CN106632919B - A kind of redox response type block copolymer vesicles and preparation method thereof - Google Patents
A kind of redox response type block copolymer vesicles and preparation method thereof Download PDFInfo
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Abstract
This application involves a kind of redox response type block copolymer vesicles and preparation method thereof, the vesica is using amphiphilic block copolymer containing ferrocenyl as object, pass through chemistry redox ferrocene group, the close and distant water distribution of change system, it is designed and prepares, the vesica is the redox response type vesica based on ferrocenyl amphiphilic block copolymer.The vesica specifically: PFCn-b-PEO-b-PFCn.
Description
Technical field
This application involves a kind of redox response type block copolymer vesicles and preparation method thereof, in particular to a kind of tool
There are amphiphilic redox response type block copolymer vesicles and preparation method thereof.
Background technique
Develop the important topic that all kinds of novel environmental response type assemblies are always Macromolecular self-assembly field.Pass through at present
The modes such as temperature, light, pH value, solvent polarity, Subjective and Objective molecular recognition, enzyme, redox prepare environmental response type assembly
Obtain fast development.
In recent years, started to cause by the report that oxidation or redox regulatory mode prepare stimuli responsive type assembly
The concern of people.Cardinal principle is that sulfur-bearing, the isotope of redox-sensitive group containing selenium, purpurine, ferrocene etc. are introduced into macromolecular
In self-assembly system, macromolecular assemblies are regulated and controled by the variation of these groups hydrophilic and hydrophobic in different redox environments
Accumulation shape, to prepare novel oxidized or redox response type assembly.For example, Hubbell etc. synthesizes one
Class sulfur-bearing amphipathic nature block polymer polyethylene glycol-b- polypropylene sulfide-b- polyethylene glycol (PEO-b-PPS-b-PEO), passes through
The oxidation of hydrogen peroxide, polypropylene sulfide part are oxidized to sulfone formula structure, and hydrophily improves, vesica knot of the aggregation from reduction-state
Allosteric transformation at oxidation state vermiculate glues.It is the key factor for influencing molecular assembly pattern that molecule is amphipathic, if can be with
The mode that dynamic controls assembly assembling then may be implemented in the hydrophilic and hydrophobic for dynamically adjusting molecule in the solution.For another example, Yuan Jin
Grain husks etc. are prepared for a kind of novel redox response supermolecule vesica body by introducing ferrocene group, and this kind of assembly is by two kinds
Homopolymer utilizes the orthogonal connection of non-covalent bond, the polystyrene homopolymer (PS- of one section of beta-cyclodextrin (β-CD) that has been end modified
β-CD), the polyethylene oxide (PEO-Fc) of the other end ferrocenyl (Fc) that has been end modified, the two passes through terminal functional groups
Host-guest interaction form non-covalent bond block copolymer (PS- β-CD/PEO-Fc), carry out rank groups again later mounted in water
Supermolecule vesica is formed in solution.The host -guest inclusion complex of β-CD and Fc can be adjusted by redox mode.
Apply a positive point appropriate in situ in the solution, it can be terminal oxidized for positively charged Fc by neutral Fc+；And Fc+
Due to electrification, electrostatic screen effect and hydrophily are greatly improved, and can be dissociateed and from the hydrophobic internal cavities of β-CD, cause
The de-assembly of PS- β-CD/PEO-Fc vesica.It is interesting that can be restored by applying a negative direction appropriate into solution
Voltage and reversible regulation, cause vesica to re-assembly.The study found that under positive negative potential stimulation repeatedly, the group of this kind of vesica
The invertibity of dress and de-assembly is good[7].In oxidation-reduction process, ferrocene group is different from sulfur-bearing, containing groups such as selenium
It is that its own structure does not change, electron exchange only has occurred, to affect its hydrophilic and hydrophobic, this process is several
Completely reversibility.This interesting property makes ferrocene group be expected to be introduced into other controllably as redox response group
Self-assembly system, the experiment sufficiently also show ferrocene group in the application potential in novel environmental response type assembly field.
Summary of the invention
The application passes through chemistry (addition redox using a kind of amphiphilic block copolymer containing ferrocenyl as research object
Reagent) redox ferrocene group, change the close and distant water distribution of system, studies block copolymer aggregation in aqueous solution
It is formed, structure change and reversible condition, designs, prepares a kind of oxidation based on ferrocenyl amphiphilic block copolymer also
Former response type vesica.
To solve above-mentioned technical problem: the application proposes a kind of redox response type block copolymer vesicles, the capsule
Bubble, by chemistry redox ferrocene group, changes the close and distant of system using amphiphilic block copolymer containing ferrocenyl as object
Water distribution is designed and prepares, and the vesica is the redox response type capsule based on ferrocenyl amphiphilic block copolymer
Bubble.
