CN104725581A - Method for preparing and applying light/temperature sensitive amphiphilic block polymer micelle - Google Patents
Method for preparing and applying light/temperature sensitive amphiphilic block polymer micelle Download PDFInfo
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Abstract
The invention provides a method for preparing a light/temperature dual-response block polymer self-assembly based on nitrophenyl ester and isopropylacetamide and application thereof. The method comprises the following steps: preparing an amphiphilic block copolymer, namely poly(N-isopropylacrylamide)-block-poly(2-nitrobenzyl methacrylate) (PNIPAM-b-PNBM) by means of twice reversible-addition chain transfer polymerizations. The polymer can be self-assembled into micelle in water, wherein the poly(N-isopropylacrylamide)-block with temperature response is used as a shell of the micelle, the poly(2-nitrobenzyl methacrylate) block with light response is used as a core of the micelle, and hydrophobic Nile red molecules can be loaded inside the micelle. Under external stimulation, the appearance of the micelle can change if light/temperature changes, and the balance of hydrophilicity and hydrophobicity of the micelle is destroyed, so that the guest molecule Nile red loaded in the micelle can be released. The light/temperature dual-response block polymer self-assembly has light response and temperature response, and has a wide application prospect in the field of drug controlled-release.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of synthesis and application of the light/temperature Amphipathilic block polymer based on nitro phenyl ester and Isopropyl amide.
Background technology
In recent years, because stimulating responsive block polymer micelle is in the application in catalysis, nanotechnology, smart membrane and drug delivery field, the extensive concern of researcher is caused.Wherein, photoresponse polymkeric substance, having advantages such as clean, remote controlled (its wavelength of fine adjustment and intensity) due to it becomes one of focus of research both at home and abroad.Be all complicated based on the many macromole bioprocesss of occurring in nature such as protein, nucleic acid and polysaccharide etc., it is very necessary for designing a multiple response polymkeric substance comprising photoresponse group.
At present, the research for the behavior of accuracy controlling polymer substance does not also reach desirable effect.Meanwhile, the macromolecular material with light/temperature double responsiveness also rarely has report, therefore, this kind ofly has multiple response, a concern that polymer materials that structure is clear and definite obtains this area researchist simultaneously.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide preparation method and the application of the polymer micelle of the Dual Sensitive had light, temperature response.
The present invention first use two steps reversible-method of addition chain tra nsfer, first Macromolecular chain transfer agent poly-(N-isopropylacrylamide) is prepared, then be polymerized with the nitrobenzene derivative 2-nitrobenzyl methacrylate monomer with photoresponse, obtain having the Amphipathilic block polymer that light/temperature double-bang firecracker is answered, this polymkeric substance is self-assembled into micella in aqueous.
Technical scheme of the present invention is: a kind of preparation method of the light/temperature responsive type Amphipathilic block polymer micelle based on nitro phenyl ester and Isopropyl amide, and wherein Macroscopic single crystal route is as Fig. 8:
The method specifically comprises the following steps:
Step 1. prepares Macromolecular chain transfer agent poly-(N-isopropylacrylamide): get a certain amount of N-isopropylacrylamide respectively, trithiocarbonate and Diisopropyl azodicarboxylate in molar ratio 80:1:0.2 ~ 160:1:0.2 ratio mixing, be dissolved in and nitrogen is housed, in the tertiary Lun Ke flask of nitrogen-dimethyl formamide/water mixed solution (volume ratio is 95:5 ~ 90:10), stir 30 ~ 40 minutes to dissolving completely, logical nitrogen 30 ~ 60 minutes removing oxygen, be placed in 65 ~ 75 DEG C of oil bath pans through " freezing-to bleed-thaw " five to eight circulations and react 4 ~ 8 hours, with liquid nitrogen cancellation and uncovered placement to stop this polyreaction.The dialysis tubing being 1000 ~ 2500 by reacted solution molecular weight cut-off is dialysed 36 ~ 48 hours in deionized water, to remove unreacted N-isopropylacrylamide and solvent nitrogen, nitrogen-dimethyl formamide, dialyzate lyophilize is obtained crude product, then three times are precipitated with cold diethyl ether, be 45 ~ 50 DEG C in temperature, vacuum-drying 36 ~ 48 hours, obtains final product Macromolecular chain transfer agent poly-(N-isopropylacrylamide);
