CN104262643A - Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof - Google Patents
Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof Download PDFInfo
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- CN104262643A CN104262643A CN201410561125.1A CN201410561125A CN104262643A CN 104262643 A CN104262643 A CN 104262643A CN 201410561125 A CN201410561125 A CN 201410561125A CN 104262643 A CN104262643 A CN 104262643A
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Abstract
The invention belongs to the fields of supramolecular polymer polymer chemistry and drop formation control, and particularly relates to supramolecular hydrogel microsphere modified with cyclodextrin water-solubility polymer and adamantine water-solubility polymer and formed by assembling subjective and objective bodies in a liquid drop, and a preparation method and application thereof. The first purpose of the invention is to provide novel supramolecular hydrogel microsphere formed by assembling subjective and objective bodies and a preparation method thereof method, the second purpose of the invention is to adopt liquid drop as a template to realize supramolecular assembly and achieve uniform particle size and controllable dimension of the supramolecular hydrogel microsphere, and the third purpose of the invention is to provide application of the type of supramolecular hydrogel microsphere in adriacin doxorubicin and taxol water-solubility antitumor drug sustained release, so as to achieve the purpose that a drug can keep a high concentration level for a long time.
Description
Technical field
The invention belongs to supermolecule polymer chemistry and manipulate field with drop formation, be particularly modified with cyclodextrin water-soluble polymers and be modified with diamantane water-soluble polymers Subjective and Objective in drop and assemble the preparation method and purposes that form supramolecular hydrogel microballoon.
Background technology
Hydrogel microsphere is also known as microgel, refer to a kind of high molecular polymer that there is intramolecule and be cross-linked, due to its specific ball form and can stimuli responsive performance, hydrogel microsphere, drug conveying, microreactor coated at cell and sensor field shows potential application prospect.
The formation of hydrogel microsphere depends on chemically crosslinked and physical crosslinking two kinds.Chemically crosslinked refers to and connects small molecules or macromole by the chemical interactions of covalent linkage, forms the three-dimensional molecular crosslinking structure of permanent stabilization; Physical crosslinking is that this gel is volatile, can change solution into by heated gel by physical force as formation such as the windings of hydrogen bond action, electrostatic interaction, chain.Recently, the method relying on supramolecular chemistry prepares the extensive concern that hydrogel block materials causes domestic and international investigator, Supramolecular Assembling refers to the weak force that multiple molecule is non-chemically set up by the effect etc. of the coulomb interaction of hydrogen bond, Van der Waals force, electric charge, л-л conjugation and parent and is automatically combined into orderly organized paradigmatic system, rely on the ability that hydrogel that this method obtains has self-identifying, self-assembly and self replication, in catalysis, transmission, self-organization synthesis etc., open up a wide Application Areas.However, adopt the method for Supramolecular Assembling to be limited to the macroscopic body phase material of millimeter or cm size at present, the supramolecular hydrogel microballoon how preparing micron order size also lacks reliable method; Meanwhile, the dimensional homogeneity of supramolecular hydrogel microballoon how controlling to prepare also is investigator's key issue urgently to be resolved hurrily.
Summary of the invention
For the problems referred to above, the present invention selects drop to be template, utilize cyclodextrin to the characteristic of the specific recognition of diamantane, propose a kind of method that polymer that self-assembly two kinds is modified with cyclodextrin and diamantane respectively in drop prepares supramolecular hydrogel microballoon, its distinguishing feature is high molecular reaction cavity with the spherical morphology of micron order drop, effectively can control size and the homogeneity of hydrogel microsphere, open a kind of highly versatile and the route of synthesis of reliable supramolecular hydrogel microballoon.
An object of the present invention is to provide a kind of supramolecular hydrogel microballoon of novel, Subjective and Objective assembling, two is utilize drop to realize supramolecular assembling for template, reach the particle diameter of supramolecular hydrogel microballoon and the controlled preparation method of form, three are to provide the application of the type supramolecular hydrogel microballoon in Zorubicin, taxol soluble antitumor drug slowly-releasing, to reach the object that medicine can maintain higher concentration level for a long time.
For achieving the above object, technique means of the present invention is: a kind of take drop as the supramolecular hydrogel microballoon of Template preparation, and polymer self-assembly in drop that the polymer modified by cyclodextrin and diamantane are modified is formed.The present invention utilizes the Subjective and Objective supermolecular mechanism power between cyclodextrin and diamantane, is dissolved in the polymer that polymer cyclodextrin modified in drop and diamantane modify and can be compounded to form supramolecular hydrogel microballoon.
Described drop refers under quiescent conditions can sedimentation, and can keep the fine liquid particle of suspended state under turbulent-flow conditions, diameter is between 500 nanometers are to 500 microns.
