Separation of nanoparticles

Patent metadata

Field	Value
Publication number	US-9067181-B2
Application number	US-201313779248-A
Country	US
Kind code	B2
Filing date	Feb 27, 2013
Priority date	Aug 27, 2010
Publication date	Jun 30, 2015
Grant date	Jun 30, 2015

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; providing a chromatography medium for size-selective separation of nano-material; wherein said perylene diimide supramolecular structure comprises a perylene, a salt thereof or metal complex thereof as a monomeric unit represented by the structure of formula I:

wherein
R 1 and R 1 ′ are independently [(CH 2 ) n O] o CH 3 , [(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 , (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)NHR 3 NH] p H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and 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)NHR 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 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, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)NHR 4 NH] s H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and 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 independently H, —OR x where R x is C 1 -C 6 alkyl or [(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 , aryl, heteroaryl, C≡C—R 7 , CH═CR 8 R 9 , NR 10 R 11 , 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 selected from halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and 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 selected from halide, aryl, heteroaryl, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
R 8 , R 9 , R 10 and R 11 are 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 selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and O—(C 1 -C 6 alkyl);
L is a linker;
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 R 5 ′ independently are amino acid or peptide; said membrane will form a chiral membrane.

2. The membrane of claim 1 , wherein said perylene supramolecular structure comprises a perylene represented by the structure of formula III, IV or V:

3. The porous membrane of claim 1 , wherein the size of the pores in said porous membrane depends on the thickness of said pore membrane wherein said size of the pores in said porous membrane has a cutoff size of between 2-100 nm.

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

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

6. A method of separation, filtration or purification of nano-materials comprising (a) transferring an aqueous solution or emulsion comprising a perylene supramolecular structure through porous solid support, thereby forming a noncovalent self-assembly perylene based membrane on said porous solid support; (b) transferring a solution of nano-materials through said noncovalent self-assembled perylene based membrane of step (a); wherein the particles size which are larger than the pores of said membrane remain on said membrane; wherein said noncovalent self-assembled perylene diimide comprises a perylene, a salt thereof or a metal thereof as a monomeric unit represented by the structure of formula I:

wherein
R 1 and R 1 ′ are independently [(CH 2 ) n O] o CH 3 , [(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 , (C 1 -C 32 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heteroaryl, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)NHR 3 NH] p H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and 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)NHR 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 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, (C 1 -C 32 )alkyl-COOH, (C 1 -C 32 )alkyl-Si-A, or [C(O)NHR 4 NH] s H wherein said aryl or heteroaryl groups are optionally substituted by 1-3 groups selected from halide, CN, CO 2 H, OH, SH, NH 2 , CO 2 —(C 1 -C 6 alkyl), and 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)NHR 4 NH] s H is an alkyl

Assignees

• Yeda Res & Dev
• Yeda Res & Dev

Inventors

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

Classifications

• C08G73/10

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• B01D71/64 Primary

  Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/1046

  Polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C08J5/2256

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title

• C08G65/33396

  having oxygen in addition to nitrogen · CPC title