Optical chemical sensor and method using same employing a multiplicity of fluorophores contained in the free volume of a polymeric optical waveguide or in pores of a ceramic waveguide

• US 5,577,137 A
• Filed: 02/22/1995
• Issued: 11/19/1996
• Est. Priority Date: 02/22/1995
• Status: Expired due to Term

• Current Assignee: American Research Corporation Of Virginia
• Original Assignee: American Research Corporation Of Virginia
• Inventors: Weiss, Martin, Lo, Peter, Groger, Howard P., Luo, Shufang, Churchill, Russell J.
• Primary Examiner(s): Healy, Brian
• Application Number:
  US08/392,152
• Time in Patent Office: 636 Days
• Field of Search: 385/12, 385/14, 385/27, 385/30, 385/33, 385/37, 385/39, 385/129, 385/130, 385/131, 385/132, 385/141, 422/68.1, 422/73, 422/50, 422/57, 250/227.11, 250/227.14, 250/227.18, 250/227.23, 250/576
• US Class Current: 385/12
• CPC Class Codes: G01N 2021/7793 Sensor comprising plural indicators
• CPC Class Codes: G01N 21/6408 with measurement of decay time, time resolved fluorescence
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: G01N 21/648 using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: G02B 6/02 Optical fibres with cladding with or without a coating
• CPC Class Codes: G02B 6/132 by deposition of thin films

Abstract

A fluorescent sensor for chemical analysis has a light source, an optical waveguide, and a detector. Fluorophores are associated with the optical waveguide. When an impervious waveguide is used, a fluorophore-containing layer is applied to a surface of the waveguide. The fluorophores are excited by a laser, a light emitting diode, an electroluminescent source or a lamp source emitting light propagating at angles to the waveguide. The light source is modulated. A mirror can be used to direct the light beam. The angle of light incidence on the waveguide can be altered by moving the waveguide itself. The waveguide traps the laser-induced fluorescence and projects fluorescence signals through a suitable filter to a photodetector or otherwise wavelength-specific photodetector positioned near the waveguide structure. Remote operation of the sensor is achieved using optical fibers. Patterned waveguides allow multiple excitation sources to illuminate multiple fluorescent probe materials. The change in fluorescence from each fluorophore is sensed as a vector response which is evaluated using digital signal processing. The sensor uses steady state fluorescence and fluorescence decay information to determine identity and concentration of analytes of interest. The invention is used for chemical analysis of gases or of liquid materials.

Claims

1. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the optical waveguide further comprises a substrate layer and a porous overlying layer, the porous overlying layer containing the fluorophores, and wherein the substrate layer has a lower refractive index than the overlying layer.

2. The apparatus of claim 1, wherein the substrate layer is glass and the overlying layer is a polymer material.

3. The apparatus of claim 1, wherein the substrate layer is a polymer material and the overlying layer is a polymer material.

4. The apparatus of claim 1, wherein the light source is modulatable and wherein the light source is directed toward the waveguide at an angle for exciting the fluorophores.

5. The apparatus of claim 1, wherein the light source is a modulated light source directed toward the waveguide for producing a modulated light signal that excites the fluorophores in the optical waveguide and generates the fluorescence signals.

6. The apparatus of claim 5, further comprising an electronic light modulator connected to the light source for modulating the light source and a signal processor connected to the light modulator and to the detector for sequentially modulating the light source and collecting an electronic signal from the detector for providing improved signal-to-noise ratio, for determining lifetimes of the fluorescence signal, for conditioning electronic signals and for identifying and measuring concentration of an analyte.

9. The apparatus of claim 1, further comprising an optical filter positioned between the optical waveguide and the detector for filtering the fluorescence signal.

10. The apparatus of claim 9, further comprising a lens positioned between the filter and the optical waveguide for focusing the fluorescence signal.

7. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the detector comprises an array of photodetectors.

8. The apparatus of claim 7, wherein the array of photodetectors comprises an intensified charge coupled device camera.

11. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the waveguide has at least two regions of differing fluorophores in different host materials.

