DETECTION OF EXPLOSIVES, TOXINS, AND OTHER COMPOSITIONS

• US 20100112715A1
• Filed: 08/02/2007
• Published: 05/06/2010
• Est. Priority Date: 08/04/2006
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Thomas, Samuel W. III, Swager, Timothy M.
• Granted Patent: US 8,158,437 B2
• Time in Patent Office: Days
• US Class Current: 436/110
• CPC Class Codes: G01N 2021/6432 Quenching
• CPC Class Codes: G01N 33/0057 for warfare agents or explosives properties of explosives G01N33/227
• CPC Class Codes: Y10T 436/17 Nitrogen containing
• CPC Class Codes: Y10T 436/173076 Nitrite or nitrate
• CPC Class Codes: Y10T 436/173845 Amine and quaternary ammonium
• CPC Class Codes: Y10T 436/174614 Tertiary amine
• CPC Class Codes: Y10T 436/175383 Ammonia

Abstract

The present invention generally relates to methods for modulating the optical properties of a luminescent polymer via interaction with a species (e.g., an analyte). In some cases, the present invention provides methods for determination of an analyte by monitoring a change in an optical signal of a luminescent polymer upon exposure to an analyte. Methods of the present invention may be useful for the vapor phase detection of analytes such as explosives and toxins. The present invention also provides methods for increasing the luminescence intensity of a polymer, such as a polymer that has been photobleached, by exposing the luminescent polymer to a species such as a reducing agent.

Claims

1. A method for determination of 2,3-dimethyl-2,3-dinitrobutane (DMNB), comprising:

exposing a luminescent polymer to a sample suspected of containing DMNB, wherein DMNB, if present, interacts with the luminescent polymer to cause a change in the luminescence of the polymer; and

determining the change in the luminescence of the polymer, thereby determining DMNB.

2. A method as in claim 1, wherein the change comprises a decrease in luminescence intensity.

3. A method as in claim 1, wherein the change comprises an increase in luminescence intensity.

4. A method as in claim 1, wherein the change comprises a change in the wavelength of the luminescence.

5. A method as in claim 1, wherein the change is caused by a photo induced charge transfer reaction between the luminescent polymer and DMNB.

6. A method as in claim 1, further comprising:

treating the DMNB to produce a nitrite ion; and

determining the presence of the nitrite ion, thereby determining the identity of DMNB.

7. A method as in claim 6, wherein the DMNB is determined by colorimetric methods.

8. A method as in claim 6, wherein the treating comprises exposure to electromagnetic radiation.

9. A method as in claim 1, wherein the luminescent polymer comprises a first monomer and a second monomer, wherein the first monomer is non-planar with respect to the second monomer.

10. A method as in claim 1, wherein the luminescent polymer is a poly(arylene), poly(arylenevinylene), poly(aryleneethylnylene), and substituted derivatives thereof.

11. A method as in claim 1, wherein the luminescent polymer is poly(arylene).

12. A method as in claim 1, wherein the luminescent polymer is poly(phenylene).

13. A method as in claim 1, wherein the luminescent polymer comprises a pendant group comprising a triazole group, optionally substituted.

14. A method as in claim 1, wherein the luminescent polymer has the structure,

wherein

Y³ is alkene, alkyne, aryl, heteroalkene, heteroalkyne, or heteroaryl, optionally substituted;

R is aryl or alkyl, optionally substituted; and

and n is greater than 1.

15. A method as in claim 1, wherein DMNB, when present, is present in trace quantities.

57. A method as in claim 1, wherein the luminescent polymer has the structure,

wherein X¹ is carbon or heteroatom, and X¹ optionally carries an alkyl substituent, Y and Z are independently hydrogen, alkyl, or heteroalkyl;

and n is greater than 1.

58. A method as in claim 57, wherein the luminescent polymer has the structure,

59. A method as in claim 57, wherein the luminescent polymer has the structure,

60. A method as in claim 57, wherein the luminescent polymer has the structure,

61. A method as in claim 1, wherein the luminescent polymer has the structure,

wherein X² and X³ are independently carbon or heteroatom, and X² and X³ optionally carry an alkyl substituent, and n is greater than 1.

62. A method as in claim 61, wherein the luminescent polymer has the structure,

63. A method as in claim 61, wherein the luminescent polymer has the structure,

64. A method as in claim 1, wherein the luminescent polymer comprises a heterocycle, optionally substituted.

65. A method as in claim 1, wherein the luminescent polymer comprises a triazole group, optionally substituted.

16. A method for determination of hydrazine or hydrazine derivatives, comprising:

exposing a luminescent polymer to a sample suspected of containing hydrazine or hydrazine derivatives, wherein hydrazine or the hydrazine derivative, if present, interacts with the luminescent polymer to cause an increase in the luminescence intensity of the polymer;

determining the increase in luminescence intensity of the polymer, thereby determining hydrazine or the hydrazine derivative.

