after starting backflow;
(3) Keep agitation also logical nitrogen, stopped reaction after continuing back flow reaction 5-16h at 50-90 DEG C;
(4) filter after being cooled to room temperature, get filtrate, dialysis 48h, gained dialyzate is the good carbon nano-particle hybrid microgel of purifying.
In step (1), the mass ratio of described fluorescent carbon nano particle, acyl chloride monomer is 10:1-50:1.
In step (1), described fluorescent carbon nano particle is fluorescent carbon nano particle prepared by hydrothermal method carbonization glucose, Mierocrystalline cellulose, chitosan, EDTA2Na, EDTA or gelatin.Be preferably fluorescent carbon nano particle prepared by hydrothermal method carbonization EDTA2Na.
In step (1), described acyl chloride monomer is acrylate chloride, methacrylic chloride, crotonyl chloride.Preferred acrylate chloride.
In step (2), double bond fluorescent carbon nano particle consumption is 1-40 weight part, and NIPA consumption is 100-400 weight part, and sodium lauryl sulphate consumption is 1-20 weight part, and Potassium Persulphate consumption is 1-10 weight part.The mass ratio that feeds intake of double bond fluorescent carbon particle, NIPA is 1:2.5-1:400, and preferred mass is than being 1:10.
In step (2), described initiator has hydrogen peroxide, ammonium persulphate or Potassium Persulphate.Preferred Potassium Persulphate.
In step (2), described linking agent has N-N methylene-bisacrylamide.
In step (3), preferable reaction temperature is 70 DEG C, preferred reaction time 12h.
The present invention also provides a kind of fluorescent carbon nano particle hybrid microgel product prepared as aforesaid method.
The fluorescent carbon nano particle hybrid microgel particle diameter that the present invention obtains is at about 300nm; When Same Wavelength excites, temperature raises, fluorescent weakening; Otherwise Fluorescence Increasing, its fluorescence has good temperature-responsive.It has good application prospect in medicine controlled releasing, temperature sensing, organizational project etc.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope collection of illustrative plates (median size is approximately 300nm) of the fluorescent carbon nano particle hybrid microgel of temperature response prepared by embodiment 3
Fig. 2 is the temperature response fluorescence pattern (temperature raises, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength is 320nm) of the fluorescent carbon nano particle hybrid microgel aqueous solution of temperature response prepared by embodiment 1.
Fig. 3 is the temperature response fluorescence pattern (temperature raises, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength is 320nm) of the fluorescent carbon nano particle hybrid microgel aqueous solution of temperature response prepared by embodiment 2.
Fig. 4 is the temperature response fluorescence pattern (temperature raises, fluorescent weakening, otherwise Fluorescence Increasing, excitation wavelength is 320nm) of the fluorescent carbon nano particle hybrid microgel aqueous solution of temperature response prepared by embodiment 3.
Embodiment
Exemplarily the present invention is described in detail further below in conjunction with non-limiting specific embodiment.The reagent used in the embodiment of the present invention is except fluorescent carbon nano particle is (according to Liao B.; Long, P.; He, B.; Yi, S.; Ou, B.; Shen, S.; Chen, J. J Mater Chem C 2013,1, prepares described in 3716), all the other are all commercially available obtains.
embodiment 1:
Take appropriate fluorescent carbon nano particle 100mg, dissolve with methylene dichloride, be mixed with the fluorescent carbon particle solution that concentration is 0.5-10mg/mL.Add acrylate chloride 5mg.At room temperature react 10h, afterwards reaction solvent is removed, add water, after being spin-dried for, obtain double bond fluorescent carbon nano particle.
