CN100532393C - Method of modifying elastin by initiation transition termination agent - Google Patents
Method of modifying elastin by initiation transition termination agent Download PDFInfo
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- CN100532393C CN100532393C CNB2007100565079A CN200710056507A CN100532393C CN 100532393 C CN100532393 C CN 100532393C CN B2007100565079 A CNB2007100565079 A CN B2007100565079A CN 200710056507 A CN200710056507 A CN 200710056507A CN 100532393 C CN100532393 C CN 100532393C
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Abstract
The invention discloses a modifying method of elastic protein through triggering transmitting terminator, which is characterized by the following: making elastic protein chlorinate through p-chloromethyl benzoyl chloride; sulfurizing diethyl sodium dithiocarbamic acid to make macromolecular triggering transmitting terminator; triggering methyl acroleic acid-beta-hydroxyethyl ester to polymerize irradiated by ultraviolet; synthesizing elastic protein polymer modified by polymethyl acroleic acid-beta-hydroxyethyl ester; modifying the hydrophobicity of elastic protein obviously; reducing heat stability of elastic protein.
Description
Technical field
The present invention relates to a kind of material modified method of iniferter agent of utilizing, relate in particular to a kind of method of utilizing the iniferter agent modifying elastin.
Background technology
Elastin (elastin) is insoluble in the extracellular matrix, high crosslinked macromole fibrous protein, can combine with microfibril in vivo and form spandex fiber, major function is passively to stretch, give place tissue and organ with retractility and reversible deformability.At present, domestic and international research to elastin mainly concentrates on the hydrolysate α-elastin and the K-elastin that utilize elastin and prepares aspects such as synthesizing of tissue engineering bracket and biological degradation elastomerics and genetic engineered product class silk elastin polymkeric substance and application, and elastin is because highly insoluble, highly hydrophobic and highly crosslinkable, not easy-to-use chemistry and physical method are processed, are produced and be difficult to machine-shaping, have greatly limited its application.
In recent years, surface modification has become traditional material and has been converted into one of most popular method of the novel material with programmable specified property.In numerous surface modifying methods, in recent years, surface modification has become traditional material and has been converted into one of most popular method of the novel material with programmable specified property.In numerous surface modifying methods, iniferter agent (iniferter) is many with its polymerisable monomer, can easily prepare grafting and segmented copolymer, and under ultraviolet lighting, carry out polyreaction and have reaction process and control easily, advantages such as equipment is simple and receiving much attention have been successfully applied to the surface modification of quartz crystal, aluminium, silicon and siloxanes, gold etc.But do not see the research report of sulfo--iniferter technology to elastin surface modification aspect.
Summary of the invention
The objective of the invention is to utilize sulfo--iniferter agent (iniferters) method, adopt the method for light initiation polymerization, hydrophilic polymethyl acrylic acid-beta-hydroxy ethyl ester is incorporated into the elastin surface, be intended to not change under the condition of elastin 26S Proteasome Structure and Function (spring function), synthetic polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance, elastin is carried out surface modification, explore the preparation method and the performance study thereof of elastin sill.
A kind of method of utilizing the iniferter agent modifying elastin of the present invention, carry out according to following steps:
(1) chlorination prepares the chlorination elastin to elastin through triethylamine with to chloromethyl benzoic acid chlorides;
(2) chlorination elastin and the Thiocarb sulfuration with (1) preparation prepares the macromole iniferter agent;
(3) be initiator with the macromole iniferter agent, under protection of inert gas and anhydrous condition, add methacrylic acid-beta-hydroxy ethyl ester and anhydrous methanol, cause its polymerization on elastin by UV-irradiation again.
Described elastin passes through the swelling of dimethyl sulfoxide (DMSO) in advance, and the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
Described macromole iniferter agent passes through the swelling of dimethyl sulfoxide (DMSO) in advance, and the mass ratio of dimethyl sulfoxide (DMSO) and macromole iniferter agent is 1～50, and swelling time is 10～24h.
Triethylamine in the described step (1) and be 0.8～1.2 to the mol ratio of chloromethyl benzoic acid chlorides, temperature of reaction is 15～35 ℃, the reaction times is 12～24h.
The mol ratio of the chloromethyl benzoic acid chlorides in Thiocarb in the described step (2) and the step (1) is 1.3～0.8, and temperature of reaction is 15～35 ℃, and the reaction times is 10～24h.
Described rare gas element is any one in nitrogen, helium and the argon gas.
The solvent that adopts in the described step (3) is any one in anhydrous methanol, dimethyl sulfoxide (DMSO) and the dimethyl formamide.
