CN104592511A - Hydrogel containing cyclodextrin and polyethylene glycol block polypeptide molecular brush as well as preparation method and application of hydrogel - Google Patents
Hydrogel containing cyclodextrin and polyethylene glycol block polypeptide molecular brush as well as preparation method and application of hydrogel Download PDFInfo
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- CN104592511A CN104592511A CN201510026333.6A CN201510026333A CN104592511A CN 104592511 A CN104592511 A CN 104592511A CN 201510026333 A CN201510026333 A CN 201510026333A CN 104592511 A CN104592511 A CN 104592511A
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- 0 C*C(c(cc1O)cc(O)c1O)=O Chemical compound C*C(c(cc1O)cc(O)c1O)=O 0.000 description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N NC(CCC(O)=O)C(O)=O Chemical compound NC(CCC(O)=O)C(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- MILZWEYTOAHZJY-UHFFFAOYSA-N NC(CCC(OCCCl)=O)C(O)=O Chemical compound NC(CCC(OCCCl)=O)C(O)=O MILZWEYTOAHZJY-UHFFFAOYSA-N 0.000 description 1
- FFTGJDKPZAFLMQ-UHFFFAOYSA-N O=C(CCC(C(O1)=O)NC1=O)OCCCl Chemical compound O=C(CCC(C(O1)=O)NC1=O)OCCCl FFTGJDKPZAFLMQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a polyethylene glycol block polypeptide molecular brush. The polyethylene glycol block polypeptide molecular brush has a structure as shown in a formula (1) in the specification, and comprises a main chain and a side chain, wherein the main chain is a two-block polymer composed of polyethylene glycol and polypeptide; the side chain is an alkoxy ether dendrimer. The preparation method comprises the following steps: preparing gamma-chloroethyl-L-glutamate from chlorohydrin and L-glutamic acid, and initiating the ring opening polymerization of alpha-amino acid-N-carboxyanhydride by use of amino polyethylene glycol monomethyl ether to obtain polyethylene glycol-b-poly(gamma-chloroethyl-L-glutamate; grafting the alkoxy ether dendrimer to the polypeptide chain by virtue of azidation and click reaction, thereby preparing the polyethylene glycol block polypeptide molecular brush. The invention also discloses a hydrogel containing alpha-cyclodextrin and the polyethylene glycol block polypeptide molecular brush. The hydrogel is prepared by mixing and stirring the molecular brush and the alpha-cyclodextrin in water and then performing ultrasonic and standing treatment. The hydrogel has unique structure and morphology and excellent biocompatibility, and has wide application prospect in the fields of functional materials, cell culture medias, medicine carrier and the like.
Description
Technical field
The invention belongs to new material technology field, be specifically related to a kind of high polymer material technology, relate more specifically to one and gather peptide molecule swabbing gel and its preparation method and application containing cyclodextrin and polyoxyethylene glycol block.
Background technology
Because polyalcohol hydrogel system has similarity in the flexibility and reticulated structure and multiple outside stimulus response performance etc. of analog cell epimatrix, be subject to scientist more and more pay close attention to widely and study, and progressively its aquogel system be applied to the field such as drug loading, organizational project.Poly-peptide has and has similar structures with bioprotein, and the effect due to hydrogen bond can form unique orderly secondary con (alpha-helix, beta sheet etc.) structure, the structure of this uniqueness makes it be different from traditional polymkeric substance, and the water gel built by it ties up to the fields such as biological medicine potential using value.At present, poly-peptide and multipolymer thereof have become and have constructed the first-selected base material of hydrogel.
In the last few years, the application based on the main-guest chemistry aquogel system of cyclodextrin also obtains paying close attention to more and more widely.As people (ACS Macro Lett.2014 such as Yaobin Wu, 3,1 145-1150) design and synthesis goes out containing Tetraaniline side base degradable multipolymer, and construct supramolecular hydrogel by host-guest interactions between γ-cyclodextrin dimer, can be used as a kind of drug delivery system of potential injection.
