Separation of nanoparticles

Patent metadata

Field	Value
Publication number	US-9623381-B2
Application number	US-201514753096-A
Country	US
Kind code	B2
Filing date	Jun 29, 2015
Priority date	Aug 27, 2010
Publication date	Apr 18, 2017
Grant date	Apr 18, 2017

Abstract

This invention is directed to separation, optimization and purification of nano-materials using self-assembled perylene diimide membranes, wherein said perylene diimide membrane is recyclable.

First claim

The invention claimed is:

1. Noncovalent self-assembled porous membrane comprising a perylene diimide supramolecular structure, which provides a chromatography medium for size-selective separation of nano-material; wherein said perylene diimide supramolecular structure comprises a mixture of perylene diimide compounds, wherein each perylene diimide compound is a monomeric unit represented by the structure of formula I:

wherein
R 1 and R 1 ′ are each independently [(CH 2 ) q O] r CH 3 , [(CH 2 ) q O] r H [(CH 2 ) q C(O)O] r CH 3 , [(CH 2 ) q C(O)NH] r CH 3 , [(CH 2 ) q CH 2 ═CH 2 ] r CH 3 , [(CH 2 ) q CH≡CH] r CH 3 , [(CH 2 ) q NH] r CH 3 , [(alkylene) q O] r CH 3 , [(alkylene) q C(O)O] r CH 3 , [(alkylene) q C(O)NH] r CH 3 , [(alkylene) q CH 2 ═CH 2 ] r CH 3 , [(alkylene) q CH≡CH] r CH 3 , [(alkylene) q NH] r CH 3 , (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, chiral group, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 3 NH] p H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups comprising halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl) or O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 3 in said [C(O)CHR 3 NH] p H is an alkyl, haloalkyl, hydroxyalkyl, hydroxyl, aryl, phenyl, alkylphenyl, alkylamino and independently the same or different when p is larger than 1;
R 2 and R 2 ′ are each independently [(CH 2 ) q O] r CH 3 , [(CH 2 ) q C(O)O] r CH 3 , [(CH 2 ) q C(O)NH] r CH 3 , [(CH 2 ) q CH 2 ═CH 2 ] r CH 3 , [(CH 2 ) q CH≡CH] r CH 3 , [(CH 2 ) q NH] r CH 3 , [(alkylene) q O] r CH 3 , [(alkylene) q C(O)O] r CH 3 , [(alkylene) q C(O)NH] r CH 3 , [(alkylene) q CH 2 ═CH 2 ] r CH 3 , [(alkylene) q CH≡CH] r CH 3 , [(alkylene) q NH] r CH 3 , (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, chiral group, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)CHR 4 NH] s H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups comprising halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl) or O—(C 1 -C 6 alkyl); wherein A comprises three same or different of the following substituents Cl, Br, I, O(C 1 -C 8 )alkyl or (C 1 -C 8 )alkyl; and wherein R 4 in said [C(O)CHR 4 NH] s H is an alkyl, haloalkyl, hydroxyalkyl, hydroxyl, aryl, phenyl, alkylphenyl, alkylamino and independently the same or different when s is larger than 1;
R 5 and R 5 ′ are each independently R 5 and R 5 ′ are each independently H, —OR x where R x is C 1 -C 6 alkyl, [(CH 2 ) n O] o CH 3 or [(CH 2 ) n O] o H; [(CH 2 ) n C(O)O] o CH 3 , [(CH 2 ) n C(O)NH] o CH 3 , [(CH 2 ) n CH 2 ═CH 2 ] o CH 3 , [(CH 2 ) n CH≡CH] o CH 3 , [(CH 2 ) n NH] o CH 3 , [(alkylene) n O] o CH 3 , [(alkylene) n C(O)O] o CH 3 , [(alkylene) n C(O)NH] o CH 3 , [(alkylene) n CH 2 ═CH 2 ] o CH 3 , [(alkylene) n CH≡CH] o CH 3 , [(alkylene) n NH] o CH 3 , aryl, heteroaryl, C≡C—R 7 , CH═CR 8 R 9 , NR 10 R 11 , chiral group, amino acid, peptide or a saturated carbocyclic or heterocyclic ring wherein said saturated heterocyclic ring or heteroaryl contains at least one nitrogen atom and R 5 or R 5 ′ are connected via the nitrogen atom and wherein said saturated carbocyclic ring, heterocyclic ring, aryl and heteroaryl groups are optionally substituted by 1-3 groups comprising halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl) or O—(C 1 -C 6 alkyl);
R 7 is H, halo, (C 1 -C 32 )alkyl, aryl, NH 2 , alkyl-amino, COOH, C(O)H, alkyl-COOH heteroaryl, Si(H) 3 or Si[(C 1 -C 8 )alkyl] 3 wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups comprising halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl) or O—(C 1 -C 6 alkyl);
R 8 , R 9 , R 10 and R 11 are each independently H, (C 1 -C 32 )alkyl, aryl, NH 2 , alkyl-amino, COOH, C(O)H, alkyl-COOH or heteroaryl wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups comprising halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl) or O—(C 1 -C 6 alkyl);
L is ethynyl group or a diethynylbenzene group;
n is an integer from 1-5;
o is an integer from 1-100;
p is an integer from 1-100;
q is an integer from 1-5;
r is an integer from 1-100; and
s is an integer from 1-100;

