CN104826119A - Preparation method of pH and glucose dual-sensitive mesoporous silica@polymer drug carrier - Google Patents
Preparation method of pH and glucose dual-sensitive mesoporous silica@polymer drug carrier Download PDFInfo
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- CN104826119A CN104826119A CN201510180823.1A CN201510180823A CN104826119A CN 104826119 A CN104826119 A CN 104826119A CN 201510180823 A CN201510180823 A CN 201510180823A CN 104826119 A CN104826119 A CN 104826119A
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Abstract
The invention relates to a preparation method of a pH and glucose dual-sensitive mesoporous silica@polymer drug carrier, and belongs to the technical field of nanomaterials. The preparation method comprises the following steps: 1, preparing catechol modified mesoporous silica; 2, preparing a phenylboric acid-containing polymer; and 3, dispersing catechol modified mesoporous silica in methanol to prepare a third solution, dissolving the phenylboric acid-containing polymer in methanol to prepare a fourth solution, adding the fourth solution to the third solution, reacting for 12-24h, and centrifuging after the reaction to remove unreacted polymer in order to obtain the carrier. Aminated mesoporous silica is modified with 3,4-dihydroxy benzaldehyde to make the surface of the mesoporous silica have a dihydroxy phenol structure and connected with a pH-sensitive imine bond; and the synthesized phenylboric acid-containing polymer and the dihydroxy phenol structure on the surface of the mesoporous silica form a glucose-sensitive borate ester bond, and the polymer is modified with polyethylene glycol, so the biocompatibility is good.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of the mesoporous silicon oxide@polymer drug carrier of a kind of pH and glucose doubling sensitivity.
Background technology
In recent years, mesoporous material becomes the focus of research and development due to the excellent properties of its uniqueness, more makes it receive much concern in the application prospect in the fields such as catalysis, adsorbing separation, drug release.From people such as Kresge in 1992 on Nature magazine since the reported first ordered mesoporous silicon-dioxide material of a kind of MCM-41 by name, the research of mesoporous silicon oxide becomes rapidly international focus.The appearance of ordered meso-porous silicon oxide is the once leap in molecular sieve and porous mass development history.
Mesoporous silicon dioxide nano particle (mesoporous silica nanoparticles, MSN) have can regulate continuously within the scope of 2 ~ 50nm homogeneous mesoporous pore size, rule duct, stable framing structure, be easy to modify surfaces externally and internally and without features such as physiological-toxicity, be suitable as very much the carrier of drug molecule.Meanwhile, MSN has huge specific surface area (> 900m
2/ g) and specific pore volume (> 0.9cm
3/ g), at the various medicine of duct internal burden, and can play slow releasing function to medicine, improve the persistency of drug effect.Therefore, the application of MSN in controlled drug transmission system is in recent years paid attention to day by day, (the Chiyoung Park such as ChiyoungPark, Kyoungho Oh et al.Angew.Chem.Int.Ed.2007, 46, 1455 – 1457) utilize APTES first to carry out surface modification to mesoporous silicon dioxide nano particle, make its surface with amino, and then recycling contains the polymer of end carboxyl and amido modified meso-porous titanium dioxide pasc reaction, at mesoporous silicon oxide finishing one deck pH responsive polymer, drug molecule in controllable release mesoporous silicon oxide duct.(the Huan Meng such as Zink, MinXue, Tian Xia et al.J.Am.Chem.Soc.2010,132 (36), 12690 – 12697) first with the MBI finishing mesoporous silicon oxide containing arylamine, being nested in by cyclodextrin molecular on MBI adds a cover on mesoporous hole again, and encapsulated drug molecule forms the drug delivery system with pH response.
In sum, current mesoporous silicon oxide@polymer drug carrier system, what adopt is the single pH sensitivity means as drug molecule Co ntrolled release more.And adopt double-response release means in mesoporous silicon oxide@polymer drug carrier system, especially have the rarely seen report of control delivery of pH and glucose responding sexual function concurrently.
