CHEMICAL SENSORS BASED ON CUBIC NANOPARTICLES CAPPED WITH AN ORGANIC COATING FOR DETECTING EXPLOSIVES

• US 20110015872A1
• Filed: 03/26/2009
• Published: 01/20/2011
• Est. Priority Date: 03/27/2008
• Status: Active Grant

• Current Assignee: TECHNION RESEARCH AND DEVELOPMENT FOUNDATION, LTD.
• Original Assignee: TECHNION RESEARCH AND DEVELOPMENT FOUNDATION, LTD.
• Inventors: Haick, Hossam, Dovgolevsky, Ekaterina
• Granted Patent: US 8,903,661 B2
• Time in Patent Office: Days
• US Class Current: 702/23
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G01N 33/0057 for warfare agents or explosives properties of explosives G01N33/227
• CPC Class Codes: Y10T 436/17 Nitrogen containing

Abstract

The present application describes a sensor apparatus, especially an electronic nose, based on 2D films or 3D assemblies of cubic nanoparticles capped with an organic coating. The organic coating is modified with unique compositions of functional moieties, e.g. cyclodextrins, to provide the detection of volatile and non-volatile compounds derived from explosive materials, e.g. PETN, RDX, TNT etc. with very high sensitivity. The nose employs pattern recognition algorithms and methods, e.g. PCA, for detecting and quantifying specific explosive compounds.

Claims

1. An apparatus for detecting volatile and non-volatile compounds derived from explosive materials, comprising at least one chemically sensitive sensor comprising cubic nanoparticle conductive cores capped with an organic coating, wherein the organic coating comprises a backbone and at least a first functional moiety and a second functional moiety bound to said backbone, wherein the first functional moiety is further bound to the nanoparticle conductive cores.

2. The apparatus according to claim 1, wherein the cubic nanoparticle conductive cores are selected from the group consisting of Au, Ag, Ni, Co, Pt, Pd, Cu, Al, Au/Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt—

Rh, Ni—

Co, and Pt—

Ni—

Fe.

3. The apparatus according to claim 1, wherein the organic coating comprises a monolayer or multilayers of organic compounds, wherein the organic compounds are selected from small molecules, monomers, oligomers and polymers.

4. The apparatus according to claim 1, wherein the backbone of the organic coating comprises C₃-C₂₄ alkyl chains.

5. The apparatus according to claim 1, wherein the first functional moiety of the organic coating comprises a thiol, a thiolate, a sulfide, a disulfide, a sulfite, a sulfate, a carbamate, an amine, a phosphine, a carboxylate, a cyanate, or an isocyanate moiety.

6. The apparatus according to claim 1, wherein the second functional moiety of the organic coating comprises at least one of an amine, an imine, an amide, an ammonium, a keto, an alcohol, an ester, a cyclodextrin, a phosphate, a thiol, a sulfonate, a sulfonyl or a carboxyl moiety.

7. The apparatus according to claim 6, wherein the second functional moiety of the organic coating is selected from the group consisting of ethyleneimine, aniline-boronic acid, diethyl ester, 2,5-dimercaptoterephthalic acid, n-(3-trifluoroethanesulfonyloxypropyl)-anthraquinone-2-carboxamide, thiophene, 1-[4-(4-dimethylamino-phenylazo)-3-[3,5-bis[3,5-bis[3,5-bis(3-butene-1-oxy)benzyloxy]benzyloxy]benzyloxy]phenyl]-2,2,2 trifluoroethanone, permethylated α

-cyclodextrin-6^A-monoalcohol nitrate, dinitrophenyl substituted β

-cyclodextrin, β

- and γ

-CD bearing a 4-amino-7-nitrobenz-2-oxa-1,3-diazole, sulfated and carboxymethylated β

-cyclodextrins, mono(6-cyclohexylamino-6-deoxy)-β

-cyclodextrin, mono(6-benzyl-imino-6-deoxy)-β

-cyclodextrin, mono[6-(o-aminophenyl)imino-6-deoxy]-β

-cyclodextrin, mono[6-(p-aminophenyl)imino-6-deoxy]-β

-cyclodextrin, mono[6-(α

-naphthyl)imino-6-deoxy]-β

-cyclodextrin, hexakis(6-O-benzoyl)-α

-cyclodextrin, heptalds(2,3,6-tri-O-benzoyl)-β

-cyclodextrin, hexakis(2,3-di-O-benzyl)-α

-cyclodextrin, hexakis(6-O-benzoyl-2,3-di-O-benzyl)-α

-cyclodextrin, 2- and 6-amino-β

-cyclodextrin, 2A,3A-alloepithio-2A,3A-dideoxy-β

-cyclodextrin, and combinations thereof.

