Flow optrode having separate reaction and detection chambers

• US 5,434,084 A
• Filed: 09/06/1989
• Issued: 07/18/1995
• Est. Priority Date: 09/06/1989
• Status: Expired due to Fees

• Current Assignee: Board of Regents of The University of Washington (University of Washington)
• Original Assignee: Board of Regents of The University of Washington (University of Washington), Washington Research Foundation (University of Washington)
• Inventors: Burgess, Lloyd W. Jr.
• Primary Examiner(s): Housel, James C.
• Assistant Examiner(s): Soderquist, Arlen
• Application Number:
  US07/404,285
• Time in Patent Office: 2,141 Days
• Field of Search: 422/68.1, 422/82.05, 422/82.06, 422/82.07, 422/82.08, 422/52, 436/172, 436/52, 436/177, 436/178, 128/633, 128/634, 128/635, 128/636, 128/673, 356/39, 356/40, 356/41
• US Class Current: 436/52
• CPC Class Codes: G01N 2021/0385 Diffusing membrane; Semipermeable membrane
• CPC Class Codes: G01N 2021/1738 Optionally different kinds of measurements; Method being valid for different kinds of measurement
• CPC Class Codes: G01N 2021/174 either absorption-reflection or emission-fluorescence
• CPC Class Codes: G01N 2021/6434 Optrodes
• CPC Class Codes: G01N 2021/754 Reagent flow and intermittent injection of sample or vice versa
• CPC Class Codes: G01N 2021/7733 Reservoir, liquid reagent
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/75 Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated systems in which material is burnt in a flame or plasma G01N21/72, G01N21/73
• CPC Class Codes: G01N 21/76 Chemiluminescence; Bioluminescence
• 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
• CPC Class Codes: G01N 2201/06126 Large diffuse sources
• CPC Class Codes: G01N 2201/0622 Use of a compensation LED
• CPC Class Codes: G01N 2201/08 Optical fibres; light guides
• CPC Class Codes: G01N 2201/082 Fibres for a reference path
• CPC Class Codes: Y10T 436/117497 with a continuously flowing sample or carrier stream
• CPC Class Codes: Y10T 436/25375 Liberation or purification of sample or separation of material from a sample [e.g., filtering, centrifuging, etc.]
• CPC Class Codes: Y10T 436/255 including use of a solid sorbent, semipermeable membrane, or liquid extraction

Abstract

There is disclosed a device capable of continuously measuring the presence and concentration of an analyte or analytes and a method for using said device in a liquid and/or a gas phase reaction volume. The inventive device comprises a sensor probe, a reservoir, and a detector. The inventive device delivers reagent to the sensor probe in a flow method to directly and continuously renew reagent, thereby allowing the continuous measurement of the presence and the concentration of an analyte or analytes.

Claims

1. A device for continuously measuring an analyte in a liquid or gas sample, comprising:

a sensor probe comprising a first reaction chamber and a second detection chamber downstream from and in fluid communication with the first reaction chamber, wherein the first reaction chamber comprises a permeable membrane separating the reaction chamber from the liquid or gas sample, an inflow opening connecting the reaction chamber to a reagent reservoir, and a reaction chamber outflow opening connecting the first reaction chamber to the second detection chamber, and wherein the second detection chamber is defined by an enclosed space which comprises a primary electromagnetic radiation source fiber, a detection fiber and a detection chamber outflow opening, wherein the primary electromagnetic radiation source fiber is capable of directing electromagnetic radiation across a defined path within the second detection chamber toward the detection fiber, wherein a reagent flows into the first reaction chamber through the inflow opening and contacts the permeable membrane and then flows out of the first reaction chamber and into the second detection chamber by way of the reaction chamber outflow opening where it passes across the defined path within the second detection chamber and flows out the detection chamber outflow opening, wherein the analyte in the liquid or gas sample diffuses across the permeable membrane and into the first reaction chamber, and wherein the first reaction chamber and second detection chamber are both located within the sensor probe;

a reagent reservoir in fluid communication with the inflow opening of the first reaction chamber, wherein the reservoir is capable of containing the reagent, and wherein the reagent chemically reacts with the analyte which diffuses across the permeable membrane to modulate the electromagnetic radiation passing across the defined path differently than reagent alone; and

a detection device communicating with the detection fiber of the second detection chamber.