Summary of the invention
The object of the present invention is to provide the preparation method of the mesoporous silicon oxide@polymer drug carrier of a kind of pH and glucose doubling sensitivity.
The present invention includes following steps:
1) mesoporous silicon oxide that catechol is modified is prepared;
2) by modifying the polymer obtained containing phenylboric acid after N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer random copolymerization through 4-formylphenylboronic acid, concrete grammar is as follows:
A, N-(4 aminophenyl)-Methacrylamide, polyethylene glycol methacrylate-styrene polymer and initiator are dissolved in solvent after, be placed in freezing degassed and lower 65 ~ 80 DEG C of reaction 24h of sealing after being filled with argon of reaction vessel, liquid nitrogen freezing 2 ~ 3min stopped reaction after polymerization, wherein, initiator is can heat to produce free radical and the compound causing polyethylene glycol methacrylate-styrene polymer and the polymerization of N-(4 aminophenyl)-Methacrylamide;
B, employing dissolving precipitated method remove unreacted monomer, by precipitant precipitation after solubilizer dilution, dry, obtain polymer;
C, step b obtained polymer and be dissolved in dichloromethane and be made into the first solution that mass concentration is 0.08 ~ 0.2g/mL, 0.1 ~ 1g 4-formylphenylboronic acid is dissolved in methanol solution and is made into the second solution that mass concentration is 0.15 ~ 0.5g/mL, and the volume ratio of the first solution and the second solution is 2 ~ 6: 0.5 ~ 2;
D, the second solution injected first solution reaction 12 ~ 14h, reaction terminates rear methanol wash, sucking filtration, drying, obtains the described polymer containing phenylboric acid;
3) mesoporous silicon oxide that catechol is modified is scattered in methanol and is made into the 3rd solution, polymer containing phenylboric acid is dissolved in methanol and is made into the 4th solution, 4th solution is added in the 3rd solution and react 12 ~ 24h, reaction terminates the unreacted polymer of centrifugal removing, obtain the mesoporous silicon oxide@polymer drug carrier of described pH and glucose doubling sensitivity, the mesoporous silicon oxide that wherein catechol is modified is 1 ~ 3: 2 ~ 5 with the mass ratio of the polymer containing phenylboric acid.
In step 1) in, the described concrete grammar preparing the mesoporous silicon oxide that catechol is modified, can comprise the steps:
A, be dissolved in distilled water by CTAB, ammonia and TEOS, collected by centrifugation white precipitate after stirring reaction 2 ~ 4h in 50 ~ 55 DEG C of oil bath pans, wash respectively with distilled water and ethanol, drying obtains white powder;
B, the white powder obtained by step a are scattered in the ammonium nitrate alcoholic solution of 0.5 ~ 0.8g/ml, reflux 6 ~ 12h, and reaction terminates collected by centrifugation white precipitate, by washing with alcohol, obtains white powder after drying;
C, be scattered in ethanol by white powder obtained for step b, add 0.2 ~ 1ml 3-aminopropyl triethoxysilane, collected by centrifugation white precipitate after reflux 6 ~ 24h at 80 ~ 85 DEG C, by washing with alcohol, drying obtains white powder;
D, be scattered in methanol by white powder obtained for step c, add 3,4-4-dihydroxy benzaldehyde, reaction end methanol wash, drying obtains yellow powder, is the mesoporous silicon oxide that catechol is modified.
Step a) in, mass concentration 0.006 ~ the 0.013g/mL of described CTAB in distilled water, 3, the mass ratio of 4-4-dihydroxy benzaldehyde and CTAB is (0.3 ~ 1): (0.3 ~ 0.8), and the volume ratio of ammonia, TEOS, 3-aminopropyl triethoxysilane and distilled water is (0.3 ~ 0.8): (0.1 ~ 0.4): (0.2 ~ 1): (40 ~ 60);
In step 2) in, described solvent can be selected from oxolane or Isosorbide-5-Nitrae-dioxane etc.;
The molar concentration of N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer is 0.2 ~ 1.0mol/L; The mol ratio of N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer can be (1 ~ 4): 1;
Described N-(4 aminophenyl)-Methacrylamide and the total mole number of polyethylene glycol methacrylate-styrene polymer and the mol ratio of described initiator can be (50 ~ 100): 1;
Described initiator can be azodiisobutyronitrile;
Described precipitant can be selected from normal hexane or petroleum ether etc.