wherein if R 5 and/or R 5 ′ are chiral; said membrane will form a chiral membrane; wherein said mixture comprises between 2 to 10 different perylene diimide compounds of formula I.

2. The porous membrane of claim 1 , wherein the pores size of said membrane have a cutoff size of between 2-100 nm.

3. The porous membrane of claim 1 , wherein said nano-materials are nanoparticles or biomolecules.

4. The porous membrane of claim 1 , wherein the size of said pores depends on the thickness of the membrane, wherein the thickness of said membrane is between 5-100 μm.

5. A method of preparing a noncovalent self-assembled perylene diimide based membrane of claim 1 comprising:
a. preparing an organic solution of a mixture of perylene diimide compounds, wherein the organic solvent in said organic solution is miscible in water;
b. adding excess of water to said solution of (a); wherein the ratio between said organic solvent to water is between about 1:99% to 8:92% v/v;
c. evaporating said organic solvent; and
d. transferring the remaining aqueous solution or emulsion through a solid support;
thereby obtaining a noncovalent self-assembled perylene diimide based membrane.

6. The method of claim 5 , wherein said method comprises further washing said membrane with ethanol.

7. The method of claim 5 , wherein said organic solvent is tetrahydrofuran (THF), dimethylacetamide (DMA), dimethylformamide (DMF), acetonitrile, acetone, methanol, ethanol or any combination thereof.

8. The method of claim 5 , wherein said solid support is a microfiltration filter comprising cellulose acetate (CA), PES, teflon (PTFE) or polycarbonate, or microfiltration filter with pores smaller or equal to 0.45 microns.

9. A method of separation/filtration or purification of nanoparticles comprising (a) transferring an aqueous solution or emulsion comprising a membrane of claim 1 through porous solid support, thereby forming a noncovalent self assembled perylene diimide based membrane on said porous solid support; (b) transferring nanoparticles through said noncovalent self-assembled perylene diimide based membrane of step (a); wherein the particles which are larger than the pores of said membrane remain on said membrane.

10. The method of claim 9 , wherein said noncovalent self-assembled perylene diimide based membrane is further recycled.

11. The method of claim 10 , wherein said recycling comprises; (a) washing said solid support with the noncovalent self-assembled perylene diimide based membrane and the retentate deposited thereon, with a solution of alcohol and water; (b) extracting said perylene diimide structure from said solution with an organic solvent; and (c) isolating said perylene diimide from said organic solvent.

12. The method of claim 11 , wherein said isolated perylene diimide can be further used to form a noncovalent self-assembled perylene diimide based membrane in aqueous conditions.

13. Noncovalent self-assembled porous membrane comprising a perylene diimide supramolecular structure, which provides a chromatography medium for size-selective separation of nano-material; wherein said perylene diimide supramolecular structure comprises a mixture of perylene diimide compounds, wherein each perylene dii

Assignees

• Yeda Res & Dev

Inventors

• Rybtchinski Boris
• Krieg Elisha M
• Weissman Haim
• Albeck Shira
• Tidhar Yaron
• Cohen Erez

Classifications

• C08G2261/3221

  containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole · CPC title

• B01D2325/20

  Specific permeability or cut-off range · CPC title

• C08G2261/374

  of Os, Ir, Pt, Ru, Rh, Pd · CPC title

• C08G2261/3328

  alkyne-based · CPC title

• C08G2261/90

  Applications · CPC title