CN103709715B - A kind of containing POSS superparamagnetic nano-micelle and preparation method thereof - Google Patents
A kind of containing POSS superparamagnetic nano-micelle and preparation method thereof Download PDFInfo
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- CN103709715B CN103709715B CN201310731941.8A CN201310731941A CN103709715B CN 103709715 B CN103709715 B CN 103709715B CN 201310731941 A CN201310731941 A CN 201310731941A CN 103709715 B CN103709715 B CN 103709715B
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Abstract
The invention provides a kind of containing POSS superparamagnetic nano-micelle and preparation method thereof, relate to a kind of composite and preparation method thereof.First the present invention is synthesized out containing the POSS big molecule of self-crosslinkable parents via simple esterification with aminopropyl POSS, maleic anhydride and polyethylene glycol；Secondly, prepare, with chemical coprecipitation, the Fe that particle diameter is 8～12nm3O4It also is modified modifying by particle；Finally, the big molecule of POSS parents and Fe will be contained3O4Particle direct-assembling under the effect of selective solvent prepares embedded Fe3O4Containing POSS superparamagnetic nano-micelle.Micella stability prepared by the present invention is high, preparation technology is simple, controllability good, is with a wide range of applications in field of biomedical materials such as catalyst carrier, medicine controlled releasing, Chemical Decomposition, magnetic resonance imagings.
Description
Technical field
The present invention relates to a kind of superparamagnetic nano-micelle and preparation method thereof, particularly a kind of containing POSS superparamagnetic nano-micelle and
Its preparation method.
Background technology
Polyhedral oligomeric silsesquioxanes, is called for short POSS, is a kind of compound with nano-scale, and three-dimensional dimension is 1～3nm,
Being minimum silicon grain, its physical size and most polymers segment are at the same order of magnitude.Exclusive hexahedron structure possesses little chi
Very little effect, surface-interface effect, quantum size effect, macro quanta tunnel effect, and show special calorifics, optics,
Magnetics and acoustic properties.POSS base polymeric material is described as " a new generation's high-performance polymer material ".
Polymer macromolecule usually contains the segment of component, polarity, dissolubility difference.In polymer body or solution,
Due to the difference of poor compatibility XOR solubility in the solution between each component, segment can pass through relaxation exercise, rearrangement, hydrogen bond action
Or the mode such as hydrophobic aggregation constructs the microstructure that pattern is different.The pattern that formed by parents' Macromolecular self-assembly, size, function
Different nano material exists in multiple fields and is widely applied value.
In recent years, the polymer micelle with magnetic responsiveness gradually attracts attention.In this field, Guang Hui Gao
Deng (Guang Hui Gao, Jae Won Lee et al.pH-responsive polymeric micelle based on PEG-poly (β
-amino ester)/(amido amine)) as intelligent vehicle for magnetic resonance imaging in detection of
Cerebral ischemic area [J] .Journal of Controlled Release, 2011,155:11-17.) to have pH response
Polymer micelle is carrier, at area load Fe3O4Obtain a kind of magnetic micella.This micella magnetic resonance imaging is respond well,
But owing to micellar surface is occupied by magnetic particle, it is impossible to make further targeting modification；And magnetic particle is exposed on surface,
Lack protection, it is impossible to stable existence in acid condition so that it is be subject to certain restrictions in biologic applications.Ni Caihua etc. (one
Plant the preparation method of magnetic responsiveness star block copolymer nano-micelle, Chinese patent, publication number: CN103360607A) with
The Fe of modified3O4For nucleation starting material, cause lactide ring-opening polymerisation, finally enter with the poly-diethanol monomethyl ether through carboxylated
Row esterification prepares a kind of star type block magnetic responsiveness nano-micelle.It is inefficient that this method prepares micella, and micella magnetic contains
Measure uncontrollable, and the catalyst etc. that esterification stays is difficult to remove, and is not suitable for applying at biomedicine field.(the tool such as Ren Jie
There are Thermo-sensitive carrier micelle, preparation method and the using method thereof of magnetothermal effect, Chinese patent, publication number: CN 101244273A)
Report a kind of Thermo-sensitive carrier micelle with magnetothermal effect.This micella is suitable as medicine controlled release carrier, but prepares work
Skill is complex, especially prepares amphipathic nature polyalcohol with RAFT method, and method is complicated, and low yield is not suitable for actual application.
At present, containing POSS superparamagnetic nano-micelle, there is not been reported.
The present invention using have big steric hindrance, super-hydrophobic effect POSS base as hydrophobic side, the big molecule of polyethylene glycol (PEG) is made
For hydrophilic chain, the maleate of band double bond be middle shot synthesized one by simple amidatioon and esterification can selfing
The big molecule of parents of connection.Utilize the big molecule of parents characteristic of self assembly in selective solvent, with the Fe through modifying and decorating3O4
Effect is prepared for containing POSS superparamagnetic nano-micelle.Meanwhile, utilize the character of parents' big molecule self-crosslinkable, can directly coupling
Targeted molecular obtains stable micella.The inventive method is simple, and preparation technology is simple, controllability good, catalyst carrier,
The field of biomedical materials such as medicine controlled releasing, Chemical Decomposition, magnetic resonance imaging are with a wide range of applications.