The solvent in the described step (3) and the volume ratio of methacrylic acid-beta-hydroxy ethyl ester are 1:1～5:1, and temperature of reaction is 15～50 ℃, and the reaction times is 10～96h.
Infrared (FTIR) and x-ray photoelectron power spectrum (XPS), thermogravimetric analysis (TGA), scanning electron microscope (SEM) and dynamic contact angle characterize modifying elastin.The result shows: methacrylic acid-beta-hydroxy ethyl ester has been keyed on the elastin (sees accompanying drawing 2,3a and 3b); SEM shows after the modification that the surface ratio of elastin becomes smooth before unmodified and (sees accompanying drawing 6a-6f), but the thermal characteristics of sample all is lower than unmodified sample after the modification, initial heat decomposition temperature 307.0 ℃ before by modification become 260.2 ℃, and maximum weight loss rate temperature drops to 316.3 ℃ (seeing accompanying drawing 4a and 4b) by 347 ℃; Sample had good hydrophilicity after dynamic contact angle experiment showed modification, and advancing angle 130.45 ° before by modification drop to 35.40 ° behind the reaction 72h, and contact angle hysteresis becomes 35.40 ° (seeing accompanying drawing 5) by 70.42 °.
Behind this method modifying elastin, the hydrophilicity of elastin be improved significantly, and reduced its thermostability.The elastin modification is the basis of elastin in the bionical study on the synthesis work of biological medical polymer material, and provides theoretical foundation for its application in medicine sustained release, bioelastomer, organizational project.
Description of drawings
Fig. 1 is the synthetic route chart of sulfo--iniferters method modifying elastin.
Fig. 2 is the infrared spectrogram of the elastin polymkeric substance of elastin, sulfuration elastin, polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 3 a is that the x-ray photoelectron of elastin can spectrogram.
Fig. 3 b is that the x-ray photoelectron of sulfuration elastin can spectrogram.
Fig. 3 c is that the x-ray photoelectron of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified can spectrogram.
Fig. 4 a is the thermogravimetric curve figure of the elastin polymkeric substance of elastin and polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 4 b is the differential thermogravimetric graphic representation of the elastin polymkeric substance of elastin and polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 5 is the graphic representation that the dynamic advancing contact angle of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified changes with polymerization time.
Fig. 6 a is the electron scanning micrograph (100 *) of elastin.
Fig. 6 b is the electron scanning micrograph (1000 *) of elastin.
Fig. 6 c is the electron scanning micrograph (100 *) of sulfuration elastin.
Fig. 6 d is the electron scanning micrograph (1000 *) of sulfuration elastin.
Fig. 6 e is the electron scanning micrograph (100 *) of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Fig. 6 f is the electron scanning micrograph (1000 *) of the elastin polymkeric substance of polymethyl acrylic acid-beta-hydroxy ethyl ester modified.
Embodiment
Further specify technical scheme of the present invention below in conjunction with embodiment.
Example 1
(1) 3g is without the swollen elastin, and the triethylamine of 1.36g, 2.03g are to chloromethyl benzoic acid chlorides, and in 20 ℃ of reaction 15h, product obtains the chlorination elastin through thorough washing and drying.
(2) 1.5g chlorination elastin and 3.84g Thiocarb are in 20 ℃ of reaction 15h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) at N
2Protection adds 11.2mL methacrylic acid-beta-hydroxy ethyl ester, 11.2mL anhydrous methanol and 0.50g macromole sulfo-iniferter agent down; reaction flask is put into 250W ultraviolet lamp reaction box; in 20 ℃ of reaction 15h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Example 2
(1) 4g is without the swollen elastin, and the triethylamine of 20g, 57.14g are to chloromethyl benzoic acid chlorides, and in 35 ℃ of reaction 12h, product obtains the chlorination elastin through thorough washing and drying.
(2) 2.5g chlorination elastin and 44.53g Thiocarb are in 25 ℃ of reaction 18h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) at N
2Protection adds 50mL methacrylic acid-beta-hydroxy ethyl ester, 60mL anhydrous methanol and 1.50g macromole sulfo-iniferter agent down; reaction flask is put into 300W ultraviolet lamp reaction box; in 40 ℃ of reaction 48h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Example 3
(1) 5g is without the swollen elastin, and the triethylamine of 40g, 74.75g are to chloromethyl benzoic acid chlorides, and in 35 ℃ of reaction 24h, product obtains the chlorination elastin through thorough washing and drying.