Step 2. prepares block polymer, i.e. poly-(N-isopropylacrylamide)-block-poly-(dimethylaminoethyl methacrylate): the ratio of Macromolecular chain transfer agent 2-nitrobenzyl methacrylic ester, step 1 prepared poly-(N-isopropylacrylamide) and Diisopropyl azodicarboxylate 80:1:0.2 ~ 160:1:0.2 in molar ratio mixes, be dissolved in nitrogen, in the mixing solutions (volume ratio is 95:5 ~ 90:10) of nitrogen-dimethyl formamide/water, be placed in tertiary Lun Ke flask.Logical 30 ~ 60 minutes nitrogen removing oxygen, is react 6 ~ 12 hours in 65 ~ 75 DEG C of oil baths in temperature after five to eight times " freezing-to bleed-thaw ", stops this polyreaction by the method identical with step 1.The dialysis tubing being 10000 ~ 25000 by reacted solution molecular weight cut-off is dialysed 48 ~ 72 hours in deionized water, and dialyzate lyophilize obtains crude product.Precipitate three times in normal hexane, vacuum-drying 24 ~ 36 hours at 45 ~ 50 DEG C, obtain pure product, product is amphipathic block, i.e. polymer poly (N-isopropylacrylamide)-block-poly-(dimethylaminoethyl methacrylate) (PNIPAM-b-PNBM);
Step 3. self-assembly process: Amphipathilic block polymer step 2 prepared and tetrahydrofuran (THF) are that 1:1 mixes vigorous stirring 4 ~ 6 hours with mass ratio, after making it dissolve completely, add deionized water, tetrahydrofuran (THF) and deionized water quality are than being 1:1, induce micelle formation, stirring gentle is again after 4 hours, mixing solutions is added to fast by disposable for 9 ml deionized water, finally this solution is positioned over lower three days of room temperature, tetrahydrofuran (THF) is volatilized completely, obtains the micellar solution with temperature and light response.
Further, in " freezing-to bleed-thaw " method in described step 1,2, freezing temp is-10 ~-20 DEG C and is refrigerated to and freezes to be as the criterion, and described pumpdown time is 10 ~ 30 minutes.
Further, the polymer micelle obtained from above-mentioned steps 2 has nucleocapsid structure; Its shell is for having hydrophilic poly-(N-isopropylacrylamide), and stratum nucleare is for having hydrophobic poly-(2-nitrobenzyl methacrylic ester).
Further, the micella that described method prepares has synergistic effect, regulates the kinetics dispose procedure of guest molecule at different outfield incentive conditions under can combining.
A kind of polymer latex pencil self-assembly prepared in accordance with the method for claim 1.Be applied to extraneous collaborative stimulation controllable release field, specific as follows:
The Amphipathilic block polymer obtain 5 milligrams of above-mentioned steps and 0.5 milligram of Nile red are dissolved in 1 milliliter of tetrahydrofuran (THF) completely, when vigorous stirring, 1 ml deionized water is added drop-wise in above-mentioned solution with the speed of 1 microlitre per second, induce micelle formation, and load Nile red in the process formed.Then mild stirring 4 hours, is added to disposable for 9 ml deionized water fast in mixing solutions, micella is shaped.By gained solution left standstill about a week, tetrahydrofuran (THF) is volatilized, the Nile red sedimentation of unentrapped, supernatant liquid is the micellar solution of loading guest molecule Nile red.
The macromolecular material of this institute is a kind of Amphipathilic block polymer.Amphipathic nature polyalcohol refers to the affinity polymkeric substance of the phase structure (as aqueous phase and oil phase, two kinds of oil phases, two kinds of inconsistent solid phases etc.) simultaneously in same polymer with two kinds of different in kinds.Amphipathic nature polyalcohol selective solvent (to wherein one section be good solvent, and be poor solvent to another section) in, can self-assembly formed micella.Wherein spherical macromolecule micelle is modal Polymer Systems, wherein the core of the formation micella of the poor segment of solvability, and the segment that solvability is good then forms the shell of micella.Due to the existence of solvation shell, the micella that amphipathic nature polyalcohol is formed can long-time stable exist within the scope of finite concentration.
