CN107541530B - Double-tellurium-containing biodegradable polymer and preparation method thereof - Google Patents
Double-tellurium-containing biodegradable polymer and preparation method thereof Download PDFInfo
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- CN107541530B CN107541530B CN201710919281.4A CN201710919281A CN107541530B CN 107541530 B CN107541530 B CN 107541530B CN 201710919281 A CN201710919281 A CN 201710919281A CN 107541530 B CN107541530 B CN 107541530B
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Abstract
The invention discloses a double tellurium-containing biodegradable polymer as shown in 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. The invention also discloses a method for preparing the double-tellurium-containing biodegradable polymer. The method takes functionalized ditellurium micromolecules and lactone as raw materials, successfully introduces ditellurium bonds into biodegradable polymers in an enzyme catalysis ring-opening reaction mode under mild reaction conditions, has few byproducts in the reaction process and high yield, and the prepared ditellurium-containing polymers have excellent light environment response performance.
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.
Claims (6)
1. A double tellurium-containing biodegradable polymer which is a compound represented by formula I:
in formula I: m is 3, n is 3, p is 1, m 'is 40, n' is 40, R is oxygen.
2. A method for preparing the ditellurium-containing biodegradable polymer as defined in claim 1, which comprises the following main steps: under the conditions of light resistance, no water and no oxygen, reacting a compound shown in a formula II and a compound shown in a formula III in toluene for 8 to 48 hours at the temperature of between 50 and 85 ℃ under the catalytic action of the Novitin lipase 435 to obtain a target substance;
wherein m, n, p and R are as defined in claim 1.
3. The method according to claim 2, wherein the molar ratio of the compound of formula II to the compound of formula III is 1:10 to 1: 1000.
4. The method of claim 2, wherein the amount of novacin lipase 435 used is 1g to 10g per 100g of the compound of formula III.
5. The method of claim 2, wherein the toluene is used in an amount of 1mL to 10mL per gram of the compound of formula III.
6. The process according to claim 2, wherein the reaction temperature of the compound represented by the formula II and the compound represented by the formula III is 60 to 75 ℃ and the reaction time is 8 to 24 hours.
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| CN101284909A (en) * | 2008-03-19 | 2008-10-15 | 华东理工大学 | Polycaprolactone/polyacrylamide graft copolymer and uses thereof |
| 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 |
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