But, in currently available technology, not yet report the research building supermolecular gel system based on the Polypeptide copolymer molecular brush and cyclodextrin acting in conjunction that contain dendrimer structure.
Summary of the invention
The object of this invention is to provide a kind of main-guest chemistry based on cyclodextrin and gather peptide molecule swabbing gel, and set up its preparation method.Described hydrogel is a kind of side chain that comprises is the binary system hydrogel that the block of alkyloxy-ethers dendrimer gathers peptide molecule brush and alpha-cylodextrin, and each moiety all has good biocompatibility and degradability.
In the present invention, the described hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block comprises alpha-cylodextrin and side chain gather peptide molecule brush binary system hydrogel containing the polyoxyethylene glycol block of alkyloxy-ethers dendrimer.
In the present invention, the described hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block, its microtexture is laminated structure.Particularly, this hydrogel is irregular polygon sheet structure, and its microscopic dimensions is 0.5 ~ 2 micron, and hydrogel is piled up layer by layer by sheet aggregate and formed.The length of the sheet aggregate of this irregular polygon sheet structure is 0.5 ~ 2 micron, and wide is 0.5 ~ 2 micron.
In the present invention, the described solid content gathering the hydrogel of peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block is 20 ~ 25%.Usually, the solid content of hydrogel is 3% ~ 10%, and visible, the solid content of subject hydrogel significantly improves.
The preparation method gathering peptide molecule swabbing gel containing cyclodextrin and polyoxyethylene glycol block of the present invention, first gathers peptide molecule brush by a certain amount of described polyoxyethylene glycol block soluble in water, makes it dissolve completely; Then appropriate alpha-cylodextrin mix and blend, ultrasonic is added; Namely the described hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block is obtained after finally leaving standstill for some time.
Preferably, it is 0.15 ~ 0.22g/mL that described polyoxyethylene glycol block gathers peptide molecule brush (PEO-b-PELG-g-G1) concentration in aqueous, and described alpha-cylodextrin concentration is in aqueous 0.08 ~ 0.12g/mL.
In the present invention, described polyoxyethylene glycol block gathers peptide molecule brush (PEO-b-PELG-g-G1), comprise main chain and side chain, described main chain is the bi-block copolymer that polyoxyethylene glycol (PEO) forms with poly-peptide, and described side chain is alkyloxy-ethers dendrimer.The structure that described polyoxyethylene glycol block gathers peptide molecule brush is as shown in following formula (1):
Wherein, n=30-100, X are methyl (Me) or ethyl (Et).
In the present invention, in described bi-block copolymer, a block is hydrophilic polyoxyethylene glycol (PEO) chain, and another block is poly-peptide segment, and the grafting of alkyloxy-ethers dendrimer thereon.In the present invention, because alkyloxy-ethers dendrimer is hydrophilic, therefore polyoxyethylene glycol block gathers peptide molecule brush (PEO-b-PELG-g-G1) and also has wetting ability.
Polyoxyethylene glycol block of the present invention gathers the preparation method of peptide molecule brush, with chloroethanol and Pidolidone for raw material, and preparation γ-chloroethyl-Pidolidone ester; With amino-polyethyleneglycols monomethyl ether (PEO
112-NH
2) cause inner-acid anhydride (NCA) ring-opening polymerization of a-amino acid-N-carboxyl, synthesis obtains polyoxyethylene glycol-b-poly-(γ-chloroethyl-Pidolidone ester) (PEO-b-PCELG), by azide and click-reaction, the alkyloxy-ethers dendrimer (G1-Propargyl) with end alkynyl radical is grafted on the side chain of poly-peptide, thus the described polyoxyethylene glycol block prepared containing alkyloxy-ethers dendrimer gathers peptide molecule brush (PEO-b-PELG-g-G1).