12. The apparatus of claim 11, wherein the detector further comprises multiple photodetectors equal in number to a number of the regions, and wherein each photodetector receives and evaluates a fluorescence signal from only one region.

13. The apparatus of claim 12, further comprising a lens positioned between the photodetectors and the waveguide for focusing the fluorescence signals and an optical filter positioned between the photodetectors and the lens for filtering the fluorescence signals.

14. The apparatus of claim 12, further comprising an optical filter positioned between the photodetectors and the waveguide for filtering the fluorescence signal.

15. The apparatus of claim 14, further comprising a movable mirror intermediate the light source and the waveguide for modulating light from a light source and directing the light on different regions of the waveguide.

16. The apparatus of claim 14, further comprising a piezoelectric mover connected to the waveguide for modulating the position of the waveguide with respect to light beams from the light source.

17. The apparatus of claim 12, further comprising a beam converter positioned between the light source and the waveguide for converting a single collimated beam to multiple beams.

18. The apparatus of claim 17, wherein the beam converter is selected from the group consisting of a fanout grating, an holographic optical element, a series of beamsplitters, and a series of beamsplitting optical couplers.

19. The apparatus of claim 17, further comprising a lens positioned between the beam converter and the waveguide for focusing the multiple beams from the converter on different regions of the waveguide.

20. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the detector comprises at least two photodetectors, and wherein a first photodetector is positioned near the waveguide for detecting reflected light, and a second photodetector is positioned above the waveguide for detecting fluorescence signals.

21. The apparatus of claim 20, further comprising an optical filter positioned between the second detector and the waveguide for filtering the fluorescence signals.

22. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the optical waveguide further comprises a substrate layer and an impervious overlying layer, the impervious overlying layer containing fluorophores, and wherein the substrate layer has a lower refractive index than the overlying layer, and further comprising a coating layer positioned over the impervious layer of the waveguide, the coating layer containing fluorophores that fluoresce upon excitation from signals emitted from fluorophores in the impervious layer that interact with a chemical analyte.

23. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, further comprising an input port on the waveguide, an output port on the waveguide, a first optical fiber optically coupled to the waveguide at the input port for delivering light signals to the waveguide, and a second optical fiber optically coupled to the waveguide at the output port for collecting the fluorescence signals.

24. The apparatus of claim 23, further comprising multiple dielectric mirrors attached to the waveguide for directing light through the waveguide for providing reflection back into the waveguide, and wherein the mirrors are coated with fluorophores.

25. The apparatus of claim 23, wherein the first optical fiber is optically coupled to the input port by a grating.

26. The apparatus of claim 23, wherein the waveguide has a free space interconnect and the light signal enters the interconnect through a lens or a lens array.

27. The apparatus of claim 23, wherein the output port is a grating.

28. The apparatus of claim 23, wherein the output port is a prism coupler.

29. A chemical sensor apparatus comprising an optical waveguide, fluorophores positioned in the waveguide, a light source for exciting the fluorophores and generating fluorescence signals, and a detector positioned near the waveguide for sensing the fluorescence signals, wherein the waveguide has first and second opposite surfaces and further comprising dielectric layers deposited on the first surface and on the second surface of the waveguide, a coating layer positioned on a top dielectric layer, and a substrate positioned below a bottom dielectric layer, and wherein the dielectric layers serve as dielectric mirrors.

30. A method for identifying and measuring concentration of a chemical analyte in either gaseous or liquid phase comprising exciting fluorophores associated with an optical waveguide by using a modulated light source and creating fluorescence signals;

trapping the fluorescence signals in the waveguide;

transmitting the fluorescence signals from the optical waveguide;

detecting the fluorescence signals;

collecting the fluorescence signals;

determining lifetime of the fluorescence signals; and

converting the fluorescence signals to electronic signals, further comprising propagating the fluorescence signals from the waveguide through an internal grating structure, further comprising propagating a collimated beam from the light source, converting the beam to multiple beams, and directing the multiple beams on multiple fluorophore/host regions in the optical waveguide.