It may be preferred that the vesica is triblock copolymer.
It may be preferred that the vesica specifically: PFCn-b-PEO-b-PFCn；Wherein, n is to synthesize altogether in this case
The block copolymer of three kinds of difference n values, i.e., 10,17,28, it can also be regulated and controled by changing the amount of monomer, b is block's
Write a Chinese character in simplified form, the meaning of block, PFC is polymethylacrylic acid ferrocene hendecane base ester), PEO is polyethylene glycol.
A kind of redox response type block copolymer vesicles, the vesica copolymer vesica as described in any of the above-described,
It has a structure that
Wherein, n is to synthesize the block copolymers of three kinds of difference n values in this case altogether, i.e., 10,17,28, it can also pass through
The amount for changing monomer is regulated and controled), b is writing a Chinese character in simplified form for block, and the meaning of block, PFC is polymethylacrylic acid ferrocene hendecane
Base ester), PEO is polyethylene glycol.
It may be preferred that synthesizing reagent selected by the vesica are as follows: polyethylene glycol (PEO), the 2- of molecular weight 20,000
Bromo isobutyl acylbromide (> 98%), N, N, N ', N ", N "-pentamethyldivinyltriamine (PMDETA, 99%), cuprous bromide
(CuBr), triethylamine (TEA), methylene chloride, toluene, pure, other reagents of analysis are to analyze pure, experimental water.
It may be preferred that the moisture of trace with toluene by subtracting in the polyethylene glycol (PEO) that the molecular weight is 20,000
Azeotropic distillation is pressed to remove；The cuprous bromide (CuBr) using it is preceding be washed till with glacial acetic acid it is colourless, then respectively with anhydrous methanol, anhydrous
Ether is washed three times, vacuum drying, is saved in nitrogen atmosphere；The triethylamine (TEA) and p-methyl benzenesulfonic acid acyl chlorides flow back, distillation,
CaH2In the presence of store；The methylene chloride is that analysis is pure, is washed with 5% sodium carbonate liquor, is washed with water and washs, then with anhydrous
Calcium chloride is dry, and 40~41 DEG C of fraction is collected in distillation, saves in a brown bottle；The toluene is that analysis is pure, and sodium is used before use
Silk reflux water removal, air-distillation；Other described reagents are that analysis is pure, use preceding drying, distillation；The experimental water is height
Pure water, Millipore purification device processing Millipore: a kind of brand of water-purifying apparatus of purified water, resistivity >=
18.2MΩ。
It may be preferred that its synthetic route are as follows:
Wherein, two-step reaction, ethylene glycol, 2- bromo isobutyl acylbromide, three of the first step raw molecule amount for 20000 are divided into
Ethamine is reacted in toluene, and product is macromole evocating agent Br-PEO20000-Br；Second step is macromole evocating agent Br-
PEO20000-Br, monomer methacrylic acid ferrocene hendecane base ester and catalyst cuprous bromide, N, N, N ' ,-five first of N ", N "
Base diethylene triamine reacts in toluene, obtains final product PFCn-b-PEO-b-PFCn.
A kind of preparation method of the vesica as described in any of the above-described, characterized by the following steps:
(1) at room temperature, a certain amount of macromole evocating agent Br-PEO20000-Br and catalyst CuBr are added to and are filled
In Schlenk bottles of 5mL of argon gas；
(2) it is sealed with rubber plug with overlapped mouth, vacuumizes deoxygenation, the toluene 2mL that degassing is added with the syringe that argon purge is crossed is molten
Macromole evocating agent is solved, the degassed monomer methacrylic acid ferrocene hendecane by design degree of polymerization metering ratio is added in (3)
Base ester, liquid nitrogen frozen-vacuumize-applying argon gas defrosting, recycle deoxygenation three times, are added with the syringe that argon purge is crossed a certain amount of
Ligand PMDETA；
(4) it immerses and is previously heated in 80 DEG C of oil bath, react 6h, the reaction of liquid nitrogen frozen Quick stop；
(5) reaction system is concentrated, petroleum ether is added: column is crossed in the dissolution of ethyl acetate=4:1 mixed solvent, will be not anti-
After answering monomer to wash out, crude product then is eluted with THF+5% triethylamine mixed solvent；
(6) crude product is dissolved in a small amount of methylene chloride, it is embedding to obtain pure three for the repeated precipitation in a large amount of n-hexanes
Section copolymer p FCn-b-PEO-b-PFCn, is dried under vacuum to constant weight.
