Heterobifunctional polymers and methods for layer-by-layer construction of multilayer films

• US 8,993,068 B2
• Filed: 11/04/2009
• Issued: 03/31/2015
• Est. Priority Date: 11/04/2008
• Status: Active Grant

• Current Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Original Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Inventors: Koberstein, Jeffrey T., Rengifo, Hernan R., Grigoras, Cristian, Lancaster, Jeffrey
• Primary Examiner(s): Meeks, Timothy
• Assistant Examiner(s): Rodriguez, Michael P
• Application Number:
  US13/127,683
• Publication Number:
  US 20120021200A1
• Time in Patent Office: 1,973 Days
• Field of Search: None
• US Class Current: 427/407.1
• CPC Class Codes: B05D 7/58 No clear coat specified
• CPC Class Codes: C03C 17/3405 with at least two coatings of organic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 2218/111 by dipping, immersion
• CPC Class Codes: C03C 2218/116 by spin-coating, centrifugation
• CPC Class Codes: C03C 2218/31 Pre-treatment
• CPC Class Codes: C08F 299/00 Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

In one aspect, the present invention is directed to methods for modification of functionalized substrates. In another aspect, the invention relates to systems and methods for fabricating multilayer polymer compositions. In certain embodiments, the multilayer polymer compositions described herein can comprise heterobifunctional polymers and heterotrifunctional molecules.

Claims

1. A method for generating a multilayer polymer composition, the method comprising:

(a) functionalizing a substrate with a surface group to form a functionalized substrate layer,

(b) forming a monomolecular layer by contacting the functionalized substrate layer with a hetero-bifunctional polymer comprising a polymer backbone, a click moiety terminus and a protected second click moiety terminus,

(c) deprotecting the protected second click moiety terminus to form a functionalized monomolecular layer and,

(d) forming a second monomolecular layer by contacting the functionalized monomolecular layer with a second hetero-bifunctional polymer comprising a polymer backbone, a first click moiety terminus and a protected second click moiety terminus.

2. The method of claim 1, further comprising a step between step (c) and step (d) of forming a functionalized monomolecular layer comprising a heterotrifunctional molecule, the step comprising

(i) contacting the functionalized monomolecular layer of step (c) with a heterotrifunctional molecule comprising a first click moiety group and at least two protected second click moiety groups, and

(ii) deprotecting the protected second click moiety groups of the heterotrifunctional molecule to form a functionalized monomolecular layer.

3. The method of claim 1, further comprising a washing step after step (d).

5. The method of claim 1, further comprising a step between step (c) and step (d) of forming a functionalized monomolecular layer comprising a heterotrifunctional molecule, the step comprising

(i) contacting the functionalized monomolecular layer of step (c) with a heterotrifunctional molecule comprising a first click moiety group and at least two second click moiety groups, to form a functionalized monomolecular layer.

6. The method of claim 1, further comprising the step of repeating steps (c) to (d) until a multilayer polymer composition having (i) a surface monomolecular layer comprising a surface hetero-bifunctional polymer, and (ii) a desired number of monomolecular layers between the substrate layer and the surface monomolecular layer is obtained.

8. The method of claim 6 or 7, further comprising a step of contacting the functionalized monomolecular layer of step (c) with a molecule having at least a first click moiety terminus and an effector moiety to form a surface effector layer.

9. The method of claim 8, wherein the molecule having at least a first click moiety terminus and an effector moiety to form a surface effector layer is a polymer.

10. The method of claim 1, wherein the heterobifunctional polymer further comprises an effector moiety.

11. The method of claim 10, wherein the effector moiety is a polypeptide, an oligonucleotide, a lipid, a carbohydrate, a small molecule, a drug, a ligand, a catalyst, a dye, a sensor, an analyte or any combination thereof.

12. The method of claim 11, wherein the polypeptide is an enzyme or an antibody.

13. The method of claim 11, wherein the dye is a fluorescent dye.

14. The method of claim 11, wherein the effector moiety is a thermochemically reactive group or a photochemically reactive group.

15. The method of claim 1, wherein the first click moiety terminus is an azide group and the protected second click moiety terminus is a trimethylsilyl alkyne group.

16. The method of claim 2, wherein the first click moiety group of the heterotrifunctional molecule is an azide group and the at least two protected second click moiety groups of the heterotrifunctional molecule are trimethylsilyl alkyne groups.

