Click-chemistry compatible structures, click-chemistry functionalized structures, and materials and methods for making the same

Patent metadata

Field	Value
Publication number	US-2018059541-A1
Application number	US-201615253654-A
Country	US
Kind code	A1
Filing date	Aug 31, 2016
Priority date	Aug 31, 2016
Publication date	Mar 1, 2018
Grant date	—

Abstract

According to various embodiments, systems, methods, and computer program products for click-chemistry compatible structures, additive manufacturing resins for forming the same, and method of formation of such structures and resins, as well as techniques for functionalizing click-chemistry compatible structures are disclosed. The inventive structures generally include a plurality of photo polymerized molecules structurally arranged according to a three-dimensional pattern, while surfaces of the structure are functionalized with one or more click-chemistry compatible molecules each having one or more click-chemistry compatible functional groups. The structures may be formed from single- or dual-component resins, each having unique synthetic pathways. The resulting structures may be functionalized for utility in a wide range of applications by leveraging click chemistry to further functionalize the structure with organic additives also compatible with click-chemistry reaction schemes.

First claim

What is claimed is:

1 . A click-chemistry compatible structure, comprising:
a plurality of photo polymerized molecules structurally arranged according to a three-dimensional pattern; and wherein surfaces of the structure are functionalized with one or more click-chemistry compatible molecules each having one or more click-chemistry compatible functional groups.

2 . The structure as recited in claim 1 , wherein the click-chemistry compatible functional groups are configured to engage in a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction.

3 . The structure as recited in claim 1 , wherein the click-chemistry compatible functional groups each independently comprise either a terminal alkyne group or a terminal azide group.

4 . The structure as recited in claim 1 , wherein the photo polymerized molecules each independently comprise one or more photo polymerized moieties; and
wherein the photo polymerized moieties are characterized by formation from polymerizing precursor compounds having one or more photo polymerizable groups selected from: acrylates, epoxies, and thiol-enes.

5 . The structure as recited in claim 1 , wherein at least some of the click-chemistry compatible molecules are functionalized with one or more organic additives selected from a group consisting of:
an antibiotic; an antibacterial compound; silica dioxide nanoparticles; a pharmacophore; one or more hydrophobic moieties; and one or more hydrophilic moieties.

6 . The structure as recited in claim 1 , wherein at least some of the click-chemistry compatible functional groups are functionalized to form a self-assembled monolayer (SAM).

7 . The structure as recited in claim 1 , wherein the structure is porous.

8 . The structure as recited in claim 1 , wherein the structure is characterized by features having a size in a range from several hundred nanometers to several hundred microns.

9 . A method of forming the structure as recited in claim 1 , the method comprising:
exposing, according to the three-dimensional pattern, portions of an additive manufacturing resin to a wavelength of light configured to cause a photo polymerizable compound in the additive manufacturing resin to polymerize into a solid layer of the structure; and wherein the additive manufacturing resin comprises at least one compound having a click-chemistry compatible functional group.

10 . The method as recited in claim 9 , wherein the portions of the additive manufacturing resin exposed to the wavelength of light are defined according to a predetermined mask.

11 . The method as recited in claim 9 , comprising iteratively repeating the following operations to form a plurality of layers of the click-chemistry compatible structure according to a predetermined pattern:
submerging the solid layer of the structure in the additive manufacturing resin; and exposing either the portions of the additive manufacturing resin or other portions of the additive manufacturing resin to the wavelength of light to form a second solid layer of the structure.

12 . A method of functionalizing the structure as recited in claim 1 , the method comprising:
reacting the structure with an organic additive; wherein the organic additive comprises one or more click-chemistry compatible functional groups other than the click-chemistry compatible functional groups of the click-chemistry compatible molecules functionalized on the surfaces of the structure; and wherein the click-chemistry compatible molecules functionalized on the surfaces of the structure are structurally configured to react with the one or more click-chemistry compatible functional groups of the organic additive and thereby attach the organic additive to the structure via the click-chemistry compatible molecules functionalized on the surfaces of the structure.

13 . The method as recited in claim 12 , wherein the click-chemistry compatible functional groups of the click-chemistry compatible molecules functionalized on the surfaces of the structure are each independently selected from a group consisting of: a terminal alkyne and a terminal azide.

14 . The method as recited in claim 13 , wherein the click-chemistry compatible functional groups of the organic additive are each independently selected from the group consisting of: the terminal alkyne and the terminal azide.

15 . The method as recited in claim 12 , wherein the reacting comprises a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction.

16 . The method as recited in claim 12 , wherein the organic additive is selected from a group consisting of:
an antibiotic; an antibacterial compound; silica dioxide nanoparticles; a pharmacophore; one or more hydrophobic moieties; and one or more hydrophilic moieties.

17 . The method as recited in claim 12 , the reacting comprising functionalizing at least some of the functional groups functionalized on the surfaces of the structure to form a self-assembled monolayer (SAM).

18 . An additive manufacturing resin suitable for fabricating a click-chemistry compatible structure, the resin comprising a click-chemistry compatible oligomer, wherein the click-chemistry compatible oligomer further comprises one or more photo polymerizable moieties.

19 . The resin as recited in claim 18 , the click-chemistry compatible oligomer comprising a terminal alkyne group or a terminal azide group.

20 . The resin as recited in claim 18 , the photo polymerizable moieties each being independently selected from a group consisting of: acrylates, epoxides, and thiol-enes.

21 . A method of forming an additive manufacturing resin suitable for fabricating a click-chemistry compatible structure, the method comprising:
reacting a compound comprising a terminal alkyne group or a terminal azide group to form a photo polymerizable oligomer precursor, the precursor comprising the terminal alkyne group or the terminal azide group; and reacting the photo polymerizable oligomer precursor with a compound comprising a photo polymerizable group to form the additive manufacturing resin.

22 . The method as recited in claim 21 , wherein the compound comprising the photo polymerizable group is an R-substituted acryloyl halide reagent.

23 . The method as recited in claim 21 , wherein reacting the compound comprising the terminal alkyne group or the terminal azide group to form the precursor is performed in the presence of an azole and an amine.

24 . The method as recited in claim 21 , wherein reacting the precursor with the compound comprising the photo polymerizable group is performed in the presence of a base.

Assignees

• L Livermore Nat Security Llc

Inventors

• Campbell Patrick
• Duoss Eric
• Oakdale James

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• A01N25/10

  Macromolecular compounds · CPC title

• G03F7/008

  Azides (G03F7/075 takes precedence) · CPC title

• A61K47/48176

  Human Necessities · mapped topic

• G03F7/0037 Primary

  Production of three-dimensional images · CPC title