Reservoir chemical sensors

• US 5,116,759 A
• Filed: 06/27/1990
• Issued: 05/26/1992
• Est. Priority Date: 06/27/1990
• Status: Expired due to Fees

• Current Assignee: FiberChem, Inc.
• Original Assignee: FiberChem, Inc.
• Inventors: Butler, Marcus S., Thomas, Johnny R., Klainer, Stanley M.
• Primary Examiner(s): Johnston, Jill
• Application Number:
  US07/544,681
• Time in Patent Office: 699 Days
• Field of Search: 422/82.05-82.011, 350/96.29, 250/227.14, 435/288, 435/808, 435/17, 435/26, 385/12, 436/68, 436/80, 436/81, 436/83, 436/84, 436/73, 436/79, 436/106, 436/109, 436/119, 436/124, 436/140, 436/163, 436/135, 436/536, 436/811
• US Class Current: 435/287.2
• CPC Class Codes: G01N 2021/0193 the sample being taken from a stream or flow to the measurement cell
• CPC Class Codes: G01N 2021/0325 Cells for testing reactions, e.g. containing reagents
• 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 21/253 for batch operation, i.e. multisample apparatus analytical automats G01N35/00
• 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 21/77 by observing the effect on a chemical indicator
• CPC Class Codes: G01N 21/80 Indicating pH value
• CPC Class Codes: G01N 2201/024 Modular construction
• CPC Class Codes: G01N 2201/0415 Carrusel, sequential
• CPC Class Codes: Y10S 436/811 Test for named disease, body condition or organ function
• CPC Class Codes: Y10T 436/17 Nitrogen containing
• CPC Class Codes: Y10T 436/172307 Cyanide or isocyanide
• CPC Class Codes: Y10T 436/18 Sulfur containing
• CPC Class Codes: Y10T 436/19 Halogen containing
• CPC Class Codes: Y10T 436/206664 Ozone or peroxide
• CPC Class Codes: Y10T 436/212 Aromatic

Abstract

Single or multi-cell reservoir sensors with single illumination sources and one or more detectors per cell unit have an arrangement whereby a gaseous, vapor or liquid sample enters the cell body and interacts with a sensing solution to detect and quantify a given species. Entrance of the sample into the sensor is through an opening in the cell body which may be covered with a membrane to contain the sensing reagent and to presort the species entering the cell. Reservoir cells can be used with organic, inorganic or biochemical sensing materials. A variety of sensors as alcohol, drugs of abuse, organic halides, cyanide and inorganic ions are provided.

Claims

1. A reservoir chemical sensor comprising:

a modular reservoir cell body made of acetal theremoplastic polymer;

a sensing reagent in the cell body;

species communication means formed in the cell body for passing a species of interest into the cell body to interact with the sensing reagent.

a light source positioned at one end of the cell body to illuminate the interior of the cell body;

a detector positioned at an opposed end of the cell body to detect effects produced by the interaction of the species of interest with the sensing reagent;

an adaptor means at each end of he cell for mounting and aligning the light source and detector to the cell body.

2. The sensor of claim 1 wherein the sensing reagent is a solution filling the reservoir cell body.

3. The sensor of claim 2 further comprising a transparent, protective window between the cell body and at least one of the source and detector.

5. The sensor of claim 1 wherein the light source and detector are aligned along a cell axis.

6. The sensor of claim 1 wherein the detector is aligned in a direction substantially at a right angle to the light source.

7. The sensor of claim 1 further comprising a color filter between the cell body and at least one of the source and detector.

8. The sensor of claim 1 further comprising a focusing or collimating lens between the cell body and at least one of the source and detector.

9. The sensor of claim 1 wherein the species communication means comprises an open port.

10. The sensor of claim 1 further comprising a pair of space parallel membranes across the cell body and enclosing the sensing reagent.

11. The sensor of claim 1 wherein the sensing reagent is immobilized in the cell body.

12. The sensor of claim 1 wherein the modular cell body has a volume of about 10 to about 200 microliters.

13. The sensor of claim 1 wherein the light source is selected form a diode, laser and lamp.

14. The sensor of claim 1 wherein the light source is a light emitting diode.

15. The sensor of claim 14 wherein the detector is a photodiode.

16. The sensor of claim 1 wherein the light source is a lamp surrounded by a fiber optic bundle.

17. The sensor of claim 1 wherein the sensing reagent is selected from the group consisting of:

(a) phenol red, cresol red, methyl violet, congo red, phenolphthalein and bromcresol purple;

pH sensitive absorption dyes and pH sensitive fluorescent dyes;

(b) the reagents of (a) in combination with eosin;

(c) fluorescein, acridine, umbelliferone and beta-naphthol;

