Sensor of species including toxins and chemical warfare agents

• US 20090215189A1
• Filed: 10/27/2006
• Published: 08/27/2009
• Est. Priority Date: 10/27/2006
• Status: Abandoned Application

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Vankatesan, Koushik, Swager, Timothy M., Thomas, Samuel W.
• Application Number:
  US11/588,881
• Publication Number:
  US 20090215189A1
• Time in Patent Office: Days
• US Class Current: 436/109
• CPC Class Codes: C07F 15/0086 Platinum compounds
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1007 Non-condensed systems
• CPC Class Codes: C09K 2211/1011 Condensed systems
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1092 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/185 of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• CPC Class Codes: G01N 21/64 Fluorescence; Phosphorescence
• CPC Class Codes: G01N 21/76 Chemiluminescence; Bioluminescence
• CPC Class Codes: G01N 2201/06113 Coherent sources; lasers
• CPC Class Codes: G01N 33/0057 Warfare agents or explosives
• CPC Class Codes: Y10T 436/172307 Cyanide or isocyanide
• CPC Class Codes: Y10T 436/196666 Carbon containing compound [e.g., vinylchloride, etc.]

Abstract

The present invention generally relates to emissive materials, devices, and related methods. In some cases, the present invention provides sensors and methods for the determination of analytes, wherein the analytes may be determined by monitoring, for example, a change in an optical signal of an emissive material upon exposure to an analyte. The analyte and the emissive material may interact via a chemical reaction, such as an oxidative addition reaction, or other chemical, biochemical or biological interaction (e.g., recognition), to form a new emissive species. In some cases, the present invention may be useful in the detection of a wide variety of analytes, such as toxins, chemical warfare agents, and explosives. The present invention also provides emissive compounds, and related methods, including metal complexes that are capable of interacting with an analyte to produce a change in the emission of the compound. Some advantages of the present invention include the determination of analytes with high specificity and sensitivity and the ability to fabricate simplified and highly portable devices.

Claims

1. A method for determination of an analyte, comprising:

exposing a metal complex having a luminescence emission to a sample suspected of containing an analyte, wherein the analyte, if present, interacts with the metal complex via an oxidative addition reaction to produce a change in the luminescence emission of the metal complex; and

determining the change in luminescence emission of the metal complex, thereby determining the analyte.

2. A method as in claim 1, wherein, in the absence of analyte, the metal complex has a substantially square planar geometry, and wherein the analyte, if present, interacts with the metal complex to produce a change in the substantially square planar geometry of the metal complex.

3. A method as in claim 2, wherein the change in the substantially square planar geometry of the metal complex comprises formation of a substantially octahedral geometry of the metal complex.

4. A method as in claim 1, wherein the metal complex has the structure,

L¹-M-L²

wherein M is a metal, and L¹ and L² can be the same or different and, when bound to the metal, L¹ and L² are bidentate cyclometallated ligands.

5. A method as in claim 4, wherein M is platinum, iridium, or palladium.

6. A method as in claim 4, wherein M is platinum.

7. A method as in claim 4, wherein the bidentate cyclometallated ligand has the structure,

wherein Ar¹ and Ar² can be the same or different and are aryl or heteroaryl, optionally substituted, or Ar¹ and Ar² together form a fused polycyclic aromatic group, optionally substituted.

8. A method as in claim 4, wherein L¹ and L² can be the same or different and are phenylthiophene, thienylpyridine, thianapthylpyridine, or substituted derivatives thereof.

9. A method as in claim 1, wherein the luminescence emission is phosphorescence emission.

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

11. A method as in claim 10, wherein the change comprises a blue-shifted change in the wavelength of the luminescence emission.

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

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

14. A method as in claim 1, wherein the analyte is an electrophilic species.

15. A method as in claim 1, wherein the analyte is an alkyl halide or cyanogen halide.

16. A method as in claim 1, wherein the analyte is cyanogen bromide, cyanogen chloride, benzyl bromide, ethyl bromide, methyl iodide, chloroform, or dichloromethane.

17. A method as in claim 1, wherein, in the absence of analyte, the metal complex has a first emission, and wherein the analyte, if present, interacts with the metal complex to produce a second emission such that the wavelength of the first emission is separated from the wavelength of the second emission by at least 30 nm.

18. A method as in claim 17, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 50 nm.

19. A method as in claim 17, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 100 nm.

20. A method as in claim 17, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 150 nm.

21. A method for determination of an analyte, comprising:

exposing a metal complex having a luminescence emission to a sample suspected of containing an analyte, wherein the analyte, if present, interacts with the metal complex to produce a change in the luminescence emission of the metal complex,

wherein the metal complex has the structure,

L¹-M-L²,

wherein M is a metal, and L¹ and L² can be the same or different and, when bound to the metal, L¹ and L² are bidentate cyclometallated ligands; and

determining the change in luminescence emission of the complex, thereby determining the analyte.