2. The device of claim 1 further comprising a waste reservoir in fluid communication with the detection chamber outflow opening.

3. The device of claim 1 further comprising a secondary source of electromagnetic radiation within the second detection chamber, wherein the secondary source of electromagnetic radiation is a means for scattering or reflecting electromagnetic radiation from the primary electromagnetic radiation source, and wherein the defined path is the distance from the secondary source to the detection fiber.

4. The device of claim 3 wherein the secondary source of electromagnetic radiation is an optically transparent or translucent material that scatters or reflects the electromagnetic radiation.

5. The device of claim 1 wherein the permeable membrane is selected from the group consisting of a semipermeable membrane, an ion exchange membrane and a combination thereof.

6. The device of claim 5 wherein the semi-permeable membrane is made from porous polytetrafluoroethylene, porous polypropylene or silicon rubber.

7. The device of claim 5 wherein the ion exchange membrane is selected from the group consisting of aminated polystyrene, aminated polypropylene, aminated polyethylene, perfluorinated membranes, sulfonated polystyrene polyacrylates and polypropylene, radiation grafted polymers having trimethyl amine, ethyl dimethyl amine and dimethylethanolamine as functional groups, and combinations thereof.

8. The device of claim 1 wherein the electromagnetic radiation is selected from the group consisting of ultraviolet light, visible light, and infrared light.

9. The device of claim 1 wherein the second detection chamber further comprises a source reference detection fiber in communication with the detection device.

10. The device of claim 1 further comprising a means for regulating the rate at which the reagent flows into the first reaction chamber.

11. A method for continuously measuring an analyte in a liquid or gas sample, comprising:

contacting a sensor probe with the liquid or gas sample, wherein the sensor probe comprises a first reaction chamber and a second detection chamber downstream from and in fluid communication with the first reaction chamber, wherein the first reaction chamber comprises a permeable membrane separating the reaction chamber from the liquid or gas sample, an inflow opening connecting the reaction chamber to a reagent reservoir, and a reaction chamber outflow opening connecting the first reaction chamber to the second detection chamber, and wherein the second detection chamber is defined by an enclosed space which comprises a primary electromagnetic radiation source fiber, a detection fiber and a detection chamber outflow opening, wherein the primary electromagnetic radiation source fiber is capable of directing electromagnetic radiation across a defined path within the second detection chamber toward the detection fiber, wherein a reagent flows into the first reaction chamber through the inflow opening and contacts the permeable membrane and then flows out the first reaction chamber and into the second detection chamber by way of the reaction chamber outflow opening where it passes across the defined path within the second detection chamber and flows out the detection chamber outflow opening, wherein the analyte in the liquid or gas sample diffuses across the permeable membrane and into the first reaction chamber, wherein the first reaction chamber and second detection chamber are both located within the sensor probe, and wherein the detection fiber of the second detection chamber is in communication with a detection device;

adjusting the concentration of the reagent and the flow rate at which the reagent flows into the first reaction chamber through the inflow opening; and

detecting the analyte in the liquid or gas sample by the analyte diffusing across the permeable membrane and into the first reaction chamber, reacting with the reagent, modulating the electromagnetic radiation directed across the defined path within the second detection chamber, and detecting the modulated signal with the detection device which is in communication with the detection fiber.

12. The method of claim 11 wherein the sensor probe further comprises a waste reservoir in fluid communication with the detection chamber outflow opening.

13. The method of claim 11 wherein the sensor probe further comprises a secondary source of electromagnetic radiation within the second detection chamber, wherein the secondary source of electromagnetic radiation is a means for scattering or reflecting electromagnetic radiation from the primary electromagnetic radiation source, and wherein the defined path is the distance from the secondary source to the detection fiber.

14. The method of claim 13 wherein the secondary source of electromagnetic radiation is an optically transparent or translucent material that scatters or reflects the electromagnetic radiation.

