IP Library Granted Patent US 9,012,241
Granted Patent B2
US 9,012,241 · App. 12/844,778 · Granted Apr 21, 2015

Rapid detection and identification of energetic materials with surface enhanced raman spectrometry (SERS)

Inventors: Thomas Yong-Jin Han (Livermore, CA); Carlos A. Valdez (San Ramon, CA); Tammy Y. Olson (Livermore, CA); Sung Ho Kim (Livermore, CA); Joe H. Satcher, Jr. (Patterson, CA)
Assignee: Lawrence Livermore National Security, LLC
G01N33/54346G01N33/54373
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Quick Facts
Patent No.
US 9,012,241
App. No.
12/844,778
Granted
Apr 21, 2015
Kind
B2
Abstract

In one embodiment, a system includes a plurality of metal nanoparticles functionalized with a plurality of organic molecules tethered thereto, wherein the plurality of organic molecules preferentially interact with one or more analytes when placed in proximity therewith. According to another embodiment, a method for detecting analytes includes contacting a fluid having one or more analytes of interest therein with a plurality of metal nanoparticles, each metal nanoparticle having a plurality of organic molecules tethered thereto, and detecting Raman scattering from an analyte of interest from the fluid, the analyte interacting with one or more of the plurality of organic molecules. In another embodiment, a method includes chemically modifying a plurality of cyclodextrin molecules at a primary hydroxyl moiety to create a chemical handle, and tethering the plurality of cyclodextrin molecules to a metal nanoparticle using the chemical handle. Other systems and methods for detecting analytes are also described.

Claims (59)

1. A system, comprising:

one or more analytes; and

a plurality of metal nanoparticles functionalized with a plurality of organic molecules tethered thereto, each organic molecule having a primary face and a secondary face,

wherein the plurality of organic molecules preferentially interact with the one or more analytes when placed in proximity therewith,

wherein the plurality of organic molecules comprise one or more of:

one or more modifying groups on the primary face in place of one or more primary hydroxyl groups; and

one or more modifying groups on the secondary face in place of one or more secondary hydroxyl groups,

wherein at least one of the one or more analytes is an energetic compound selected from a group consisting of: trinitrotoluene (TNT), tetrahexamine tetranitramine (HMX), cyclotrimethylenetrinitramine (RDX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrophenylmethylnitramine (Tetryl), and peroxides.

2. The system of claim 1 , wherein at least some of the plurality of organic molecules are molecules of modified cyclodextrin.

3. The system of claim 2 , wherein the cyclodextrin molecules are chemically modified at a primary hydroxyl moiety to tether to a surface of the plurality of metal nanoparticles via a chemical handle.

4. The system of claim 3 , wherein the chemical handle is at least one of: a thiol functionality and an amine functionality.

5. The system of claim 2 , wherein the plurality of cyclodextrin molecules include at least one modifying group on a primary face in place of one or more primary hydroxyl groups.

6. The system of claim 5 , wherein the modifying groups are selected from a group consisting of: N 3 , RSH, ROH, RNH 2 , RO ⊖ , RS ⊖ , and R 2 N ⊖ , wherein R is any carbon containing group, or any modifying group.

7. The system of claim 2 , wherein the plurality of cyclodextrin molecules include at least one modifying group on a secondary face in place of one or more secondary hydroxyl groups.

8. The system of claim 7 , wherein the modifying groups are selected from a group consisting of: N 3 , RSH, ROH, RNH 2 , RO ⊖ , RS ⊖ , and R 2 N ⊖ , wherein R is any carbon containing group, or any modifying group.

9. The system of claim 2 , wherein the plurality of cyclodextrin molecules include one or more modifying groups on a primary face in place of one or more primary hydroxyl groups and one or more modifying groups on a secondary face in place of one or more secondary hydroxyl groups.

10. The system of claim 9 , wherein the modifying groups are selected from a group consisting of: N 3 , RSH, ROH, RNH 2 , RO ⊖ , RS ⊖ , and R 2 N ⊖ , wherein R is any carbon containing group, or any modifying group.

11. The system of claim 4 , wherein the chemical handle is a functional group selected from a group consisting of: of a thiol (—SH) functional group; and an amine (—NH 2 ) functional group.

