Apparatus for continuously monitoring a plurality of chemical analytes through a single optical fiber and method of making

• US 5,098,659 A
• Filed: 09/24/1990
• Issued: 03/24/1992
• Est. Priority Date: 09/24/1990
• Status: Expired due to Term

• Current Assignee: Hospira Incorporated (Pfizer Inc.)
• Original Assignee: Abbott Laboratories Incorporated
• Inventors: Yim, Jeffrey B., Huss, Bradley D., Pihl, Roger J., Khalil, Gamal-Eddin, Vurek, Gerald G.
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): NOT, DEFINED
• Application Number:
  US07/587,234
• Time in Patent Office: 547 Days
• Field of Search: 422/82.06, 422/82.07, 128/634, 128/636, 350/96.29, 356/39, 427/2
• US Class Current: 422/82.07
• CPC Class Codes: A61B 5/14539 for measuring pH
• CPC Class Codes: A61B 5/1459 invasive, e.g. introduced into the body by a catheter A61B5/1464 takes precedence
• CPC Class Codes: G01N 2021/6434 Optrodes
• CPC Class Codes: G01N 2021/772 Tip coated light guide
• CPC Class Codes: G01N 2021/773 Porous polymer jacket; Polymer matrix with indicator
• CPC Class Codes: G01N 2021/7793 Sensor comprising plural indicators
• CPC Class Codes: G01N 21/643 non-biological material
• 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: G01N 21/80 Indicating pH value

Abstract

A CO₂ /O₂ or pH/O₂ gas sensor comprising a single optical fiber and a method for making the same. The optical fiber carries light signals at different wavelengths for monitoring either CO₂ concentration or pH level, in combination with O₂ concentration. Attached to the distal end of the fiber-optic probe is a cylindrical pellet that has one surface covered by a light reflective material (gold foil) and the other surface attached adjacent to the distal end of the optical fiber. Depending on whether the sensor is to monitor either CO₂ or pH, the pellet comprises either a CO₂ analyte indicator molecule or a pH analyte indicator molecule covalently bonded to a polymer matrix material. Also adjacent to the distal end of the optical fiber is disposed a second polymer matrix material which is codissolved with an O₂ analyte reactive indicator molecule. The second polymer matrix material is either interposed between the cylindrical pellet and the distal end of the optical fiber or surrounds the cylindrical pellet. If pH is being measured, the distal end of the optical fiber is coated with a hydrophilic material that is permeable to water. Conversely, if CO₂ is being monitored, the distal end is coated with a hydrophobic material.

Claims

1. A probe for monitoring a plurality of chemical parameters comprising:

(a) an optical fiber having a longitudinal axis along which light signals at a plurality of wavelengths are propagated bidirectionally;

(b) an optical sensor attached adjacent to a distal end of the optical fiber, said sensor comprising a first analyte indicator, light signals of a first wavelength being absorbed by the first analyte indicator to an extent dependent upon the amount of a first analyte present; and

(c) a polymer matrix material in which a second analyte indicator is provided, said polymer matrix material being disposed adjacent to the distal end of the optical fiber and adjacent the optical sensor, light signals of a second wavelength transmitted to the distal end of the optical fiber exciting the second analyte indicator to emit light, a decay time of the light emission varying in response to a concentration of the second analyte.

2. The probe of claim 1, wherein the first analyte indicator is sensitive to a carbon dioxide concentration.

3. The probe of claim 1, wherein the first analyte indicator is sensitive to a pH level.

4. The probe of claim 1, wherein the optical sensor is attached to the distal end of the optical fiber with a thin coat of said polymer matrix material and second analyte indicator.

5. The probe of claim 4, wherein the optical sensor and the distal end of the optical fiber are covered with a coating comprising said polymer matrix material and said second analyte indicator.

6. The probe of claim 1, wherein the optical sensor comprises a pellet attached to a transverse surface of the optical fiber at its distal end, said pellet covering only a portion of the transverse surface, a coating comprising said polymer matrix material and said second analyte indicator enclosing said pellet, said transverse surface, and said distal end of the optical fiber.

