CN104592511B - Containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block and its preparation method and application - Google Patents
Containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block and its preparation method and application Download PDFInfo
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- CN104592511B CN104592511B CN201510026333.6A CN201510026333A CN104592511B CN 104592511 B CN104592511 B CN 104592511B CN 201510026333 A CN201510026333 A CN 201510026333A CN 104592511 B CN104592511 B CN 104592511B
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Abstract
The invention discloses a kind of poly- peptide molecule brush of polyethylene glycol block, structure is such as with following formula (1) Suo Shi；It includes main chain and side chain, and the main chain is the bi-block copolymer that polyethylene glycol is constituted with poly- peptide, and the side chain is alkyloxy-ethers dendrimer.Its preparation method is to prepare γ chloroethyl L glutamates with chlorethanol and L glutamic acid, and alpha amino acid N carboxyl inner-acid anhydride ring-opening polymerisations are triggered with amino-polyethyleneglycols monomethyl ether, obtains polyethylene glycol b poly- (γ chloroethyl L glutamates)；By Azide and click-reaction, alkyloxy-ethers dendrimer is grafted on poly- peptide chain so as to prepare poly- polypeptide block copolymer molecule brush.The invention also discloses a kind of hydrogel, it includes α cyclodextrin and the poly- peptide molecule brush of described polyethylene glycol block.It is mixed by by molecular brush and α cyclodextrin in water, ultrasound, standing are prepared.Hydrogel of the invention has unique structure and morphology and good biocompatibility, is with a wide range of applications in fields such as functional material, cell culture medium, load medicines.
Description
Technical field
The invention belongs to new material technology field, and in particular to a kind of high polymer material technology, relate more specifically to one kind
Containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block and its preparation method and application.
Background technology
Because polyalcohol hydrogel system is in the flexibility and network structure and multiple outside thorn of analog cell epimatrix
Swashing the aspects such as response performance has similitude, is widely paid close attention to by scientist and studied more and more, and progressively by its water
Gel rubber system is applied to the fields such as drug loading, organizational project.Poly- peptide has has a similar structures with bioprotein, and by
Unique orderly secondary con (alpha-helix, beta sheet etc.) structure can be formed in the effect of hydrogen bond, this unique structure makes
It is different from traditional polymer, and tying up to the fields such as biological medicine by its water gel for building has potential application value.
At present, poly- peptide and its copolymer turned into construct hydrogel first-selection base material.
In the last few years, the application of the main-guest chemistry aquogel system based on cyclodextrin also obtains more and more extensive pass
Note.As Yaobin Wu et al. (ACS Macro Lett.2014,3,1 145-1150) design synthesizes side containing Tetraaniline
Supramolecular hydrogel is constructed by host-guest interactions between base biodegradable block copolymer, with gamma-cyclodextrin dimer, can be made
It is a kind of drug delivery system of potential injection.
But, not yet report is based on Polypeptide copolymer molecular brush and ring containing dendrimer structure in currently available technology
Dextrin collective effect builds the research of supermolecular gel system.
The content of the invention
It is an object of the invention to provide a kind of poly- peptide molecule swabbing gel of main-guest chemistry based on cyclodextrin, and set up
Its preparation method.The hydrogel is a kind of comprising the poly- peptide molecule brush of block and α that side chain is alkyloxy-ethers dendrimer-ring paste
The binary system hydrogel of essence, each constituent all has good biocompatibility and degradability.
In the present invention, the hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block includes alpha-cyclodextrin and side
The binary system hydrogel of polyethylene glycol block poly- peptide molecule brush of the chain containing alkyloxy-ethers dendrimer.
In the present invention, the hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block, its microstructure is piece
Rotating fields.Specifically, the hydrogel be irregular polygon laminated structure, its microscopic dimensions be 0.5~2 micron, hydrogel by
Sheet aggregation layer upon layer and formed.A length of 0.5~2 micron of the sheet aggregation of the irregular polygon laminated structure,
A width of 0.5~2 micron.
In the present invention, the solid content of the hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block for 20~
25%.Generally, the solid content of hydrogel is 3%~10%, it is seen then that the solid content of subject hydrogel is significantly improved.
Preparation method containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block of the present invention, first will be certain
The described poly- peptide molecule brush of polyethylene glycol block of amount is soluble in water, is completely dissolved it；Appropriate alpha-cyclodextrin is subsequently adding to mix
Close stirring, ultrasound；The water containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block is obtained after finally standing a period of time
Gel.