The present invention gathers the preparation method of peptide molecule swabbing gel containing cyclodextrin and polyoxyethylene glycol block; mainly comprise with lower part: (1) with methyl gallate, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether etc. for 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 introduces the avtive spot as grafting in poly-peptide main chain, amino-polyethyleneglycols monomethyl ether (PEO is adopted
112-NH
2) cause NCA (γ-chloroethyl-Pidolidone ester-N-carboxyl inner-acid anhydride) ring-opening polymerization, synthesize polyoxyethylene glycol-b-poly-(γ-chloroethyl-Pidolidone ester) (PEO-b-PCELG).(3) by azide and click-reaction, by the poly-polypeptide block copolymer molecule brush (PEO-b-PELG-g-G1) that the alkyloxy-ethers dendrimer (G1-Propargyl) with end alkynyl radical and the side chain being grafted to poly-peptide are prepared containing alkyloxy-ethers dendrimer.(4) polypeptide block copolymer molecule brush (PEO-b-PELG-g-G1) and alpha-cylodextrin mix and blend, ultrasonic, standing in water will be gathered, obtain poly-peptide hydrogel.
In one embodiment, the present invention containing cyclodextrin and polyoxyethylene glycol block gather peptide molecule swabbing gel preparation method, comprise the steps:
1, side chain is the synthesis that dendrimer block gathers peptide molecule brush (PEO-b-PELG-g-G1)
(1) end is the synthesis of alkyloxy-ethers dendroid (G1-Propargyl) molecule of alkynyl
With Triethylene glycol list first (second) ether and methyl gallate for initial feed, obtain through polystep reaction the alkyloxy-ethers dendrimer (G1-Propargyl) that end is alkynyl.Concrete synthetic method is see reference: Li, W; Zhang, A.; Schluter, A, D.Chem.Commun.2008,5523..Its reaction process is as follows:
(2) side chain gathers the synthesis of peptide molecule brush (PEO-b-PELG-g-G1) containing alkyloxy-ethers dendrimer polyoxyethylene glycol block
With chloroethanol and Pidolidone for initial feed, prepare γ-chloroethyl-Pidolidone ester (CELG).Adopt amino-polyethyleneglycols monomethyl ether (PEO
112-NH
2) causing NCA (γ-chloroethyl-Pidolidone ester-N-carboxyl inner-acid anhydride) ring-opening polymerization, synthesis obtains polyoxyethylene 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, thus prepares the poly-polypeptide block copolymer molecule brush (PEO-b-PELG-g-G1) containing alkyloxy-ethers dendrimer.Its concrete synthetic route is as follows:
2, the preparation of peptide molecule swabbing gel is gathered containing cyclodextrin and polyoxyethylene glycol block
Get side chain to gather peptide molecule brush containing the block of alkyloxy-ethers dendrimer and be dissolved in the water of appropriate amount, fully stir, then add alpha-cylodextrin, vigorous stirring, ultrasonic, finally leave standstill, obtain the hydrogel gathering peptide molecule brush containing cyclodextrin and block.When temperature to 80 DEG C, gel is destroyed, and after returning to room temperature, system changes gel into again.Above-mentioned block gathers peptide molecule brush (PEO-b-PELG-g-G1) concentration in water and is not less than 0.15g/mL, the concentration be suitable for is 0.15 ~ 0.22g/mL, the concentration of alpha-cylodextrin in water is not less than 0.08g/mL, and applicable concentration is 0.08 ~ 0.12g/mL.
Innovative point of the present invention comprises, and utilize the Intermolecular Forces between the Subjective and Objective compound action of cyclodextrin and PEO and dendrimer, poly-peptide, water molecules, prepared a kind of novel block and gathered peptide molecule swabbing gel, its microtexture is laminar structured.The block obtained synthesized by the present invention gathers peptide molecule brush, and structure is unique, and good biocompatibility, is easy to the metabolic adsorption in human body; Have no side effect; Good stability, excellent in mechanical performance.Subject hydrogel integral part such as polyoxyethylene glycol, poly-peptide, alkyloxy-ethers dendrimer, alpha-cylodextrin all have good biocompatibility and degradability.The preparation method of hydrogel that the present invention proposes is easy, be easy to control.Application prospect is widely there is in hydrogel of the present invention in drug loading, functional materials, cell culture medium, organizational project etc.
