Granted Patent B2

US 12,415,939 · App. 15/764,467 · Granted Sep 16, 2025

Inventors: Kollbe B. Ahn (Goleta, CA); Herbert J. Waite (Goleta, CA)

Assignee: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA

C09J4/00A61L24/06A61L27/34C07C57/42C07F9/12C09J5/00H10K10/466H10K10/476A61L2400/12

Abstract

Claims (80)

1. A compound, comprising:

an end group attached to a spacer group, wherein

the spacer group is -L 3 -Q-L 2 -M-L 1 ; and

the end group is E;

wherein the spacer group is selected from the group consisting of alkyl, non-polar, zwitterionic, cationic, anionic, and non-charged polar moiety;

wherein each of L 2 and L 1 is C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein L 3 , when present, is a bond, C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein M comprises a first anionic moiety or first cationic moiety and Q comprises a second anionic moiety or second cationic moiety;

wherein E is selected from the group consisting of acrylate, methacrylate, epoxy, amine, substituted phenyl, unsubstituted phenyl, catechol, alkyl, alkylenyl, cationic, anionic, non-charged polar, and non-polar moiety;

wherein the compound is capable of adhering to at least one of a bone surface, a tooth enamel surface, a silicon surface, a SiO 2 surface, a glass surface, or a metal containing surface such that the spacer group is between the surface and the end group, and

wherein the compound further comprises a catechol group attached to the end group through the spacer group.

2. The compound of claim 1 , wherein E is selected from a group consisting of C 2 -C 6 alkenyl, C 1 -C 6 alkyl, and optionally substituted or unsubstituted phenyl.

3. The compound of claim 2 , wherein the substituted phenyl is an aromatic moiety selected from a group consisting of dihydroxyphenyl, catechol, and di(trifluoromethyl)phenyl.

4. The compound of claim 1 , wherein the end group comprises a polymer.

5. The compound of claim 1 , comprising a surfactant.

6. The compound of claim 1 , wherein M is NRR′ or PO 4− , Q is NRR′ or PO 4− , R is H or C 1 -C5 alkyl, and R′ is H or C 1 -C5 alkyl.

7. The compound of claim 1 , wherein the compound is capable of adhering to at least one of the glass surface, the metal containing surface, or a hydroxyapatite surface.

8. An adhesive system comprising the compound of claim 1 and a monomer:

wherein the monomer is polymerizable in a presence of the end group to form a dental cement or a bone cement attached to the catechol group, the spacer group between the cement and the catechol group.

9. A nano-adhesive and surface primer comprising the compound of claim 1 .

10. A compound, comprising a catechol group attached to an end group E through a spacer group, wherein the catechol group, the end group E and spacer group satisfy Formula:

wherein:

each of L 1 and L 2 is C 2 -C 6 alkyl;

L 3 is a bond or C 2 -C 15 alkyl;

E is selected from a group consisting of C 4 -C 12 alkyl, phenyl, dihydroxyphenyl, catechol, and 3,5-di(trifluoromethyl)phenyl.

11. The compound of claim 10 selected from a group consisting of:

12. At least one of an adhesive or surface primer comprising the compound of claim 10 .

13. A method of using a compound, comprising:

obtaining a compound comprising a catechol group attached to an end group through a spacer group;

providing a first surface comprising at least one of a first oxide containing surface or a metal containing surface;

applying a first layer of the compound onto the first surface, wherein the compound self-assembles by attaching the catechol group onto the first surface;

generating a first secondary surface layer with the end group of the compound;

applying a second layer of the compound onto a second surface comprising at least one of an oxide containing surface or a metal containing surface thereby forming a second secondary surface layer with the end group of the compound; and

affixing the second surface onto the first secondary surface layer.

14. The method of claim 13 , wherein the first surface is an oxide containing surface and the catechol group of the compound forms an H-bond with the oxide containing surface.

15. The method of claim 13 , wherein the first surface is a metal containing surface and the catechol group of the compound forms a chelating-bond with the metal containing surface.

16. The method of claim 13 , wherein the oxide containing surface is selected from the group consisting of mica, silica, kaolin, zirconia, aluminum, copper, chrome, chrome-cobalt, silicon, calcium, aluminum oxide, copper oxide, titanium oxide, zinc oxide, calcium oxide, tin oxide, indium-tin oxide, steal, and hydroxylapatite.

