IP Library Granted Patent US 9,207,234
Granted Patent B2
US 9,207,234 · App. 13/319,624 · Granted Dec 8, 2015

Thermally stable SERS taggants

Inventors: Marcelo Eduardo Piotti (Freemont, CA); Michael J. Natan (Los Altos, CA)
Assignee: SICPA Holding SA
G01N33/532G01N21/658G01N33/28
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Quick Facts
Patent No.
US 9,207,234
App. No.
13/319,624
Granted
Dec 8, 2015
Kind
B2
Abstract

An optically active particle and a method of manufacturing said particles, plus methods of tagging a material of interest with said particles are disclosed. The particle comprises a surface-enhanced spectroscopy (SES) active core and a SES active reporter associated with the SES core wherein the particle produces a measurable and thermally stable SES spectrum upon optical interrogation. As used in the disclosure, thermally stable may be defined as maintaining a measurable SES spectrum after the particle or any material tagged with the particle has been exposed to a temperature substantially higher than room temperature.

Claims (27)

1. A particle comprising:

a surface-enhanced spectroscopy (SES)-active metal core; and

a SES-active reporter associated with said SES-active metal core, wherein said SES-active reporter comprises a conjugated polyaromatic system modified to have one or more carbon atoms replaced with one or more nitrogen atoms, wherein said particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 200° C.

2. The particle of claim 1 wherein the conjugated polyaromatic system comprises at least one of the following before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms: pentafluoropyridine, perfluoro-4,4′-bipyridine, perfluoro-2,2′-bipyridine, perfluoro-2,7-diazapyrene, quinoline, isoquinoline, pyrimidine, pyridine, thiophene, dibenzothiophene, 2,2′-bithiophene, 1,4-di-(4-pyridyl) benzene, 1,3,5-tri-(4-pyridyl)benzene, 4-phenylquinoline, 6-phenylquinoline, 6-(4-pyridyl)isoquinoline, 1,10-phenanthroline, 1,7-phenanthroline, 4,7-phenanthroline, 3,8-phenanthroline, 1-azapyrene, 2-azapyrene, 2,7-diazapyrene, 1,8-naphthyridine, 1,6-naphthyridine, 1,5-naphthyridine, 2-azaanthracene, 2,7-diazaanthracene, benzothiazole, benzoxazole, 4-phenylpyridine, 2-phenylpyridine, 4-(4-pyridyl)imidazole, 4 phenylimidazole and 4-(4-pyridyl)biphenyl.

3. The particle of claim 1 wherein the SES-active reporter comprises at least one of a porphyrin and phthalocyanine compound before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms.

4. The particle of claim 1 wherein the SES-active reporter comprises a large network fused carbon structure before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms.

5. The particle of claim 1 wherein the SES-active metal core comprises a hollow shell and the SES-active reporter is located within the hollow shell.

6. The particle of claim 1 wherein the particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 300° C.

7. The particle of claim 1 wherein the particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 400° C.

8. A method of manufacturing a particle comprising:

providing a surface-enhanced spectroscopy (SES)-active metal core;

providing a conjugated polyaromatic system molecule;

modifying the conjugated polyaromatic system molecule by replacing one or more carbon atoms with one or more nitrogen atoms to create a SES-active reporter; and

associating a SES-active reporter with said SES-active metal core, wherein said particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 200° C.

9. The method of manufacturing a particle of claim 8 wherein the conjugated polyaromatic system comprises at least one of a porphyrin and phthalocyanine compound before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms.

10. The method of manufacturing a particle of claim 8 wherein conjugated polyaromatic system comprises a large network fused carbon structure before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms.

11. The method of manufacturing a particle of claim 8 wherein the SES-active metal core comprises a hollow shell and the SES-active reporter is located within the hollow shell.

12. The method of manufacturing a particle of claim 8 wherein the particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 300° C.

