Colloids with valence: fabrication, functionalization and directional bonding
A method for creating the colloidal analogs of atoms with valence: colloidal particles with chemically distinct surface patches that imitate hybridized atomic orbitals, including sp, sp2, sp3, sp3 d, sp3 d2 and sp3 d3. Functionalized with DNA with single-stranded sticky ends, patches on different particles can form highly directional bonds through programmable, specific and reversible DNA hybridization. These features allow the particles to self-assemble into ‘colloidal molecules’ with triangular, tetrahedral and other bonding symmetries, and should also give access to a rich variety of new microstructured colloidal materials.
1. A method for creating a colloidal particle of manufacture, comprising the steps of,
providing a plurality of functionalized colloidal particles;
assembling functionalized colloidal particles from the plurality of colloidal particles, forming a plurality of functionalized patchy particle having at least one patch comprising an exposed surface of a functionalized colloidal particle of the plurality of colloidal particles;
mixing the plurality of functionalized patchy particles, wherein the at least one patch enables selective bonding of a first of the plurality of functionalized patchy particles to a second of the plurality of functionalized patchy particles.
2. The method as defined in claim 1 further comprising selecting a valency for the plurality of functionalized patchy particles wherein the patch has a well-defined bond symmetry characteristic of atomic orbitals.
3. The method as defined in claim 2 wherein the atomic orbitals are selected from the group of s, p, sp, sp 2 , sp 3 , sp 3 d, sp 3 d 2 and sp 3 d 3 .
4. The method as defined in claim 1 wherein the step of providing a plurality of colloidal particles
comprises forming clusters of colloidal microspheres and performing an encapsulation method.
5. The method as defined in claim 4 wherein the clusters of colloidal microspheres include at least one of an amidinated surface functionality, a carboxylated surface functionality and a sulfonated surface functionality.
6. The method as defined in claim 4 wherein the clusters are encapsulated by swelling and polymerizing.
7. The method as defined in claim 4 wherein at least one colloidal particle includes a distinct patch which differs from the patch.
8. The method as defined in claim 7 wherein the distinct patch includes at least one of an amidinated surface functionality, a carboxylated surface functionality and a sulfonated surface functionality.
9. The method as defined in claim 4 further including a step of controlling morphology of the patchy particle.
10. The method as defined in claim 9 wherein the step of controlling the morphology includes a step of changing patch size by changing monomer amount added.
11. The method as defined in claim 1 wherein the step of functionalizing the patchy particle comprises forming at least one of a biotin, streptavidin and DNA conjugated patchy particle.
12. The method as defined in claim 11 wherein the step of functionalizing the patchy particle includes employing amidinated patchy particles and forming at least one of an amide bond, a biotin-streptavidin bond and a biotin-streptavidin-biotin bond.
13. The method as defined in claim 11 wherein the step of functionalizing the patchy particle includes a step of using an amidine-NHS coupling on a surface of the patchy particle.
14. The method as defined in claim 1 wherein the step of functionalizing the patchy particle comprises attaching synthetic molecules and polymers to a carboxylated surface functionalized one of the patchy particle.
15. The method as defined in claim 14 wherein the step of functionalizing the carboxylated patchy particle includes forming a covalent ester bond in conjunction with an organic solvent.
16. The method as defined in claim 14 wherein the step of functionalizing the carboxylated patchy particles a step of synthesizing the synthetic molecules and the polymers by a plurality of steps including an organic synthesis step and a living polymerization method step selected from the group of ROMP, ATRP, NMR and RAFT.
17. The method as defined in claim 16 wherein the step of synthesizing the synthetic molecules and the polymers having molecular structures includes incorporating into the synthetic molecules and the polymers having a molecular structure component capable of undergoing noncovalent attractions selected from the group of a palladated-pincer and a pyridine.
18. The method as defined in claim 14 wherein the step of functionalizing the carboxylated patchy particle comprising attaching streptavidin and DNA by forming a covalent amide bond in aqueous solution.