8. The apparatus according to claim 1, wherein the explosive materials to be detected are selected from the group consisting of pentaerythitol tetranitrate (PETN), tetranitro-tetrazacylooctane (HMX), nitroglycerin (NG), ethylene glycol dinitrate (EGDN), NH₄NO₃, dinitrotoluene (DNT), trinitrotoluene (TNT), tetryl, picric acid, cyclotrimethylenetrinitramine (RDX), mixtures and fragments thereof.

9. The apparatus according to claim 1, wherein the cubic nanoparticles capped with an organic coating are in a configuration selected from 1D wires, 2D films and 3D assemblies.

10. The apparatus according to claim 1, further comprising at least one of a chemiresistor, chemicapacitor, quartz crystal microbalance, bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonator, electrochemical cell, surface plasmon resonance (SPR), and optical spectroscope.

11. A system having:

(i) an apparatus for detecting volatile and non-volatile compounds derived from explosive materials comprising an array of chemically sensitive sensors comprising cubic nanoparticle conductive cores capped with an organic coating, wherein the organic coating Comprises a backbone and at least a first functional moiety and a second functional moiety bound to said backbone, wherein the first functional moiety is further bound to the nanoparticle conductive cores, and

(ii) a learning and pattern recognition analyzer, wherein the learning and pattern recognition analyzer receives sensor output signals and compares them to stored data.

14. The system according to claim 11, wherein the cubic nanoparticle conductive cores are selected from the group consisting of Au, Ag, Ni, Co, Pt, Pd, Cu, Al, Au/Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt—

Rh, Ni—

Co, and Pt—

Ni—

Fe.

15. The system according to claim 11, wherein the organic coating comprises a monolayer or multilayers of organic compounds, wherein the organic compounds are selected from small molecules, monomers, oligomers and polymers.

16. The system according to claim 11, wherein the backbone of the organic coating comprises C₃-C₂₄ alkyl chains.

17. The system according to claim 11, wherein the first functional moiety of the organic coating comprises a thiol, a thiolate, a sulfide, a disulfide, a sulfite, a sulfate, a carbamate, an amine, a phosphine, a carboxylate, a cyanate, or an isocyanate moiety.

18. The system according to claim 11, wherein the second functional moiety of the organic coating comprises at least one of an amine, an imine, an amide, an ammonium, a keto, an alcohol, an ester, a cyclodextrin, a phosphate, a thiol, a sulfonate, a sulfonyl or a carboxyl moiety.

19. The system according to claim 18, wherein the second functional moiety of the organic coating is selected from the group consisting of ethyleneimine, aniline-boronic acid, diethyl ester, 2,5-dimercaptoterephthalic acid, n-(3-trifluoroethanesulfonyloxypropyl)-anthraquinone-2-carboxamide, thiophene, 1-[4-(4-dimethylamino-phenylazo)-3-[3,5-bis[3,5-bis[3,5-bis(3-butene-1-oxy)benzyloxy]benzyloxy]benzyloxy]phenyl]-2,2,2 trifluoroethanone, permethylated α

-cyclodextrin-6^A-monoalcohol nitrate, dinitrophenyl substituted β

-cyclodextrin, β

- and γ

-CD bearing a 4-amino-7-nitrobenz-2-oxa-1,3-diazole, sulfated and carboxymethylated β

-cyclodextrins, mono(6-cyclohexylamino-6-deoxy)-β

-cyclodextrin, mono(6-benzyl-imino-6-deoxy)-β

-cyclodextrin, mono[6-(o-aminophenyl)imino-6-deoxy]-β

-cyclodextrin, mono[6-(p-aminophenyl)imino-6-deoxy]-β

-cyclodextrin, mono[6-α

-naphthyl)imino-6-deoxy]-β

-cyclodextrin, hexakis(6-O-benzoyl)-α

-cyclodextrin, heptakis(2,3,6-tri-O-benzoyl)-β

-cyclodextrin, hexakis(2,3-di-O-benzyl)-α

-cyclodextrin, hexakis(6-O-benzoyl-2,3-di-O-benzyl)-α

-cyclodextrin, 2- and 6-amino-β

-cyclodextrin, 2A,3A-alloepithio-2A,3A-dideoxy-β

-cyclodextrin, and combinations thereof.

