Guanidine-Functionalized Particles and Methods of Making and Using

• US 20150307526A1
• Filed: 11/20/2013
• Published: 10/29/2015
• Est. Priority Date: 12/04/2012
• Status: Active Grant

• Current Assignee: Solventum Intellectual Properties Company (Solventum Corp.)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Griesgraber, George W., Fitzsimons, Robert T. Jr., Hanggi, Douglas A., Nakamura, Masayuki, Rasmussen, Jerald K.
• Granted Patent: US 9,657,038 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• CPC Class Codes: B01D 24/00 Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof B01D27/02 takes precedence
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/28085 being more than 50 nm, i.e. macropores
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/289 bonded via a spacer
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3219 involving a particular spacer or linking group, e.g. for attaching an active group
• CPC Class Codes: B01J 20/3244 Non-macromolecular compounds
• CPC Class Codes: B01J 20/3293 Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
• CPC Class Codes: B01J 2220/80 Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C07F 7/1872 Preparation; Treatments not provided for in C07F7/20
• CPC Class Codes: C07F 7/1892 by reactions not provided for in C07F7/1876 - C07F7/1888
• CPC Class Codes: C12M 25/16 Particles; Beads; Granular material; Encapsulation chemical or physical processes conducted in the presence of fluids and solid particles B01J8/00
• CPC Class Codes: G01N 1/405 by adsorption or absorption

Abstract

Guanidine-functionalized particles and methods of making and using such particles.

Claims

1. A method of making a guanidine-functionalized particle, comprising:

reacting O-methylisourea hemisulfate with a linker molecule comprising the formula

(RO)_nR_3-n^a—

Si—

S_m—

X

where RO is an alkoxy group comprising one or two carbons, or is an acetoxy group,

where n is 1, 2 or 3,

where R^a is an unreactive group,

where S is a spacer group comprising a backbone with m atoms,

m is from 2-16, inclusive, and

where X is a primary amine that is capable of reacting with the O-methylisourea to form a guanidine group;

and,

reacting at least one of the RO groups of the linker molecule with a hydroxyl group of the particle to form a covalent bond between the linker molecule and the particle.

2. The method of claim 1 wherein the (RO)_nSi moiety comprises a trimethoxysilane moiety.

3. The method of claim 1 wherein the linker molecule is 3-aminopropyltrimethoxysilane.

4. The method of claim 1 wherein all m atoms of the backbone of the spacer group S are carbon atoms.

5. The method of claim 1 wherein the spacer group S comprises at least one hetero atom.

6. The method of claim 5 wherein the spacer group S comprises at least one secondary amine.

7. The method of claim 1 wherein the particle comprises a silica particle.

8. The method of claim 7 wherein the particle comprises silica gel.

9. The method of claim 8 wherein the silica gel particle comprises a particle size of about 25-100 microns and a pore size of about 60-2000 Angstroms.

10. The method of claim 1 wherein the step of reacting at least one of the RO groups of the linker molecule with a hydroxyl group of the particle to form a covalent bond between the linker molecule and the particle, is performed after the reacting of the O-methylisourea hemisulfate with the linker molecule.

11. The method of claim 1 wherein the step of reacting at least one of the RO groups of the linker molecule with a hydroxyl group of the particle to form a covalent bond between the linker molecule and the particle, is performed before the reacting of the O-methylisourea hemisulfate with the linker molecule.

12. A guanidine-functionalized silica gel particle, comprising:

a silica gel particle comprising at least one ligand comprising a guanidine group, the ligand comprising the formula

—

O_nSi—

S_m-G,

where —

O is an oxygen atom that is covalently bonded to the surface of the silica gel particle,

n is 1, 2 or 3,

S is a spacer group comprising a backbone with m atoms,

m is 2-16, inclusive,

G is a guanidine group of the formula NH—

C(NH)—

NH₂,

and wherein the guanidine group is charged and comprises an associated counterion and wherein the counterion does not comprise a halogen.

13. The particle of claim 12 wherein all m atoms of the backbone of the spacer group S are carbon atoms.

14. The particle of claim 13 wherein m=3.

15. The particle of claim 12 wherein the spacer group S comprises a secondary amine.

16. The particle of claim 12 wherein the guanidine group is the reaction product of a primary amine and O-methylisourea hemisulfate.

17. The particle of claim 12 wherein the silica gel particle comprises a particle size of about 25-100 microns and a pore size of about 60-2000 Angstroms.

18. The particle of claim 12 wherein the ligand is the reaction product of one or more hydroxyl groups of the silica particle with one or more reactive groups of a silane coupling agent moiety of the ligand.

19. A fluid-purification device comprising a plurality of the particles of claim 12, entrapped within a container that is configured to accept a fluid to be purified and to allow the purified fluid to be removed therefrom.

20. A method of separating a target biological species from a fluid, comprising:

contacting the fluid with a guanidine-functionalized particle;

allowing the target biological species to non-specifically bind with a guanidine group of the guanidine-functionalized particle wherein the guanidine group is of the formula NH—

C(NH)—

NH₂;

and,

separating the fluid and the guanidine-functionalized particle with the target biological species non-specifically bound thereto, from each other.

21. The method of claim 20 wherein the guanidine group is provided by the reaction product of a primary amine with O-methylisourea hemisulfate.

22. The method of claim 20 wherein the guanidine group is present on a ligand that is attached to the particle by way of one or more Si—

O bonds.

23. The method of claim 22 wherein the ligand comprises a spacer group that comprises a backbone with from 2-16 atoms, inclusive.

24. The method of claim 20 wherein the particle is a silica gel particle.

25. The method of claim 20 wherein the particle comprises a particle size of about 25-100 microns and a pore size of about 60-2000 Angstroms.

26. The method of claim 20 wherein the fluid has an NaCl content of from about 150 millimolar to about 300 millimolar.

27. The method of claim 20 wherein the target biological species comprises at least one negatively-charged moiety and wherein the guanidine group comprises a negatively-charged counterion associated therewith, and wherein the non-specific binding of the target biological species with the guanidine group comprises exchanging the negatively-charged counterion with the negatively-charged moiety of the target biological species.

28. The method of claim 27 wherein the negatively-charged counterion does not comprise a halogen atom.

29. The method of claim 20 wherein the target biological species comprises one or more biomacromolecules chosen from the group including proteins, enzymes, nucleic acids, and fragments derived from any of these;

and/or,

wherein the target biological species comprises one or more microbiological species chosen from the group including bacteria, viruses, cells, spores, and fragments or debris derived from any of these.

30. The method of claim 20 wherein a plurality of the guanidine-functionalized particles are provided in a container that is configured to accept the fluid to be purified and wherein the method includes the step of removing the purified fluid from the container while retaining the guanidine-functionalized particles in the container with at least some target species having been captured by the guanidine-functionalized particles and remaining in the container therewith when the purified fluid is removed.