22. A method as in claim 21, wherein, in the absence of analyte, the metal complex has a substantially square planar geometry, and wherein the analyte, if present, interacts with the metal complex to produce a change in the substantially square planar geometry of the metal complex.

23. A method as in claim 22, wherein the change in the substantially square planar geometry of the metal complex comprises formation of a substantially octahedral geometry of the metal complex.

24. A method as in claim 21, wherein the metal complex has the structure,

L¹-M-L²

wherein M is a metal, and L¹ and L² can be the same or different and, when bound to the metal, L¹ and L² are bidentate cyclometallated ligands.

25. A method as in claim 24, wherein M is platinum, iridium, or palladium.

26. A method as in claim 24, wherein M is platinum.

27. A method as in claim 24, wherein the bidentate cyclometallated ligand has the structure,

wherein Ar¹ and Ar² can be the same or different and are aryl or heteroaryl, optionally substituted, or Ar¹ and Ar² together form a fused polycyclic aromatic group, optionally substituted.

28. A method as in claim 24, wherein L¹ and L² can be the same or different and are phenylthiophene, thienylpyridine, thianapthylpyridine, or substituted derivatives thereof.

29. A method as in claim 21, wherein the luminescence emission is phosphorescence emission.

30. A method as in claim 21, wherein the change comprises a change in the wavelength of the luminescence emission.

31. A method as in claim 21, wherein the change comprises a blue-shifted change in the wavelength of the luminescence emission.

32. A method as in claim 21, wherein the change comprises a decrease in luminescence intensity.

33. A method as in claim 21, wherein the change comprises an increase in luminescence intensity.

34. A method as in claim 21, wherein the analyte is an electrophilic species.

35. A method as in claim 21, wherein the analyte is an alkyl halide or cyanogen halide.

36. A method as in claim 21, wherein the analyte is cyanogen bromide, cyanogen chloride, benzyl bromide, ethyl bromide, methyl iodide, chloroform, or dichloromethane.

37. A method as in claim 21, wherein, in the absence of analyte, the luminescent material has a first emission, and wherein the analyte, if present, interacts with the luminescent material to produce a second emission such that the wavelength of the first emission is separated from the wavelength of the second emission by at least 30 nm.

38. A method as in claim 37, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 50 nm.

39. A method as in claim 37, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 100 nm.

40. A method as in claim 37, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 150 nm.

41. A sensor, comprising:

a metal complex having the structure,

L¹-M-L²

wherein M is a metal, and L¹ and L² can be the same or different and, when bound to the metal, L¹ and L² are bidentate cyclometallated ligands;

a source of energy applicable to the metal complex to cause an emission of radiation; and

an emission detector positioned to detect the emission.

42. A sensor as in claim 41, wherein the bidentate cyclometallated ligand has the structure,

wherein Ar¹ and Ar² can be the same or different and are aryl or heteroaryl, optionally substituted, or Ar¹ and Ar² together form a fused polycyclic aromatic group, optionally substituted.

43. A sensor as in claim 41, wherein M is platinum, iridium, or palladium.

44. A sensor as in claim 41, wherein M is platinum.

45. A sensor as in claim 41, wherein L¹ and L² can be the same or different and are phenylthiophene, thienylpyridine, thianapthylpyridine, or substituted derivatives thereof.

46. A sensor as in claim 41, wherein the metal complex is in solution.

47. A sensor as in claim 41, further comprising a support material.

48. A sensor as in claim 47, wherein the metal complex is dispersed within the support material.

49. A sensor as in claim 47, wherein the metal complex is bonded to the support material.

50. A sensor as in claim 47, wherein the support material is a polymer.

51. A sensor as in claim 50, wherein the polymer is poly(methyl methacrylate), polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl benzoate), poly(vinyl acetate), cellulose, corn starch, poly(vinyl pyrrolidinone), polyacrylamide, epoxy, silicone, poly(vinyl butyral), polyurethane, nylon, polacetal, polycarbonate, polyester, polyether, polybutadiene, or combinations thereof.

52. A sensor as in claim 50, wherein the polymer is poly(methylmethacrylate), poly(vinylpyrrolidinone), or poly(4-vinylpyridine).

53. A sensor as in claim 50, wherein the polymer is poly(methylmethacrylate).

54. A sensor as in claim 41, wherein the source of energy is an electric, magnetic, optical, acoustic, electromagnetic, or mechanical field.

55. A sensor as in claim 41, wherein the source of energy is electromagnetic radiation.

56. A sensor as in claim 41, wherein the emission is phosphorescence emission.

57. A composition of matter, comprising:

a compound having the following structure,

L¹-M-L²

wherein M is a metal, and L¹ and L² can be the same or different and each is a bidentate ligand having the structure,

wherein Ar¹ and Ar² can be the same or different and are aryl or heteroaryl, optionally substituted, or Ar¹ and Ar² together form a fused polycyclic aromatic group, optionally substituted,

provided that when L¹ and L² are the same, L¹ and L² are not phenylthiophene, thienylpyridine, benzoquinoline, 1-phenylpyrazole, or 2-thienylpyrazole.