First the present invention synthesizes a kind of mesoporous silicon oxide of surface amination, then uses 3,4-4-dihydroxy benzaldehyde and amidized meso-porous titanium dioxide pasc reaction, makes catechol group on mesoporous silicon oxide surface band.Afterwards with containing the polymer of phenylboric acid and having modified the meso-porous titanium dioxide pasc reaction of catechol, mesoporous silicon oxide polymer drug carrier can be obtained.Because mesoporous silicon oxide and polymer are connected with boric acid ester bond by imine linkage, imine linkage is the dynamic key that a class has pH sensitivity, boric acid ester bond is the dynamic key that a class has glucose-sensitive, and therefore mesoporous silicon oxide polymer drug carrier provided by the invention has pH and glucose doubling sensitivity concurrently.
The invention has the beneficial effects as follows:
1) the present invention modifies amidized mesoporous silicon oxide by 3,4-4-dihydroxy benzaldehyde, makes two hydroxyl phenol structure on mesoporous silicon oxide surface band, has connected the imine linkage with pH sensitivity simultaneously.
2) the present invention has the polymer of phenylboric acid structure by synthesis, can have the boric acid ester bond of glucose-sensitive with two hydroxyl phenol structures formation of meso-porous titanium dioxide silicon face, and this polymer-modified Polyethylene Glycol, good biocompatibility.
3) the equal no cytotoxicity of polymer of mesoporous silicon oxide of the present invention, 3,4-4-dihydroxy benzaldehydes, phenylboric acid structure, good biocompatibility, has broad application prospects in drug controlled release field.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram containing the polymer of phenylboric acid in embodiment 1, and wherein, abscissa is chemical shift Chemicalshift (ppm); Solvent is MeOD.
Fig. 2 is Flied emission transmission electron microscope (TEM) photo that embodiment 1 has modified 3,4-4-dihydroxy benzaldehydes.
Fig. 3 is Flied emission transmission electron microscope (TEM) photo of embodiment 1 intermediary hole silicon dioxide@polymer.
Detailed description of the invention
By reference to the accompanying drawings technical scheme of the present invention is further described below by way of specific embodiment.
Embodiment 1
(1) mesoporous silicon oxide that catechol is modified is prepared
A, 0.3g CTAB, 0.3mL ammonia and 0.2mLTEOS to be dissolved in 50mL distilled water, to be placed in the single necked round bottom flask of 100mL, stirring reaction 2h in 50 DEG C of oil bath pans.Reaction terminates collected by centrifugation white precipitate, and wash 3 ~ 5 times respectively with distilled water and ethanol, drying obtains white powder.
B, the white powder obtained by step a are scattered in the ammonium nitrate alcoholic solution of 0.6g/mL, reflux 12h, and reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
C, be scattered in ethanol by white powder obtained for step b, add 0.2mL 3-aminopropyl triethoxysilane, reflux 24h at 80 DEG C, reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
D, be scattered in methanol by white powder obtained for step c, add 0.5g 3,4-4-dihydroxy benzaldehyde, reaction end methanol wash 3 ~ 5 times, drying obtains yellow powder, is the mesoporous silicon oxide that catechol is modified.
(2) preparation is containing the polymer of phenylboric acid
A, take N-(4 aminophenyl)-Methacrylamide 0.176g and polyethylene glycol methacrylate-styrene polymer 0.475g and initiator 10mg and be dissolved in 1.5mL THF, solution is placed in reaction vessel freezing degassed and seal after being filled with argon lower 65 DEG C reaction 24h, polymerization after liquid nitrogen freezing 2min stopped reaction.
B, by reacted solution 100mL normal hexane precipitation twice, dry.