15. The method of claim 11 wherein the second detection chamber further comprises a source reference detection fiber in communication with the detection device.

16. The method of claim 11 wherein the electromagnetic radiation is selected from the group consisting of ultraviolet light, visible light, and infrared light.

17. The method of claim 11 wherein the permeable membrane allows for diffusion of the analyte into the first reaction chamber by passive diffusion through a semipermeable membrane, wherein the composition of the semipermeable membrane is selected from the group consisting of porous polytetrafluoroethylene, porous polypropylene, and silicone rubber.

18. The method of claim 11 wherein the rate at which the reagent flows into the first reaction chamber through the inflow opening is adjusted by a valve communicating with either the inflow opening or the detection chamber outflow opening.

19. The method of claim 11 wherein the detection device measures absorbance, fluorescence or chemiluminescence.

20. A device for continuously measuring an analyte in a liquid or gas sample by chemiluminescence, comprising:

a sensor probe comprising a first reaction chamber and a second detection chamber downstream from and in fluid communication with the first reaction chamber, wherein the first reaction chamber comprises a permeable membrane separating the reaction chamber from the liquid or gas sample, an inflow opening connecting the reaction chamber to a reagent reservoir, and a reaction chamber outflow opening connecting the first reaction chamber to the second detection chamber, and wherein the second detection chamber is defined by an enclosed space which comprises a detection fiber and a detection chamber outflow opening, wherein a reagent flows through the inflow opening and into the first reaction chamber and contacts the permeable membrane and then flows out the first reaction chamber and into the second detection chamber by way of the reaction chamber outflow opening and then flows out the detection chamber outflow opening, wherein the analyte in the liquid or gas sample diffuses across the permeable membrane and into the first reaction chamber where it reacts with the reagent to produce photons by a chemiluminescent reaction, wherein the photons are detected by the detection fiber in the second detection chamber, and wherein the first reaction chamber and the second detection chamber are located within the sensor probe;

a reagent reservoir in fluid communication with the inflow opening of the first reaction chamber wherein the reservoir is capable of containing the reagent; and

a detection device in communication with the detection fiber of the second detection chamber and capable of detecting the photons detected by the detection fiber.

21. A method for continuously measuring an analyte in a liquid or gas sample by chemiluminescence, comprising:

contacting a sensor probe with the liquid or gas sample, wherein the sensor probe comprises a first reaction chamber and a second detection chamber downstream from and in fluid communication with the first reaction chamber, wherein the first reaction chamber comprises a permeable membrane separating the reaction chamber from the liquid or gas sample, an inflow opening connecting the reaction chamber to a reagent reservoir, and a reaction chamber outflow opening connecting the first reaction chamber to the second detection chamber, and wherein the second detection chamber is defined by an enclosed space which comprises a detection fiber and a detection chamber outflow opening, wherein a reagent flows through the inflow opening and into the first reaction chamber and contacts the permeable membrane and then flows out the first reaction chamber and into the second detection chamber by way of the reaction chamber outflow opening and flows out the detection chamber outflow opening, wherein the analyte in the liquid or gas sample diffuses across the permeable membrane and into the first reaction chamber where it reacts with the reagent to produce photons by a chemiluminescent reaction, wherein the photons are detected by the detection fiber in the second detection chamber, wherein the first reaction chamber and second detection chamber are located within the sensor probe, and wherein the detection fiber of the second detection chamber is in communication with a detection device;

adjusting the concentration of the reagent and the rate at which the reagent flows into the first reaction chamber through the inflow opening; and

detecting the analyte in the liquid or gas sample with the detection device which is in communication with the detection fiber.

22. The method of claim 21 wherein the permeable membrane is a semipermeable membrane which allows for diffusion of the analyte into the first reaction chamber by passive diffusion through the semipermeable membrane, wherein the composition of the semipermeable membrane is selected from the group consisting of porous polytetrafluoroethylene, porous polypropylene, and silicone rubber.

23. The method of claim 21 wherein the detection device is a photomultiplier tube.