19. The method as defined in claim 15 wherein the step of attaching the synthetic molecules, and the synthetic polymers onto the patchy particle includes using EDC to make an activated ester coupling intermediate component in the organic solvent.
20. The method as defined in claim 18 wherein the step of attaching the synthetic molecules, the polymers, the streptavidin and the DNA onto the patchy particle includes using EDC to make an activated ester coupling intermediate component in the aqueous solvent.
21. The method as defined in claim 1 further including the step of self-assembly of the plurality of the functionalized patchy particles.
22. The method as defined in claim 21 wherein the step of self-assembly is accomplished by at least one a step of non-covalent interaction between the patches on different ones of the patchy particle.
23. The method as defined in claim 22 wherein the non-covalent interaction step includes forming hydrogen bonds and metal-coordination bonds.
24. The method as defined in claim 23 wherein the hydrogen bonds are formed by a step comprising using DNA hybridization between complementary and palindrome strands and forming of the metal coordination bonds comprise using palladated-pincer pyridine recognition units.
25. The method as defined in claim 21 wherein the step of self-assembly of the plurality of the patchy particle includes forming a bonding geometry selected from the group of s, p, sp, sp 2 , sp a , sp 3 d, sp 3 d 2 and sp 3 d 3 .
26. The method as defined in claim 21 wherein the patchy particle is constructed with a geometry characteristic of a chemical bond valence state.
27. The method as defined in claim 21 further including the step of monitoring kinetics of molecule formation.
28. The method as defined in claim 24 wherein the step of patchy particle bonding by DNA hybridization is selected from the group of specific bonding, programmable bonding and reversible bonding with temperature.
29. The method as defined in claim 24 wherein the step of patchy particle bonding by metal coordination includes designing the bonding for a selected strength.
30. The method as defined in claim 24 wherein the step of patchy particle bonding by metal coordination can be activated and deactivated by the step of providing selected small molecules.
31. An article of manufacture, comprising:
a plurality of functionalized patchy particles comprising N colloidal particles assembled into a cluster, wherein N is 1 to 7, with each of the plurality of functionalized patchy particles plurality of colloidal particles having surface patches; and
the patches functionalized to have at least one of recognition unit, thereby enabling bonding of surface patches of each of the plurality of functionalized patchy particles with surface patches of another of the plurality of functionalized patchy particles.
32. The article of manufacture as defined in claim 31 wherein the patch adopts a well-defined bond symmetry characteristic of a (hybridized) atomic orbital, including at least one orbital of a spherical linear, triangular, tetrahedral, trigonal bipyramidal, octahedral, pentagonal bipyramidal configuration.
33. The article of manufacture as defined in claim 31 wherein the patch comprises at least one of an amidinated surface functionality, a carboxylated surface functionality and a sulfonated surface functionality.
34. The article of manufacture as defined in claim 31 wherein the patch can be further functionalized using multiple coupling strategies including use of at least one of an EDC or NHS activated ester coupling methodology thereby yielding a covalent amide or ester bond.
35. The article of manufacture as defined in claim 31 wherein the patch can be further functionalized with a synthetic small molecule, a polymer, a bio-molecules and a macromolecule, including at least one of a biotin, streptavidin, oligonucleotides, and a norbornene based triblock copolymer.
36. The article of manufacture as defined in claim 31 wherein the bonding between a plurality of the particle patch has a valence characterization analogous to a chemical bond.
37. The article of manufacture as defined in claim 31 wherein the bonding between a plurality of the particle patch are realized by at least one of hydrogen bonding and metal coordination.
38. The article of manufacture as defined in claim 31 wherein the bonding between a plurality of the particle patch can be adjusted by external stimuli, selected from the group of temperature and use of a small guest molecule.
39. The article of manufacture as defined in claim 31 wherein the patch is selected from the group of a plurality of different patches and different symmetry, thereby enabling formation of clusters of the plurality of colloidal particles having controlled symmetry.