17. The method of claim 13 , wherein the first layer has a thickness between 0.1 to 10 nm.

18. The method of claim 13 , wherein the compound is treated with an oxidizing agent.

19. The method of claim 18 , wherein the oxidizing agent is periodate.

20. The method of claim 13 , wherein the compound is used as a dental/bone adhesive, a surface primer for a dental/medical implant, a surface primer for a polymer composite including dental and bone cement, or for a battery anode/binder, electro circuit, a semiconductor device, a nanosensing device, an organic solar cell, an opto-electronic device, a hetero-junction, or an electron tunneling junction.

21. The method of claim 13 , wherein the end group of the compound of the first secondary surface layer interacts with the end group of the compound of the second secondary surface layer.

22. The method of claim 21 , wherein an interaction between the first secondary surface layer and the second secondary surface layer includes a hydrophobic interaction or π-π stacking.

23. The method of claim 13 , wherein a third and a fourth layer of the compound are applied onto the first secondary surface layer and the second secondary surface layer, wherein the compound self-assembles onto the first secondary surface layer and the second secondary surface layer creating a third and a fourth secondary surface layer with the catechol group of the compound.

24. The method of claim 23 , wherein the catechol group of the third secondary surface layer interacts with the fourth secondary surface layer.

25. The method of claim 24 , wherein an interaction of the third secondary surface layer and the fourth secondary surface layer is crosslinking or H-bonding.

26. The method of claim 13 , wherein the catechol group, the end group and spacer group satisfy Formula (II):

wherein:

each of L 1 and L 2 is C 2 -C 6 alkyl;

L 3 is a bond or C 2 -C 15 alkyl;

E is selected from a group consisting of C 4 -C 12 alkyl, phenyl, dihydroxyphenyl, catechol, and 3,5-di(trifluoromethyl)phenyl, or

the compound satisfies the formula:

Formula (I):

or

wherein:

the catechol group is

the spacer group is -L 3 -Q-L 2 -M-L 1 ; and

the end group is E;

wherein the spacer group is selected from the group consisting of alkyl, non-polar, zwitterionic, cationic, anionic, and non-charged polar moiety;

wherein each of L 2 and L 1 is C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein L 3 , when present, is a bond, C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein M, when present, is —(CO 2 )—, NRR′, —RCOH or PO 4 , wherein Q, when present, is —(CO 2 )—, NRR′, —RCOH or PO 4 , wherein R is H or C 1 -C5 alkyl; wherein R′ is H or C 1 -C5 alkyl; and

wherein E is selected from the group consisting of acrylate, methacrylate, epoxy, amine, substituted phenyl, unsubstituted phenyl, catechol, alkyl, alkylenyl, cationic, anionic, non-charged polar, and non-polar moiety.

27. A composition of matter useful as an adhesive, comprising:

a first layer of compound on a first surface, the compound comprising a catechol group attached to an end group through a spacer group, wherein the catechol group is:

wherein:

the spacer group is -L 3 -Q-L 2 -M-L 1 ; and

the end group is E;

wherein the spacer group is selected from the group consisting of alkyl, non-polar, zwitterionic, cationic, anionic, and non-charged polar moiety;

wherein each of L 2 and L 1 is C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein L 3 , when present, is a bond, C 1 -C 15 alkyl, or optionally substituted C 2 -C 15 alkenyl;

wherein M is optional and when present is —(CO 2 )—, NRR′, —RCOH or PO 4 ,

wherein Q is optional and when present is —(CO 2 )—, NRR′, —RCOH or PO 4 , wherein R is H or C 1 -C5 alkyl; wherein R′ is H or C 1 -C5 alkyl; and

wherein:

E is selected from the group consisting of acrylate, methacrylate, epoxy, amine, substituted phenyl, unsubstituted phenyl, and catechol;

the first layer comprises a first secondary surface layer with the end group;

a second layer of the compound is on the first secondary surface; and

the end group of the first layer interacts with the end group of the second layer to affix the first layer to the second layer.

28. The composition of matter of claim 27 comprising a bioadhesive.

29. The compound of claim 27 , wherein E comprises a dihydroxyphenyl.

Assignments (1)

Continuity (3)

References Cited (20)