C, polymer obtained for step b got 0.4g and be dissolved in 5mL dichloromethane and be made into the first solution, 0.15g 4-formylphenylboronic acid is dissolved in 1mL methanol solution and is made into the second solution.
D, the second solution is injected the first solution react 12h, reaction terminates rear washed with dichloromethane, sucking filtration, drying, obtains the polymer containing phenylboric acid.
(3) being prepared as follows of mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity:
The mesoporous silicon oxide that 0.1g catechol is modified is scattered in 20mL methanol and is made into the 3rd solution, polymer 0.2g being contained phenylboric acid is dissolved in methanol and is made into the 4th solution, 4th solution is added in the 3rd solution and reacts 12h, reaction terminates centrifugal unreacted polymer of going out, and obtains the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity.
The nuclear magnetic spectrogram of the polymer of phenylboric acid is contained see Fig. 1 in embodiment 1, embodiment 1 has modified 3, Flied emission transmission electron microscope (TEM) photo of 4-4-dihydroxy benzaldehyde is see Fig. 2, and Flied emission transmission electron microscope (TEM) photo of embodiment 1 intermediary hole silicon dioxide@polymer is see Fig. 3.
Embodiment 2
(1) mesoporous silicon oxide that catechol is modified is prepared
A, 0.5g CTAB, 0.5mL ammonia and 0.2mLTEOS to be dissolved in 50mL distilled water, to be placed in the single necked round bottom flask of 100mL, stirring reaction 4h in 50 DEG C of oil bath pans.Reaction terminates collected by centrifugation white precipitate, and wash 3 ~ 5 times respectively with distilled water and ethanol, drying obtains white powder.
B, the white powder obtained by step a are scattered in the ammonium nitrate alcoholic solution of 0.6g/mL, reflux 12h, and reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
C, be scattered in ethanol by white powder obtained for step b, add 0.5mL 3-aminopropyl triethoxysilane, reflux 24h at 80 DEG C, reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
D, be scattered in methanol by white powder obtained for step c, add 0.5g 3,4-4-dihydroxy benzaldehyde, reaction end methanol wash 3 ~ 5 times, drying obtains yellow powder, is the mesoporous silicon oxide that catechol is modified.
(2) preparation is containing the polymer of phenylboric acid
A, take N-(4 aminophenyl)-Methacrylamide 0.352g and polyethylene glycol methacrylate-styrene polymer 0.475g and initiator 10mg and be dissolved in 1.5mL THF, solution is placed in reaction vessel freezing degassed and seal after being filled with argon lower 65 DEG C reaction 24h, polymerization after liquid nitrogen freezing 2min stopped reaction.
B, by reacted solution 100mL normal hexane precipitation twice, dry.
C, step b is obtained polymer get 0.4g and be dissolved in 5mL dichloromethane and be made into the first solution, 0.3g 4-formylphenylboronic acid is dissolved in 1mL methanol solution and is made into the second solution.
D, the second solution is injected the first solution react 12h, reaction terminates rear washed with dichloromethane, sucking filtration, drying, obtains the polymer containing phenylboric acid.
(3) being prepared as follows of mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity:
The mesoporous silicon oxide that 0.3g catechol is modified is scattered in 40mL methanol and is made into the 3rd solution, polymer 0.5g being contained phenylboric acid is dissolved in methanol and is made into the 4th solution, 4th solution is added in the 3rd solution and reacts 24h, reaction terminates centrifugal unreacted polymer of going out, and obtains the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity.
Embodiment 3
(1) mesoporous silicon oxide that catechol is modified is prepared
A, 0.8g CTAB, 0.8mL ammonia and 0.4mLTEOS to be dissolved in 60mL distilled water, to be placed in the single necked round bottom flask of 100mL, stirring reaction 4h in 50 DEG C of oil bath pans.Reaction terminates collected by centrifugation white precipitate, and wash 3 ~ 5 times respectively with distilled water and ethanol, drying obtains white powder.