Described cyclodextrin is alpha-cylodextrin, one or several in beta-cyclodextrin or γ-cyclodextrin.
Described cyclodextrin modified polymer is water-soluble polymer, can be the blend of homopolymer, multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer, comprise the blend of poly hydroxy ethyl acrylate, polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyvinylpyrolidone (PVP), sodium alginate polymkeric substance, chitosan, polyamino acid etc. and their multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer.
The polymer that described diamantane is modified is water-soluble polymer, can be the blend of homopolymer, multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer, comprise the blend of poly hydroxy ethyl acrylate, polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyvinylpyrolidone (PVP), sodium alginate polymkeric substance, chitosan, polyamino acid etc. and their multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer.
The preparation method of described with drop the is supramolecular hydrogel microballoon of Template preparation, is achieved through the following technical solutions:
1) water-soluble polymer of side chain with cyclodextrin is obtained by method that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of cyclodextrin modification, the polymer that the cyclodextrin of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtains cyclodextrin water-soluble polymers;
2) water-soluble polymer of side chain with adamantyl is obtained by mode that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of diamantane modification, and the polymer that the diamantane of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtain adamantyl water-soluble polymers;
3) preparation of supramolecular hydrogel microballoon: cyclodextrin water-soluble polymers and adamantyl water-soluble polymers form drop by interfacial tension, be dissolved in polymer that cyclodextrin in drop modifies and the polymer Urine scent that diamantane is modified, by the reactive force of Subjective and Objective, the high molecular crosslink of line style forms supramolecular hydrogel microballoon, as shown in Figure 1.
The described method by interfacial tension formation drop comprises liquid/liquid interface formation, gas/liquid interface is formed and solid/liquid interfaces is formed, as shown in Figure 2; The technique means adopted can as the liquid liquid directly drop formation technology such as blended, film emulsifying technology, drop microfluidic chip technology, spraying formation technology, optical tweezer technology, hydrophobic or super hydrophobic surface formation technology, electric jet technology, inkjet technology.
Described take drop as the application of the supramolecular hydrogel microballoon of Template preparation, for direct coated water-soluble antitumor drug, as Zorubicin, taxol.
Described packaging method is: the polymer that cyclodextrin is modified and the polymer modified of diamantane direct coated water-soluble antitumor drug in self-assembly forming process in drop, these medicines are present in the middle of microballoon three-dimensional network with the form of physically trapping, reach long slowly-releasing and Co ntrolled release characteristic.
Compared to the preparation method of existing microballoon, beneficial effect of the present invention is:
(1) supermolecular mechanism power is adopted to prepare supramolecular hydrogel microballoon first, compared with preparing hydrogel microsphere with polyreaction, the method is a kind of covalently cross-linked high molecular method of physics, without the need to the use of catalyzer or initiator, avoiding the pollution problems such as the monomer residue that chemical reaction causes, is a kind of preparation method of eco-friendly hydrogel microsphere.
(2) clearly proposing take drop as Template preparation micron order supramolecular hydrogel microballoon, and by the size regulating the size of drop effectively can regulate and control hydrogel microsphere, the homogeneity of drop size also ensure that the high single dispersing index of supramolecule microballoon.
Accompanying drawing explanation
The Supramolecular Assembling schematic diagram of Fig. 1 to be drop that the present invention adopts be Template preparation microballoon;
The drop of Fig. 2 to be drop that the present invention adopts be Template preparation microballoon forms schematic diagram;
Fig. 3 is that the present invention first example adopts micro-fluidic chip to prepare the schematic diagram of supramolecular hydrogel microballoon;
Fig. 4 is the microscope figure of drop described in the present invention first example and supramolecular hydrogel microballoon;
Fig. 5 is that the present invention second example adopts micro-fluidic chip to prepare the schematic diagram of supramolecular hydrogel micro-ball load Zorubicin;
Fig. 6 is the schematic diagram that the present invention the 3rd example spray droplet formation technology prepares supramolecular hydrogel microballoon;
Fig. 7 is the electron microscope picture of the supramolecular hydrogel microballoon described in the present invention the 3rd example;
Fig. 8 is the schematic diagram that the present invention the 4th example inkjet technology prepares supramolecular hydrogel microballoon.
Embodiment
The following examples will be further described the present invention, but the present invention is not merely defined in these embodiments.