Summary of the invention
Present invention aim at providing one containing POSS superparamagnetic nano-micelle and preparation method thereof.
Described containing POSS superparamagnetic nano-micelle by the parents big molecule (POSS-MA-PEG of a kind of self-crosslinkable
-MA-POSS) and through modified Fe3O4Particle assembles in water.Micella has core shell structure, and particle diameter is
80～150nm, Fe3O4The particle diameter of particle is 8～12nm to be embedded in inside micella.
The described preparation method containing POSS superparamagnetic nano-micelle is as follows:
(1) by POSS-MA-PEG-MA-PEG, Fe3O4Particle is dissolved in oxolane (THF) jointly, obtains mixed solution
A。
(2) solution A is slowly dropwise entered in deionized water under ultrasonication, vapor away THF, obtain containing POSS super suitable
Magnetic nano-micelle.
In described solution A, the concentration of POSS-MA-PEG-MA-POSS is 5～25mg/mL, Fe3O4Particle consumption is
The 5～30wt% of POSS-MA-PEG-MA-POSS, the content that solution A is added dropwise in deionized water is 0.1%-3wt%.
The molecular structure of described POSS-MA-PEG-MA-POSS is as follows:
Wherein R is POSS drift angle organic group, and n is the degree of polymerization of polyethylene glycol.
Described POSS official can drift angle group be aminopropyl, and remaining seven drift angle R base is isobutyl group.
Described polyethylene glycol (PEG) molecular weight is 600-4000.
The preparation method of described POSS-MA-PEG-MA-POSS is as follows:
(1) aminopropyl POSS, maleic anhydride (MA) and polymerization inhibitor are dissolved in toluene, at 90 DEG C, react 24h
Rear separating-purifying obtains POSS-MA.Wherein aminopropyl POSS, the molar feed ratio of maleic anhydride are 1:1.02～1:1.05.
(2) by POSS-MA, PEG, polymerization inhibitor, catalyst dissolution in toluene, separate after reacting 36h at 135 DEG C
Purification obtains POSS-MA-PEG-MA-POSS.Wherein, the molar feed ratio of POSS-MA, PEG is 2.01:1～2.05:1.
Described polymerization inhibitor is phenolic compound, quinones, aromatic nitro compound etc., and consumption is for accounting for monomer total amount
0.1%-1wt%。
Described catalyst is p-methyl benzenesulfonic acid or the concentrated sulfuric acid, and consumption is for accounting for monomer total amount 0.1%-1wt%.
After described process for separation and purification is for being evaporated off solvent with rotation steaming instrument, the petroleum ether/ethyl ether mixed solution using volume ratio to be 1:1 enters
Row extraction precipitation, then use centrifuge precipitation and separation, it is placed in vacuum drying oven and is dried 24h.
Described Fe3O4Prepared by employing chemical coprecipitation, and utilize oleic acid the most modified, oleic acid and Fe3O4Mass ratio be
1:1.05～1:1.15.
Accompanying drawing explanation
Fig. 1 is the TEM figure containing POSS superparamagnetic nano-micelle.
Fig. 2 is the high-resolution TEM figure containing POSS superparamagnetic nano-micelle.
Fig. 3 is the diffraction pattern containing POSS superparamagnetic nano-micelle.
Fig. 4 is the DLS figure of POSS superparamagnetic nano-micelle
Fig. 5 is the hysteresis curve figure containing POSS superparamagnetic nano-micelle.
Detailed description of the invention
Below by embodiment, the present invention will be further described.
Embodiment 1
(1) preparation of the big molecule of the parents Han POSS
By miscible uniformly to 8.00g POSS, 0.90g maleic anhydride (MA), 0.045g hydroquinones and 50mL toluene, logical
Nitrogen, after reacting 24h at 90 DEG C, separating-purifying obtains POSS-MA；By 2.00g POSS-MA, 4.11g PEG2000,
0.025g p-methyl benzenesulfonic acid, 0.051g hydroquinones and 50mL toluene are miscible uniformly, logical nitrogen, react at 135 DEG C
After 24h, separating-purifying obtains parents big molecule POSS-MA-PEG2000-MA-POSS.