58. A composition of matter as in claim 57, wherein M is platinum, iridium, or palladium.

59. A composition of matter as in claim 57, wherein M is platinum.

60. A composition of matter as in claim 57, wherein L¹ and L² can be the same or different and are phenylthiophene, thienylpyridine, thianapthylpyridine, or substituted derivatives thereof.

61. A composition of matter as in claim 57, wherein the compound has the structure,

62. A composition of matter as in claim 57, wherein the compound has the structure,

63. A composition of matter as in claim 57, wherein the compound has the structure,

64. A composition of matter as in claim 57, wherein the compound has the structure,

65. A composition of matter as in claim 57, wherein the compound has the structure,

66. A composition of matter as in claim 57, wherein the compound has the structure,

67. A composition of matter as in claim 57, wherein the compound has the structure,

68. A method of synthesizing a bis-cyclometallated metal complex, comprising:

halogenating at least one bidentate ligand having the follow structure,

to form a halogenated bidentate ligand, wherein Ar¹ and Ar² can be the same or different and are aryl or heteroaryl, optionally substituted, or Ar¹ and Ar² together form a fused polycyclic aromatic group, optionally substituted; and

forming a metal complex between the halogenated bidentate ligand and a metal.

69. A method as in claim 68, wherein halogenating comprises exposure to bromine or N-bromosuccinimide (NBS).

70. A method as in claim 68, further comprising lithiating the halogenated bidentate ligand.

71. A method as in claim 68, wherein the metal is platinum, iridium, or palladium.

72. A method as in claim 68, wherein the metal is platinum.

73. A method as in claim 68, wherein each bidentate ligand can be the same or different and can be phenylthiophene, thienylpyridine, thianapthylpyridine, benzoquinoline, or a substituted derivative thereof.

74. A method for determination of an analyte, comprising:

providing a luminescent material having a first emission at a wavelength;

exposing the luminescent material to a sample suspected of containing an analyte, wherein the analyte, if present, interacts with the luminescent material to produce a second emission at said wavelength, wherein the luminescence intensity of the second emission is at least 10 times greater than the luminescence intensity of the first emission; and

determining the second emission, thereby determining the analyte.

75. A method as in claim 74, wherein, in the absence of analyte, the first emission has substantially no luminescence intensity at said wavelength.

76. A method as in claim 74, wherein the luminescence intensity of the second emission is at least 10² times greater than the luminescence intensity of the first emission at said wavelength.

77. A method as in claim 74, wherein the luminescence intensity of the second emission is at least 10³ times greater than the luminescence intensity of the first emission at said wavelength.

78. A method as in claim 74, wherein the luminescence intensity of the second emission is at least 10⁴ times greater than the luminescence intensity of the first emission at said wavelength.

79. A method as in claim 74, wherein the luminescence intensity of the second emission is at least 10⁵ times greater than the luminescence intensity of the first emission at said wavelength.

80. A method as in claim 74, wherein the luminescence intensity of the second emission is at least 10⁶ times greater than the luminescence intensity of the first emission at said wavelength.

81. A method as in claim 74, wherein the luminescence emission is phosphorescence emission.

82. A method as in claim 74, wherein the analyte, if present, interacts with the luminescent material to produce a change in the wavelength of the luminescence emission.

83. A method as in claim 82, wherein the change comprises a blue-shifted change in the wavelength of the luminescence emission.

84. A method as in claim 74, wherein the wavelength of the emission of the luminescent material in the presence of analyte is separated from the wavelength of the emission of the luminescent material in the absence of analyte by at least 30 nm.

85. A method as in claim 74, wherein the wavelength of the emission of the luminescent material in the presence of analyte is separated from the wavelength of the emission of the luminescent material in the absence of analyte by at least 50 nm.

86. A method as in claim 74, wherein the wavelength of the emission of the luminescent material in the presence of analyte is separated from the wavelength of the emission of the luminescent material in the absence of analyte by at least 100 nm.

87. A method as in claim 74, wherein the wavelength of the emission of the luminescent material in the presence of analyte is separated from the wavelength of the emission of the luminescent material in the absence of analyte by at least 150 nm.

88. A method as in claim 74, wherein the luminescent material is a metal complex having the structure,

L¹-M-L²

wherein M is a metal, and L¹ and L² can be the same or different and, when bound to the metal, L¹ and L² are bidentate cyclometallated ligands.

89. A method as in claim 74, wherein the interaction between the metal complex and the analyte comprises an oxidative addition reaction.

90. A method as in claim 74, wherein the analyte is an electrophilic species.

91. A method as in claim 74, wherein the analyte is an alkyl halide or cyanogen halide.

92. A method as in claim 74, wherein the analyte is cyanogen bromide, cyanogen chloride, benzyl bromide, ethyl bromide, methyl iodide, chloroform, or dichloromethane.