Preferably, the poly- peptide molecule brush (PEO-b-PELG-g-G1) of polyethylene glycol block concentration in aqueous is
0.15~0.22g/mL, alpha-cyclodextrin concentration in aqueous is 0.08~0.12g/mL.
In the present invention, the poly- peptide molecule brush (PEO-b-PELG-g-G1) of polyethylene glycol block, including main chain and side chain,
The main chain is the bi-block copolymer that polyethylene glycol (PEO) is constituted with poly- peptide, and the side chain is alkyloxy-ethers dendrimer.Institute
The structure of the poly- peptide molecule brush of polyethylene glycol block is stated such as with following formula (1) Suo Shi：
Wherein, n=30-100, X are methyl (Me) or ethyl (Et).
In the present invention, in the bi-block copolymer, a block is hydrophilic polyethylene glycol (PEO) chain, another block
It is poly- peptide segment, alkyloxy-ethers dendrimer is grafted thereon.In the present invention, due to alkyloxy-ethers dendrimer be it is hydrophilic,
Therefore the poly- peptide molecule brush (PEO-b-PELG-g-G1) of polyethylene glycol block also has hydrophily.
The preparation method of the poly- peptide molecule brush of polyethylene glycol block of the present invention, with chlorethanol and Pidolidone as raw material, prepares
γ-chloroethyl-Pidolidone ester；With amino-polyethyleneglycols monomethyl ether (PEO112-NH2) trigger a-amino acid-N- carboxyl inner-acid anhydrides
(NCA) ring-opening polymerisation, synthesis obtains polyethylene glycol-b- poly- (γ-chloroethyl-Pidolidone ester) (PEO-b-PCELG), by folded
Nitridation and click-reaction, the alkyloxy-ethers dendrimer (G1-Propargyl) with end alkynyl radical is grafted to the side chain of poly- peptide
On, so as to prepare the poly- peptide molecule brush (PEO-b-PELG-g- of the polyethylene glycol block containing alkyloxy-ethers dendrimer
G1)。
Preparation method of the present invention containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block, it is main to include with bottom
Point：(1) with gallicin, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether etc. as raw material, by protection,
The methods such as deprotection synthesize alkyloxy-ethers dendroid (G1-Propargyl) molecule that end is alkynyl.(2) in order to chlorine atom is drawn
Enter the avtive spot as grafting in poly- peptide backbone, using amino-polyethyleneglycols monomethyl ether (PEO112-NH2) trigger NCA (γ-chlorine
Ethyl-L-glutamate ester-N- carboxyls inner-acid anhydride) ring-opening polymerisation, synthesize the poly- (γ-chloroethyl-Pidolidone of polyethylene glycol-b-
Ester) (PEO-b-PCELG).(3) by Azide and click-reaction, by the alkyloxy-ethers dendrimer (G1- with end alkynyl radical
Propargyl) the poly- polypeptide block copolymer molecule containing alkyloxy-ethers dendrimer is prepared with being grafted on the side chain of poly- peptide
Brush (PEO-b-PELG-g-G1).(4) by poly- polypeptide block copolymer molecule brush (PEO-b-PELG-g-G1) and alpha-cyclodextrin in water
Middle mixing, ultrasound, standing, obtain poly- peptide hydrogel.