17. The method of claim 3, wherein the first click moiety terminus is an alkyne group and the second click moiety terminus is an azide group.

18. The method of claim 5, wherein the first click moiety group of the heterotrifunctional molecule is an alkyne group and the at least two second click moiety groups of the heterotrifunctional molecule are azide groups.

19. The method of claim 1, wherein the substrate is a planar surface, a colloidal particle, a nanoparticle, a microparticle, or any combination thereof.

20. The method of claim 1, wherein the substrate comprises glass.

21. The method of claim 1, wherein the substrate comprises a ceramic, a crystal, a silicon, a metal oxide, a metal alloy, gold, quartz, indium tin oxide, antimony tin oxide, a semiconductor, a semiconductor alloy or any combination thereof.

22. The method of claim 1, wherein the substrate is electrically conducting, electrically insulating or semi-conducting.

23. The method of claim 1, wherein the substrate is a carbon nanotube.

24. The method of claim 1, wherein the substrate is a polymer.

25. The method of claim 24, wherein the polymer is a polypeptide, an organic polymer, a polymer precursor, a thermoplastic polymer, a thermosetting polymer, a copolymer, a terpolymer, an oligomer, a homopolymer, a block copolymer, an alternating block copolymer, a random polymer, a random copolymer, a random block copolymer, a graft copolymer, a star block copolymer, a dendrimer or any combination thereof.

26. The method of claim 1, wherein the contacting of the heterobifunctional polymer and the functionalized substrate surface is performed by spin coating, dip coating, spray coating, layer by layer assembly, drop casting, electrostatic painting, or a combination thereof.

27. The method of claim 1, wherein the contacting of the heterobifunctional polymer and the functionalized monomolecular layer is performed by spin coating, dip coating, spray coating, layer by layer assembly, drop casting, electrostatic painting, or a combination thereof.

28. The method of claim 5, wherein the contacting of the heterotrifunctional molecule and the functionalized monomolecular layer is performed by spin coating, dip coating, spray coating, layer by layer assembly, drop casting, electrostatic painting, or a combination thereof.

29. The method of claim 1, wherein the heterobifunctional polymer is a TMS-alkyne-PS-N₃, TMS-alkyne-PtBA-N₃, or TMS-alkyne-PMMA-N₃.

30. The method of claim 1, wherein the polymer backbone is α

-trimethylsilyl alkyne-β

-azide-poly(styrene), α

-trimethylsilyl alkyne-β

-azide-poly(tert-butyl acrylate) or α

-trimethylsilyl alkyne-β

-azide-poly(methyl methacrylate).

31. The method of claim 1, wherein the polymer backbone is a polymer, a blend of polymers, a polymer precursor, a thermoplastic polymer, or a thermosetting polymer.

32. The method of claim 1, wherein the polymer backbone is a copolymer, a homopolymer, a copolymer, a block copolymer, an alternating block copolymer, a random polymer, a random copolymer, a random block copolymer, a dendrimer, or any combination thereof.

33. The method of claim 1, wherein the substrate is glass.

34. The method of claim 1 wherein the substrate comprises silicon, metal oxide, metal alloy, gold, quartz, indium tin oxide materials, antimony tin oxide materials, a semiconductor, a semiconductor alloy, an organic material, polymer or any combination thereof.

35. The method of claim 1, wherein the substrate is a polypeptide or an oligonucleotide.

4. A method for generating a multilayer polymer composition, the method comprising:

(a) functionalizing a substrate with a surface group to form a functionalized substrate layer,

(b) forming a functionalized monomolecular layer by contacting the functionalized substrate layer with a hetero-bifunctional polymer comprising a polymer backbone, a click moiety terminus and a second click moiety terminus,

(c) washing the functionalized monomolecular layer,

(d) forming a second monomolecular layer by contacting the functionalized monomolecular layer with a second hetero-bifunctional polymer comprising a polymer backbone, a first click moiety terminus and a second click moiety terminus.

7. The method of claim 4, further comprising the step of repeating steps (b) to (d) until a multilayer polymer composition having (i) a surface monomolecular layer comprising a surface hetero-bifunctional polymer, and (ii) a desired number of monomolecular layers between the substrate layer and the surface monomolecular layer is obtained.