Accompanying drawing explanation
Figure 1 shows that the polyoxyethylene glycol block prepared in embodiment gathers the nucleus magnetic hydrogen spectrum of peptide molecule brush PEO-b-PELG-g-G1.
Figure 2 shows that the preparation effect schematic diagram of hydrogel in embodiment.
Figure 3 shows that scanning electron microscope after frozen dried of hydrogel in embodiment and transmission electron microscope picture.
Figure 4 shows that the storage modulus (G ') of hydrogel in embodiment, out-of-phase modulus (G ") and dynamic viscosity (η *) are with sweep rate variation diagram.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation method gathering peptide molecule swabbing gel containing cyclodextrin and polyoxyethylene glycol block that the present invention proposes, specifically comprises the steps:
1, side chain is the synthesis that dendrimer block gathers peptide molecule brush (PEO-b-PELG-g-G1)
The synthesis of (a) monomer
Pidolidone (10.0g 0.068mol) is mixed with chloroethanol (18.25mL 0.27mol), obtain white paste material, under ice-water bath condition, the vitriol oil (3.60mL 0.066mol) is dripped in reaction flask, white paste can be dissolved gradually, after question response liquid becomes clarification, remove ice-water bath, stirring at room temperature reacts two days.Configuration concentration 1molL
-1naOH and massfraction be the NaHCO of 5%
3the some conbined usage of solution, under ice-water bath, regulate the pH of reaction solution to neutral, have a large amount of White Flocculus to separate out, suction filtration goes out insolubles, with water: methyl alcohol volume ratio=1: 3 mixing solutionss carry out recrystallization, after its cooling, suction filtration goes out precipitate, and vacuum-drying obtained white needle-like crystals after 2 days, i.e. γ-chloroethyl-Pidolidone ester (CELG).Productive rate is 65%.
(b) Macroscopic single crystal
Be dispersed in dried THF after monomer CELG (5.0g 0.024mol) grinding, after logical nitrogen gas stirring 30min, be transferred to back flow reaction in 50 DEG C of oil bath pans, stablize after micro-boiling until it, add triphosgene (2.48g 0.0084mol), system becomes clarification rapidly, continue backflow 2h, reaction solution presents water white transparency and is slightly with yellow, revolves and steams removing THF, add dry ethyl acetate, then use distilled water, NaHCO at low ambient temperatures
3dry after buck and saturated common salt water washing, revolve and steam the most of solvent of removing, petroleum ether precipitation, and vacuum-drying.Under nitrogen protection with the N of drying; dinethylformamide is solvent; with amino-polyethyleneglycols monomethyl ether for initiator; after lucifuge reaction 48h; precipitate in ether; suction filtration, obtain white polyoxyethylene glycol-b-poly-(chloroethyl glutamate) (PEO-b-PCELG) after drying, productive rate is 85%.
In reaction flask, add poly-polypeptide block copolymer p EO-b-PCELG (1.0g), sodiumazide (2.3g, 35.9mmol) and 25mL, through the DMF of drying treatment, stir, and react 48h under 60 DEG C of oil baths.Stopped reaction, the unreacted sodiumazide of centrifugal removing, is spin-dried for DMF, adds methylene dichloride, precipitate in ether, suction filtration, and obtain white solid powder (the poly-polypeptide block copolymer p EO-b-PCELG after azide) 0.78g after drying, productive rate is 78%.
