CN107541530B - Double-tellurium-containing biodegradable polymer and preparation method thereof - Google Patents
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- 229920002988 biodegradable polymer Polymers 0.000 title claims abstract description 14
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 14
- 229910052714 tellurium Inorganic materials 0.000 title description 13
- 238000002360 preparation method Methods 0.000 title description 5
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Chemical group 0.000 claims abstract description 4
- 239000001301 oxygen Chemical group 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 12
- 108090001060 Lipase Proteins 0.000 claims description 6
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- 102000004882 Lipase Human genes 0.000 claims description 6
- 235000019421 lipase Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 abstract description 8
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- 230000004044 response Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 229920001610 polycaprolactone Polymers 0.000 description 22
- 239000004632 polycaprolactone Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 5
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 5
- 235000010703 Modiola caroliniana Nutrition 0.000 description 5
- 244000038561 Modiola caroliniana Species 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004787 125Te NMR spectroscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- JCERKCRUSDOWLT-UHFFFAOYSA-N 1-bromopropan-1-ol Chemical compound CCC(O)Br JCERKCRUSDOWLT-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000003959 diselenides Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明公开了一种如式(I)所示的含双碲生物可降解聚合物，
The invention discloses a ditellurium-containing biodegradable polymer represented by formula (I),
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and relates to a double-tellurium-containing biodegradable polymer and a preparation method thereof.
Background
Polycarbonate (PTMC) and Polycaprolactone (PCL) are biodegradable materials approved by the FDA for use in the biomedical field. The polyesters have good biocompatibility and excellent mechanical properties, and are widely applied to the fields of tissue engineering, drug sustained release, gene therapy, implantation instruments, regenerative medicine and the like.
Recently, disulfide compounds and diselenide compounds have many applications in self-healing polymers and environmental responsiveness due to the property that disulfide bonds and diselenide bonds can be cleaved and reformed under specific environments (Otsuka H, Nano S et al Chemical communications 2010; 46: 1150-2; Ji S et al advanced materials 2015; 27: 7740-5).
The double tellurium linkage has low bond energy (127KJ/mol) (Kildahl NK. journal of Chemical evolution 1995; 72: 423-4), is lower than the double sulfur linkage and double selenium linkage, and can be cleaved and recombined under milder environment (Granger Petal. journal of organic Chemistry 1981; 220:149-58.) and has more application prospect in self-repairing polymers and environmental responsiveness. However, the ditellurium compound or the intermediate is unstable and easy to decompose or agglomerate under the conditions of light and oxygen, so that the preparation of the ditellurium compound is difficult, and the application of the ditellurium compound is limited. Few studies of ditellurium-containing polymers are currently available and these polymers are not biodegradable (Al-Rubaietial. applied organic Chemistry 2002; 16: 649-54.). The introduction of ditellurium bonds into biodegradable Polycarbonate (PTMC) and Polycaprolactone (PCL) backbones is of great significance in dynamically covalent bonding polymers and environmentally responsive polymers.
Disclosure of Invention
Therefore, the invention aims to introduce double tellurium bonds into a main chain of biodegradable Polycarbonate (PTMC) and Polycaprolactone (PCL), and provides a double tellurium-containing biodegradable polymer and a preparation method thereof.
The structure of the double-tellurium-containing biodegradable polymer is shown as a formula (I),
wherein m is an integer of 1-20; n is an integer of 1-20; p is an integer of 1-10; m' is an integer of 10 to 1000; n' is an integer of 10 to 1000; r is carbon or oxygen.
Preferably, m is an integer of 2 to 6, preferably 2 or 3; n is an integer of 2-6, preferably 2 or 3; p is an integer of 1-6, preferably 1 or 2; m' is an integer of 10 to 100, preferably 30 to 50; n' is an integer of 10 to 100, preferably 30 to 50.