In one embodiment, system of the present invention containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block
Preparation Method, comprises the following steps：
1st, side chain is the synthesis of the poly- peptide molecule brush (PEO-b-PELG-g-G1) of dendrimer block
(1) end is the synthesis of alkyloxy-ethers dendroid (G1-Propargyl) molecule of alkynyl
With triethylene-glycol list first (second) ether and gallicin as initial feed, end is obtained by multistep reaction
It is the alkyloxy-ethers dendrimer (G1-Propargyl) of alkynyl.Specific synthetic method is referring to bibliography：Li, W；Zhang,
A.；Schluter, A, D.Chem.Commun.2008,5523..Its course of reaction is as follows：
(2) conjunction of the poly- peptide molecule brush (PEO-b-PELG-g-G1) of side chain dendrimer containing alkyloxy-ethers polyethylene glycol block
Into
With chlorethanol and Pidolidone as initial feed, γ-chloroethyl-Pidolidone ester (CELG) is prepared.Using
Amino-polyethyleneglycols monomethyl ether (PEO112-NH2) trigger NCA (γ-chloroethyl-Pidolidone ester-N- carboxyls inner-acid anhydride) open loop to gather
Close, synthesis obtains polyethylene glycol-b- poly- (γ-chloroethyl-Pidolidone ester) (PEO-b-PCELG).By azido reaction and
Click chemistry method, the alkyloxy-ethers dendrimer (G1-Propargyl) with end alkynyl radical is grafted on the side chain of poly- peptide, from
And prepare the poly- polypeptide block copolymer molecule brush (PEO-b-PELG-g-G1) containing alkyloxy-ethers dendrimer.It is specifically closed
It is as follows into route：
2nd, the preparation containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block
Take block poly- peptide molecule brush of the side chain containing alkyloxy-ethers dendrimer to be dissolved in the water of appropriate amount, be sufficiently stirred for, then
Alpha-cyclodextrin is added, is stirred vigorously, ultrasound finally stands, obtain the hydrogel with the poly- peptide molecule brush of block containing cyclodextrin.Work as temperature
When degree is warming up to 80 DEG C, gel is destroyed, and recovers to room temperature, and system is again transformed into gel.The above-mentioned poly- peptide molecule brush of block
(PEO-b-PELG-g-G1) concentration in water is not less than 0.15g/mL, and applicable concentration is 0.15~0.22g/mL, α-ring paste
Concentration of the essence in water is not less than 0.08g/mL, and applicable concentration is 0.08~0.12g/mL.
Innovative point of the invention includes, using the Subjective and Objective compound action and dendrimer of cyclodextrin and PEO, gathers
Intermolecular force between peptide, hydrone, is prepared for a kind of poly- peptide molecule swabbing gel of novel block, and its microstructure is lamella
Shape structure.The poly- peptide molecule brush of block obtained synthesized by the present invention, unique structure, good biocompatibility, it is easy to the generation in human body
Thank to absorption；Have no toxic side effect；Good stability, excellent in mechanical performance.Subject hydrogel part for example polyethylene glycol, poly- peptide,
Alkyloxy-ethers dendrimer, alpha-cyclodextrin all have good biocompatibility and degradability.Hydrogel proposed by the present invention
Preparation method is simple, easily controllable.Hydrogel of the invention is in drug loading, functional material, cell culture medium, organizational project
Etc. aspect exist be widely applied prospect.
Brief description of the drawings
Fig. 1 show the nuclear-magnetism hydrogen of the poly- peptide molecule brush PEO-b-PELG-g-G1 of polyethylene glycol block prepared in embodiment
Spectrum.
Fig. 2 show the preparation effect diagram of hydrogel in embodiment.
Fig. 3 show embodiment in hydrogel by the ESEM and transmission electron microscope picture after frozen dried.
Fig. 4 show storage modulus (G '), loss modulus (G ") and the dynamic viscosity (η *) of hydrogel in embodiment with sweeping
Retouch frequency variation diagram.
Specific embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail.Implement process of the invention,
Condition, reagent, experimental technique etc., in addition to the following special content for referring to, are the universal knowledege and common knowledge of this area,
The present invention is not particularly limited content.
Preparation method containing cyclodextrin and the poly- peptide molecule swabbing gel of polyethylene glycol block proposed by the present invention, specifically includes
Following steps：
1st, side chain is the synthesis of the poly- peptide molecule brush (PEO-b-PELG-g-G1) of dendrimer block
The synthesis of (a) monomer
Pidolidone (10.0g 0.068mol) is well mixed with chlorethanol (18.25mL 0.27mol), white is obtained
Pasty mass, under the conditions of ice-water bath, to the concentrated sulfuric acid (3.60mL 0.066mol) is added dropwise in reaction bulb, white paste can be gradually
Gradually dissolve, after question response liquid becomes clarification, remove ice-water bath, reaction two days is stirred at room temperature.Configuration concentration 1molL-1NaOH
With the NaHCO that mass fraction is 5%3Solution is some to be used in combination, and the pH of reaction solution is adjusted under ice-water bath to neutrality, is had big
Amount White Flocculus are separated out, and suction filtration goes out insoluble matter, with water: methyl alcohol volume ratio=1: 3 mixed solutions are recrystallized, treat that its is cooled down
Suction filtration goes out precipitate afterwards, and vacuum drying obtains white needle-like crystals after 2 days, i.e. γ-chloroethyl-Pidolidone ester (CELG).Produce
Rate is 65%.