C () end is the synthesis of alkyloxy-ethers dendroid (G1-Propargyl) molecule of alkynyl
With Triethylene glycol list first (second) ether and methyl gallate for initial feed, obtain through polystep reaction the methoxy ether dendrimer (G1-Propargyl) that end is alkynyl.Concrete synthetic method is see reference: Li, W; Zhang, A.; Schluter, A, D.Chem.Commun.2008,5523..
The synthesis of (d) molecular brush
By the methyl alkyloxy-ethers generation G1 (1.08g of the poly-polypeptide block copolymer p EO-b-PCELG (0.5g) after azide with terminal acetylene, 1.71mmol) be dissolved in the N of 25mL, in dinethylformamide, add micro-copper powder in addition, logical nitrogen 20min, and add CuBr (0.23g under nitrogen protection, 1.61mmol) with PMDETA (268 μ L), sealing bottleneck, lucifuge 50 DEG C of oil baths react 3 days, saturated common salt water washing, precipitate in ether, suction filtration, vacuum-drying obtains faint yellow custard shape thing, namely target product side chain gathers peptide molecule brush PEO-b-PCELG-g-G1 containing alkyloxy-ethers dendrimer polyoxyethylene glycol block, productive rate 70.8%.Its chemical structural formula is as follows:
The present embodiment product nuclear magnetic spectrogram as shown in Figure 1,
1h-NMR (CDCl
3, δ): be-CH in PEO segmental repeat unit as can be seen from the peak-to-peak signal of nucleus magnetic hydrogen spectrum figure, 3.78ppm
2-characteristic peak (a, b), 4.51ppm place is the fignal center of-CH-CO-(d) in poly-peptide main chain, 2.19ppm and 2.57ppm place is-CH on poly-peptide side chain chain respectively
2cH
2cO-(e) and-CH
2cH
2the fignal center of CO-(f), 6.65ppm is the characteristic peak (k) of hydrogen on methylene radical in alkyloxy-ethers dendrimer phenyl ring, 3.8ppm is the characteristic peak (l) on alkyloxy-ethers dendrimer methylene radical, and 23.5ppm is alkyloxy-ethers dendrimer end CH
3-characteristic peak (m).As can be seen here, the block of the polymkeric substance that the present embodiment prepares namely to be target product side chain be dendrimer gathers peptide molecule brush (PEO-b-PELG-g-G1).
2, the preparation of the hydrogel of peptide molecule brush (PEO-b-PELG-g-G1) is gathered containing cyclodextrin and polyoxyethylene glycol block
Get side chain to gather peptide molecule brush 0.18g containing the block of alkyloxy-ethers dendrimer and be dissolved in 1.0mL water, abundant stirring, add 0.1g alpha-cylodextrin again, vigorous stirring 1h, ultrasonic 0.5h, finally leave standstill 3h, obtain gathering peptide molecule brush (PEO-b-PELG-g-G1) hydrogel containing cyclodextrin and block.When temperature to 80 DEG C, gel is destroyed, and after returning to room temperature, system changes gel into again.This transition process, i.e. the preparation effect of subject hydrogel, as shown in Figure 2.
To the method that preparation-obtained poly-peptide hydrogel is identified be: sample bottle is inverted 5min, this system can overcome gravity and is steady state and occurs without any flowing, determines to define the hydrogel based on poly-peptide molecule brush Subjective and Objective compound action in the present invention thus.
The relevant characterization of peptide molecule swabbing gel is gathered containing cyclodextrin and polyoxyethylene glycol block
Subject hydrogel, after lyophilize, characterizes can obtain through transmission electron microscope and scanning electron microscope: gel micro-dimension is that the irregular polygon of 0.5 ~ 2 micron is laminar structured.Fig. 3 is shown in by its structure iron, and according to visible in figure, its microtexture is sheet structure.
