CN102443199A - Photoresponsive polymer microsphere system and preparation method thereof - Google Patents
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Abstract
The invention discloses a photoresponsive polymer microsphere system and a preparation method thereof. The system is a solution containing cyclodextrin, an azo compound having cis-trans isomerism respectively under the irradiation of ultraviolet light and visible light, and amphiphilic polyelectrolyte containing a hydrophobic alkyl chain. Polymer microspheres are generated when the system is under the irradiation of visible light, and the polymer microspheres in the system are decomposed under the irradiation of ultraviolet light. The preparation method comprises the following steps of: dissolving the amphiphilic polyelectrolyte in a solvent; completely stirring a microsphere solution; and then adding cyclodextrin and stirring for dissolving cyclodextrin; and finally adding the azo compound to obtain the photoresponsive polymer microsphere system after the azo compound is dissolved. The photoresponsive polymer microsphere system provided by the invention has the characteristics that the preparation conditions are moderate, the formation and decomposition of microspheres are reversible, quick and controllable. The photoresponsive polymer microsphere system has a bright application prospect in the biomedicine field such as medicine transfer, medicine slow release and the like, as well the anti-counterfeiting filed relating to trademarks, bills, even military industry, national defense and the like.
Description
Technical field
The present invention relates to intelligent macromolecule material (response polymer material) field; Be particularly related to a kind ofly at tensio-active agent, biomedicine field, aspect such as confidential transmissions field and trade mark, banknote are false proof has response type polymer microsphere system material and its implementation method of potential using value.
Background technology
In recent years, polymer microballoon, the microballoon that is especially formed by the method for amphipathic (hydrophobicity and wetting ability) polymkeric substance through self-assembly has caused that people study interest greatly.Advantage (Supramol.Sci., 1996,3,157-163 such as compare with the formed microballoon of low molecular weight surfactants, it is lower that amphiphilic polymer microballoon has critical microballoon concentration, and thermodynamics is more stable; Langmuir, 2002,18,3780-3786; Biomacromoles, 2005,6,1154-1158.).Therefore (Discher, D.E. have broad application prospects in biotechnology, biomedicine fields such as (like the medicine sustained release); Eisenberg, A.Science 2002,297, and 967; Haag, R.Angew Chem Int Ed 2004,43,278; Torchilin, V. P. Adv.Drug Deliv Rev 1995,16,295.).As a rule, an ideal medicine sustained release process comprises following three steps: the first step is with stable being encapsulated in the middle of the polymer microsphere of medicine.After this means in medicine gets into human body, microballoon will protect medicine before arriving the appointment affected part, to be unlikely to too fast leaking away.Second step was that microballoon can optionally arrive the affected part.The 3rd step was that medicine discharges the performance curative effect after arriving the affected part from microballoon.Wherein, the drug release mode in the 3rd step both can slowly carry out through the degraded of micro-sphere material, also can carry out through the stimulation collapsing microballoons in the external world.The many responsiveness microballoons of Recent study are mainly pH or temperature sensitive microsphere system (Gillies, E.R.; Frechet, J.M.J.Chem Commun 2003,1640; Bellomo, E. G.; Wyrsta, M.D.; Pakstis, L.; Pochan, D.J.; Deming, T.J.Nat Mater 2004,3,244; Chung, J.E.; Yokoyama, M.; Okano, T.J.Control Release 2000,65,93-103; Schilli, C.M.; Zhang, M.; Rizzardo, E.; Thang, S.H.; Chong, Y. K.; Edwards, K.; Karlsson, G.; Muller, A. H. E. Macromolecules 2004,37,7861.).But the polymer microballoon system that can produce response to light but relatively seldom.People such as Zhao Yue the have taken the lead in development research polymer microballoon of two types of photoresponses.In the first kind; People such as Zhao Yue have synthesized a kind of terpolymer that gathers butylacrylic acid ester, ROHM and Rohm tech inc nitrogen