Hydrophobic silk fibroin compositions and methods of making the same

Patent metadata

Field	Value
Publication number	US-12403176-B2
Application number	US-202117907404-A
Country	US
Kind code	B2
Filing date	Mar 25, 2021
Priority date	Mar 25, 2020
Publication date	Sep 2, 2025
Grant date	Sep 2, 2025

Abstract

The present disclosure relates to compositions, methods of making, and methods of using a modified silk-based composition having a selectively tunable hydrophobicity. The provided compositions include silk fibroin having a haloalkyl substituent. The haloalkyl substituent is coupled to an amino acid of the silk fibroin though a linking agent.

First claim

The invention claimed is:

1. A composition comprising:
a modified silk comprising one or more haloalkyl substituents; and
one or more linking agents, wherein each of the one or more linking agents couples a respective one of the one or more haloalkyl substituents to a respective amino acid of the modified silk.

2. The composition of claim 1 , wherein the one or more haloalkyl substituents each comprises one or more halogen substituent selected from the group consisting of fluoro, bromo, chloro, and iodo.

3. The composition of claim 1 , wherein the one or more haloalkyl substituents each comprises a structure of —CxH 0-2 R 0-3 , wherein:
R is a halo substituent selected from the group consisting of fluoro, chloro, bromo, and iodo; and
x ranges from 1 to 20 carbon atoms.

4. The composition of claim 3 , wherein the carbon atoms form a linear chain.

5. The composition of claim 3 , wherein x ranges from 1 to 10 carbon atoms.

6. The composition of claim 1 , wherein the one or more linking agents covalently bonds the respective one of the one or more haloalkyl substituents to the respective amino acid.

7. The composition of claim 1 , wherein each of the one or more linking agents comprises one or more chemical moiety to covalently bond the respective one of the one or more haloalkyl substituents to the respective amino acid.

8. The composition of claim 7 , wherein the one or more chemical moiety includes a reaction product of an amino acid in the modified silk and one or more chemical moiety selected from the group consisting of a sulfonic acid group, a carboxylic acid group, an amine group, a ketone group, an alkyl group, an alkoxy group, a thiol group, a disulfide group, a nitro group, an aromatic group, an ester group, an amide group, and a hydroxyl group.

9. The composition of claim 7 , wherein the one or more linking agents each comprises a diamine.

10. The composition of claim 8 , wherein the one or more linking agents each is covalently bonded to a hydroxyl substituent in the amino acid in the modified silk fibroin, and wherein the one or more linking agents each comprises a structure of —R 1 (CO)(NR 2 R 3 )R 4 (NR 5 R 6 ) X , wherein:
R 1 comprises C 1 -C 6 alkyl;
R 2 comprises a C 1 -C 10 alkyl;
R 3 comprises hydrogen, a C 1 -C 10 alkyl, or an aryl group;
R 4 comprises a C 1 -C 10 alkyl;
R 5 comprises a C 1 -C 10 alkyl;
R 6 comprises hydrogen or a C 1 -C 10 alkyl; and
X comprises the haloalkyl substituent.

11. The composition of claim 1 , the modified silk having one or more of the following properties:
(i) a water contact angle greater than 50°;
(ii) a halo content greater than 20 atomic percentage (at. %) as determined by X-ray photoelectron spectroscopy (XPS); and
(iii) a primary amine content less than 0.7 mM.

12. The composition of claim 1 , wherein the modified silk has a water contact angle ranging from 50° to 150°.

13. The composition of claim 1 , wherein the modified silk has a halo content ranging from 20 atomic percentage (at. %) to 50 at. % as determined by XPS.

14. The composition of claim 1 , wherein the modified silk has a primary amine content ranging from 0.01 mM to 0.7 mM.

15. A method for making a modified silk having a predetermined hydrophobicity, the method comprising:
a) designing one or more haloalkyl substituents and selecting a substitution pattern of the one or more haloalkyl substituents in order to produce the predetermined hydrophobicity; and
b) making the modified silk having the substitution pattern of the one or more haloalkyl substituents.

16. A method for making a modified silk having a predetermined hydrophobicity, the method comprising:
a) selecting a substitution pattern of one or more haloalkyl substituents in order to produce the predetermined hydrophobicity; and
b) making the modified silk having the substitution pattern of the one or more haloalkyl substituents.

17. The composition of claim 1 , wherein the modified silk has all of the following properties:
(i) a water contact angle greater than 50°;
(ii) a halo content greater than 20 at. % as determined by X-ray photoelectron spectroscopy (XPS); and
(iii) a primary amine content less than 0.7 mM.

18. The composition of claim 1 , wherein the modified silk is a silk fibroin solution.

19. The composition of claim 1 , wherein the modified silk is a solid form.

20. The composition of claim 1 , wherein the modified silk is a modified silk fibroin.

Assignees

• Tufts College

Inventors

• Kaplan David L
• Kumar Krishna
• Montanari Vittorio
• Hawker Morgan
• Fountain Julia
• Wu Junqi

Classifications

• C08L89/00

  Compositions of proteins; Compositions of derivatives thereof (foodstuff preparations A23J3/00) · CPC title

• C08H1/00 Primary

  Macromolecular products derived from proteins (food proteins A23; glue, gelatine C09H) · CPC title

• A61K38/1767 Primary

  from invertebrates · CPC title