Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer

A technology of cysteine ​​hydrochloride and cysteine, applied in the field of polymer materials, can solve problems such as weak physical and mechanical properties, complicated preparation process, and strict conditions

Active Publication Date: 2013-09-04
SUZHOU UNIV
View PDF2 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007]In the traditional technology, functional polyamino acids need to be prepared by protection and deprotection methods, the preparation process is complicated and the conditions are strict, which limits the α-amino acid-N-carboxyl Industrial Production of Polyamino Acid by Internal Anhydride Polymerization
Chinese patent application CN201210424521.0 discloses a polyamino acid copolymer with a propargyl group and its preparation method and application. In the process of preparing the polymer, the process of protection and deprotection is eliminated. The polyamino acid copolymer containing a propargyl group Amino acid materials are directly bonded to some bioactive molecules through click chemistry to modify functionalized polymers with different functional groups in their side chains; however, the click chemistry involved in the above invention requires the use of toxic metallic copper catalysts
For example, Yang et al. prepared block copolymers of lysine and leucine to prepare polyamino acid hydrogels through self-assembly. This hydrogel is used in the nervous system to better integrate with brain tissue and attract blood vessels and Growth of glial cells (see: Yang CY, Song B, Ao Y, et al. Biomaterials, 2009, 30, 2881-2898); Jeong et al. with polyethylene glycol-poly(alanine-phenylalanine) Copolymers have prepared thermosensitive hydrogels and achieved controlled release of insulin (see: Jeong Y, Joo MK, Bahk KH, et al. J Control Release 2009, 137, 25-30.); however, the physical properties of these products Relatively weak mechanical properties and poor stability

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer
  • Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer
  • Vinyl sulfone-substituted cysteine-N-carboxyanhydride, polymer thereof and application of polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0073] Example 1 Synthesis of vinylsulfone substituted cysteine ​​N-carboxyl internal anhydride (VSCys-NCA).

[0074] (1) Dissolve 4.45 g (25 mmol) of cysteine ​​hydrochloride in 80 ml of methanol, drop by drop into the methanol solution of divinyl sulfone (12.55 ml, 125 mmol); stir in an oil bath at 50°C and react for 100 hours The resulting solution was concentrated under reduced pressure and precipitated with ethyl acetate, filtered, and dried to obtain 6.58 g of white solid powder (vinylsulfone substituted L-cysteine, VSCys), with a yield of 94.4%.

[0075] (2) Weigh VSCys (3.75 g, 13.6 mmol) in a dry three-necked round bottom flask, add anhydrous THF (100 ml), then add pinene (α-pinene) (5.0 ml, 31.5 mmol), The reaction system was placed in an oil bath at 50°C for 30 minutes, and then solid triphosgene (2.02 g, 6.8 mmol) was added; the reaction temperature was increased to 70°C, and after 1 hour of reaction, the crude product of VSCys-NCA was obtained by precipitation with pet...

Embodiment 2

[0077] Example 2: Synthesis of vinylsulfone substituted cysteine ​​N-carboxyl internal anhydride (VSCys-NCA)

[0078] (1) Dissolve 4.45 g (25 mmol) of cysteine ​​hydrochloride in 80 ml of methanol, drop by drop into the methanol solution of divinyl sulfone (50.2 ml, 500 mmol); stir and react in an oil bath at 40°C for 60 hours The resulting solution was concentrated under reduced pressure and precipitated with ethyl acetate, filtered, and dried to obtain 6.97 g of white solid powder (vinylsulfone substituted L-cysteine, VSCys) with a yield of 95.7%.

[0079] (2) Weigh VSCys (3.75 g, 13.6 mmol) in a dry three-necked round bottom flask, add anhydrous THF (100 ml), then add pinene (α-pinene) (6.5 ml, 40.8 mmol), The reaction system was placed in an oil bath at 50°C for 30 minutes, and then solid triphosgene (2.02 g, 13.6 mmol) was added; the reaction temperature was increased to 70°C, and after 1 hour of reaction, the crude product of VSCys-NCA was obtained by precipitation with petro...

Embodiment 3

[0080] Example 3 Preparation of polyamino acid random copolymer by copolymerization of VSCys-NCA and other α-amino acid-N-carboxyl internal acid anhydride

[0081] According to the ratio of each component in Table 1, dissolve other α-amino acid-N-carboxyl internal acid anhydride and VSCys-NCA solid in anhydrous DMF in a glove box; add the small molecule initiator propylene trimethylsilazane The reaction of alkane in DMF solution was placed in an oil bath at 40°C for 48 h under anhydrous conditions, and the reaction was terminated with two drops of acetic acid; the polymer solution was precipitated in glacial ether, filtered and vacuum dried at room temperature to obtain the product polyamino acid.

[0082] Attached figure 2 Schematic diagram of the above random copolymerization reaction. The reaction was monitored by infrared: After the reaction was carried out for 48 h, the carbonyl absorption peak of the two monomer anhydrides in the infrared spectrum was 1869 cm -1 (VS-Cys NCA)...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a vinyl sulfone-substituted cysteine-N-carboxyanhydride, a polymer thereof and application of the polymer. Preparation comprises the following steps: preparing a vinyl sulfone-substituted cysteine-N-carboxyanhydride monomer; preparing a vinyl sulfone-modified polymer from the monomer; and finally, performing side chain modification on the polymer to prepare a functional polymer, a functional polymer film and injectable hydrogel. According to the invention, vinyl sulfone functional groups are not influenced by the preparation of the -N-carboxyanhydride monomer and the polymer, so that steps of protection and deprotection are not needed in the whole preparation process of the polymer; the prepared vinyl sulfone-modified polymer can be easily prepared into the functional polymer, the functional polymer film and the injectable hydrogel through Michael addition reaction at room temperature without the presence of a catalyst; and these materials can be used for preparation of tissue engineering scaffolds and medicinal slow release carriers.

Description

technical field [0001] The invention relates to a biodegradable material modified by vinyl sulfone, in particular to the synthesis of a vinyl sulfone substituted cysteine-N-carboxyl internal acid anhydride, the polymer material obtained by its polymerization and its application. Background technique [0002] Biodegradable polymers have good biocompatibility and can be degraded in vivo, and the degradation products can be absorbed by the human body or excreted through the normal physiological channels of the human body. Biodegradable polymers have been widely used in various fields of biomedicine, such as surgical sutures, bone fixation devices, bioengineering scaffold materials, and drug controlled release carriers. [0003] Synthetic biodegradable polymers have attracted attention due to their low immunogenicity, good degradation and mechanical properties, and controllable properties. Synthetic biodegradable polymers mainly include aliphatic polyesters, polycarbonates, pol...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07D263/44C08G69/42C08G69/48C08J7/12C08J5/18C08J3/075
Inventor 邓超孟凤华程茹钟志远
Owner SUZHOU UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com