benzide that is called; When under UV-irradiation, the chromophoric group nitrogen benzide is by the trans cis that is converted into, and this change has caused the polarity of Rohm tech inc nitrogen benzide to increase significantly; This just makes that hydrophobic part Rohm tech inc nitrogen benzide is not enough to become the motivating force that microballoon forms, and then causes disintegrating of microballoon.When under radiation of visible light, nitrogen benzide is by the trans cis that is converted into, and micella forms (Wang, G. once more; Tong, X.; Zhao, Y. Macromolecules 2004,37,8911-8917).In another kind of, they have synthesized a kind of polyoxyethylene and the multipolymer that gathers 1-pyrenyl methyl polyacrylic ester.Under UV-irradiation, gather the ester linkage breaking of 1-pyrenyl methyl ROHM ester moiety, and then change carboxyl into.This makes that hydrophobic portion segregation 1-pyrenyl methyl polyacrylic ester changes hydrophilic polymethyl acrylic acid into originally.Thereby make the whole polymeric system total hydrophilic that becomes, and then make micella disintegrate (Jiang, J.Q.; Tong, X.; Zhao, Y. J.Am.Chem.Soc.2005,127,8290-8291; Zhao, Y. The Chemical Record 2007,7,286-294.).But first kind photoresponse microballoon is because the ratio and the character of polymer hydrophobic part are not easy accurate control, so microballoon usually disintegrating under UV-light is thorough inadequately, responds effective inadequately.Though and second type of photoresponse microballoon response thoroughly; But its respondent behavior is irreversible; In a single day microballoon is just disintegrated and can not be regenerated again, and illumination simultaneously makes hydrophobic part come off from main chain needs to destroy covalent linkage, needs higher energy and long time; This can limit light-operated microballoon range of application undoubtedly, increases its preparation cost.
Summary of the invention
To the present Research and the deficiency of prior art photoresponse polymer microballoon, the purpose of this invention is to provide a kind of photoresponse thorough and microballoon formation and the polymer microballoon system of disintegrating the photoresponse of process reversible.
Above-mentioned purpose of the present invention can be achieved through following technical proposals:
The polymer microballoon system of photoresponse provided by the invention; For containing the solution of following three kinds of components: Schardinger dextrins, shine the amphipathic ionogen that produces the azo class synthetics of cis-trans isomerism down and contain the hydrophobic alkyl chain (promptly contain simultaneously hydrophilic with polyelectrolyte hydrophobic segment) respectively at UV-light and visible light; Wherein the weight concentration of Schardinger dextrins is 0.1-40.0%; The weight concentration of azo class synthetics is 0.1-20.0%; The electrolytical weight concentration of amphipathic is 0.1-10.0%, and system polymer microballoon under the radiation of visible light environment forms, and the polymer microballoon under the UV-irradiation environment in the system is disintegrated.
The preferred version of technique scheme: the weight concentration of Schardinger dextrins is 0.5-10.0%, and the weight concentration of azo class synthetics is 0.5-5.0%, and the weight concentration that contains the polyelectrolyte of hydrophilic and hydrophobic segment simultaneously is 0.5-3.0%.
In technique scheme, the described amphipathic ionogen that contains the hydrophobic alkyl chain can be anionic amphiphilic property polyelectrolyte, cationic amphiphilic property polyelectrolyte or zwitter-ion amphipathic ionogen.It is the amphipathic ionogen of 2-20 that the amphipathic ionogen is preferably selected its alkyl hydrophobic chain side chain carbon number for use.The amphipathic ionogen specifically can be selected from but be not limited to ROHM, Lalgine, chitosan, polylysine, gelatin, carboxy methyl konjaku konjac glucomanna and CMC 99.5 etc.
In technique scheme, cyclic oligosaccharide and verivate thereof that described Schardinger dextrins is preferably formed by the Glucopyranose molecule that is no less than 6.Schardinger dextrins can be further concrete from but be not limited to alpha-cylodextrin, beta-cyclodextrin, γ-Huan Hujing, hydroxypropyl, and corresponding Schardinger dextrins dipolymer, trimer and polymer etc.