(2) 4g chlorination elastin and 115.78g Thiocarb are in 30 ℃ of reaction 24h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) under the Ar protection, add 60mL methacrylic acid-beta-hydroxy ethyl ester, 90mL anhydrous methanol and 3g macromole sulfo-iniferter agent; reaction flask is put into 400W ultraviolet lamp reaction box; in 35 ℃ of reaction 96h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
(1) 5g is without the swollen elastin, and the triethylamine of 40g, 74.75g are to chloromethyl benzoic acid chlorides, and in 15 ℃ of reaction 24h, product obtains the chlorination elastin through thorough washing and drying.
(2) 4g chlorination elastin and 115.78g Thiocarb are in 15 ℃ of reaction 24h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) under the He protection, add 60mL methacrylic acid-beta-hydroxy ethyl ester, 240mL dimethyl formamide and 3g macromole sulfo-iniferter agent; reaction flask is put into 400W ultraviolet lamp reaction box; in 50 ℃ of reaction 10h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 5
(1) 5g is without the swollen elastin, and the triethylamine of 40g, 74.75g are to chloromethyl benzoic acid chlorides, and in 25 ℃ of reaction 20h, product obtains the chlorination elastin through thorough washing and drying.
(2) 4g chlorination elastin and 115.78g Thiocarb are in 35 ℃ of reaction 10h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) at N
2Protection adds 60mL methacrylic acid-beta-hydroxy ethyl ester, 120mL dimethyl sulfoxide (DMSO) and 3g macromole sulfo-iniferter agent down; reaction flask is put into 400W ultraviolet lamp reaction box; in 15 ℃ of reaction 85h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 6
(1) earlier 4g elastin and 4g dimethyl sulfoxide (DMSO) are mixed, swelling 24h, then with the triethylamine of the elastin after the swelling, 20g, 57.14g is to chloromethyl benzoic acid chlorides, and in 35 ℃ of reaction 12h, product obtains the chlorination elastin through thorough washing and drying.
(2) 2.5g chlorination elastin and 44.53g Thiocarb are in 25 ℃ of reaction 18h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) at N
2Protection adds 50mL methacrylic acid-beta-hydroxy ethyl ester, 100mL anhydrous methanol and 1.50g macromole sulfo-iniferter agent down; reaction flask is put into 300W ultraviolet lamp reaction box; in 40 ℃ of reaction 48h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 7
(1) earlier 3g elastin and 150g dimethyl sulfoxide (DMSO) are mixed, swelling 20h is then with the triethylamine of the elastin after the swelling, 1.59g, 2.03g to chloromethyl benzoic acid chlorides, in 20 ℃ of reaction 15h, product obtains the chlorination elastin through thorough washing and drying.
(2) 1.5g chlorination elastin and 2.37g Thiocarb are in 20 ℃ of reaction 15h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) under the Ar protection, add 12mL methacrylic acid-beta-hydroxy ethyl ester, 60mL dimethyl formamide and 0.50g macromole sulfo-iniferter agent; reaction flask is put into 250W ultraviolet lamp reaction box; in 20 ℃ of reaction 15h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
(1) earlier 3g elastin and 75g dimethyl sulfoxide (DMSO) are mixed, swelling 10h is then with the triethylamine of the elastin after the swelling, 1.06g, 2.03g to chloromethyl benzoic acid chlorides, in 20 ℃ of reaction 15h, product obtains the chlorination elastin through thorough washing and drying.
(2) 1.5g chlorination elastin and 3.03g Thiocarb are in 20 ℃ of reaction 15h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) under the Ar protection, add 12mL methacrylic acid-beta-hydroxy ethyl ester, 60mL dimethyl formamide and 0.50g macromole sulfo-iniferter agent; reaction flask is put into 250W ultraviolet lamp reaction box; in 20 ℃ of reaction 15h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Embodiment 9
(1) earlier 3g elastin and 75g dimethyl sulfoxide (DMSO) are mixed, swelling 15h is then with the triethylamine of the elastin after the swelling, 1.06g, 2.03g to chloromethyl benzoic acid chlorides, in 20 ℃ of reaction 15h, product obtains the chlorination elastin through thorough washing and drying.
(2) 1.5g chlorination elastin and 3.03g Thiocarb are in 20 ℃ of reaction 15h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) 0.50g macromole sulfo-iniferter agent and 25g dimethyl sulfoxide (DMSO) are mixed swelling 10h; under the Ar protection, add 12mL methacrylic acid-beta-hydroxy ethyl ester, 60mL dimethyl formamide and 0.50g then through swollen macromole sulfo-iniferter agent; reaction flask is put into 250W ultraviolet lamp reaction box; in 20 ℃ of reaction 15h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.Swelling, the mass ratio of dimethyl sulfoxide (DMSO) and macromole iniferter agent is 1～50, swelling time is 10～24h.