The micella that amphipathic nature polyalcohol is self-assembled into as pharmaceutical carrier, and can have lot of advantages.As all more stable in vivo and in vitro, have good biocompatibility, the medicine very little to solubleness has solublization, and on surface, the micella of specific modified can as targeting drug administration carrier in addition.The hydrophobic inner core of micella can as the storage of medicine, and hydrophilic outer shell can reduce cytophagous effect in micella and body, is conducive to the dispersiveness of micella in water.
Stimulating responsive polymer nanogel has good application prospect in Co ntrolled release field.Because the temperature of lesions position cell is than Normocellular temperature drift, so when temperature-responsive polymer micelle arrives focal part, micella pattern changes, and makes medicine be released.Photoresponse polymer micelle can realize Drug controlled release of fixed place and time, realizes drug release more accurately.
The invention has the beneficial effects as follows: polymkeric substance used in the present invention is light/temperature susceptibility amphipathic nature polyalcohol polymer, the micella prepared by series of process can load hydrophobic drug Nile red, this micella under light illumination, owing to there is photodegradation reaction, the hydrophobe balance of micella is destroyed, micella breaks, and the problem molecule wherein loaded is discharged.When temperature is elevated to the critical inversion temperature of polymkeric substance, hydrophilic polymer segment becomes hydrophobic originally, thus micella is shunk, and a part of guest molecule is out squeezed.The behavior of above-mentioned polymkeric substance under external stimulus is demonstrated by the instrument such as transmission electron microscope and UV detector.The present invention has broad application prospects in medicine controlled releasing field.
Accompanying drawing explanation
Fig. 1 is the hydrogen spectrum nuclear magnetic spectrum of obtained block polymer.
Fig. 2 is obtained poly-(N-isopropylacrylamide), segmented copolymer and the critical inversion temperature figure through the segmented copolymer of UV-irradiation after 2 hours.
Fig. 3 is the transmission electron microscope photo of obtained polymer micelle.
Fig. 4 is the transmission electron microscope photo of polymer micelle when temperature is 37 DEG C.
Fig. 5 is that polymer micelle is at the UV-irradiation transmission electron microscope photo of 2 hours.
Fig. 6 is loaded in the release graphics of the Nile red in polymer micelle with UV-irradiation time variations.
Fig. 7 is loaded in the release graphics of the Nile red in polymer micelle with the change of soaking time, and under UV-light and temperature work in coordination with stimulation the release graphics of Nile red.
Fig. 8 is polymer micelle synthetic route chart.
Embodiment
According to concrete enforcement, technical scheme of the present invention is described further below.
Embodiment 1
Preparation Macromolecular chain transfer agent poly-(N-isopropylacrylamide): N-isopropylacrylamide, Diisopropyl azodicarboxylate and trithiocarbonate are dissolved in nitrogen is housed, in the tertiary Lun Ke flask of the mixing solutions of nitrogen-dimethyl formamide/water (volume ratio is 90:10), stir 30 minutes to dissolving completely, logical nitrogen 30 minutes removing oxygen, be placed in 70 DEG C of oil bath pans through " freezing-to bleed-thaw " six times circulation and react 4 hours, with liquid nitrogen cancellation and uncovered placement to stop this polyreaction.The dialysis tubing being 1000 by reacted solution molecular weight cut-off is dialysed 48 hours in deionized water, to remove unreacted N-isopropylacrylamide and solvent nitrogen, nitrogen-dimethyl formamide, dialyzate lyophilize is obtained crude product, then three times are precipitated with cold diethyl ether, vacuum 45 DEG C of dryings 48 hours, obtain faint yellow final product, i.e. Macromolecular chain transfer agent poly-(N-isopropylacrylamide).Wherein, Diisopropyl azodicarboxylate is initiator, and trithiocarbonate is chain-transfer agent.And the mol ratio of N-isopropylacrylamide, trithiocarbonate and Diisopropyl azodicarboxylate is 80:1:0.2;
Prepare poly-(the N-isopropylacrylamide)-block of block polymer-poly-(dimethylaminoethyl methacrylate): the Macromolecular chain transfer agent poly-(N-isopropylacrylamide) of 2-nitrobenzyl methacrylic ester, Diisopropyl azodicarboxylate and above-mentioned preparation is dissolved in nitrogen, in the mixing solutions of nitrogen-dimethyl formamide/water, be placed in tertiary Lun Ke flask, logical 30 molecule nitrogen removing oxygen, after six times " freezing-to bleed-thaw " temperature be in 70 DEG C of oil baths react 6 hours, stop this polyreaction by method same as described above.The dialysis tubing being 10000 by reacted solution molecular weight cut-off is dialysed 48 hours in deionized water, and dialyzate lyophilize obtains crude product.Precipitate three times in normal hexane, vacuum-drying 48 hours at 50 DEG C, obtain final product, i.e. poly-(the N-isopropylacrylamide)-block of Amphipathilic block polymer-poly-(dimethylaminoethyl methacrylate) (PNIPAM-b-PNBM).Wherein, the mol ratio of 2-nitrobenzyl methacrylic ester, poly-(N-isopropylacrylamide) and Diisopropyl azodicarboxylate is 80:1:0.2, and the molecular weight of gained block polymer is 18350g/mol, hydrophilic section Molecules and hydrophobic section number are 2:1.