The following are some specific double tellurium-containing biodegradable polymers of the present invention:
the method for preparing the double-tellurium-containing biodegradable polymer comprises the following steps: which comprises the following steps: the functional ditellurium micromolecule shown in the formula II and the lactone shown in the formula III react for 8 to 48 hours in toluene at the temperature of between 50 and 85 ℃ under the catalytic action of the Novoxil lipase 435 to obtain the ditellurium-containing biodegradable polymer shown in the formula (I),
wherein m, n, p, m ', n' and R are as defined in claim 1.
Preferably, the molar ratio of the functionalized ditellurium small molecule shown in the formula II to the lactone shown in the formula III is 1: 10-1: 1000.
Preferably, the dosage of the Novoxil lipase 435 is 1-10 g/100g of the lactone shown in the formula III.
Preferably, the amount of toluene used is 1-10 mL/g of the lactone represented by the formula III.
Preferably, the reaction conditions of the functionalized ditellurium micromolecule shown in the formula II and the lactone shown in the formula III are light-proof, anhydrous and oxygen-free, the reaction temperature is 60-75 ℃, and the reaction time is 8-24 hours.
Preferably, m and n are the same, and the functionalized ditellurium small molecule shown in the formula II is prepared by the following steps: dissolving sodium borohydride in water, adding tellurium powder, and reacting at 60-80 ℃ to obtain mauve Na2Te2A solution; then adding a tetrahydrofuran solution of bromohydrin under the protection of inert gas, and reacting in the dark at 40-60 ℃ to generate a functional ditellurium micromolecule shown in a formula II, wherein the functional ditellurium micromolecule is directly used for reacting with lactone shown in a formula III;
the positive progress effects of the invention are as follows: the method takes the functional ditellurium micromolecule shown as the formula II and the lactone shown as the formula III as raw materials, successfully introduces ditellurium bonds into the biodegradable polymer in a mode of enzyme-catalyzed ring-opening reaction under mild reaction conditions, has few byproducts in the reaction process and high yield, and the prepared ditellurium-containing polymer has excellent light environment response performance.
Drawings
FIG. 1 shows ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) of1HNMR spectrogram;
FIG. 2 shows a diagram of a ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) Raman spectrum;
FIG. 3 shows a schematic diagram of a ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) UV-Vis spectrum;
FIG. 4 shows a polycarbonate with ditellurium (PTMCTE)2(I-1b) of1HNMR spectrogram;
FIG. 5 shows ditellurium-containing Polycaprolactone (PCLTE)2(I-2a) of1HNMR spectrogram;
FIG. 6 is a ditellurium-containing polycarbonateEster (PTMCTE)2(I-2b) of1HNMR spectrogram;
FIG. 7 shows a schematic representation of a ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) a spectrum of uv-visible absorption as a function of illumination time;
FIG. 8 shows bis-tellurium-containing Polycaprolactone (PTMCTE)2(I-1b) spectrum of ultraviolet-visible absorption as a function of illumination time.
Detailed Description
The following series of specific examples are given to further illustrate the present invention, but the present invention is not limited to these specific examples, and any modification of the present invention that would be obvious to those skilled in the art to achieve similar results would also be included in the present invention.