It may be preferred that the macromole evocating agent Br-PEO20000-Br and catalyst CuBr in the step (1)
It is added in Schlenk bottles of 5mL of applying argon gas by the molar ratio of 1:2.
It may be preferred that the metering that ligand PMDETA is added in the step (3) is 2 times of macromole evocating agent meter.
Detailed description of the invention
Fig. 1 PFCn-b-PEO-b-PFCn triblock copolymer schematic diagram.
The synthetic route schematic diagram of Fig. 2 PFCn-b-PEO-b-PFCn triblock copolymer.
Dependence linearity curve of the equilibrium surface tension to concentration that Fig. 3 is PFCn-b-PEO-b-PFCn.
Fig. 4 is that the SEM of block copolymer M28-b-E454-b-M28 aggregation schemes (C=1.0g/L).
Fig. 5 is that the TEM of block copolymer M28-b-E454-b-M28 aggregation schemes (C=1.0g/L).
Fig. 6 is aqueous solution (C=1.0g/L) state of aggregation change of size figure of M10-b-E454-b-M10.
Fig. 7 is aqueous solution (C=1.0g/L) state of aggregation change of size figure of M17-b-E454-b-M17.
Fig. 8 is aqueous solution (C=1.0g/L) state of aggregation change of size figure of M28-b-E454-b-M28.
Specific embodiment
The application is described in further detail with reference to the accompanying drawing, it is necessary to it is indicated herein to be, implement in detail below
Mode is served only for that the present invention is further detailed, and should not be understood as limiting the scope of the invention, the field
Technical staff can make some nonessential modifications and adaptations to the application according to following the description.
As shown in Figure 1, for the application PFCn-b-PEO-b-PFCn triblock copolymer structure wherein, n be this case in
Synthesize the block copolymer of three kinds of difference n values altogether, i.e., 10,17,28, it can also be regulated and controled by changing the amount of monomer, b is
Block's writes a Chinese character in simplified form, the meaning of block), PFC is polymethylacrylic acid ferrocene hendecane base ester), PEO is polyethylene glycol).
Synthesize reagent selected by the vesica are as follows: polyethylene glycol (PEO), the 2- bromo isobutyl acylbromide of molecular weight 20,000
(> 98%), N, N, N ', N ", N "-pentamethyldivinyltriamine (PMDETA, 99%), cuprous bromide (CuBr), triethylamine
(TEA), methylene chloride, toluene, pure, other reagents of analysis are to analyze pure, experimental water.
The moisture of trace with toluene decompression co-boiling distiling by removing in the polyethylene glycol (PEO) that the molecular weight is 20,000
It goes；The cuprous bromide (CuBr) is washed till colourless using preceding with glacial acetic acid, then is washed three times with anhydrous methanol, anhydrous ether respectively,
It is dried in vacuo, is saved in nitrogen atmosphere；The triethylamine (TEA) and p-methyl benzenesulfonic acid acyl chlorides flow back, distillation, CaH2In the presence of store up
It deposits；The methylene chloride is that analysis is pure, is washed with 5% sodium carbonate liquor, is washed with water and washs, then dry with anhydrous calcium chloride,
40~41 DEG C of fraction is collected in distillation, is saved in a brown bottle；The toluene is that analysis is pure, is removed water using preceding with the reflux of sodium silk,
Air-distillation；Other described reagents are that analysis is pure, use preceding drying, distillation；The experimental water is high purity water,
The processing of Millipore purification device, a kind of Millipore: the brand of water-purifying apparatus of purified water), resistivity >=18.2M
Ω。
Fig. 2 show PFCn-b-PEO-b-PFCnThe synthetic route of triblock copolymer.
Polymerization reaction detailed process: at room temperature, by a certain amount of macromole evocating agent Br-PEO20000-Br and catalysis
Agent CuBr (by the molar ratio of 1:2) is added in Schlenk bottles of 5mL of applying argon gas, is sealed with rubber plug with overlapped mouth, is vacuumized deoxygenation,
Macromole evocating agent is dissolved with the toluene 2mL that degassing is added in the syringe that argon purge is crossed, is added and measures ratio by the design degree of polymerization
Degassed monomer methacrylic acid ferrocene hendecane base ester, liquid nitrogen frozen-vacuumizes-applying argon gas thaws, circulation three
Secondary deoxygenation, a certain amount of ligand PMDETA is added with the syringe that argon purge is crossed, and (it is macromole evocating agent meter 2 that metering, which is added,
Times).Immersion is previously heated in 80 DEG C of oil bath, reacts 6h, the reaction of liquid nitrogen frozen Quick stop.Reaction system is concentrated, is added
Enter petroleum ether: column (elution and solvent: oily ether/ethyl acetate=4/1) is crossed in the dissolution of ethyl acetate=4:1 mixed solvent, will
After unreacted monomer washes out, crude product then is eluted with THF+5% triethylamine mixed solvent.Crude product is dissolved in a small amount of two
In chloromethanes, the repeated precipitation in a large amount of n-hexanes obtains pure triblock copolymer PFCn-b-PEO-b-PFCn, vacuum
It dries to constant weight.
