Phototpolymerized macromolecules self-assembled around carbon nanotubes, a method of producing them, and their applications

• US 20070184267A1
• Filed: 04/13/2004
• Published: 08/09/2007
• Est. Priority Date: 04/10/2003
• Status: Active Grant

• Current Assignee: Centre National De La Recherche Scientifique, Université Louis Pasteur
• Original Assignee: Centre National De La Recherche Scientifique, Université Louis Pasteur
• Inventors: Mioskowski, Charles, Rickling, Stephane
• Granted Patent: US 7,517,587 B2
• Time in Patent Office: Days
• US Class Current: 428/403
• CPC Class Codes: A61K 47/34 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers A61K47/10 takes precedence
• CPC Class Codes: A61K 9/0092 Hollow drug-filled fibres, tubes of the core-shell type, coated fibres, coated rods, microtubules or nanotubes
• CPC Class Codes: A61K 9/1274 Non-vesicle bilayer structures, e.g. liquid crystals, tubules, cubic phases, cochleates; Sponge phases
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 2202/30 Purity
• CPC Class Codes: C01B 32/17 Purification
• CPC Class Codes: C08F 292/00 Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• CPC Class Codes: Y10S 977/756 Lipid layer
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

The invention relates to macromolecules auto-assembled and photopolymerised around carbon nanotubes. Said macromolecules are essentially formed from rings of lipid compounds, polymerised about the nanotubes, said polymerised compounds being obtained from lipid molecules with one or two chains A, bonded to a group Z where A is a chain, CH₃—(CH₂)_m—C≡C—C≡C—(CH₂)_n—, where n and m, independently=whole numbers from 1 to 16 and Z is a polar head group embodied by a —COOH, —CO—NH—Y, —NH₂ or N⁺(R)₃, where R is an alkyl with C₁, to C₄ and Y is a —(CH₂)₄—C(R₁)—N(CH₂—COOH)₂ group with R=H, or a COOH group, where A is a single lipid chain or a group of structure (I) or (II), where R2=a COOH, or —CO—NH—Y₁ group with Y₁=a —(CH₂)₄—C (R₃)—N(CH₂COOH)₂ group with R₃=H or a COOH group, where Z and R₂ can also be neutral polar head groups of the sugar or polysaccharide type. The above is of application particularly to the protection and purification of nanotubes, as a hydrophobic molecule or membrane protein vector or as a molecular motor.

Claims

1. A novel structure with macromolecules self-organized around nanotubes, characterized in that they are essentially formed from rings of polymerized lipid compounds surrounding the nanotubes, these polymerized compounds being obtained from lipid compounds comprising one or two chains A linked to a group Z:

A representing a CH₃—

(CH₂)_m—

C≡

C—

C≡

C—

(CH₂)_n—

chain, n and m, which are the same or different, being integers from 1 to 16; and

Z representing a polar head formed by a —

COOH, —

CO—

NH—

Y, —

NH₂ or N⁺(R)₃ group, R being a C₁ to C₄ alkyl and Y being a —

(CH₂)₄—

C(R₁)—

N(CH₂—

COOH)₂ radical, with R₁ representing H or a COOH radical if A represents a single lipid chain, or a group of the following structure;

where R₂ represents a —

COOH or —

CO—

NH—

Y—

₁ group, Y₁ being a —

(CH₂)₄—

C(R₃)—

N(CH₂—

COOH)₂ radical and where R₃ represents H or a COOH radical;

or Z or R₂ may also be hydrophilic or neutral polar heads of the sugar or polysaccharide type.

or Z or R₂ may also be hydrophilic or neutral polar heads, of the sugar or polysaccharide type.

2. The structures as claimed in claim 1, characterized in that the lipid compounds to be polymerized are amine lipids of formula:

CH₃—

(CH₂)_m—

C≡

C—

C≡

C—

(CH₂)_n—

NH₂.

3. The structures as claimed in claim 1, characterized in that the lipid compounds to be polymerized are quaternary ammoniums of formula:

CH₃—

(CH₂)_m—

C≡

C—

C≡

C—

(CH₂)_n—

N⁺(R)₃.

4. The structures as claimed in claim 1, characterized in that the lipid compounds to be polymerized are acid lipids with two chains A attached to Z.

5. The structures as claimed in claim 2, characterized in that the lipid compounds to be polymerized are functionalized by a chelating group.

6. The structures as claimed in claim 1, characterized in that the lipid compounds to be polymerized are functionalized by a neutral hydrophilic head of the sugar or polysaccharide type.

7. A method of obtaining the structures as claimed in claim 1, characterized in that it comprises the steps consisting in:

bringing the raw nanotubes into contact with a solution of lipids so as to form a stable suspension;

polymerizing the lipids, which are self-organized around the nanotubes; and

recovering the nanotubes coated with rings formed by the polymerized lipids.

8. The method as claimed in claim 7, characterized in that the raw nanotubes are sonicated in a lipid solution in a buffered aqueous medium advantageously containing a detergent, the latter being subsequently removed by dialysis, and then the suspension of nanotubes in the aqueous buffer is subjected to a treatment for polymerizing the lipids.

9. A method of purifying nanotubes, characterized in that the structures as claimed in claim 1 are subjected to a treatment so as to remove the rings of polymerized lipid compounds around the nanotubes.

10. The method as claimed in claim 9, characterized in that said structures are subjected to size exclusion chromatography.

11. The method as claimed in claim 9, characterized in that an electric field is applied in order to remove the rings.

12. The method as claimed in claim 9, characterized in that said structures are heated in a Tris buffer at a temperature above 90°

C. for about 14 hours in order to remove the polymer and restore the stripped nanotubes.

13. Application of the structures as claimed in claim 1 for protecting the nanotubes and, if required, for shortening these nanotubes in a controlled manner.

14. Application of the structures as claimed in claim 1 as vectors for hydrophobic molecules or membrane proteins.

15. Application of the structures as claimed in claim 1 as molecular motors.

16. Application of the structures as claimed in claim 1 to the vectorization of products, especially in the pharmaceutical or cosmetic or perfumery field.