Following examples be all first through following two steps, then form supramolecular hydrogel microballoon by the mode of specific embodiment:
1) water-soluble polymer of side chain with cyclodextrin is obtained by method that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of cyclodextrin modification, the polymer that the cyclodextrin of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtains cyclodextrin water-soluble polymers;
2) water-soluble polymer of side chain with adamantyl is obtained by mode that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of diamantane modification, and the polymer that the diamantane of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtain adamantyl water-soluble polymers.
embodiment 1
As shown in Figure 3, a kind of in the present invention is in the first example of the method for Template preparation supramolecular hydrogel microballoon with drop, is adopt drop microfluidic chip technology to form the water in oil drop of single dispersing.As shown in Figure 3, comprising 3 entrances, 1 outlet, is all connected by plastics microtubular the microfluidic chip structure that preparation uses.3 entrances are respectively used to the injection of discontinuous phase (massfraction is the poly hydroxy ethyl acrylate-acrylamide copolymer CD-PHEMA-PAM aqueous solution of the beta-cyclodextrin modified of 30% and massfraction is poly hydroxy ethyl acrylate-acrylamide copolymer Ad-PHEMA-PAM aqueous solution that 30% diamantane is modified) and external phase (3M FC40 fluorocarbon oil), export the collection for product.The CD-PHEMA-PAM aqueous solution and the flow velocity of the Ad-PHEMA-PAM aqueous solution in micro-fluidic chip passage is kept to be 200 μ L/h, the flow velocity of FC40 fluorocarbon oil in micro-fluidic chip passage is 800 μ L/h, due to the shearing action of FC40 fluorocarbon oil, the infall of continuous print single dispersing drop in microchannel is formed and collects in exit.Meanwhile, CD-PHEMA-PAM and Ad-PHEMA-PAM forms hydrogel supramolecule mono-dispersion microballoon by Host guest complexation.Fig. 4 is the microscope figure of single dispersing drop and the supramolecular hydrogel microballoon adopting micro-fluidic chip to prepare, as can be seen from figure a, the single dispersing mean droplet size adopting micro-fluidic chip to generate is 197 microns, the ratio variation coefficient of its standard deviation and mean number is 1.7%, demonstrates the high single dispersing index of drop; Figure b is that the supramolecular hydrogel microballoon microscope figure of preparation, this figure show that the hydrogel microsphere prepared is 37 microns, and its variation coefficient is 3.5%, illustrates that the supramolecular hydrogel microballoon prepared based on micro-fluidic chip has good dimensional homogeneity.Single dispersing drop is regulated to be 302,271,242,209,181 microns in micro-fluidic chip inside dimension, the hydrogel microsphere particle diameter obtained is respectively 64,53,46,39,31 microns, shows the final size that effectively can be regulated and controled supramolecular hydrogel microballoon by the size controlling drop.
embodiment 2
The implementation procedure of Zorubicin embedding as shown in Figure 5.The present embodiment is from the different of embodiment 1, the entrance of micro-fluidic chip is increased to 4, massfraction is that the Zorubicin aqueous solution of 0.1% is with the speed of 100 μ L/h injection microfluidic channel, keep massfraction be 30% the CD-PHEMA-PAM aqueous solution and massfraction be that the flow velocity of the 30%Ad-PHEMA-PAM aqueous solution in micro-fluidic chip passage is 200 μ L/h, the flow velocity of FC40 fluorocarbon oil in micro-fluidic chip passage is 800 μ L/h, the final supramolecular hydrogel mono-dispersion microballoon forming Zorubicin and embed under the shearing action and Subjective and Objective assembling effect of FC40 fluorocarbon oil.
embodiment 3
As shown in Figure 6, a kind of in the present invention is in the 3rd example of the method for Template preparation supramolecular hydrogel microballoon with drop, drop be formed by spray droplet formation technology.The taxol blend that massfraction is the Polyvinylpyrolidone (PVP)-acrylamide copolymer CD-PVP-PAM aqueous solution of the beta-cyclodextrin modified of 50%, massfraction is poly hydroxy ethyl acrylate-acrylamide copolymer Ad-PHEMA-PAM aqueous solution of modifying of 50% diamantane and massfraction 0.1% in spray injection moisture eliminator, under the effect of nozzle, blend atomization forms drop at cavity inner drying.Supermolecular mechanism power between CD-PVP-PAM and Ad-PHEMA-PAM obtains process intensification in drying process, the dry composite thing of CD-PVP-PAM and the Ad-PHEMA-PAM complexing of final formation taxol embedding, this mixture expands and forms supramolecular hydrogel microballoon under the rehydration effect of deionized water.Fig. 7 is the electron microscope picture of supramolecular hydrogel microballoon, can find out that the supramolecular hydrogel microballoon of lyophilize has good space three-dimensional pass structure by figure a, the electron microscope picture b amplified shows that obvious microphase-separated does not appear in supramolecular hydrogel microballoon, further illustrates taxol and effectively can be carried on this microballoon inside.