7. The probe of claim 1, wherein said polymer matrix material and said second analyte indicator comprises a layer interposed between the optical sensor and the distal end of the optical fiber.

8. The probe of claim 1, wherein the first analyte is carbon dioxide and said first analyte indicator is sensitive to a carbon dioxide concentration.

9. The probe of claim 1, wherein the first analyte comprises hydrogen ions, and said first analyte indicator is sensitive to a pH level.

10. The probe of claim 7, wherein the first analyte is ionized in water, further comprising a hydrophilic coating applied over the layer of said polymer matrix material and second analyte indicator, and over the optical sensor.

11. The probe of claim 7, wherein the first analyte is a gaseous substance, further comprising a hydrophobic coating applied over the layer of said polymer matrix material and second analyte indicator and over the optical sensor.

12. The probe of claim 6, wherein said first analyte is ionized in water, said polymer matrix being hydrophilic and thus permeable to water.

13. The probe of claim 6, wherein said first analyte is a gaseous substance, said polymer matrix being hydrophobic and thus permeable to the gaseous substance.

14. The probe of claim 1, wherein said second analyte is oxygen and said second analyte indicator comprises a porphyrin compound.

15. The probe of claim 1, wherein the second analyte indicator is substantially unaffected by light signals at the first wavelength.

16. A blood gas sensor comprising:

(a) an optical fiber having a longitudinal axis along which light signals are propagated bidirectionally at a plurality of wavelengths;

(b) a first polymer matrix material containing a first indicator molecule, said first indicator molecule exhibiting phosphorescence when excited by light of a first wavelength, the duration of phosphorescence depending upon an oxygen gas concentration around the sensor;

(c) a second polymer matrix material containing a second indicator molecule, said second indicator molecule absorbing light at a second wavelength as a function of a selected chemical parameter; and

(d) a light reflectance material disposed adjacent said second polymer matrix material such that light transmitted by said optical fiber is substantially reflected back into said optical fiber, wherein said first polymer matrix material is disposed adjacent to said second polymer matrix material and adjacent the distal end of said optical fiber.

17. The blood gas sensor of claim 16, wherein said second polymer matrix material comprises a pellet that is attached to the distal end of said optical fiber.

18. The blood gas sensor of claim 17, wherein said light reflective material is disposed on a surface of said pellet transverse to the longitudinal axis of the optical fiber such that light is substantially reflected back into the optical fiber by the light reflectance material.

19. The blood gas sensor of claim 18, wherein said pellet is attached to the distal end of said optical fiber by said polymer matrix material.

20. The blood gas sensor of claim 17, wherein said distal end of said optical fiber and said pellet are overcoated with said first polymer matrix material.

21. The blood gas sensor of claim 17, wherein said pellet is smaller in diameter than a transverse area of said distal end of said optical fiber and covers only a portion of said transverse area, said first polymer matrix material completely covering the pellet and a remaining portion of the distal end of said optical fiber that is not covered by the pellet.

22. The blood gas sensor of claim 16, wherein a hydrophobic coating is applied over said distal end of said optical fiber, said first polymer matrix material, said second polymer matrix material, and said light reflective material.

23. The blood gas sensor as claimed in claim 16, wherein a hydrophilic coating is applied over said distal end of said fiber-optic light transmission means, covering said first polymer matrix material, said second polymer matrix material, and said light reflective material.

24. The blood gas sensor as claimed in claim 16, wherein said first indicator molecule is substantially unaffected by light of said second wavelength.

25. The blood gas sensor of claim 16, wherein said first indicator molecule comprises a porphyrin compound.

26. The blood gas sensor of claim 16, wherein the second indicator molecule comprises phenol red.

27. The blood gas sensor of claim 22, wherein the selected chemical parameter is carbon dioxide concentration.

28. The blood gas sensor of claim 23, wherein the selected chemical parameter is a hydrogen ion concentration, expressed in terms of a pH level.