Self-assembly process: be that 1:1 mixes with tetrahydrofuran (THF) with mass ratio by Amphipathilic block polymer obtained for above-mentioned steps, vigorous stirring 5 hours, makes it dissolve completely.1 ml deionized water is added drop-wise in this tetrahydrofuran solution with the speed of 2 microliters per second, induces micelle formation.Continue mild stirring after 5 hours, be added to disposable for 9 ml deionized water fast in mixing solutions.Finally it is at room temperature left standstill one week, tetrahydrofuran (THF) is volatilized, obtain the micellar solution with light and temperature dual response.
Embodiment 2
Preparation Macromolecular chain transfer agent: by N-isopropylacrylamide, Diisopropyl azodicarboxylate and trithiocarbonate are dissolved in and nitrogen are housed, in the tertiary Lun Ke flask of the mixing solutions (volume ratio is 95:5) of nitrogen-dimethyl formamide/water, stir 40 minutes to dissolving completely, logical nitrogen 60 minutes removing oxygen, be placed in 70 DEG C of oil bath pans through " freezing-to bleed-thaw " six times circulation and react 8 hours, with liquid nitrogen cancellation and uncovered placement to stop this polyreaction.The dialysis tubing being 2500 by reacted solution molecular weight cut-off is dialysed 48 hours in deionized water, to remove unreacted N-isopropylacrylamide and solvent nitrogen, nitrogen-dimethyl formamide, dialyzate lyophilize is obtained crude product, then three times are precipitated with cold diethyl ether, vacuum 50 DEG C of dryings 48 hours, obtain faint yellow final product poly-(N-isopropylacrylamide).Wherein, Diisopropyl azodicarboxylate is initiator, and trithiocarbonate is chain-transfer agent.And the mol ratio of N-isopropylacrylamide, trithiocarbonate and Diisopropyl azodicarboxylate is 80:1:0.2;
Prepare block polymer: the Macromolecular chain transfer agent of above-mentioned preparation poly-(N-isopropylacrylamide), 2-nitrobenzyl methacrylic ester and Diisopropyl azodicarboxylate are dissolved in nitrogen, in the mixing solutions of nitrogen-dimethyl formamide/water, be placed in tertiary Lun Ke flask, logical 60 minutes nitrogen removing oxygen, after five times " freezing-to bleed-thaw " temperature be in 70 DEG C of oil baths react 12 hours, stop this polyreaction by the method identical with above-mentioned steps.The dialysis tubing being 25000 by reacted solution molecular weight cut-off is dialysed 48 hours in deionized water, and dialyzate lyophilize obtains crude product.Precipitate three times in normal hexane, vacuum-drying 48 hours at 50 DEG C, obtain final product, i.e. poly-(the N-isopropylacrylamide)-block of Amphipathilic block polymer-poly-(dimethylaminoethyl methacrylate) (PNIPAM-b-PNBM).Wherein, the mol ratio of 2-nitrobenzyl methacrylic ester, poly-(N-isopropylacrylamide) and Diisopropyl azodicarboxylate is 160:1:0.2, the molecular weight of gained block polymer is 32780g/mol, and hydrophilic section Molecules and hydrophobic section Molecules are than being 3:1.
