Sensor of species including toxins and chemical warfare agents

• US 9,429,522 B2
• Filed: 07/15/2014
• Issued: 08/30/2016
• Est. Priority Date: 10/27/2006
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy M., Thomas, Samuel W. III, Venkatesan, Koushik
• Primary Examiner(s): Gakh, Yelena G
• Assistant Examiner(s): Adams, Michelle
• Application Number:
  US14/332,231
• Publication Number:
  US 20150247805A1
• Time in Patent Office: 777 Days
• Field of Search: None
• US Class Current: 1/1
• 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;

determining the change in luminescence emission of the metal complex, wherein the change in luminescence emission comprises a blue-shifted change in the wavelength of the luminescence emission; and

determining the presence or absence of the analyte based on the change in luminescence emission of the metal complex.

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 at least one bidentate cyclometallated ligand has the structure,

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 analyte is an electrophilic species.

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

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

13. 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.

14. A method as in claim 13, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 50 nm.

15. A method as in claim 13, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 100 nm.

16. A method as in claim 13, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 150 nm.

17. 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;

determining the change in luminescence emission of the complex, wherein the change comprises a blue-shifted change in the wavelength of the luminescence emission; and

determining the presence or absence of the analyte based on the change in luminescence emission of the complex.

18. A method as in claim 17, 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.

19. A method as in claim 18, wherein the change in the substantially square planar geometry of the metal complex comprises formation of a substantially octahedral geometry of the metal complex.

20. A method as in claim 17, wherein M is platinum, iridium, or palladium.

21. A method as in claim 17, wherein M is platinum.

22. A method as in claim 17, wherein at least one bidentate cyclometallated ligand has the structure,

23. A method as in claim 17, wherein L¹ and L² can be the same or different and are phenylthiophene, thienylpyridine, thianapthylpyridine, or substituted derivatives thereof.

24. A method as in claim 17, wherein the luminescence emission is phosphorescence emission.

25. A method as in claim 17, wherein the analyte is an electrophilic species.

26. A method as in claim 17, wherein the analyte is an alkyl halide or cyanogen halide.

27. A method as in claim 17, wherein the analyte is cyanogen bromide, cyanogen chloride, benzyl bromide, ethyl bromide, methyl iodide, chloroform, or dichloromethane.

28. A method as in claim 17, 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.

29. A method as in claim 28, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 50 nm.

30. A method as in claim 28, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 100 nm.

31. A method as in claim 28, wherein the wavelength of the first emission is separated from the wavelength of the second emission by at least 150 nm.