Take double bond fluorescent carbon particle 15mg, add dispersing and dissolving in 100mL distilled water, and transferred in the there-necked flask that agitator, reflux condensing tube and thermometer are housed.Open agitator, and even logical nitrogen, the air in complete amount discharge container and solution.Add the NIPA that 5mg linking agent N-N methylene-bisacrylamide, 5mg sodium laurylsulfonate (SDS), 200mg are refining.Continue logical nitrogen, the air in complete amount discharge container and solution.Heating, after reaction solution backflow, adds in there-necked flask by 7mg Potassium Persulphate, fully stirs.Maintaining nitrogen purge, continues stopped reaction after back flow reaction 12h at 60 DEG C, filters after being cooled to room temperature, and get filtrate and be placed in dialysis tubing and dialyse 48h, gained dialyzate is the good carbon nano-particle hybrid microgel of purifying.
embodiment 2:
Take appropriate fluorescent carbon nano particle 100mg, dissolve with methylene dichloride, be mixed with the fluorescent carbon particle solution that concentration is 0.5-10mg/mL.Add acrylate chloride 10mg.At room temperature react 10h, afterwards reaction solvent is removed, add water, after being spin-dried for, obtain double bond fluorescent carbon nano particle.
Take double bond fluorescent carbon particle 25mg, add dispersing and dissolving in 100mL distilled water, and transferred in the there-necked flask that agitator, reflux condensing tube and thermometer are housed.Open agitator, and even logical nitrogen, the air in complete amount discharge container and solution.Add the NIPA that 10mg linking agent N-N methylene-bisacrylamide, 10mg sodium laurylsulfonate (SDS), 200mg are refining.Continue logical nitrogen, the air in complete amount discharge container and solution.Heating, after reaction solution backflow, adds 7mg Potassium Persulphate in there-necked flask.Maintaining nitrogen purge and stirring, continue stopped reaction after back flow reaction 10h at 80 DEG C, filter after being cooled to room temperature, and get filtrate and be placed in dialysis tubing and dialyse 48h, gained dialyzate is the good carbon nano-particle hybrid microgel of purifying.
embodiment 3:
Take appropriate fluorescent carbon nano particle 200mg, dissolve with methylene dichloride, be mixed with the fluorescent carbon particle solution that concentration is 0.5-10mg/mL.Add acrylate chloride 10mg.At room temperature react 10h, afterwards reaction solvent is removed, add water, after being spin-dried for, obtain double bond fluorescent carbon nano particle.
Take double bond fluorescent carbon particle 20mg, add dispersing and dissolving in 100mL distilled water, and transferred in the there-necked flask that agitator, reflux condensing tube and thermometer are housed.Open agitator, and even logical nitrogen, the air in complete amount discharge container and solution.Add the NIPA that 5mg linking agent N-N methylene-bisacrylamide, 15mg sodium laurylsulfonate (SDS), 200mg are refining.Continue logical nitrogen, the air in complete amount discharge container and solution.Heating, after reaction solution backflow, adds 7mg Potassium Persulphate in there-necked flask.Maintaining nitrogen purge, stirring, continue stopped reaction after back flow reaction 12h at 70 DEG C, filter after being cooled to room temperature, and get filtrate and be placed in dialysis tubing and dialyse 48h, gained dialyzate is the good carbon nano-particle hybrid microgel of purifying.
Claims (10)
1. a preparation method for the fluorescent carbon nano particle hybrid microgel of temperature response, is characterized in that, comprise the following steps:
(1) take appropriate fluorescent carbon nano particle, dissolve with methylene dichloride, be mixed with the fluorescent carbon particle solution that concentration is 0.5-10mg/mL, add acyl chloride monomer, at room temperature react 10h, removing reaction solvent, add water, be then spin-dried for, obtain double bond fluorescent carbon nano particle;
(2) take double bond fluorescent carbon nano particle, add dispersing and dissolving in 100mL distilled water; And transferred in the there-necked flask that agitator, reflux condensing tube and thermometer are housed; Open agitator, and even logical nitrogen, the air in complete amount discharge container and solution, adds linking agent, sodium laurylsulfonate, refining NIPA; Keep agitation, and continue logical nitrogen, the air in complete amount discharge container and solution, heating, question response liquid takes initiator and is added in there-necked flask after starting backflow;
(3) Keep agitation and logical nitrogen, after continuing back flow reaction 5-16h at 50-90 DEG C, stopped reaction;
(4) filter after being cooled to room temperature, get filtrate, dialysis 48h, gained dialyzate is the good carbon nano-particle hybrid microgel of purifying.
2. the preparation method of the fluorescent carbon nano particle hybrid microgel of temperature response according to claim 1, is characterized in that, in step (1), the mass ratio of described fluorescent carbon nano particle and acyl chloride monomer is 10:1-50:1.