(1) earlier 4g elastin and 4g dimethyl sulfoxide (DMSO) are mixed, swelling 24h, then with the triethylamine of the elastin after the swelling, 20g, 57.14g is to chloromethyl benzoic acid chlorides, and in 35 ℃ of reaction 12h, product obtains the chlorination elastin through thorough washing and drying.
(2) 2.5g chlorination elastin and 44.53g Thiocarb are in 25 ℃ of reaction 18h, and product obtains vulcanizing elastin, i.e. macromole sulfo-iniferter agent through thorough washing and drying.
(3) 1.50g macromole sulfo-iniferter agent and 1.5g dimethyl sulfoxide (DMSO) are mixed swelling 24h, then at N
2Protection adds 50mL methacrylic acid-beta-hydroxy ethyl ester, 100mL anhydrous methanol and 1.50g down through swollen macromole sulfo-iniferter agent; reaction flask is put into 300W ultraviolet lamp reaction box; in 40 ℃ of reaction 48h; product obtains polymethyl acrylic acid-beta-hydroxy ethyl ester modified elastin polymkeric substance through thorough washing and drying.
Claims (5)
1. a method of utilizing the iniferter agent modifying elastin is characterized in that, carries out according to following steps:
(1) chlorination prepares the chlorination elastin to elastin through triethylamine with to chloromethyl benzoic acid chlorides, triethylamine and be 0.8-1.2 wherein to the mol ratio of chloromethyl benzoic acid chlorides, and temperature of reaction is 15～35 ℃, the reaction times is 12～24h;
(2) chlorination elastin and the Thiocarb sulfuration with (1) preparation prepares macromole sulfo-iniferter agent, wherein the mol ratio to chloromethyl benzoic acid chlorides in Thiocarb and the step (1) is 1.3～0.8, temperature of reaction is 15～35 ℃, and the reaction times is 10～24h;
(3) be initiator with macromole sulfo-iniferter agent; under protection of inert gas and anhydrous condition; add methacrylic acid-beta-hydroxy ethyl ester and solvent; cause its polymerization on elastin by UV-irradiation again; wherein the volume ratio of solvent and methacrylic acid-beta-hydroxy ethyl ester is 1:1～5:1; temperature of reaction is 15～50 ℃, and the reaction times is 10～96h.
2. a kind of method of utilizing the iniferter agent modifying elastin according to claim 1, it is characterized in that, described elastin passes through the swelling of dimethyl sulfoxide (DMSO) in advance, and the mass ratio of dimethyl sulfoxide (DMSO) and elastin is 1～50, and swelling time is 10～24h.
3. a kind of method of utilizing the iniferter agent modifying elastin according to claim 1, it is characterized in that, described macromole iniferter agent passes through the swelling of dimethyl sulfoxide (DMSO) in advance, the mass ratio of dimethyl sulfoxide (DMSO) and macromole iniferter agent is 1～50, and swelling time is 10～24h.
4. a kind of method of utilizing the iniferter agent modifying elastin according to claim 1 is characterized in that described rare gas element is any one in nitrogen, helium and the argon gas.
5. a kind of method of utilizing the iniferter agent modifying elastin according to claim 1 is characterized in that, the solvent that adopts in the described step (3) is any one in anhydrous methanol, dimethyl sulfoxide (DMSO) and the dimethyl formamide.
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| CNB2007100565079A CN100532393C (en) | 2007-01-23 | 2007-01-23 | Method of modifying elastin by initiation transition termination agent |
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| CNB2007100565079A CN100532393C (en) | 2007-01-23 | 2007-01-23 | Method of modifying elastin by initiation transition termination agent |
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| CN100532393C true CN100532393C (en) | 2009-08-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186718B (en) * | 2007-11-22 | 2010-07-14 | 天津大学 | Method for modifying elastin by utilizing layer assembling technique and product thereof |
| CN102250045A (en) * | 2010-05-21 | 2011-11-23 | 复旦大学附属华山医院 | Mycobacterium tuberculosis resisting compounds, and applications thereof |
| CN104710644B (en) * | 2015-03-04 | 2017-09-22 | 中国科学院长春应用化学研究所 | A kind of method that antimicrobial surface is prepared on medical macromolecular materials surface |
| CN105670000B (en) * | 2016-03-02 | 2018-02-23 | 唐爱兰 | A kind of method for preparing hydrophobic protein |
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