embodiment 4
As shown in Figure 8, a kind of in the present invention is in the 3rd example of the method for Template preparation supramolecular hydrogel microballoon with drop, drop be formed by inkjet technology.Specific implementation method be by massfraction be 1% Polyvinylpyrolidone (PVP)-acrylamide copolymer CD-PVP-PAM aqueous solution of modifying of γ-cyclodextrin and massfraction be that poly hydroxy ethyl acrylate-acrylamide copolymer Ad-PHEMA-PAM aqueous solution that 1% diamantane is modified is blended and inject Jetlab 4 (production of Microfab company of the U.S.) economical print platform, setup parameter makes drop directly fall into polydimethylsiloxane (PDMS) collector, wherein, micro array structure for caving in bottom PDMS collector, the methyl-silicone oil of surface coverage 100 micron thickness.Utilize the mechanical arm of Jetlab 4 to make each drop all fall into the microarray that caves in of PDMS, along with the volatilization of moisture in drop, the supermolecular mechanism power between CD-PVP-PAM and Ad-PHEMA-PAM is ordered about crosslinked polymer and is formed supramolecular hydrogel micro-sphere array.
Claims (10)
1. be a supramolecular hydrogel microballoon for Template preparation with drop, it is characterized in that, polymer self-assembly in drop that the polymer modified by cyclodextrin and diamantane are modified is formed.
2. according to claim 1 take drop as the supramolecular hydrogel microballoon of Template preparation, it is characterized in that, described drop refers under quiescent conditions can sedimentation, and can keep the fine liquid particle of suspended state under turbulent-flow conditions, diameter is between 500 nanometers are to 500 microns.
3. according to claim 1 take drop as the supramolecular hydrogel microballoon of Template preparation, and it is characterized in that, described cyclodextrin is alpha-cylodextrin, one or several in beta-cyclodextrin or γ-cyclodextrin.
4. according to claim 1 take drop as the supramolecular hydrogel microballoon of Template preparation, it is characterized in that, polymer in the polymer that described cyclodextrin modified polymer and diamantane are modified is water-soluble polymer, is the blend of homopolymer, multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer.
5. according to claim 4 take drop as the supramolecular hydrogel microballoon of Template preparation, it is characterized in that, polymer in the polymer that described cyclodextrin modified polymer and diamantane are modified is the blend of poly hydroxy ethyl acrylate, polyvinyl alcohol, polyacrylic acid, polyacrylamide, Polyvinylpyrolidone (PVP), sodium alginate polymkeric substance, chitosan or polyamino acid etc. and their multipolymer, different copolymer thing or homopolymer, the blend of different homopolymer or the blend between multipolymer and homopolymer.
6. described in any one of claim 1-5 take drop as the preparation method of the supramolecular hydrogel microballoon of Template preparation, it is characterized in that, comprises the following steps:
1) water-soluble polymer of side chain with cyclodextrin is obtained by method that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of cyclodextrin modification, the polymer that the cyclodextrin of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtains cyclodextrin water-soluble polymers;
2) water-soluble polymer of side chain with adamantyl is obtained by mode that is free-radical polymerized or polymer side chain graft modification, the i.e. polymer of diamantane modification, and the polymer that the diamantane of the 1-100 weight part prepared is modified fully is dissolved in the deionized water of 100 weight parts, obtain adamantyl water-soluble polymers;
3) preparation of supramolecular hydrogel microballoon: cyclodextrin water-soluble polymers and adamantyl water-soluble polymers form drop by interfacial tension, be dissolved in polymer that cyclodextrin in drop modifies and the polymer Urine scent that diamantane is modified, by the reactive force of Subjective and Objective, the high molecular crosslink of line style forms supramolecular hydrogel microballoon.
7. the preparation method of supramolecular hydrogel microballoon according to claim 6, is characterized in that, the described method by interfacial tension formation drop comprises liquid/liquid interface formation, gas/liquid interface is formed and solid/liquid interfaces is formed.
8. the preparation method of supramolecular hydrogel microballoon according to claim 7, it is characterized in that, described to form the technique means that adopts of drop by interfacial tension be liquid liquid directly blended, film emulsifying technology, drop microfluidic chip technology, spraying formation technology, optical tweezer technology, hydrophobic or super hydrophobic surface formation technology, electric jet technology or inkjet technology.
9. described in any one of claim 1-5 take drop as the application of the supramolecular hydrogel microballoon of Template preparation, it is characterized in that, for direct coated water-soluble antitumor drug.
10. the application of supramolecular hydrogel microballoon according to claim 9, it is characterized in that, described packaging method is: the polymer that cyclodextrin is modified and the polymer modified of diamantane direct coated water-soluble antitumor drug in self-assembly forming process in drop.
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| CN109721738A (en) * | 2018-12-29 | 2019-05-07 | 广东工业大学 | Supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof |
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Application publication date: 20150107 |