(b) Macroscopic single crystal
It is dispersed in dried THF after monomer CELG (5.0g 0.024mol) grindings, after leading to nitrogen gas stirring 30min, is turned
Back flow reaction in 50 DEG C of oil bath pans is moved to, after after its stable micro-boiling, triphosgene (2.48g 0.0084mol) is added, system is rapid
Become clarification, continue the 2h that flows back, reaction solution is presented water white transparency slightly band yellow, and revolving removes THF, adds dry ethyl acetate,
Then distilled water, NaHCO are used at low ambient temperatures3Dried after buck and saturated common salt water washing, revolving removes most of molten
Agent, petroleum ether precipitation, and be vacuum dried.It is poly- with amino under nitrogen protection with dry DMF as solvent
Glycol monoethyl ether is initiator, after lucifuge reaction 48h, is precipitated in ether, suction filtration, and white polyethylene glycol-b- is obtained after drying
Poly- (chloroethyl glutamate) (PEO-b-PCELG), yield is 85%.
To adding poly- polypeptide block copolymer p EO-b-PCELG (1.0g), sodium azide (2.3g, 35.9mmol) in reaction bulb
And 25mL stirs by the DMF of dried process, 48h is reacted under 60 DEG C of oil baths.Stop reaction, be centrifuged off unreacted
Sodium azide, be spin-dried for DMF, add dichloromethane, precipitated in ether, suction filtration, obtain white solid powder (nitrine after drying
Poly- polypeptide block copolymer p EO-b-PCELG after change) 0.78g, yield is 78%.
C () end is the synthesis of alkyloxy-ethers dendroid (G1-Propargyl) molecule of alkynyl
With triethylene-glycol list first (second) ether and gallicin as initial feed, end is obtained by multistep reaction
It is methoxy ether dendrimer (G1-Propargyl) of alkynyl.Specific synthetic method is referring to bibliography：Li, W；Zhang,
A.；Schluter, A, D.Chem.Commun.2008,5523..
The synthesis of (d) molecular brush
A methyl alkyloxy-ethers generation for poly- polypeptide block copolymer p EO-b-PCELG (0.5g) and terminal acetylene after by Azide
G1 (1.08g, 1.71mmol) is dissolved in the DMF of 25mL, it is possible to additionally incorporate micro copper powder, leads to nitrogen
20min, and CuBr (0.23g, 1.61mmol) and PMDETA (268 μ L) is added under nitrogen protection, seal bottleneck, 50 DEG C of lucifuge
Oil bath is reacted 3 days, saturated common salt water washing, is precipitated in ether, and suction filtration, vacuum drying obtain faint yellow custard shape thing, i.e. target and produce
The thing side chain poly- peptide molecule brush PEO-b-PCELG-g-G1 of polyethylene glycol block of dendrimer containing alkyloxy-ethers, yield 70.8%.Its
Chemical structural formula is as follows：
The present embodiment product nuclear magnetic spectrogram as shown in figure 1,1H-NMR(CDCl3, δ)：Be can be seen that from nucleus magnetic hydrogen spectrum figure
The peak-to-peak signal of 3.78ppm is-CH in PEO segmental repeat units2- characteristic peak (a, b), at 4.51ppm being poly- peptide backbone-
It is respectively-CH on poly- peptide side chain chain at the signal peak of CH-CO- (d), 2.19ppm and 2.57ppm2CH2CO- (e) and-
CH2CH2The signal peak of CO- (f), 6.65ppm is the characteristic peak (k) of hydrogen in alkyloxy-ethers dendrimer phenyl ring methylene,
3.8ppm is the characteristic peak (l) on alkyloxy-ethers dendrimer methylene, and 23.5ppm is alkyloxy-ethers dendrimer end CH3-
Characteristic peak (m).As can be seen here, the polymer that the present embodiment is prepared is that target product side chain is the embedding of dendrimer
The poly- peptide molecule brush (PEO-b-PELG-g-G1) of section.
The preparation of the hydrogel the 2nd, containing cyclodextrin and the poly- peptide molecule brush (PEO-b-PELG-g-G1) of polyethylene glycol block
Take block poly- peptide molecule brush 0.18g of the side chain containing alkyloxy-ethers dendrimer to be dissolved in 1.0mL water, be sufficiently stirred for,
0.1g alpha-cyclodextrins are added, 1h, ultrasonic 0.5h is stirred vigorously, 3h is finally stood, obtained containing cyclodextrin and the poly- peptide molecule of block
Brush (PEO-b-PELG-g-G1) hydrogel.When temperature is warming up to 80 DEG C, gel is destroyed, and recovers to room temperature, and system is again
It is changed into gel.The preparation effect of the transition process, i.e. subject hydrogel, as shown in Figure 2.