29. An optrode for monitoring blood gases comprising:

(a) an optical fiber for propagating light bidirectionally along a longitudinal axis at a plurality of wavelengths;

(b) a first polymer matrix having a first analyte indicator molecule codissolved within said first polymer matrix, said first polymer matrix being disposed at the distal end of said optical fiber such that said propagated light is incident upon said first polymer matrix;

(c) a second polymer matrix having an O₂ analyte indicator molecule codissolved within said second polymer matrix, said second polymer matrix being disposed at the distal end of said optical fiber and separate from the first polymer matrix such that said propagated light is incident upon said second polymer matrix; and

(d) a light reflective material disposed at the distal end of said optical fiber such that said propagated light that is incident upon said first polymer matrix is reflected by said light reflective material back into said optical fiber.

30. The optrode of claim 29, wherein the first analyte indicator molecule is sensitive to a carbon dioxide concentration.

31. The optrode of claim 29, wherein the first analyte indicator molecule is sensitive to a hydrogen ion concentration.

32. The optrode of claim 29, wherein said first polymer matrix is formed into a cylindrical pellet and said light reflective material is disposed directly adjacent to a first circular face of said cylindrical pellet, and wherein said cylindrical pellet is attached to a transverse surface of the distal end of said optical fiber at a second circular face of said cylindrical pellet that is opposite the first circular face.

33. The optrode of claim 32, wherein said cylindrical pellet is attached to said distal end of said optical fiber by the application of a thin coat of said second polymer matrix.

34. The optrode of claim 32, wherein said cylindrical pellet and said distal end of said optical fiber are overcoated with said second polymer matrix.

35. The optrode of claim 29, wherein said first analyte indicator molecule comprises phenol red.

36. The optrode as claimed in claim 29, wherein said first analyte indicator molecule comprises a porphyrin compound.

37. A method for making a chemical sensor, comprising the steps of:

(a) mounting a first polymer matrix on at least a portion of a distal end of an optical fiber so that light propagating through the optical fiber passes into the first polymer matrix, said first polymer matrix containing a first indicator molecule, said first indicator molecule absorbing light of a first wavelength in proportion to the concentration of a first analyte;

(b) applying a thin film of light reflective material adjacent to said first polymer matrix such that light of said first wavelength propagated distally along said optical fiber and through said first polymer matrix is reflected by said thin film of light reflective material, said reflected light propagating back towards a proximal end of said optical fiber; and

(c) applying to the distal end of said optical fiber a second polymer matrix that is separate from said first polymer matrix, said second polymer matrix containing a second indicator molecule, said second indicator molecule emitting light when excited by light of a second wavelength to an extent that is proportional to the concentration of a second analyte disposed around the sensor.

38. The method of claim 37, wherein said first analyte is carbon dioxide, further comprising the step of coating the first polymer matrix and the distal end of the optical fiber with a hydrophobic material.

39. The method of claim 37, wherein said first analyte to be sensed comprises hydrogen ions, further comprising the step of coating the first polymer matrix and the distal end of the optical fiber with a hydrophilic material.

40. The method of claim 37, wherein the second analyte comprises oxygen, further comprising the step of overcoating the distal end of said optical fiber with a material that is permeable to oxygen gas and to said first analyte, such that said material encompasses said first polymer matrix, said thin film of light reflective material, and said second polymer matrix.

41. The method of claim 37, wherein said first analyte comprises hydrogen ions in water and said second analyte comprises oxygen, further comprising the steps of overcoating the distal end of said optical fiber with a hydrophilic material that is permeable to oxygen gas and water, such that said hydrophilic material encompasses said first polymer matrix, said thin film of light reflective material, and said second polymer matrix.

42. The method of claim 37, wherein said second polymer matrix is applied prior to the step of coating said first polymer matrix such that said second polymer matrix is substantially interposed between the distal end of said optical fiber and said first polymer matrix.

43. The method of claim 37, wherein said first polymer matrix covers only a portion of a transverse area of the distal end of said optical fiber such that light of said second wavelength is incident upon said second polymer matrix through a remainder of the transverse area of said distal end.

44. The method of claim 37, wherein said second polymer matrix is substantially transparent to light signals at said first wavelength and said second analyte indicator is generally unaffected by such light signals.