Method to control the biodegradation rates of polymer structures

• US 9,066,996 B1
• Filed: 01/15/2010
• Issued: 06/30/2015
• Est. Priority Date: 10/13/2006
• Status: Active Grant

• Current Assignee: HRL Laboratories LLC (The Boeing Co.)
• Original Assignee: HRL Laboratories LLC (The Boeing Co.)
• Inventors: Zhou, Chaoyin, Jacobsen, Alan J.
• Primary Examiner(s): YAMASAKI, ROBERT J
• Application Number:
  US12/687,875
• Time in Patent Office: 1,992 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/30 Inorganic materials
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: C12M 25/14 Scaffolds; Matrices in general C12N5/0068

Abstract

Methods to selectively control the bio-degradation rates of biologically compatible microstructures and methods to control the bio-degradation rates of three-dimensional biological scaffolds, such as ordered open-cellular polymer structures used as biological growth templates are disclosed. Medical uses and application of these materials are disclosed.

Claims

1. A method for selectively degrading a three-dimensional biological scaffold, comprising:

providing a three-dimensional biodegradable biological scaffold in an aqueous medium, wherein the scaffold is comprised of a polymer;

subjecting the scaffold to a treatment capable of selectively degrading the polymer, the treatment selected from the group consisting of base, acid, oxidation, heat and combinations thereof, wherein the treatment includes an effective amount of base, acid, oxidant, heat or combinations thereof that is capable of partially degrading the polymer, wherein the effective amount of heat includes temperatures between about 80°

C. to about 250°

C.; and

incubating the scaffold under conditions which create a partially degraded three-dimensional biodegradable biocompatible biological scaffold;

wherein the three-dimensional biodegradable biocompatible biological scaffold is a three-dimensional ordered open-cellular polymer structure which (i) is formed by a plurality of polymer waveguides which interpenetrate each other at a plurality of nodes and (ii) has a micro-truss architecture comprising a repeating pattern of ordered interconnected pores;

wherein the three-dimensional ordered open-cellular polymer structure is made by photopolymerization of a monomer composition, the monomer composition comprising;

a first molecule comprising at least one C═

C double bond or C≡

C triple bond;

a second molecule having the structure R—

X₁—

H, wherein X₁ is one of O, S, or N; and

a photoinitiator.

2. The method of claim 1, wherein the treatment capable of selectively degrading the polymer includes an effective amount of base selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, barium hydroxide, cesium hydroxide, strontium hydroxide, calcium hydroxide, pyridine, ammonia, and mixtures thereof.

3. The method of claim 2, wherein the base is present at a concentration in aqueous solution between about micromolar to about molar level.

4. The method of claim 3, wherein the base is present between about 10 micrograms to about 10 milligrams for every milligram of polymer structure.

5. The method of claim 2, wherein during the incubating step, the conditions under which the biological scaffold is incubated are between about 1 minute to about 1 hour with agitation at room temperature.

6. The method of claim 1, wherein the treatment capable of selectively degrading the polymer includes an effective amount of acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and mixtures thereof.

7. The method of claim 6, wherein the acid is present at a concentration in aqueous solution between about a micromolar to about a molar level.

8. The method of claim 7, wherein the acid is present between about 1 micromole to about 1 mole for every milligram of polymer structure.

9. The method of claim 6, wherein during the incubating step, the conditions under which the biological scaffold is incubated are between about 1 minute to about 1 hour with agitation.

10. The method of claim 6, wherein during the incubating step, the conditions comprise temperatures between about room temperature to about 80°

C.

11. The method of claim 1, wherein the treatment capable of selectively degrading the polymer includes an effective amount of oxidant selected from the group consisting of potassium permanganate, potassium dichromate, ozone, hydrogen peroxide, chlorite, hypochlorite, chlorate, nitric acid, pyridinium chlorochromate, osmium tetraoxide, persulfuric acid or salts, cerium (IV) salts, and mixtures thereof.

12. The method of claim 11, wherein the oxidant is present between about 1 micromole an 1 mole for every milligram of polymer structure.

13. The method of claim 11, wherein during the incubating step, the conditions under which the biological scaffold is incubated are between about 1 minute to about 1 hour with agitation at room temperature.