Fig. 3 is the equilibrium surface tension of PFCn-b-PEO-b-PFCn to the dependence linearity curve of concentration, can be calculated from figure
M out10-b-E454-b-M10CMC (critical micelle concentration) be 0.06g/L；M17-b-E454-b-M17CMC be 0.07g/L；M28-
b-E454-b-M28CMC be 0.11g/L.The result shows that the CMC of three kinds of block copolymers is very close.With M28-b-E454-b-M28
For, intuitive state of aggregation photo is as shown in Figure 4 and Figure 5；From TEM and SEM photograph, it can be seen that block copolymer forms ball
Shape imitated vesicle structure.M10-b-E454-b-M10And M17-b-E454-b-M17Also form similar imitated vesicle structure.
Three kinds of block polymer concentration of aqueous solution are 1g/L, and vesicle size is distributed as shown in Fig. 6, Fig. 7, Fig. 8.It can see
Out, M10-b-E454-b-M10The vesica average grain diameter of formation is 142nm, M17-b-E454-b-M17The vesica average grain diameter of formation is
164nm, M28-b-E454-b-M28The vesica average grain diameter of formation is 190nm.With polymethylacrylic acid ferrocene undecyl
The increase of ester block, vesicle diameter are gradually increased.
In order to further study its vesica changing rule, we have carried out chemical method redox to three kinds of polymer,
The variation of its vesica is inquired into.M10-b-E454-b-M10Before and after chemistry redox, vesica change of size is distributed such as Fig. 6 institute
Show.It can be seen from the figure that when ferrocene is in original reduction-state, the sulphur of 1.1 times of moles is added in average grain diameter 142nm
After sour iron is fully oxidized, for solution colour from faint yellow transformation au bleu, average grain diameter increases to 164nm, it is presumed that ferrocene
After oxidation, become hydrophilic radical, caused by vesica is further swollen.For above-mentioned system, we, which continuously add, slightly excessively has
The ascorbic acid (Vc) of reproducibility, vesica partial size are reduced to partial size when 122nm, slightly less than original reduction-state again, this explanation is gathered
Close object M10-b-E454-b-M10Ferrocene group be in hydrophobic contraction state again, the color of system also transforms back into faint yellow.On
Result explanation is stated, we can successfully pass the self assembly form of chemistry redox adjustment and control system.
Study Polymer Melts M17-b-E454-b-M17And M28-b-E454-b-M28When, it has been found that similar rule.It is specific next
It says, for M17-b-E454-b-M17Before and after chemistry redox, the distribution of vesica change of size is as shown in Figure 7.Original reduction-state
When average grain diameter be 164nm, vesica partial size increases to 190nm after oxidation, is restored to 140nm after reduction；For M28-b-E454-b-
M28Before and after chemistry redox, change of size distribution is as shown in Figure 8.Average grain diameter is 190nm when original reduction-state, after oxidation
Vesica increases to 220nm, is restored to 164nm after reduction；In conclusion we successfully have found a kind of redox response type
Block copolymer vesicles.
Amphipathic PFCn-b-PEO-b-PFCn triblock copolymer can form imitated vesicle structure in water.Chemistry can be passed through
Redox regulatory vesicle size.A kind of redox response type capsule based on ferrocenyl amphiphilic block copolymer is invented
Bubble.
Herein described triblock copolymer can be with the polymethylacrylic acid ferrocene undecyl of the copolymer
The increase of ester block, vesicle diameter are gradually increased.And it can adapt to redox reaction, have good invertibity, meanwhile,
The hydrophily of copolymer is substantially increased, and has hydrophobicity, can be adjusted in the hydrophilic and hydrophobic for being easy middle dynamic regulation molecule
The assembling morphology for being integrally changes particle size, has good adaptability.