20. The system according to claim 11, wherein the explosive materials to be detected are selected from the group consisting of pentaerythitol tetranitrate (PETN), tetranitro-tetrazacylooctane (HMX), nitroglycerin (NG), ethylene glycol dinitrate (EGDN), NH₄NO₃, dinitrotoluene (DNT), trinitrotoluene (TNT), tetryl, picric acid, cyclotrimethylenetrinitramine (RDX), mixtures and fragments thereof.

21. The system according to claim 11, wherein the cubic nanoparticles capped with an organic coating are in a configuration selected from 1D wires, 2D films and 3D assemblies.

22. The system according to claim 11, further comprising at least one of a chemiresistor, chemicapacitor, quartz crystal microbalance, bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonator, electrochemical cell, surface plasmon resonance (SPR), and optical spectroscope.

23. The system according to claim 11, wherein the learning and pattern recognition analyzer comprises at least one algorithm selected from the group consisting of artificial neural network algorithms, principal component analysis (PCA), multi-layer perception (MLP), generalized regression neural network (GRNN), fuzzy inference systems (FIS), self-organizing map (SOM), radial bias function (RBF), genetic algorithms (GAS), neuro-fuzzy systems (NFS), adaptive resonance theory (ART), partial least squares (PLS), multiple linear regression (MLR), principal component regression (PCR), discriminant function analysis (DFA), linear discriminant analysis (LDA), cluster analysis, and nearest neighbor.

12. (canceled)

13. (canceled)

24. (canceled)

25. A method for detecting volatile and non-volatile compounds derived from explosive materials in a sample, comprising the steps of:

i) providing a system comprising an apparatus comprising an array of chemically sensitive sensors comprising cubic nanoparticle conductive cores capped with an organic coating, wherein the organic coating comprises a backbone and at least a first functional moiety and a second functional moiety bound to said backbone, wherein the first functional moiety is further bound to the nanoparticle conductive cores, and further comprising a learning and pattern recognition analyzer, wherein the learning and pattern recognition analyzer receives sensor output signals from the apparatus and compares them to stored data,

ii) exposing the sensor array of the apparatus to the sample, and

iii) using pattern recognition algorithms to detect the presence of volatile and non-volatile compounds derived from explosive materials in the sample.

28. The method according to claim 25, wherein the system further comprises at least one of a chemiresistor, chemicapacitor, quartz crystal microbalance, bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonator, electrochemical cell, surface plasmon resonance (SPR), and optical spectroscope.

29. The method according to claim 25, wherein the learning and pattern recognition analyzer comprises at least one algorithm selected from the group consisting of artificial neural network algorithms, principal component analysis (PCA), multi-layer perception (MLP), generalized regression neural network (GRNN), fuzzy inference systems (FIS), self-organizing map (SOM), radial bias function (RBF), genetic algorithms (GAS), neuro-fuzzy systems (NFS), adaptive resonance theory (ART), partial least squares (PLS), multiple linear regression (MLR), principal component regression (PCR), discriminant function analysis (DFA), linear discriminant analysis (LDA), cluster analysis, and nearest neighbor.

31. The method according of claim 25, wherein the explosive materials to be detected are selected from the group consisting of pentaerythitol tetranitrate (PETN), tetranitro-tetrazacylooctane (HMX), nitroglycerin (NG), ethylene glycol dinitrate (EGDN), NH₄NO₃, dinitrotoluene (DNT), trinitrotoluene (TNT), tetryl, picric acid, cyclotrimethylenetrinitramine (RDX), mixtures and fragments thereof.

26. (canceled)

27. (canceled)

30. (canceled)