Biopolymer-based inks and use thereof

Patent metadata

Field	Value
Publication number	US-10035920-B2
Application number	US-201314647470-A
Country	US
Kind code	B2
Filing date	Nov 27, 2013
Priority date	Nov 27, 2012
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

The present application discloses biopolymer-based ink formulations that are useful for inkjet printing and other applications. Related methods are also disclosed.

First claim

What is claimed is:

1. A printable silk ink, comprising:
an aqueous silk fibroin solution, substantially free of an organic solvent having
a molecular weight of about 3.5 kD to about 350 kD; and
a concentration of silk fibroin in a range of about 0.3 (wt/vol) % to at least about 10 (wt/vol) %;

wherein when it is printed to a substrate, a droplet volume of about 0.1 pL to about 5 nL of the aqueous silk fibroin solution is characterized by
a viscosity of about 1 centipoise to about 20 centipoise when viscosity is measured at room temperature; and
a surface tension of about 15 dynes/cm and about 50 dynes/cm when measured at room temperature.

2. The printable silk ink of claim 1 , having a pH value between 5-9.

3. The printable silk ink of claim 1 , further comprising a viscosity-modifying agent, a surfactant, or combination thereof.

4. The printable silk ink of claim 3 , wherein the viscosity-modifying agent is present at about 5-30 wt % of the aqueous unit composition.

5. The printable silk ink of claim 3 , wherein the surfactant is present at about 0.1-10 wt % of the aqueous unit composition.

6. The printable silk ink of claim 1 , further comprising an additive.

7. The printable silk ink of claim 1 , further comprising a structural protein selected from the group consisting of: fibroins, actins, collagens, catenins, claudins, coilins, elastins, elaunins, extensins, fibrillins, lamins, laminins, keratins, tublins, viral structural proteins, zein proteins and any combinations thereof.

8. The printable silk ink of claim 7 , wherein the structural protein is a low molecular weight structural protein selected from the group consisting of: low molecular weight actins, low molecular weight collagens, low molecular weight catenins, low molecular weight claudins, low molecular weight coilins, low molecular weight elastins, low molecular weight elaunins, low molecular weight extensins, low molecular weight fibrillins, low molecular weight lamins, low molecular weight laminins, low molecular weight keratins, low molecular weight tublins, low molecular weight viral structural proteins, and any combinations thereof.

9. The printable silk ink of claim 1 , wherein the printable silk ink is substantially free of silk fibroin having a molecular weight over 200 kDa.

10. The printable silk ink of claim 1 , wherein the droplet unit printed to the substrate, has a gel, semi-solid, or solid form and a diameter measured at its smallest cross-section of about 0.1 μm to about 250 μm.

11. The printable silk ink of claim 1 , wherein the aqueous silk fibroin solution is characterized such that when it is printed to a substrate, a gel, semi-solid, or solid unit forms having a resolution about 50 dpi to about 20,000 dpi.

12. A printed array comprising:
a substrate; and
a plurality of dot units,
wherein the plurality of dot units is in a gel form, a semi-solid form or a solid form,

wherein
dot units of the plurality of dot units were formed, jetted, printed and/or deposited from the printable silk ink of claim 1 upon the substrate, such that they form in a predetermined spatial pattern on a surface of the substrate.

13. The printed array of claim 12 , wherein the printed array has a resolution of between about 50-20,000 dpi.

14. The printed array of claim 12 , wherein the printed array forms substantially a two-dimensional (2D) structure having a predetermined spatial pattern of substantially even thickness.

15. The printed array of claim 12 , wherein the printed array forms substantially a three-dimensional (3D) structure having a predetermined spatial pattern of varying thickness across the predetermined spatial pattern.

16. The printed array of claim 12 , wherein the dot units of the plurality of dot units are about 0.1 μm to about 250 μm in diameter.

17. The printed array of claim 12 , wherein the dot units of the plurality of dot units have a volume of about 0.1 pL to about 5 nL.

18. A method for printing a structure, the method comprising steps of:
providing the printable silk ink of claim 1
depositing the printable silk ink through a nozzle in liquid droplet units onto a substrate in a predetermined spatial pattern,
wherein each of the liquid droplet units has a volume of about 0.1 pL to about 5 nL.

19. The method of claim 18 , wherein the depositing step is or comprises a jetting velocity of about 7 m/sec to about 9 m/sec.

20. The method of claim 18 , further comprising a step of piezoelectrically actuating the nozzle.

21. The method of claim 18 , wherein the nozzle has a diameter in a range of 10 and 50 μm.

22. The method of claim 18 , further comprising a step of applying at least one of (a) heat and (b) ultraviolet irradiation to the aqueous silk ink after depositing the aqueous silk ink onto the substrate.

23. The method of claim 18 , wherein the aqueous silk ink further comprises a dopant.

24. The method of claim 23 , wherein the dopant comprises a nanoparticle.

Assignees

• Univ Tufts

Inventors

• Omenetto Fiorenzo
• Kaplan David
• Tao Hu
• Marelli Benedetto
• Yang Miaomiao

Classifications

• C09D11/04

  based on proteins · CPC title

• C08K5/1535

  Five-membered rings · CPC title

• C09D11/30 Primary

  Inkjet printing inks · CPC title

• C09D11/38

  characterised by non-macromolecular additives other than solvents, pigments or dyes · CPC title

• A61K47/42

  Proteins; Polypeptides; Degradation products thereof; Derivatives thereof, e.g. albumin, gelatin or zein (oligopeptides having up to five amino acids {A61K47/183}; polyamino acids A61K47/34) · CPC title