Claims (8)
1. a kind of redox response type block copolymer vesicles, the vesica is pair with amphiphilic block copolymer containing ferrocenyl
As changing the close and distant water distribution of system by chemistry redox ferrocene group, it is characterised in that: the vesica be based on
The redox response type vesica of ferrocenyl amphiphilic block copolymer；The vesica is triblock copolymer；The vesica tool
Body are as follows: PFCn-b-PEO-b-PFCn；Wherein, n is the structural unit number of block copolymer PFC segment, and b is block, and PFC is poly-
Methacrylic acid ferrocene hendecane base ester, PEO is polyethylene glycol.
2. a kind of redox response type block copolymer vesicles, it is characterised in that: the vesica has a structure that
Wherein, n is the structural unit number of block copolymer PFC segment, and b is block, and PFC is polymethylacrylic acid ferrocene 11
Arrcostab, PEO are polyethylene glycol.
3. vesica as claimed in claim 2, it is characterised in that: synthesize reagent selected by the vesica are as follows: molecular weight 20000
Polyethylene glycol (PEO), 2- bromo isobutyl acylbromide, N, N, N ', N ", N "-pentamethyldivinyltriamine, cuprous bromide
(CuBr), triethylamine (TEA), methylene chloride, toluene, other reagents are experimental water.
4. vesica as claimed in claim 3, it is characterised in that: trace in the polyethylene glycol (PEO) that the molecular weight is 20000
Moisture by with toluene decompression co-boiling distiling remove；The cuprous bromide (CuBr) using it is preceding be washed till with glacial acetic acid it is colourless, then
It is washed three times with anhydrous methanol, anhydrous ether, vacuum drying, is saved in nitrogen atmosphere respectively；The triethylamine (TEA) with to toluene
The reflux of sulfonic acid acyl chlorides, distillation, CaH2In the presence of store；The methylene chloride is that analysis is pure, is washed with 5% sodium carbonate liquor, then
It is washed with water, then dry with anhydrous calcium chloride, 40~41 DEG C of fraction is collected in distillation, is saved in a brown bottle；The toluene
It is pure to analyze, using preceding with the reflux water removal of sodium silk, air-distillation；Other described reagents are that analysis is pure, use preceding drying, steaming
It evaporates；The experimental water is high purity water, and resistivity >=18.2M Ω, the high purity water is handled using Millipore purification device
It obtains, Millipore is a kind of purifying water purification installation.
5. vesica as claimed in claim 3, it is characterised in that: its synthetic route are as follows:
Wherein, two-step reaction, ethylene glycol, 2- bromo isobutyl acylbromide, triethylamine of the first step raw molecule amount for 20000 are divided into
It is reacted in toluene, product is macromole evocating agent Br-PEO20000-Br；Second step is macromole evocating agent Br-PEO20000-
Br, monomer methacrylic acid ferrocene hendecane base ester and catalyst cuprous bromide, N, N, N ', N ", N "-pentamethyl divinyl
Triamine reacts in toluene, obtains final product PFCn-b-PEO-b-PFCn.
6. a kind of preparation method of the vesica as described in claim 1-5 is any, characterized by the following steps:
(1) at room temperature, a certain amount of macromole evocating agent Br-PEO20000-Br and catalyst CuBr are added to applying argon gas
Schlenk bottles of 5mL in；
(2) it is sealed with rubber plug with overlapped mouth, vacuumizes deoxygenation, dissolved with the toluene 2mL that degassing is added in the syringe that argon purge is crossed big
The degassed monomer methacrylic acid ferrocene hendecane base ester by design degree of polymerization metering ratio is added in initiator molecule, (3),
Liquid nitrogen frozen-vacuumizes-applying argon gas defrosting, recycles deoxygenation three times, a certain amount of matches is added in the syringe crossed with argon purge
Body PMDETA；
(4) it immerses and is previously heated in 80 DEG C of oil bath, react 6h, the reaction of liquid nitrogen frozen Quick stop；
(5) reaction system is concentrated, petroleum ether is added: the dissolution of ethyl acetate=4:1 mixed solvent crosses column, by unreacted list
After body washes out, crude product then is eluted with THF+5% triethylamine mixed solvent；
(6) crude product is dissolved in a small amount of methylene chloride, the repeated precipitation in a large amount of n-hexanes, it is total obtains pure three block
Polymers PFCn-b-PEO-b-PFCn, is dried under vacuum to constant weight.
7. a kind of preparation method as claimed in claim 6, it is characterised in that: the macromolecular in the step (1) causes
Agent Br-PEO20000-Br and catalyst CuBr is added in Schlenk bottles of 5mL of applying argon gas by the molar ratio of 1:2.
8. a kind of preparation method as claimed in claim 6, it is characterised in that: ligand PMDETA is added in the step (3)
Metering is 2 times of macromole evocating agent meter.
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|---|---|
| CN106632919A (en) | 2017-05-10 |
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