In technique scheme, described to shine the azo class synthetics that produces cis-trans isomerism down respectively at UV-light and visible light can be small molecules or the polymkeric substance that contains azobenzene group.Scope as azobenzene derivatives is very extensive; Can be selected from but be not limited to small molecules and nitrogen benzide grafted polyacrylic acids such as nitrogen benzide, mono carboxylic nitrogen benzide, dicarboxyl nitrogen benzide, monohydroxy nitrogen benzide, dihydroxyl nitrogen benzide, methylol nitrogen benzide; Nitrogen benzide grafting polyoxyethylene, polymkeric substance such as nitrogen benzide grafting sodium-alginate.
The preparation method of the polymer microballoon system of above-mentioned photoresponse mainly may further comprise the steps:
The amphipathic ionogen that (1) will contain the hydrophobic alkyl chain is dissolved in the solution that solvent is mixed with setting weight concentration, fully stirs then and makes it to form microballoon;
(2) connect step (1) and add Schardinger dextrins, stir and make it dissolving by the Schardinger dextrins weight concentration of setting;
(3) connect step (2) and add azo class synthetics by the azo class synthetics weight concentration of setting, fully dissolving promptly obtains the polymer microballoon system of photoresponse.
In last preparation method, when existing do not form microballoon residual to gather electrolysis in the microspheres solution that step (1) obtains, before adding Schardinger dextrins, must dialyse to resulting microspheres solution, remove the residual polyelectrolyte that does not form microballoon.
In last preparation method, its pH value of microspheres solution that obtains when step (1) with add cyclodextrin composition when incompatible, before adding Schardinger dextrins, need the pH value of adjustment microspheres solution, it is transferred to and the Schardinger dextrins that adds adapts.
The polymer microballoon system of above-mentioned photoresponse, it implements used UV-light and visible light, and its power range is generally 1-3000W, and the irradiation time of UV-light is generally at 3s-72h, and the visible light radiation time is generally at 10s-72h.
The polymer microballoon system of photoresponse provided by the invention is one and includes Schardinger dextrins, azo quasi-molecule, and the ternary complex system that contains the polyelectrolyte of hydrophilic and hydrophobic segment simultaneously.This system is to utilize azo class synthetics to shine generation cis-trans isomerism down respectively at UV-light and visible light; And produce the characteristics of selectivity inclusion with Schardinger dextrins, through selectivity inclusion and self-assembly preparation and the collapsing microballoons between the amphipathic ionogen, Schardinger dextrins and the azo class synthetics ternary system that contain the hydrophobic alkyl chain.Under the environment of radiation of visible light, azo class synthetics is in transconfiguration, preferential and its generation inclusion of Schardinger dextrins meeting, and the amphipathic ionogen self aggregation in water that contains the hydrophobic alkyl side chain in the system forms polymer microballoon.And under UV-irradiation; Azo class synthetics transfers the structure of taking advantage of a situation to by transconfiguration; Therefore enclose takes place in azo class synthetics-cyclodextrin inclusion compound originally; Schardinger dextrins behind the enclose and the alkyl group side chain generation inclusion that contains in the amphipathic ionogen of hydrophobic side chain cause the water-soluble increase of hydrophobic part, so polymer microballoon is disintegrated.Accompanying drawing 1 forms and the principle schematic of disintegrating for polymer microballoon according to the invention changes with visible light and UV-light.
Photoresponse polymer microballoon system provided by the invention; The formation of its microballoon realizes with the method for disintegrating through molecular recognition and polymer self-assembly; Have the formation of preparation condition gentleness, microballoon and disintegrate reversible, and rapidly controlled and light transmission change outstanding feature, overcome fully that the microsphere system of prior art exists, or under UV-light, disintegrated thorough inadequately; Respond effective inadequately; Or respondent behavior is irreversible, and in a single day microballoon is just disintegrated and can not be regenerated again, and microballoon is disintegrated needs higher energy and long defectives such as time.False proof fields such as biomedicine fields such as photoresponse polymer microballoon system of the present invention can transmit at medicine, medicament slow release and trade mark, banknote even military affairs, national defence have broad application prospects.
Description of drawings
Accompanying drawing 1 forms and the principle schematic of disintegrating for polymer microballoon of the present invention changes with visible light and UV-light
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description, but the working of an invention mode is not limited thereto.In following each embodiment, said concentration is weight concentration except that specifying.