B, the white powder obtained by step a are scattered in the ammonium nitrate alcoholic solution of 0.6g/mL, reflux 12h, and reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
C, be scattered in ethanol by white powder obtained for step b, add 1mL 3-aminopropyl triethoxysilane, reflux 24h at 80 DEG C, reaction terminates collected by centrifugation white precipitate, and by washing with alcohol 3 ~ 5 times, drying obtains white powder.
D, be scattered in methanol by white powder obtained for step c, add 0.3 ~ 1g 3,4-4-dihydroxy benzaldehyde, reaction end methanol wash 3 ~ 5 times, drying obtains yellow powder, is the mesoporous silicon oxide that catechol is modified.
(2) preparation is containing the polymer of phenylboric acid
A, take N-(4 aminophenyl)-Methacrylamide 0.176g and polyethylene glycol methacrylate-styrene polymer 0.475g and initiator 10mg and be dissolved in 1.5mL THF, solution is placed in reaction vessel freezing degassed and seal after being filled with argon lower 75 DEG C reaction 24h, polymerization after liquid nitrogen freezing 2min stopped reaction.
B, by reacted solution 100mL normal hexane precipitation twice, dry.
C, polymer obtained for step b got 0.4g and be dissolved in 5mL dichloromethane and be made into the first solution, 0.15g 4-formylphenylboronic acid is dissolved in 1mL methanol solution and is made into the second solution.
D, the second solution is injected the first solution react 12h, reaction terminates rear washed with dichloromethane, sucking filtration, drying, obtains the polymer containing phenylboric acid.
(3) being prepared as follows of mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity:
The mesoporous silicon oxide that 0.3g catechol is modified is scattered in 50mL methanol and is made into the 3rd solution, polymer 0.5g being contained phenylboric acid is dissolved in methanol and is made into the 4th solution, 4th solution is added in the 3rd solution and reacts 24h, reaction terminates centrifugal unreacted polymer of going out, and obtains the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity.
Claims (10)
- The preparation method of the mesoporous silicon oxide@polymer drug carrier of 1.pH and glucose doubling sensitivity, is characterized in that comprising the steps:1) mesoporous silicon oxide that catechol is modified is prepared;2) by modifying the polymer obtained containing phenylboric acid after N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer random copolymerization through 4-formylphenylboronic acid;3) mesoporous silicon oxide that catechol is modified is scattered in methanol and is made into the 3rd solution, polymer containing phenylboric acid is dissolved in methanol and is made into the 4th solution, 4th solution is added in the 3rd solution and react 12 ~ 24h, reaction terminates the unreacted polymer of centrifugal removing, obtain the mesoporous silicon oxide@polymer drug carrier of described pH and glucose doubling sensitivity, the mesoporous silicon oxide that wherein catechol is modified is 1 ~ 3: 2 ~ 5 with the mass ratio of the polymer containing phenylboric acid.
- 2. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 1, it is characterized in that in step 1) in, the described concrete grammar preparing the mesoporous silicon oxide that catechol is modified, comprises the steps:A, be dissolved in distilled water by CTAB, ammonia and TEOS, collected by centrifugation white precipitate after stirring reaction 2 ~ 4h in 50 ~ 55 DEG C of oil bath pans, wash respectively with distilled water and ethanol, drying obtains white powder;B, the white powder obtained by step a are scattered in the ammonium nitrate alcoholic solution of 0.5 ~ 0.8g/ml, reflux 6 ~ 12h, and reaction terminates collected by centrifugation white precipitate, by washing with alcohol, obtains white powder after drying;C, be scattered in ethanol by white powder obtained for step b, add 0.2 ~ 1ml 3-aminopropyl triethoxysilane, collected by centrifugation white precipitate after reflux 6 ~ 24h at 80 ~ 85 DEG C, by washing with alcohol, drying obtains white powder;D, be scattered in methanol by white powder obtained for step c, add 3,4-4-dihydroxy benzaldehyde, reaction end methanol wash, drying obtains yellow powder, is the mesoporous silicon oxide that catechol is modified.
