Fiber optic analyte sensor with integrated in situ total pressure correction

• US 9,316,554 B1
• Filed: 12/23/2014
• Issued: 04/19/2016
• Est. Priority Date: 12/23/2014
• Status: Active Grant

• Current Assignee: MOCON, Inc. (Ametek Incorporated)
• Original Assignee: MOCON, Inc. (Ametek Incorporated)
• Inventors: Eastman, John, Mayer, Daniel W.
• Primary Examiner(s): Wallenhorst, Maureen
• Application Number:
  US14/580,873
• Time in Patent Office: 483 Days
• Field of Search: 436/68, 436/127, 436/133, 436/136, 436/148, 436/164, 436/165, 436/167, 436/169, 436/172, 436/181, 422/416, 422/417, 422/420, 422/68.1, 422/82.05, 422/82.08, 422/82.13, 422/83, 422/88, 422/91
• US Class Current: 1/1
• CPC Class Codes: G01N 1/2226 Sampling from a closed space, e.g. food package, head space
• CPC Class Codes: G01N 2021/6432 Quenching
• CPC Class Codes: G01N 2021/6439 with indicators, stains, dyes, tags, labels, marks
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/766 of gases
• 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 2201/08 Optical fibres; light guides
• CPC Class Codes: G01N 33/004 for CO, CO2
• CPC Class Codes: G01N 33/02 Food
• CPC Class Codes: G01N 33/15 Medicinal preparations ; Physical properties thereof, e.g. dissolubility drug screening with animal cells G01N33/5008
• CPC Class Codes: Y10T 436/207497 Molecular oxygen

Abstract

A fiber optic analyte sensing needle employing an analyte-partial-pressure-sensitive photoluminescent probe, characterized by (i) a void volume channel extending axially along the length of the lumen between the inner surface of the tube and the outer surface of the fiber optic filament, and (ii) a total pressure sensor in pressure communication with the distal tip of the needle via the void volume channel, whereby total pressure of a volume sampled by the sensing needle can be routinely measured and used in pressure compensation of analyte-concentration values calculated from the analyte-partial-pressure readings taken from the analyte-partial-pressure-sensitive photoluminescent probe.

Claims

1. An in situ analyte-sensing fiber optic instrument, comprising (i) a tube having a distal end and an inner surface defining a lumen, (ii) an analyte-partial-pressure-sensitive photoluminescent probe located proximate a distal end of the lumen and in fluid communication with a fluid occupying a volume external to the distal end of the tube through an opening in the tube, and (iii) at least one fiber optic filament having an outer surface, extending axially along the length of the lumen and in optical communication with the analyte-partial-pressure-sensitive photoluminescent probe, the instrument further comprising:

(a) a void volume channel extending axially along the length of the lumen between the inner surface of the tube and the outer surface of the at least one fiber optic filament, and

(b) a pressure sensor in pressure communication via the void volume channel in the lumen of the tube with the fluid from the volume communicating with the analyte-partial-pressure-sensitive photoluminescent probe via the opening in the tube.

2. The in situ analyte-sensing fiber optic instrument of claim 1 wherein the pressure sensor generates a P_TOTAL electronic signal representative of the total-pressure of a fluid in fluid communication with the probe, and the instrument further comprises:

(a) a detector in optical communication with the analyte-partial-pressure-sensitive photoluminescent probe via the at least one fiber optic filament for receiving radiant energy emitted by the probe and generating a P_ANALYTE electrical signal representative of the analyte-partial-pressure of a fluid in fluid communication with the probe,

(b) a microprocessor in electrical communication with the pressure sensor and the detector for receiving temporally paired P_TOTAL and P_ANALYTE electrical signals respectively, and calculating an analyte concentration from the temporally paired electrical signals based upon an algorithm ANALYTE %=P_ANALYTE/P_TOTAL, and

(c) an electronic display in electrical communication with the microprocessor for displaying calculated analyte concentration values.

3. The in situ analyte-sensing fiber optic instrument of claim 2 further comprising a user activatable trigger operable for simultaneously generating temporally paired P_TOTAL and P_ANALYTE electrical signals each time the trigger is activated.

4. The in situ analyte-sensing fiber optic instrument of claim 1 wherein the tube is a blunt-tipped needle with a nominal inner diameter of 1.0 to 3.5 mm.

5. The in situ analyte-sensing fiber optic instrument of claim 1 wherein the tube is a sharp-tipped needle with a nominal inner diameter of 1.0 to 3.5 mm.

6. The in situ analyte-sensing fiber optic instrument of claim 1 wherein the void volume channel is an amorphous channel.

7. The in situ analyte-sensing fiber optic instrument of claim 1 wherein the pressure sensor is in fluid communication with fluid communicating with the analyte-partial-pressure-sensitive photoluminescent probe via the void volume channel in the lumen of the tube.