Example 1 ditellurium-containing Polycaprolactone (PCLTE)2(I-1a)
Synthesis of 2,2' -ditelluridipropanol (II-1)
Weighing (2.2698g, 60mmol) sodium borohydride and deionized water (150mL) and adding the sodium borohydride and the deionized water into a 500mL reaction bulb bottle, stirring until the sodium borohydride is completely dissolved, then adding tellurium powder (7.26g, 60mmol) and reacting for 30min at 70 ℃ to obtain mauve Na2Te2And (3) solution. Then, a solution of bromopropanol (8.34g, 60mmol) in tetrahydrofuran (150mL) was added under nitrogen, and the mixture was reacted at 50 ℃ for 5 hours with exclusion of light. After the reaction, the mixture was extracted with oxygen-free dichloromethane, dried over anhydrous magnesium sulfate, and separated by column chromatography (eluent dichloromethane: ethyl acetate ═ 1:2(v/v)) to obtain a mauve compound, i.e., 2' -ditelluridipropanol (II-1).1H NMR(400MHz,CDCl3)δ(ppm):3.72(4H,t, HOCH2),3.19(4H,t,TeTeCH2),2.00(4H,m,HOCH2CH2CH2TeTe) and 1.70(2H, s, HOCH)2)。13C NMR(125MHZ,CDCl3)δ(ppm):63.36,35.94,-0.34。125Te NMR(189MHz, CDCl3)δ(ppm):373.2。
Double tellurium Polycaprolactone (PCLTE)2Synthesis of (I-1a)
2,2' -ditelluridipropanol (0.372g,1mmol) and epsilon-caprolactone (4.56g, 40mmol) were added to a previously baked eggplant-shaped reaction flask, vacuum was applied at 40 ℃ for 3 hours to remove a trace of moisture, and then under nitrogen protection, novinoxin lipase 435(0.456g) and anhydrous, oxygen-free toluene (10mL) were added and reacted at 60 ℃ for 24 hours. And (3) ending the reaction, adding oxygen-free dichloromethane for dissolution, filtering to remove the enzyme, settling in glacial ethyl ether, and drying in vacuum to obtain the target product ditellurium-containing polycaprolactone (I-1a) with the yield of 94%.
1H NMR(400MHz,CDCl3) Delta (ppm) (as shown in FIG. 1): a (4.06), b (2.31), c (1.65), d (2.31), e (1.38), f (4.10), g (3.10), h (2.07).
125Te NMR(189MHz,CDCl3)δ(ppm):391.7。
The Raman spectrum and the ultraviolet-visible (UV-Vis) absorption spectrum are shown in fig. 2 and 3.
Example 2 ditellurium-containing Polycarbonate (PTMCTE)2(I-1b)
2,2' -ditelluridipropanol (0.372g,1mmol), trimethylene carbonate (TMC) (4.08g, 40mmol) were added to a pre-baked eggplant-shaped reaction flask, vacuum was applied at 40 ℃ for 3 hours to remove a trace of water, and then under nitrogen protection, novinoxin lipase 435(0.408g) and anhydrous oxygen-free toluene (10mL) were added and reacted at 60 ℃ for 24 hours. After the reaction is finished, the enzyme is removed by filtration, and the target product of polycarbonate (I-1b) containing ditellurium is obtained by vacuum drying after being settled in ethyl acetate, and the yield is 91%.
1H NMR(400MHz,CDCl3) Delta (ppm) (as shown in FIG. 4): a (4.24), b (2.05), c (4.10), e (3.10), d (2.07).
125Te NMR(189MHz,CDCl3)δ(ppm):388.4。
Example 3 ditellurium-containing Polycaprolactone (PCLTE)2(I-2a)
Synthesis of 2,2' -ditelluritol (II-2)
Weighing sodium borohydride (2.2698g, 60mmol) and deionized water (150mL), adding into a 500mL reaction bulb, stirring until the sodium borohydride is completely dissolved, then adding tellurium powder (7.26g, 60mmol), and reacting at 70 ℃ for 30min to obtain mauve Na2Te2And (3) solution. Then, a solution of bromoethanol (7.49g, 60mmol) in tetrahydrofuran (150mL) was added under nitrogen, and the mixture was reacted at 50 ℃ for 6 hours with exclusion of light. After the reaction is finished, the mixture is extracted by oxygen-free dichloromethane, dried by anhydrous magnesium sulfate and separated by column chromatography (eluent is dichloromethane: ethyl acetate ═ 1:1(v/v)) to obtain a mauve compound, namely 2,2' -ditelluritol.1H NMR(400MHz,CDCl3)δ(ppm):3.87(4H,t,HOCH2),3.32 (4H,t,TeTeCH2) And 2.11(2H, s, HOCH)2)。13C NMR(125MHz,CDCl3)δ(ppm):64.5,8.2。125Te NMR(189MHz,CDCl3)δ(ppm):307.7。
Double tellurium Polycaprolactone (PCLTE)2Synthesis of (I-2a)
With reference to example 1, ditellurium-containing polycaprolactone (I-2a) was prepared by reacting 2,2' -ditelluril diethanol prepared as described above with epsilon-caprolactone.1H NMR(400MHZ,CDCl3) Delta (ppm) (as shown in FIG. 5): a (4.06), b (2.31), c (1.65), d (2.31), e (1.38), f (4.27), g (3.65).