14. The method of claim 1, wherein the treatment capable of selectively degrading the polymer includes an effective amount of heat.

15. The method as claimed in claim 1, wherein the first molecule comprises at least one functional group selected from the group consisting of ethynyl, vinyl ether, vinyl ester, vinyl amide, vinyl triazine, vinyl isocyanurate, acrylate, methacrylate, diene and triene.

16. The method as claimed in claim 1, wherein the first molecule is selected from the group consisting of pentaerythritol tetraacrylate;

2,4,6-triallyloxy-1,3,5-triazine; and

triallyl-1,3,5-triazine-2,4,6-trione.

17. The method of claim 1, the method further comprising:

sterilizing the partially degraded biodegradable biocompatible biological scaffold; and

inserting the partially degraded biodegradable biocompatible biological scaffold into living tissue.

18. A method for selectively degrading a three-dimensional biodegradable biological scaffold having an ordered open-cellular polymer structure, comprising:

providing a three-dimensional biodegradable biological scaffold having an ordered open-cellular polymer structure made by photopolymerization of monomer composition, the monomer composition comprising a first molecule comprising at least one C═

C double bond or C≡

C triple bond, a second molecule having a structure of R—

X₁—

H, wherein X₁ is one of O, S, or N, and a photoinitiator, wherein the three-dimensional ordered open-cellular polymer structure;

(i) is in an aqueous medium, (ii) is formed by a plurality of self-propagating polymer waveguides which interpenetrate each other at a plurality of nodes, and (iii) has a micro-truss architecture comprising a repeating pattern of ordered interconnected pores;

subjecting the scaffold to a treatment capable of selectively degrading the three-dimensional biological scaffold, the treatment selected from the group consisting of base, acid, oxidation, heat and combinations thereof wherein the treatment includes an effective amount of base, acid, oxidant, heat or combinations thereof being capable of partially degrading the polymer,

wherein the effective amount of base is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, barium hydroxide, cesium hydroxide, strontium hydroxide, calcium hydroxide, pyridine, ammonia, and mixtures thereof,

wherein the effective amount of acid is selected from the a group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and mixtures thereof, and

wherein the effective amount of oxidant is selected from the group consisting of potassium permanganate, potassium dichromate, ozone, hydrogen peroxide, chlorite, hypochlorite, chlorate, nitric acid, pyridinium chlorochromate, osmium tetraoxide, persulfuric acid or salts, cerium (IV) salts, and mixtures thereof, and

wherein the effective amount of heat includes temperatures from about 80°

C. to about 250°

C.; and

incubating the scaffold under conditions sufficient to selectively degrade the polymer to create a partially degraded three-dimensional biodegradable biocompatible biological scaffold.

19. A medical implant device made by a method of selectively degrading a three-dimensional biological scaffold, the method comprising the steps of:

providing a three-dimensional biodegradable biological scaffold in an aqueous medium, wherein the scaffold is a polymer structure;

subjecting the three-dimensional biological polymer scaffold to a treatment capable of selectively degrading the polymer, the treatment selected from the group consisting of base, acid, oxidation, heat and combinations thereof, wherein the treatment includes an effective amount of base, acid, oxidant, heat or combinations thereof that is capable of partially degrading the polymer, wherein the effective amount of heat includes temperatures between about 80°

C. to about 250°

C.; and

incubating the scaffold under conditions which create a partially degraded biodegradable biocompatible biological scaffold,

wherein the three-dimensional biodegradable biocompatible biological scaffold has a three-dimensional ordered open-cellular polymer structure which (i) is formed by a plurality of self-propagating polymer waveguides which interpenetrate each other at a plurality of nodes and (ii) has a micro-truss architecture comprising a repeating pattern of ordered interconnected pores,

wherein the three-dimensional ordered open-cellular polymer structure is made by photopolymerization of a monomer composition, the monomer composition comprising;

a first molecule comprising at least one C═

C double bond or C≡

C triple bond;

a second molecule having a structure of R—

X₁—

H, wherein X₁ is one of O, S, or N; and

a photoinitiator.