8. A method for measuring an analyte concentration within a space enclosed by a structure, comprising the steps of:

(a) obtaining an analyte-sensing fiber optic instrument according to claim 1,

(b) penetrating the structure with the tube of the instrument so as to place the distal end of the lumen into fluid communication with the space enclosed by the structure, whereby both the analyte-partial-pressure-sensitive photoluminescent probe and the pressure sensor on the instrument are placed into sensible communication with the enclosed space,

(c) allowing the concentration of analyte in sensible communication with the photoluminescent probe to equilibrate with the analyte concentration within the enclosed space,

(d) allowing the pressure in sensible communication with the pressure sensor to equilibrate with the pressure of the enclosed space, and

(e) ascertaining an analyte concentration within the enclosed space by;

(i) measuring the total pressure of the enclosed space with the equilibriated pressure sensor to obtain a measured total pressure value for the enclosed space, (ii) exposing the equilibriated photoluminescent probe to excitation radiation, (iii) measuring radiation emitted by the excited photoluminescent probe, and (iv) converting the measured emission to an analyte concentration based upon a known pressure compensated conversion algorithm that employs the measured total pressure value for the enclosed space.

9. The method of claim 8 wherein the analyte is oxygen.

10. The method of claim 9 wherein the space is a retention chamber of a hermetically sealed package containing an oxygen labile pharmaceutical or foodstuff.

11. A handheld instrument for impromptu in situ concomitant sensing of oxygen partial pressure and total pressure of a hermetically sealed volume, comprising an integrated combination of at least:

(a) a hollow shank having a proximal end, a distal end and an inner surface defining a lumen in fluid communication with a volume external to the distal end,

(b) an oxygen-partial-pressure-sensitive photoluminescent probe within the lumen proximate the distal end of the shank and in fluid communication with a fluid occupying a volume external to the distal end of the shank through an opening in the shank,

(c) an electronics package proximate the proximal end of the shank, including at least;

(i) a source of excitation radiant energy,

(ii) a photoluminescence detector, and

(iii) a pressure sensor, and

(d) at least one fiber optic filament having an outer surface and extending axially along the length of the lumen operable for (i) transmitting excitation radiant energy from the source of excitation radiant energy to the oxygen-partial-pressure-sensitive photoluminescent probe, and (ii) transmitting radiant energy emitted by the oxygen-partial-pressure-sensitive photoluminescent probe to the photoluminescence detector, and configured relative to the lumen to form a void volume channel extending axially along the length of the lumen between the inner surface of the shank and the outer surface of the at least one fiber optic filament, wherein

(e) the pressure sensor is in pressure communication via the void volume channel in the lumen of the shank with the fluid from the volume communicating with the oxygen-partial-pressure-sensitive photoluminescent probe via the opening in the shank.

12. The handheld instrument of claim 11 wherein (i) the photoluminescence detector generates a P_OXYGEN electrical signal representative of the oxygen-partial-pressure of a fluid in fluid communication with the probe, (ii) the pressure sensor generates a P_TOTAL electronic signal representative of the total-pressure of a fluid in fluid communication with the probe, and the electronics package further comprises:

(a) a microprocessor in electrical communication with the photoluminescence detector and the pressure sensor for receiving temporally paired P_OXYGEN and P_TOTAL electrical signals respectively, and calculating an oxygen concentration from the temporally paired electrical signals based upon the algorithm OXYGEN %=P_OXYGEN/P_TOTAL, and

(b) an electronic display in electrical communication with the microprocessor for displaying calculated oxygen concentration values.

13. The handheld instrument of claim 12 further comprising a user activatable trigger operable for simultaneously generating temporally paired P_TOTAL and P_OXYGEN electrical signals each time the trigger is activated.

14. A method for monitoring changes in oxygen concentration within a space enclosed by a structure, comprising the steps of:

(a) obtaining an instrument according to claim 12,

(b) penetrating the structure with the hollow shank of the instrument so as to place a distal end of the lumen into fluid communication with the space enclosed by the structure, whereby both the oxygen-partial-pressure-sensitive photoluminescent probe and the pressure sensor on the instrument are placed into sensible communication with the enclosed space,

(c) allowing the concentration of oxygen in sensible communication with the photoluminescent probe to equilibrate with the oxygen concentration within the enclosed space,

(d) allowing the pressure in sensible communication with the pressure sensor to equilibrate with the pressure of the enclosed space,

(e) ascertaining an oxygen concentration within the enclosed space over time by;

(i) coincidentally and repeatedly measuring the total pressure of the enclosed space with the equilibriated pressure sensor to obtain a measured total pressure value for the enclosed space, and the partial pressure of oxygen in the enclosed spaced with the equilibriated photoluminescent probe, (ii) measuring passage of time during the repeated coincidental measurements to establish a time interval between repeated coincidental measurements, and (iii) converting at least some of the coincidental measurements to an oxygen concentration based upon a known pressure compensated conversion algorithm that employs the measured total pressure value for the enclosed space, and

(f) reporting at least one of (i) at least two ascertained oxygen concentrations and the time interval between those reported concentrations, and (ii) a rate of change in oxygen concentration within the enclosed space calculated from data obtained in step (e).

15. The method of claim 14 wherein the space is a retention chamber of a hermetically sealed package containing an oxygen labile pharmaceutical or foodstuff.

16. The handheld instrument of claim 11 wherein the shank is a blunt-tipped needle with a nominal inner diameter of 1.0 to 3.5 mm.

17. The handheld instrument of claim 11 wherein the shank is a sharp-tipped needle with a nominal inner diameter of 1.0 to 3.5 mm.

18. The handheld instrument of claim 11 wherein the void volume channel is an amorphous channel.

19. The handheld instrument of claim 11 wherein the pressure sensor is in fluid communication with fluid communicating with the oxygen-partial-pressure-sensitive photoluminescent probe via the void volume channel in the lumen of the shank.