3. the preparation method of the fluorescent carbon nano particle hybrid microgel of temperature response according to claim 1, it is characterized in that, in step (1), described fluorescent carbon nano particle is fluorescent carbon nano particle prepared by hydrothermal method carbonization glucose, Mierocrystalline cellulose, chitosan, EDTA2Na, EDTA or gelatin.
4. the preparation method of the fluorescent carbon nano particle hybrid microgel of the temperature response according to claim 1 or 3, is characterized in that, in step (1), described fluorescent carbon nano particle is fluorescent carbon nano particle prepared by hydrothermal method carbonization EDTA2Na.
5. the preparation method of the fluorescent carbon nano particle hybrid microgel of temperature response according to claim 1 and 2, is characterized in that, in step (1), described acyl chloride monomer is acrylate chloride, methacrylic chloride, crotonyl chloride.
6. the preparation method of the fluorescent carbon nano particle hybrid microgel of temperature response according to claim 1, it is characterized in that, in step (2), double bond fluorescent carbon amount of particles is 1-40 weight part, NIPA consumption is 100-400 weight part, sodium laurylsulfonate consumption is 1-20 weight part, and Potassium Persulphate consumption is 1-10 weight part.
7. the preparation method of the fluorescent carbon nano particle hybrid microgel of the temperature response according to claim 1 or 6, is characterized in that, the mass ratio optimum that feeds intake of double bond fluorescent carbon particle and NIPA is 1:10.
8. the preparation method of the fluorescent carbon nano particle hybrid microgel of temperature response according to claim 1, is characterized in that, in step (2), described initiator has hydrogen peroxide, ammonium persulphate or Potassium Persulphate.
9. the preparation method of the fluorescent carbon nano particle hybrid microgel of a kind of temperature response according to claim 1, is characterized in that, in step (3), back flow reaction optimum temps is 70 DEG C, and optimum reacting time is 12h.
10. the temperature response type fluorescent carbon nano particle hybrid microgel product prepared of the method for claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131207A (en) * | 2015-07-16 | 2015-12-09 | 复旦大学 | Core halo/core-shell halo structure fluorescent microgel having double responsiveness and preparation method thereof |
| CN105315473A (en) * | 2015-11-13 | 2016-02-10 | 安徽师范大学 | Preparation method of chitosan nanospheres |
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| JPH04298203A (en) * | 1991-03-27 | 1992-10-22 | Kohjin Co Ltd | Temperature sensitive type flocculant |
| CN101775112A (en) * | 2010-02-05 | 2010-07-14 | 苏州大学 | Preparation method of magnetic fluorescence dual functional thermo-sensitive nano particle |
| WO2013192629A1 (en) * | 2012-06-22 | 2013-12-27 | William Marsh Rice University | Temperature responsive nanoparticles for magnetically detecting hydrocarbons in geological structures |
| CN103769052A (en) * | 2014-02-28 | 2014-05-07 | 广东药学院 | Magnetism and temperature double-responded mesoporous carbon material as well as preparation method and application thereof |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298203A (en) * | 1991-03-27 | 1992-10-22 | Kohjin Co Ltd | Temperature sensitive type flocculant |
| CN101775112A (en) * | 2010-02-05 | 2010-07-14 | 苏州大学 | Preparation method of magnetic fluorescence dual functional thermo-sensitive nano particle |
| WO2013192629A1 (en) * | 2012-06-22 | 2013-12-27 | William Marsh Rice University | Temperature responsive nanoparticles for magnetically detecting hydrocarbons in geological structures |
| CN103769052A (en) * | 2014-02-28 | 2014-05-07 | 广东药学院 | Magnetism and temperature double-responded mesoporous carbon material as well as preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131207A (en) * | 2015-07-16 | 2015-12-09 | 复旦大学 | Core halo/core-shell halo structure fluorescent microgel having double responsiveness and preparation method thereof |
| CN105131207B (en) * | 2015-07-16 | 2017-10-10 | 复旦大学 | A kind of core with dual responsiveness is dizzy/the fluorescence microgel of nucleocapsid dizzy structure and preparation method thereof |
| CN105315473A (en) * | 2015-11-13 | 2016-02-10 | 安徽师范大学 | Preparation method of chitosan nanospheres |
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