Example 4 bis-tellurium-containing Polycarbonate (PTMCTE)2(I-2b)
Reference example 2 the reaction of 2,2' -ditelluride diethanol prepared above with trimethylene carbonate produced ditelluride-containing polycaprolactone ditelluride-containing polycarbonate (I-2 b).1H NMR(400MHz,CDCl3) Delta (ppm) (as shown in FIG. 6): a (4.24), b (2.05), c (4.45), d (3.74).
Effect examples light response Properties
Weighing 5mg of ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) was dissolved in 10mL of chloroform at room temperature in the absence of light, and the solution was tested for its ultraviolet absorption intensity at 389nm (absorption peak of Te-Te bond) by an ultraviolet-visible absorption spectrometer under irradiation with a visible light irradiation intensity of 558lux at different irradiations. The change in the absorption intensity of the solution at 389nm with the illumination time is shown in FIG. 7.
With reference to the above procedure, a ditellurium-containing Polycarbonate (PTMCTE) was used2(I-1b) in place of ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) the results of the photoresponse experiment are shown in FIG. 8.
As can be seen from FIGS. 7 and 8, ditellurium-containing Polycaprolactone (PCLTE)2(I-1a) and ditellurium-containing Polycarbonate (PTMCTE)2The (I-1b) has excellent light environment response performance.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full range of equivalents.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284909A (en) * | 2008-03-19 | 2008-10-15 | 华东理工大学 | Polycaprolactone/polyacrylamide graft copolymer and its application |
| CN101831468A (en) * | 2010-05-28 | 2010-09-15 | 上海交通大学 | Synthesis of medicinal biodegradable poly(epsilon-caprolactone) and application method thereof |
| CN105251013A (en) * | 2015-09-28 | 2016-01-20 | 湘潭大学 | Degradable water-soluble antitumor polymer prodrug with redox responsiveness and preparation method thereof |
| CN105384920A (en) * | 2015-11-13 | 2016-03-09 | 复旦大学 | Selenium or tellurium containing polymer as well as preparation method and application of selenium or tellurium containing polymer |
| CN105732990A (en) * | 2016-04-01 | 2016-07-06 | 华东理工大学 | Method for preparing selenium-containing degradable polymer through ring-opening polymerization and application thereof to hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101284909A (en) * | 2008-03-19 | 2008-10-15 | 华东理工大学 | Polycaprolactone/polyacrylamide graft copolymer and its application |
| CN101831468A (en) * | 2010-05-28 | 2010-09-15 | 上海交通大学 | Synthesis of medicinal biodegradable poly(epsilon-caprolactone) and application method thereof |
| CN105251013A (en) * | 2015-09-28 | 2016-01-20 | 湘潭大学 | Degradable water-soluble antitumor polymer prodrug with redox responsiveness and preparation method thereof |
| CN105384920A (en) * | 2015-11-13 | 2016-03-09 | 复旦大学 | Selenium or tellurium containing polymer as well as preparation method and application of selenium or tellurium containing polymer |
| CN105732990A (en) * | 2016-04-01 | 2016-07-06 | 华东理工大学 | Method for preparing selenium-containing degradable polymer through ring-opening polymerization and application thereof to hydrogel |
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