It is to the method that preparation-obtained poly- peptide hydrogel is identified：Sample bottle is inverted 5min, system energy gram
Take gravity to occur in stable state and without any flowing, thereby determine that to form in the present invention and answered based on poly- peptide molecule brush Subjective and Objective
The hydrogel of cooperation.
Relevant characterization containing cyclodextrin Yu the poly- peptide molecule swabbing gel of polyethylene glycol block
Subject hydrogel through transmission electron microscope and ESEM by after freeze-drying, characterizing and can obtain：Gel micro-dimension is
0.5~2 micron of irregular polygon is laminar structured.Its structure chart is shown in Fig. 3, and according to visible in figure, its microstructure is piece
Shape structure.
The viscoelastic sexual behaviour of Subjective and Objective composite aquogel of the present invention is characterized by rheometer, as a result as shown in Figure 4：Whole
The storage modulus (G ') of hydrogel is far longer than loss modulus (G ") in the range of individual test frequency, so as to confirm gel rubber system
Formed.Meanwhile, experimental result is also shown that the Subjective and Objective composite intelligent hydrogel that the present invention is constructed has preferable mechanical property,
Can be applied to the aspects such as tissue engineering bracket.On the other hand, the dynamic viscosity (η *) of hydrogel is with the increase of shearing frequency
Reduce, it is seen that it has the performance of shear shinning, shows that Subjective and Objective compound system of the present invention belongs to pseudoplastic fluid.
Protection content of the invention is not limited to above example.Under the spirit and scope without departing substantially from inventive concept, this
Art personnel it is conceivable that change and advantage be all included in the present invention, and with appending claims be protect
Shield scope.
Claims (8)
1. the poly- peptide molecule brush of a kind of polyethylene glycol block, it is characterised in that the poly- peptide molecule brush of polyethylene glycol block includes master
Chain and side chain, the main chain are the bi-block copolymer that polyethylene glycol is constituted with poly- peptide, and the side chain is alkyloxy-ethers dendroid point
Son；The poly- peptide molecule brush configuration of polyethylene glycol block is such as with following formula (1) Suo Shi：
Wherein, n=30-100, X are methyl or ethyl.
2. the preparation method of the poly- peptide molecule brush of polyethylene glycol block according to claim 1, it is characterised in that with chlorethanol and
Pidolidone is raw material, prepares γ-chloroethyl-Pidolidone ester；γ-chloroethyl-Pidolidone the ester is converted into γ-chlorine
Ethyl-L-glutamate ester-N- carboxyl inner-acid anhydrides；γ-chloroethyl-the Pidolidone is triggered with amino-polyethyleneglycols monomethyl ether
Ester-N- carboxyl inner-acid anhydride ring-opening polymerisations, synthesis obtains polyethylene glycol-b- poly- (γ-chloroethyl-Pidolidone ester)；Through Azide
And click-reaction, the alkyloxy-ethers dendrimer is grafted on poly- peptide segment, prepare the polyethylene glycol block and gather
Peptide molecule brush.
3. a kind of hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block, it is characterised in that it is to include α-ring paste
The binary system hydrogel of the smart and as claimed in claim 1 poly- peptide molecule brush of polyethylene glycol block.
4. the hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block according to claim 3, it is characterised in that
Its microstructure is irregular polygon laminated structure, and the hydrogel is formed by laminated structure layer upon layer.
5. the hydrogel containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block according to claim 3, it is characterised in that
The solid content of the hydrogel is 20~25%.
6. the preparation method of the hydrogel of cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block is contained according to claim 3, its
It is characterised by, the poly- peptide molecule brush of polyethylene glycol block as claimed in claim 1 is soluble in water, it is completely dissolved it；Add
Alpha-cyclodextrin is mixed, ultrasound；A period of time is stood, is prepared described containing cyclodextrin and the poly- peptide molecule of polyethylene glycol block
Swabbing gel.
7. preparation method according to claim 6, it is characterised in that the poly- peptide molecule brush of polyethylene glycol block is in water
Concentration be 0.15~0.22g/mL, concentration of the alpha-cyclodextrin in water be 0.08~0.12g/mL.
8. the hydrogel according to claim 3 containing cyclodextrin and the poly- peptide molecule brush of polyethylene glycol block is as drug loading
In application.
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| CN105348506B (en) * | 2015-12-01 | 2017-06-13 | 沈阳药科大学 | The preparation of glutamic acid TPGS block copolymers and its application in targeted drug transmission |
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