Self-assembly process: Amphipathilic block polymer above-mentioned steps obtained and Nile red (mass ratio is 10:1) are dissolved in 1 milliliter of tetrahydrofuran (THF) completely, when vigorous stirring, 1 ml deionized water is added drop-wise in above-mentioned solution with the speed of 2 microlitres per second, induce micelle formation, and load Nile red in the process formed.Then mild stirring 4 hours, is added to disposable for 9 ml deionized water fast in mixing solutions, micella is shaped.By gained solution left standstill about a week, tetrahydrofuran (THF) is volatilized, the Nile red sedimentation of unentrapped, supernatant liquid is the micellar solution of loading guest molecule Nile red.
Claims (4)
1. the preparation method of light/temperature responsive type Amphipathilic block polymer micelle, is characterized in that, preparation process is as follows:
Step 1). preparation Macromolecular chain transfer agent i.e. poly-(N-isopropylacrylamide): respectively by a certain amount of N-isopropylacrylamide, Diisopropyl azodicarboxylate, trithiocarbonate and nitrogen, the mixing solutions of nitrogen-dimethyl formamide/water, join in dry tertiary Lun Ke flask, stir 30 ~ 40 minutes to dissolving completely, logical nitrogen 30-60 minute removing oxygen, through five to eight times " freezing-to bleed-thaw " circulation be placed in the oil bath pan of 65 ~ 75 DEG C react 4 ~ 8 hours, with liquid nitrogen cancellation and uncovered placement to stop this polyreaction; The dialysis tubing being 1000 ~ 2500 by reacted solution molecular weight cut-off is dialysed 36 ~ 48 hours in deionized water, to remove unreacted N-isopropylacrylamide monomer and solvent nitrogen, nitrogen-dimethyl formamide, the crude product that lyophilize dialyzate obtains, three times are precipitated with cold diethyl ether, the vacuum drying oven being 45 ~ 50 DEG C in temperature is placed 36 ~ 48 hours, obtains final product Macromolecular chain transfer agent poly-(N-isopropylacrylamide); Wherein, Diisopropyl azodicarboxylate is initiator, and trithiocarbonate is chain-transfer agent, and the mol ratio of N-isopropylacrylamide, trithiocarbonate and Diisopropyl azodicarboxylate is 80:1:0.2 ~ 160:1:0.2; Nitrogen, the mixed liquor volume of nitrogen-dimethyl formamide/water is than being 95:5 ~ 90:10;
Step 2). prepare block polymer, i.e. poly-(N-isopropylacrylamide)-block-poly-(dimethylaminoethyl methacrylate): by 2-nitrobenzyl methacrylic ester, poly-(N-isopropylacrylamide) that Diisopropyl azodicarboxylate and step 1 prepare is dissolved in the nitrogen that volume ratio is 95:5 ~ 90:10, in the mixing solutions of nitrogen-dimethyl formamide/water, be placed in tertiary Lun Ke flask, logical 30 ~ 60 minutes nitrogen removing oxygen, after five to eight times " freezing-to bleed-thaw " temperature be in 65 ~ 75 DEG C of oil baths react 6 ~ 12 hours, with liquid nitrogen cancellation and uncovered placement to stop this polyreaction, the dialysis tubing being 10000 ~ 25000 by reacted solution molecular weight cut-off is dialysed 48 ~ 72 hours in deionized water, and dialyzate lyophilize obtains crude product, precipitate three times in normal hexane, vacuum-drying 24 ~ 36 hours at 45 ~ 50 DEG C, obtain pure product, product is Amphipathilic block polymer, i.e. poly-(N-isopropylacrylamide)-block-poly-(2-nitrobenzyl methacrylic ester), wherein, the mol ratio of 2-nitrobenzyl methacrylic ester, Macromolecular chain transfer agent poly-(N-isopropylacrylamide) and Diisopropyl azodicarboxylate is 80:1:0.2 ~ 160:1:0.2,
Step 3). self-assembly process: by step 2) Amphipathilic block polymer for preparing is that 1:1 mixes with tetrahydrofuran (THF) with mass ratio, vigorous stirring 4 ~ 6 hours, after making it dissolve completely, add deionized water, tetrahydrofuran (THF) and deionized water quality are than being 1:1, induce micelle formation, stirring gentle is again after 4 ~ 6 hours, be added to disposable for 8 ~ 9 ml deionized water fast in mixing solutions, finally this solution is at room temperature placed three days, tetrahydrofuran (THF) is volatilized completely, obtains the micellar solution with temperature and light response.