The visco-elasticity behavior of Subjective and Objective composite aquogel of the present invention is characterized by rheometer, result is as shown in Figure 4: within the scope of whole test frequency, the storage modulus (G ') of hydrogel is far longer than out-of-phase modulus (G "), thus confirm the formation of gelling system.Meanwhile, experimental result also shows, the Subjective and Objective composite intelligent hydrogel that the present invention constructs has good mechanical property, can be applicable to the aspects such as tissue engineering bracket.On the other hand, the dynamic viscosity (η *) of hydrogel reduces along with the increase of shearing frequency, and it has the performance of shear shinning as seen, shows that Subjective and Objective compound system of the present invention belongs to pseudoplastic fluid.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.
Claims (9)
1. polyoxyethylene glycol block gathers a peptide molecule brush, it is characterized in that, described polyoxyethylene glycol block gathers peptide molecule brush and comprises main chain and side chain, and described main chain is the bi-block copolymer that polyoxyethylene glycol and poly-peptide form, and described side chain is alkyloxy-ethers dendrimer; Described polyoxyethylene glycol block gathers peptide molecule brush configuration as shown in following formula (1):
Wherein, n=30-100, X are methyl or ethyl.
2. polyoxyethylene glycol block according to claim 1 gathers peptide molecule brush, it is characterized in that, in described bi-block copolymer, a block is hydrophilic polyglycol chain, and another block is poly-peptide segment; Described alkyloxy-ethers dendrimer grafts on described poly-peptide segment.
3. polyoxyethylene glycol block gathers the preparation method of peptide molecule brush according to claim 1, it is characterized in that, with chloroethanol and Pidolidone for raw material, and preparation γ-chloroethyl-Pidolidone ester; Cause the ring-opening polymerization of a-amino acid-N-carboxyl inner-acid anhydride with amino-polyethyleneglycols monomethyl ether, synthesis obtains polyoxyethylene glycol-b-poly-(γ-chloroethyl-Pidolidone ester); Through azide and click-reaction, described alkyloxy-ethers dendrimer is grafted on poly-peptide segment, prepares described polyoxyethylene glycol block and gather peptide molecule brush.
4. gather a hydrogel for peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block, it is characterized in that, it is comprise the binary system hydrogel that alpha-cylodextrin and polyoxyethylene glycol block as claimed in claim 1 or 2 gather peptide molecule brush.
5. the hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block according to claim 4, it is characterized in that, its microtexture is laminated structure; Described hydrogel is irregular polygon sheet structure, and its length is 0.5 ~ 2 micron, and wide is 0.5 ~ 2 micron; Described hydrogel is piled up layer by layer by sheet aggregate and is formed.
6. the hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block according to claim 4, it is characterized in that, the solid content of described hydrogel is 20 ~ 25%.
7. gather the preparation method of the hydrogel of peptide molecule brush according to claim 4 containing cyclodextrin and polyoxyethylene glycol block, it is characterized in that, polyoxyethylene glycol block as claimed in claim 1 or 2 is gathered peptide molecule brush soluble in water, make it dissolve completely; Add alpha-cylodextrin mix and blend, ultrasonic; Leave standstill for some time, described in preparing, gather peptide molecule swabbing gel containing cyclodextrin and polyoxyethylene glycol block.
8. preparation method according to claim 7, is characterized in that, it is 0.15 ~ 0.22g/mL that described polyoxyethylene glycol block gathers the concentration of peptide molecule brush in water, and the concentration of described alpha-cylodextrin in water is 0.08 ~ 0.12g/mL.
9. the hydrogel gathering peptide molecule brush containing cyclodextrin and polyoxyethylene glycol block is according to claim 4 being used as the application in drug loading.
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| CN109897179A (en) * | 2019-04-02 | 2019-06-18 | 中国科学院长春应用化学研究所 | A kind of poly- (Pidolidone ester) block copolymer of multi-arm polyethylene glycol-and its preparation method and application |
| CN109897179B (en) * | 2019-04-02 | 2021-08-17 | 中国科学院长春应用化学研究所 | Multi-arm polyethylene glycol-poly (L-glutamate) block copolymer, and preparation method and application thereof |
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