Polyalliin and preparation method thereof

Abstract

The invention discloses polyalliin and a method for synthesizing polyalliin through selective oxidation of polydeoxy alliin. According to the invention, the homopolymer of polyalliin or the block copolymer of polyalliin and polyethylene glycol is synthesized by selectively oxidizing the homopolymer of polydeoxy alliin or the block copolymer of polydeoxy alliin and polyethylene glycol for the first time. The oxidation condition is mild, and the polydeoxyalliin can be selectively oxidized into polyalliin in hexafluoroisopropanol. The invention provides a new path for synthesizing polyalliin, and has a huge application prospect in the field of biological materials.

Description

technical field

[0001] The invention belongs to the field of macromolecules, and in particular relates to a polyaliin and a method for synthesizing polyaliin through the polymerization of polydeoxyalliin after polymerization. Background technique

[0002] Polyamino acids have secondary structures similar to natural proteins, and are polymers with excellent biocompatibility and degradability, which are widely used in drug delivery, bioimaging, antibacterial and other fields. N-carboxyanhydride (NCA) and N-phenoxycarbonylα-amino acids (NPC) are two important methods for synthesizing polyamino acids.

[0003] Deoxyaliin (also known as S-allyl cysteine) and alliin (also known as S-allyl cysteine ​​sulfoxide) are sulfur-containing amino acids unique to garlic, which have anti-tumor, Antibacterial and antivirus, scavenging free radicals and other functions (J.Agr.FoodChem., 2015, 63, 10778-10784). In previous studies, the edible and medicinal value of alliin was focused on small...

Examples

Embodiment 1

[0044] (1) 2.8130g (10.0mmol) of deoxyalliin-NPC was added to the reaction flask, dissolved with 7.4mL DMSO, and then the DMSO solution (0.1270mol / L, 0.3303mmol) of 2.6mL neopentylamine was added, and the The molar ratio of amino acid-NPC monomer to neopentylamine was 30:1, sealed and placed in an oil bath at 80 °C for 2 days. After the reaction, the original solution was directly poured into ether for precipitation, centrifugation, and the supernatant was discarded. , the obtained polymer was vacuum-dried for 1 day to obtain neopentylamine-terminated polydeoxyalliin with a yield of 71% and a number-average molecular weight of 3.7kDa.

[0045] (2) 0.0603 g of polydeoxyalliin (end-capped with neopentylamine, number-average molecular weight of 3.7kDa) (containing 0.4195 mmol of repeating units of deoxyalliin), dissolved in 6 mL of hexafluoroisopropanol, and added with 85 μL (30 wt% ) of H 2 O 2 (0.8485mmol), H 2 O 2The molar ratio with the repeating unit of polydeoxyalliin i...

Embodiment 2

[0047] Polydeoxyalliin (n-hexylamine-terminated) was prepared according to step (1) of Example 1, except that neopentylamine was replaced with n-hexylamine.

[0048] Polydeoxyalliin (n-hexylamine end-capped, number-average molecular weight is 4.8kDa) is a raw material, and other oxidation conditions are the same as in Example 1, except that H 2 O 2 The molar ratio with the repeating unit of polydeoxyalliin is 5:1, and the reaction time is 3h. The yield of the obtained product polyaliin was 96%.

Embodiment 3

[0050] Other conditions are the same as in Example 1, the difference is that the number-average molecular weight of polydeoxyalliin is 2.5kDa, and the H 2 O 2 The ratio of the repeating unit to polydeoxyalliin is 8:1, the reaction temperature is 10° C., the reaction time is 3h, and the yield of the obtained product polyaliin is 94%.

technical field

[0001] The invention belongs to the field of macromolecules, and in particular relates to a polyaliin and a method for synthesizing polyaliin through the polymerization of polydeoxyalliin after polymerization. Background technique

[0002] Polyamino acids have secondary structures similar to natural proteins, and are polymers with excellent biocompatibility and degradability, which are widely used in drug delivery, bioimaging, antibacterial and other fields. N-carboxyanhydride (NCA) and N-phenoxycarbonylα-amino acids (NPC) are two important methods for synthesizing polyamino acids.

[0003] Deoxyaliin (also known as S-allyl cysteine) and alliin (also known as S-allyl cysteine ​​sulfoxide) are sulfur-containing amino acids unique to garlic, which have anti-tumor, Antibacterial and antivirus, scavenging free radicals and other functions (J.Agr.FoodChem., 2015, 63, 10778-10784). In previous studies, the edible and medicinal value of alliin was focused on small...

Examples

Embodiment 1

[0044] (1) 2.8130g (10.0mmol) of deoxyalliin-NPC was added to the reaction flask, dissolved with 7.4mL DMSO, and then the DMSO solution (0.1270mol / L, 0.3303mmol) of 2.6mL neopentylamine was added, and the The molar ratio of amino acid-NPC monomer to neopentylamine was 30:1, sealed and placed in an oil bath at 80 °C for 2 days. After the reaction, the original solution was directly poured into ether for precipitation, centrifugation, and the supernatant was discarded. , the obtained polymer was vacuum-dried for 1 day to obtain neopentylamine-terminated polydeoxyalliin with a yield of 71% and a number-average molecular weight of 3.7kDa.

[0045] (2) 0.0603 g of polydeoxyalliin (end-capped with neopentylamine, number-average molecular weight of 3.7kDa) (containing 0.4195 mmol of repeating units of deoxyalliin), dissolved in 6 mL of hexafluoroisopropanol, and added with 85 μL (30 wt% ) of H 2 O 2 (0.8485mmol), H 2 O 2The molar ratio with the repeating unit of polydeoxyalliin i...

Embodiment 2

[0047] Polydeoxyalliin (n-hexylamine-terminated) was prepared according to step (1) of Example 1, except that neopentylamine was replaced with n-hexylamine.

[0048] Polydeoxyalliin (n-hexylamine end-capped, number-average molecular weight is 4.8kDa) is a raw material, and other oxidation conditions are the same as in Example 1, except that H 2 O 2 The molar ratio with the repeating unit of polydeoxyalliin is 5:1, and the reaction time is 3h. The yield of the obtained product polyaliin was 96%.

Embodiment 3

[0050] Other conditions are the same as in Example 1, the difference is that the number-average molecular weight of polydeoxyalliin is 2.5kDa, and the H 2 O 2 The ratio of the repeating unit to polydeoxyalliin is 8:1, the reaction temperature is 10° C., the reaction time is 3h, and the yield of the obtained product polyaliin is 94%.

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