13. The method of manufacturing a particle of claim 8 wherein the particle has a measurable and thermally stable SES spectrum after being heated to a temperature of 400° C.

14. The method of claim 8 wherein the conjugated polyaromatic system comprises at least one of the following before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms: pentafluoropyridine, perfluoro-4,4′-bipyridine, perfluoro-2,2′-bipyridine, perfluoro-2,7-diazapyrene, quinoline, isoquinoline, pyrimidine, pyridine, thiophene, dibenzothiophene, 2,2′-bithiophene, 1,4-di-(4-pyridyl) benzene, 1,3,5-tri-(4-pyridyl)benzene, 4-phenylquinoline, 6-phenylquinoline, 6-(4-pyridyl)isoquinoline, 1,10-phenanthroline, 1,7-phenanthroline, 4,7-phenanthroline, 3,8-phenanthroline, 1-azapyrene, 2-azapyrene, 2,7-diazapyrene, 1,8-naphthyridine, 1,6-naphthyridine, 1,5-naphthyridine, 2-azaanthracene, 2,7-diazaanthracene, benzothiazole, benzoxazole, 4-phenylpyridine, 2-phenylpyridine, 4-(4-pyridyl)imidazole, 4 phenylimidazole and 4-(4-pyridyl)biphenyl.

15. A method of tagging a material comprising:

providing a particle comprising a surface-enhanced spectroscopy (SES)-active metal core and a SES-active reporter associated with said SES-active metal core, wherein said SES-active reporter comprises a conjugated polyaromatic system modified to have one or more carbon atoms replaced with one or more nitrogen atoms, wherein said particle has a measurable and thermally stable SES spectrum; and

associating the particle with a material of interest; and

obtaining a SES spectrum from the particle in association with the material of interest after the material of interest has been heated to a temperature of 200° C.

16. The method of tagging a material of claim 15 further comprising obtaining a SES spectrum from the particle in association with the material of interest after the material of interest has been heated to a temperature of 300° C.

17. The method of tagging a material of claim 15 further comprising obtaining a SES spectrum from the particle in association with the material of interest after the material of interest has been heated to a temperature of 400° C.

18. The method of claim 15 wherein the conjugated polyaromatic system comprises at least one of the following before being modified to have one or more carbon atoms replaced with one or more nitrogen atoms: pentafluoropyridine, perfluoro-4,4′-bipyridine, perfluoro-2,2′-bipyridine, perfluoro-2,7-diazapyrene, quinoline, isoquinoline, pyrimidine, pyridine, thiophene, dibenzothiophene, 2,2′-bithiophene, 1,4-di-(4-pyridyl) benzene, 1,3,5-tri-(4-pyridyl)benzene, 4-phenylquinoline, 6-phenylquinoline, 6-(4-pyridyl)isoquinoline, 1,10-phenanthroline, 1,7-phenanthroline, 4,7-phenanthroline, 3,8-phenanthroline, 1-azapyrene, 2-azapyrene, 2,7-diazapyrene, 1,8-naphthyridine, 1,6-naphthyridine, 1,5-naphthyridine, 2-azaanthracene, 2,7-diazaanthracene, benzothiazole, benzoxazole, 4-phenylpyridine, 2-phenylpyridine, 4-(4-pyridyl)imidazole, 4 phenylimidazole and 4-(4-pyridyl)biphenyl.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 13, 2014
From: CABOT SECURITY MATERIALS INC.
To: SICPA HOLDING SA
Reel/Frame 034160/0830 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 22, 2013
From: CABOT CORPORATION
To: CABOT SECURITY MATERIALS, INC.
Reel/Frame 031060/0443 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 4, 2012
From: PIOTTI, MARCELO EDUARDO; NATAN, MICHAEL J.
To: CABOT CORPORATION
Reel/Frame 028160/0448 →
Continuity (3)
Provisional Application 61179281 · May 18, 2009
Provisional Application 61181598 · May 27, 2009
Related Publication 20120062886A1 · Mar 15, 2012