(2) Fe3O4The preparation of particle is with modified
By 8.12g FeCl3·6H2O and 4.17g FeSO4·7H2O is dissolved in 60mL deionized water；5.31g NaOH is dissolved in
10mL deionized water, is slowly added to, 65 DEG C reaction 1 hour after add 3.00mL oleic acid, be warming up to 75 DEG C cure one hour,
Obtain the magnetic Fe with superparamagnetism of size 8～12nm3O4Nano particle.By modified magnetic Fe3O4Nano particle
2-3 time is washed to neutrality, dry for standby with ethanol
(3) preparation containing POSS superparamagnetic nano-micelle
0.11g POSS-MA-PEG2000-MA-POSS、0.015g Fe3O4Particle is jointly dissolved in 10mL THF and must mix
Liquid A；Take 150 μ L solution A slowly the most dropwise to instill in 10mL deionized water under ultrasonication, uncovered standing one day to THF
Volatilize completely, obtain the preparation containing POSS superparamagnetic nano-micelle.Being recorded micella particle diameter by DLS is 105.4nm, by SQUID
It is 18.6emu/g that superconductive quantum interference magnetometer records the saturated magnetic intensity of ratio of micella.
Embodiment 2～5
With embodiment 1 technique, change the molecular weight of PEG in step (1) and be respectively 600,800,1000,4000,
As shown in table 1 to result.
Embodiment 6～8
With embodiment 1 technique, change Fe in step (3)3O4Particle feed intake as 0.020g, 0.025g, 0.30g, obtain
Result is as shown in table 2.
Table 1
| Embodiment | Micella particle diameter (nm) | Micella is than saturated magnetic intensity (emu/g) |
| 2 | 88.4 | 24.6 |
| 3 | 90.1 | 25.8 |
| 4 | 96.5 | 23.9 |
| 5 | 120.7 | 26.2 |
Table 2
| Embodiment | Micella particle diameter (nm) | Micella is than saturated magnetic intensity (emu/g) |
| 6 | 106.7 | 24.8 |
| 7 | 109.5 | 29.3 |
| 8 | 115.9 | 34.5 |
Claims (8)
1. a superparamagnetic nano-micelle Han POSS, it is characterised in that will contain POSS superparamagnetic nano-micelle can selfing by one
The parents big molecule POSS-MA-PEG-MA-POSS joined and the Fe passing through modification3O4Particle assembles in water, described glue
Bundle has core shell structure, and particle diameter is 80～150nm, Fe3O4The particle diameter of particle is 8～12nm to be embedded in inside micella；
The molecular structure of described POSS-MA-PEG-MA-POSS is as follows:
Wherein R is POSS drift angle organic group, and n is the degree of polymerization of polyethylene glycol；
Described POSS official can drift angle group be aminopropyl, and remaining seven drift angle R base is isobutyl group.
2. the preparation method containing POSS superparamagnetic nano-micelle is as follows:
(1) by POSS-MA-PEG-MA-PEG, Fe3O4Particle is dissolved in tetrahydrofuran THF jointly, obtains mixed solution A；
(2) solution A is slowly dropwise entered in deionized water under ultrasonication, vapor away THF, obtain containing POSS super suitable
Magnetic nano-micelle；
In described solution A, the concentration of POSS-MA-PEG-MA-POSS is 5～25mg/mL, Fe3O4Particle consumption is
The 5～30wt% of POSS-MA-PEG-MA-POSS, the content that solution A is added dropwise in deionized water is 0.1%-3wt%；
The molecular structure of described POSS-MA-PEG-MA-POSS is as follows:
Wherein R is POSS drift angle organic group, and n is the degree of polymerization of polyethylene glycol；
Described POSS official can drift angle group be aminopropyl, and remaining seven drift angle R base is isobutyl group.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 2, it is characterised in that described poly-
Ethylene glycol PEG molecular weight is 600 4000.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 2, it is characterised in that described
The preparation method of POSS-MA-PEG-MA-POSS is as follows:
(1) aminopropyl POSS, maleic anhydride MA and polymerization inhibitor are dissolved in toluene, divide after reacting 24h at 90 DEG C
POSS-MA is obtained from purification；Wherein aminopropyl POSS, the molar feed ratio of maleic anhydride are 1:1.02～1:1.05；
(2) by POSS-MA, PEG, polymerization inhibitor, catalyst dissolution in toluene, separate after reacting 36h at 135 DEG C and carry
Pure obtain POSS-MA-PEG-MA-POSS；Wherein, the molar feed ratio of POSS-MA, PEG is 2.01:1～2.05:1.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 4, it is characterised in that described resistance
Poly-agent is phenolic compound, quinones, aromatic nitro compound, and consumption is for accounting for monomer total amount 0.1% 1wt%.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 4, it is characterised in that described in urge
Agent is p-methyl benzenesulfonic acid or the concentrated sulfuric acid, and consumption is for accounting for monomer total amount 0.1% 1wt%.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 4, it is characterised in that described point
After method of purification is for being evaporated off solvent with rotation steaming instrument, the petroleum ether/ethyl ether mixed solution using volume ratio to be 1:1 carries out extraction precipitation,
Use centrifuge precipitation and separation again, be placed in vacuum drying oven and be dried 24h.
A kind of preparation method containing POSS superparamagnetic nano-micelle the most according to claim 2, it is characterised in that described
Fe3O4Prepared by employing chemical coprecipitation, and utilize oleic acid the most modified, oleic acid and Fe3O4Mass ratio be 1:1.05～1:1.15.
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