2. the preparation method of light/temperature responsive type Amphipathilic block polymer micelle according to claim 1, it is characterized in that: described step 1) and 2) in " freezing-to bleed-thaw " method in, freezing temp is-10 ~-20 DEG C, be refrigerated to and freeze to be as the criterion, described pumpdown time is 10 ~ 30 minutes.
3. the preparation method of light/temperature responsive type Amphipathilic block polymer micelle according to claim 1, is characterized in that: described step 3) block polymer micelle that obtains has nucleocapsid structure; Its shell is hydrophobic poly-(2-nitrobenzyl methacrylic ester), and its stratum nucleare is hydrophilic poly-(N-isopropylacrylamide).
4. the application method of light/temperature responsive type Amphipathilic block polymer micelle according to claim 1, it is characterized in that: the micella that described method prepares has synergistic effect, the kinetics dispose procedure of guest molecule can be regulated under different outfield incentive conditions.
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| CN108333198A (en) * | 2018-03-15 | 2018-07-27 | 长春黄金研究院有限公司 | A kind of method for observing block copolymer micelle pattern under high temperature of efficiently and accurately |
| CN108426903A (en) * | 2018-03-14 | 2018-08-21 | 长春黄金研究院有限公司 | A method of observation is higher than block copolymer micelle pattern under room temperature state |
| CN110483706A (en) * | 2019-07-11 | 2019-11-22 | 江苏大学 | A kind of preparation method and application based on the amphiphilic difunctional fluorescence probe of Thermo-sensitive block polymer of oligonucleotides |
| CN112625266A (en) * | 2020-12-17 | 2021-04-09 | 合肥工业大学 | Adjustable temperature-sensitive and inverse thermal response type hydrogel and preparation method thereof |
| CN113429517A (en) * | 2021-06-23 | 2021-09-24 | 中国热带农业科学院南亚热带作物研究所 | Photothermal dual-response type chitosan-based derivative and preparation method and application thereof |
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| CN108426903A (en) * | 2018-03-14 | 2018-08-21 | 长春黄金研究院有限公司 | A method of observation is higher than block copolymer micelle pattern under room temperature state |
| CN108333198A (en) * | 2018-03-15 | 2018-07-27 | 长春黄金研究院有限公司 | A kind of method for observing block copolymer micelle pattern under high temperature of efficiently and accurately |
| CN110483706A (en) * | 2019-07-11 | 2019-11-22 | 江苏大学 | A kind of preparation method and application based on the amphiphilic difunctional fluorescence probe of Thermo-sensitive block polymer of oligonucleotides |
| CN110483706B (en) * | 2019-07-11 | 2021-10-12 | 江苏大学 | Preparation method and application of bifunctional fluorescent probe based on oligonucleotide amphiphilic temperature-sensitive block polymer |
| CN112625266A (en) * | 2020-12-17 | 2021-04-09 | 合肥工业大学 | Adjustable temperature-sensitive and inverse thermal response type hydrogel and preparation method thereof |
| CN113429517A (en) * | 2021-06-23 | 2021-09-24 | 中国热带农业科学院南亚热带作物研究所 | Photothermal dual-response type chitosan-based derivative and preparation method and application thereof |
| CN113429517B (en) * | 2021-06-23 | 2022-03-01 | 中国热带农业科学院南亚热带作物研究所 | Photothermal dual-response type chitosan-based derivative and preparation method and application thereof |
| CN114377558A (en) * | 2022-02-25 | 2022-04-22 | 南京理工大学 | Modified polyacrylonitrile water treatment membrane and preparation method and application thereof |
| CN114377558B (en) * | 2022-02-25 | 2024-05-17 | 南京理工大学 | Modified polyacrylonitrile water treatment membrane and preparation method and application thereof |
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