Sodium-alginate-TTAB mixture is dissolved in (concentration is 5%) in the MES solution, stirs and to get the polymer formation microballoon in 30 minutes.PH with liquid transfers to 14 then, adds alpha-cylodextrin (concentration is 5%), in system, adds mono carboxylic nitrogen benzide (concentration is 1.25%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.The structure of its polymer microballoon and size are shown in flying-spot microscope photo in the accompanying drawing 2.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 500W after following 10 minutes, the system transmittance rises to 95% by 65%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 500W once more after following 10 minutes, the system transmittance drops to 55% by 95%, explains that microballoon generates once more.Shown in accompanying drawing 3, this microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
With the water-soluble concentration that is mixed with of the ROHM (percentage of grafting 15%) of grafting dodecyl is 1.5% the aqueous solution, stirs and makes it to form microballoon in 3 hours.Add hydroxypropyl (concentration is 1%) again, stir and make it dissolving.In system, add dicarboxyl nitrogen benzide (concentration is 0.125%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 200W after following 1 hour minute, the system transmittance rises to 90% by 50%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 1 hour minute, the system transmittance drops to 60% by 90%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
With (sodium alginate concentration is 0.5%) in the water-soluble solution of the polylysine of grafting tetradecyl, stirs and made it to form microballoon in 3 hours.PH with aforesaid liquid transfers to 4 then, adds alpha-cylodextrin (concentration is 3%), stirs to make it dissolving.In system, add monohydroxy nitrogen benzide (concentration is 0.75%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 600W after following 10 minutes, the system transmittance rises to 79% by 40%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 1 hour minute, the system transmittance drops to 47% by 79%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
Earlier Poly Dimethyl Diallyl Ammonium Chloride is dissolved in (concentration is 1.0%) in the MES solution, adds LAURIC ACID 99 MIN (concentration is 0.5%) then, stirred 30 minutes, form and contain hydrophilic simultaneously and polyelectrolyte system hydrophobic segment.With gained solution dialysis 48h, remove residual part LAURIC ACID 99 MIN and can get polymer microballoon.The pH of the liquid after the above-mentioned dialysis is transferred to 14, add beta-cyclodextrin (concentration is 5%), stir and make it dissolving.In system, add monohydroxy nitrogen benzide (concentration is 1.0%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 500W after following 10 minutes, the system transmittance rises to 80% by 50%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 300W once more after following 1 hour, the system transmittance drops to 60% by 80%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
Earlier polymer A is dissolved in (concentration is 1.0%) in the MES solution, adds n-capric acid (concentration is 0.4%) then, stirred 30 minutes.With gained solution dialysis 48h, contain hydrophilic simultaneously and polyelectrolyte hydrophobic segment.Remove residual part n-capric acid and can get polymer microballoon.The pH of the liquid after the above-mentioned dialysis is transferred to 12, add alpha-cylodextrin (concentration is 12%), stir and make it dissolving.In system, add mono carboxylic nitrogen benzide (concentration is 5%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 400W after following 50 minutes, the system transmittance rises to 83% by 40%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 1 hour, the system transmittance drops to 50% by 83%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
Earlier bovine serum albumin is dissolved in (concentration is 5.0%) in the MES solution, adds Trimethyllaurylammonium bromide (concentration is 2.0%) then, stirred 30 minutes, contain hydrophilic simultaneously and polyelectrolyte hydrophobic segment.With gained solution dialysis 48h, remove residual part Trimethyllaurylammonium bromide and can get polymer microballoon.Liquid after above-mentioned dialysis adds alpha-cylodextrin (concentration is 8%), stirs to make it dissolving.In system, add mono carboxylic nitrogen benzide (concentration is 4.0%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 600W after following 30 minutes, the system transmittance rises to 90% by 30%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 2 hours, the system transmittance drops to 40% by 90%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
In the water-soluble solution of carboxy methyl konjaku konjac glucomanna with the grafting undecyl (concentration is 6.0%), stir and made it to form microballoon in 3 hours.PH with aforesaid liquid transfers to 4 then, adds alpha-cylodextrin (concentration is 5%), stirs to make it dissolving.In system, add monohydroxy nitrogen benzide (concentration is 1.25%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 600W after following 10 minutes, the system transmittance rises to 82% by 40%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 1 hour minute, the system transmittance drops to 47% by 82%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
With (concentration is 7%) in the water-soluble solution of poly acrylic acid-poly NSC 11786 multipolymer, stirs and made it to form microballoon in 3 hours.Add alpha-cylodextrin (concentration is 10%), stir and make it dissolving.In system, add nitrogen benzide grafting polyethylene imine (concentration is 18%) then, can obtain having the polyelectrolyte microsphere of ultraviolet-visible photoresponse.