12. The system of claim 1 , wherein the plurality of organic molecules comprise molecules of modified cyclodextrin,

wherein the cyclodextrin molecules are chemically modified at a primary hydroxyl moiety to tether to a surface of the plurality of metal nanoparticles via a chemical handle, and

wherein the chemical handle is an amine functionality.

13. The system of claim 1 , wherein the metal nanoparticles comprise one or more of silver nanoparticles and platinum nanoparticles.

14. The system of claim 1 , further comprising a substrate,

wherein the plurality of metal nanoparticles are attached to the substrate, and

wherein the substrate comprises one of: silicon, glass, an aerogel having an inorganic matrix, and an aerogel having an organic matrix.

15. The system of claim 1 , wherein the metal nanoparticles have a mean diameter of between about 5 nm and about 100 nm.

16. The system of claim 1 , further comprising a Raman probe for detecting the presence of the one or more analytes interacting with the organic molecules.

17. The system of claim 1 , further comprising:

a housing;

an inlet;

an outlet;

a fan configured to draw vapor through the housing from the inlet toward the outlet;

a substrate;

a Raman probe for detecting a presence of the one or more analytes in the vapor; and

a fibre optic cable adapted to couple a laser to a spectrograph.

18. The system of claim 1 , further comprising:

a housing;

an inlet;

an outlet;

a fan configured to draw vapor through the housing from the inlet toward the outlet;

a surface-enhanced Raman Spectroscopy (SERS) substrate comprising an aerogel having an organic matrix;

a Raman probe for detecting a presence of the one or more analytes in the vapor; and

a fibre optic cable adapted to couple a laser to a spectrograph,

wherein the plurality of metal nanoparticles are attached to the substrate;

wherein the chemical handle consists of a functional group selected from a group consisting of: of a thiol (—SH) functional group; and an amine (—NH 2 ) functional group,

wherein the metal nanoparticles have a mean diameter of between about 5 nm and about 100 nm,

wherein the metal nanoparticles comprise one or more of silver nanoparticles and platinum nanoparticles, and

wherein the modifying groups are selected from a group consisting of: N 3 , RSH, ROH, RNH 2 , RO ⊖ , RS ⊖ , and R 2 N ⊖ , wherein R is any carbon containing group, or any modifying group.

19. A method for detecting one or more energetic analytes, the method comprising:

contacting a fluid having one or more of the energetic analytes of interest therein with a plurality of metal nanoparticles, each metal nanoparticle having at least one modified cyclodextrin molecule tethered thereto; and

detecting Raman scattering from an energetic analyte of interest from the fluid, the energetic analyte of interest interacting with one or more of the modified cyclodextrin molecules via a modifying group present on one or more of:

a primary face of the modified cyclodextrin molecule; and

a secondary face of the modified cyclodextrin molecule,

wherein each of the modified cyclodextrin molecules comprises one or more of:

one or more modifying groups on the primary face in place of one or more primary hydroxyl groups; and

one or more modifying groups on the secondary face in place of one or more secondary hydroxyl groups,

wherein the modifying group comprises a functional group selected from N 3 , RSH, ROH, RNH 2 , RO ⊖ , RS ⊖ , and R 2 N ⊖ , wherein R is any carbon containing group, or any modifying group, and

wherein the energetic analyte of interest is selected from a group consisting of: trinitrotoluene (TNT), tetrahexamine tetranitramine (HMX), cyclotrimethylenetrinitramine (RDX), pentaerythritol tetranitrate (PETN), 2,4,6-trinitrophenylmethylnitramine (Tetryl), and peroxides.

20. The method of claim 19 , wherein the plurality of metal nanoparticles are attached to a substrate comprising one of: an aerogel having an inorganic matrix, and an aerogel having an organic matrix.

Assignments (3)
CONFIRMATORY LICENSE Recorded Sep 15, 2010
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 024988/0282 →
CONFIRMATORY LICENSE Recorded Sep 15, 2010
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 024989/0921 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 23, 2010
From: HAN, THOMAS YONG-JIN; VALDEZ, CARLOS A.; OLSON, TAMMY Y.; KIM, SUNG HO; SATCHER, JOE H., JR.
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC (LLNS)
Reel/Frame 024873/0397 →
Continuity (1)
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