- 3. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 2, it is characterized in that step a) in, mass concentration 0.006 ~ the 0.013g/mL of described CTAB in distilled water, 3, the mass ratio of 4-4-dihydroxy benzaldehyde and CTAB is (0.3 ~ 1): (0.3 ~ 0.8), and the volume ratio of ammonia, TEOS, 3-aminopropyl triethoxysilane and distilled water is (0.3 ~ 0.8): (0.1 ~ 0.4): (0.2 ~ 1): (40 ~ 60).
- 4. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 1; it is characterized in that in step 2) in, described as follows by modifying through 4-formylphenylboronic acid the concrete grammar obtained containing the polymer of phenylboric acid after N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer random copolymerization:A, N-(4 aminophenyl)-Methacrylamide, polyethylene glycol methacrylate-styrene polymer and initiator are dissolved in solvent after, be placed in freezing degassed and lower 65 ~ 80 DEG C of reaction 24h of sealing after being filled with argon of reaction vessel, liquid nitrogen freezing 2 ~ 3min stopped reaction after polymerization, wherein, initiator is can heat to produce free radical and the compound causing polyethylene glycol methacrylate-styrene polymer and the polymerization of N-(4 aminophenyl)-Methacrylamide;B, employing dissolving precipitated method remove unreacted monomer, by precipitant precipitation after solubilizer dilution, dry, obtain polymer;C, step b obtained polymer and be dissolved in dichloromethane and be made into the first solution that mass concentration is 0.08 ~ 0.2g/mL, 0.1 ~ 1g 4-formylphenylboronic acid is dissolved in methanol solution and is made into the second solution that mass concentration is 0.15 ~ 0.5g/mL, and the volume ratio of the first solution and the second solution is 2 ~ 6: 0.5 ~ 2;D, the second solution injected first solution reaction 12 ~ 14h, reaction terminates rear methanol wash, sucking filtration, drying, obtains the described polymer containing phenylboric acid.
- 5. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, it is characterized in that step a) in, described solvent is selected from oxolane or Isosorbide-5-Nitrae-dioxane.
- 6. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, it is characterized in that step a) in, the molar concentration of N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer is 0.2 ~ 1.0mol/L.
- 7. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, it is characterized in that step a) in, the mol ratio of N-(4 aminophenyl)-Methacrylamide and polyethylene glycol methacrylate-styrene polymer is (1 ~ 4): 1.
- 8. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, it is characterized in that step a) in, described N-(4 aminophenyl)-Methacrylamide and the total mole number of polyethylene glycol methacrylate-styrene polymer and the mol ratio of described initiator are (50 ~ 100): 1.
- 9. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, it is characterized in that step a) in, described initiator is azodiisobutyronitrile.
- 10. the preparation method of the mesoporous silicon oxide@polymer drug carrier of pH and glucose doubling sensitivity as claimed in claim 4, is characterized in that in step b) in, described precipitant is selected from normal hexane or petroleum ether.
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| CN111074282B (en) * | 2019-10-15 | 2021-11-05 | 东营施普瑞石油工程技术有限公司 | PH-responsive degradable intelligent corrosion inhibitor, and preparation method and application thereof |
| CN114917415A (en) * | 2022-03-21 | 2022-08-19 | 四川大学 | Degradable composite membrane for heart occluder and preparation method and application thereof |
| CN114917415B (en) * | 2022-03-21 | 2023-01-06 | 四川大学 | Degradable composite membrane for heart occluder and preparation method and application thereof |
| CN116355385A (en) * | 2023-04-17 | 2023-06-30 | 苏州易昇光学材料股份有限公司 | Thixotropic buffering energy-absorbing GPU film |
| CN116355385B (en) * | 2023-04-17 | 2023-09-12 | 苏州易昇光学材料股份有限公司 | Thixotropic buffering energy-absorbing GPU film |
| CN116572336A (en) * | 2023-04-18 | 2023-08-11 | 湖南省林业科学院 | Bamboo-wood board modifier and preparation method and application thereof |
| CN116572336B (en) * | 2023-04-18 | 2024-03-19 | 湖南省林业科学院 | Bamboo-wood board modifier and preparation method and application thereof |
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