Response to ultraviolet-visible light: when the uv lamp that the thus obtained microsphere system is placed 600W after following 10 minutes, the system transmittance rises to 88% by 20%, and microballoon is disintegrated in the explanation system.When the incandescent light that places 200W once more after following 1 hour minute, the system transmittance drops to 24% by 88%, explains that microballoon generates once more.This microballoon is disintegrated with the process that forms and can repeatedly be repeated with the variation of ultraviolet-visible light.
Claims (10)
1. the polymer microballoon system of a photoresponse; It is characterized in that for containing the solution of following three kinds of components: Schardinger dextrins, shine azo class synthetics that produces cis-trans isomerism down and the amphipathic ionogen that contains the hydrophobic alkyl chain respectively at UV-light and visible light; Wherein the weight concentration of Schardinger dextrins is 0.1-40.0%; The weight concentration of azo class synthetics is 0.1-20.0%; The electrolytical weight concentration of amphipathic is 0.1-10.0%, and system polymer microballoon under the radiation of visible light environment forms, and the polymer microballoon under the UV-irradiation environment in the system is disintegrated.
2. the polymer microballoon system of photoresponse according to claim 1, it is characterized in that: the weight concentration of Schardinger dextrins is 0.5-10.0%, and the weight concentration of azo class synthetics is 0.5-5.0%, and the electrolytical weight concentration of amphipathic is 0.5-3.0%.
3. the polymer microballoon system of photoresponse according to claim 2, it is characterized in that: described amphipathic ionogen is anionic amphiphilic property polyelectrolyte, cationic amphiphilic property polyelectrolyte or zwitter-ion amphipathic ionogen.
4. the polymer microballoon system of photoresponse according to claim 3, it is characterized in that: the electrolytical alkyl hydrophobic chain of described amphipathic is the alkyl hydrophobic chain of side chain carbon number 2-20.
5. according to the polymer microballoon system of the described photoresponse of one of claim 1 to 4, it is characterized in that: described Schardinger dextrins cyclic oligosaccharide and the verivate thereof that the Glucopyranose molecule that is no less than 6 forms of serving as reasons.
6. according to the polymer microballoon system of the described photoresponse of one of claim 1 to 4, it is characterized in that: described can to shine the azo class synthetics that produces cis-trans isomerism down respectively at UV-light and visible light be small molecules or the polymkeric substance that contains azobenzene group.
7. the polymer microballoon system of photoresponse according to claim 5 is characterized in that: described can to shine the azo class synthetics that produces cis-trans isomerism down respectively at UV-light and visible light be small molecules or the polymkeric substance that contains azobenzene group.
8. the polymer microballoon system preparation method of the described photoresponse of one of claim 1 to 7 is characterized in that mainly may further comprise the steps:
The amphipathic ionogen that (1) will contain the hydrophobic alkyl chain is dissolved in the solution that solvent is mixed with setting weight concentration, fully stirs then and makes it to form microballoon;
(2) connect step (1) and add Schardinger dextrins, stir and make it dissolving by the Schardinger dextrins weight concentration of setting;
(3) connect step (2) and add azo class synthetics by the azo compound weight concentration of setting, fully dissolving promptly obtains the polymer microballoon system of photoresponse.
9. the polymer microballoon system preparation method of photoresponse according to claim 8, it is characterized in that: the microspheres solution to step (1) obtains is dialysed, and removes the residual polyelectrolyte that does not form microballoon.
10. according to Claim 8 or the polymer microballoon system preparation method of 9 described photoresponses, it is characterized in that: before adding the azo compound component, the pH value of microspheres solution is transferred to and the azo compound that adds adapts.
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