17. A method as in claim 16, wherein, in the absence of hydrazine or the hydrazine derivative, the luminescent polymer comprises non-radiative pathways, and, in the presence of hydrazine or the hydrazine derivative, hydrazine or the hydrazine derivative interacts with the luminescent polymer to reduce the number of non-radiative pathways, thereby increasing the luminescence intensity of the polymer.

18. A method as in claim 16, wherein the increase in luminescence intensity further comprises a change in the wavelength of the luminescence.

19. A method as in claim 16, wherein the luminescent polymer is a poly(arylene), poly(arylenevinylene), poly(aryleneethylnylene), and substituted derivatives thereof.

20. A method as in claim 16, wherein the luminescent polymer is poly(aryleneethylnylene).

21. A method as in claim 16, wherein the luminescent polymer has the structure,

wherein n is at least 1, A and C are optionally substituted aromatic groups, and B and D are alkene, alkyne, heteroalkene, or heteroalkyne.

22. A method as in claim 16, wherein the luminescent polymer has the structure,

wherein Y² and Z² are independently alkyl, alkoxy, amino, and substituted derivatives thereof.

23. A method as in claim 22, wherein Y² and Z² are alkoxy.

24. A method as in claim 22, wherein Y² and Z² are NR¹R², wherein R¹ and R² are alkyl.

25. A method as in claim 22, wherein Y² is hydrogen and Z² is NR¹R², wherein R¹ and R² are alkyl.

26. A method as in claim 22, wherein the luminescent polymer has the structure,

27. A method as in claim 22, wherein the luminescent polymer has the structure,

28. A method as in claim 16, wherein the luminescent polymer comprises a heterocycle, optionally substituted.

29. A method as in claim 16, wherein the luminescent polymer comprises a triazole group, optionally substituted.

30. A method as in claim 16, wherein the luminescent polymer comprises a pendant group comprising a triazole group, optionally substituted.

31. A method as in claim 16, wherein the luminescent polymer has the structure,

wherein

Y³ is alkene, alkyne, aryl, heteroalkene, heteroalkyne, or heteroaryl, optionally substituted;

and

R is aryl or alkyl, optionally substituted; and

and n is greater than 1.

32. A method as in claim 16, wherein the luminescent polymer comprises oxidized sites and the hydrazine or hydrazine derivative reduces the oxidized sites.

33. A method as in claim 16, wherein the luminescent polymer comprises a quenching molecule associated with the luminescent polymer and the hydrazine or hydrazine derivative reduces the quenching molecule.

34. A method as in claim 32, wherein the quenching molecule is I₂.

35. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 25% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

36. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 50% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

37. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 75% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

38. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 100% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

39. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 250% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

40. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 500% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

41. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 750% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

42. A method as in claim 16, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 1000% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

43. A method as in claim 16, wherein hydrazine or the hydrazine derivative, when present, is present in trace quantities.

48. A method as in claim 39, wherein the quenching molecule is I₂.

44. A method for increasing the luminescence intensity of a polymer, comprising:

exposing a luminescent polymer to hydrazine or the hydrazine derivative,

wherein, in the absence of hydrazine or the hydrazine derivative, the luminescent polymer comprises non-radiative pathways, and, in the presence of hydrazine or the hydrazine derivative, hydrazine or the hydrazine derivative interacts with the luminescent polymer to reduce the number of non-radiative pathways, thereby increasing the luminescence intensity of the polymer.

45. A method as in claim 44, wherein the increase in luminescence intensity further comprises a change in the wavelength of the luminescence.

46. A method as in claim 44, wherein the luminescent polymer comprises oxidized sites and the hydrazine or hydrazine derivative reduces the oxidized sites.

47. A method as in claim 44, wherein the luminescent polymer comprises a quenching molecule associated with the luminescent polymer and the hydrazine or hydrazine derivative reduces the quenching molecule.

49. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 25% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

50. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 50% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

51. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 75% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

52. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 100% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

53. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 250% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

54. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 500% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

55. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 750% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.

56. A method as in claim 44, wherein, in the presence of hydrazine or the hydrazine derivative, the luminescence intensity of the polymer increases by at least 1000% relative to the luminescence intensity of the polymer in the absence of hydrazine or the hydrazine derivative upon exposure to the same conditions of electromagnetic radiation.