(d) thorium-morin chelate, a luminol-(NH₄)₂ MoO₄ -NH₄ NO₃ mixture, an ammonium molybdate/stannous chloride mixture and an N-ethyl-8-hydroxtetrahydroquinoline/ferric chloride mixture;

(e) a solvent for benzene with a lower refractive index than benzene;

(f) p-benzoquinone;

(g) cupric neocuprine;

(h) 2,2'"'"'-dipyridylketone hyrazone solution and lumpocupferron solution;

(i) a solvent for TCE with a lower refractive index than TCE;

(j) 2,2'"'"'-dipyridylketone hydrazone solution and indole-3-propionic acid;

(k) ferrozine;

(l) bis(2,4,6 trichlorophenyl) oxalate-H₂ O₂ -per-5ylene, acidified diphenylcarbazide, and a lphine/KOH/H₂ O₂ mixture;

(m) 2,3-diaminmonaphthalene, 3,3'"'"'-diaminobenzidine, and dithizone;

(n) 2,3 napthotriazole and a 1,10 phenanthroline/eosin mixture;

(o) butylrhodamine B/chloride mixture and 5-hydroxy-2-hydroxmethyl-1,4-pyrone;

(p) N-(4-methylumbelliferone-8-methyl)-1,10-diazo-18-crown-6;

q) p-nitrophenyl hydrazine;

(r) benzidine and tetramethyldiaminotriphenylmethane;

(s) acidified vanillin and an alcohol dehydrogenase/zinc hydroxide mixture;

(t) dihydroacridane and indigo blue;

(u) Malachite green;

(v) red thorin-barium complex;

(w) a mixture of MM and BB monoclonal antibodies and MB polyclonal antibody tagged with a fluorescent compound;

(x) antibodies specific to cocaine, caffeine, chlordane, methadone, morphine, hepatitis and influenza;

(y) an enzyme selected form 3α

-hydroxysteroid dehydrogenase, pyruvate dehydrogenase, aldehyde dehydrogenase and cholesterol dehydrogenase.

4. The sensor of claim wherein the window has a surface energy which matches the surface tension of the reagent solution to prevent bubble formation.

18. A reservoir chemical sensor comprising:

a modular reservoir cell body;

a sensing reagent in the cell body;

species communication means formed in the cell body for passing a species of interest into the cell body to interact with the sensing reagent;

a light source positioned at one end of the cell body to illuminate the interior of the cell body;

a detector positioned at an opposed end of the cell body and aligned with the light source along a cell axis top detect effects produced by the interaction of the species of interest with the sensing reagent;

at least one additional detector mounted to the cell body and aligned in a direction substantially at a right angle to the cell axis;

an adapter means for mounting and aligning each light source and detector to the cell body.

19. A reservoir chemical sensor comprising:

a modular reservoir cell body;

a sensing reagent in the cell body;

species communication means formed in the cell body for passing a species of interest into the cell body to interact with the sensing reagent wherein the species communication means comprises a flow-through port on a lateral surface of the cell body and a species-permeable, sensing-reagent-impermeable membrane across the flow-through port and a membrane retaining means for holding the membrane in place across the flow-through port and maintaining a liquid tight seal;

a light source positioned at one end of the cell body to illuminate the interior of the cell body;

a detector positioned at an opposed end of the cell body to detect effects produced by the interaction of the species of interest with the sensing reagent;

an adapter means at each end of the cell for mounting and aligning the light source and detector to the cell body;

wherein the membrane and sensing reagent are selected from the group consisting of the following combinations;

(a) the membrane is a hydrogen ion/hydronium ion permeable membrane and the sensing reagent is a pH sensitive absorption dye in combination with eosin;

(b) the membrane is an arsenic ion permeable membrane and the sensing reagent is selected from thorium-morin chelate, a luminol-(NH₄)₂ MoO₄ -NH₄ NO₃ mixture, an ammonium molybdate/stannous chloride mixture and an N-ethyl-8-hydroxtetrahydroquinoline/ferric chloride mixture;

(c) the membrane is selected form high density polyethylene, high density polypropylene and fluorinated forms thereof, and the sensing reagent is a solvent for benzene with refractive index lower than benzene;

(d) the membrane is a cyanide permeabel membrane and the sensing reagent is p-benzene;

(e) the membrane is a hydrazine permeable membrane and the sensing reagent is cupric neocuprine solution;

(f) the membrane is a cupric ion permeable membrane and the sensing reagent is selected form 2,2'"'"'-dipyridylketone hydrazone solution and lumpocupferron solution;

(g) the membrane is a trichloroethylene permeable silicone polymer and the sensing reagent is a solvent for trichloroethylene with refractive index lower than trichloroethylene;

(h) the membrane is a mercuric ion permeable membrane and the sensing reagent is selected form 2,2'"'"'-dipyridylketone hydrazone solution and indole-3- propionic acid;

(i) the membrane is an iron(2+) permeable membrane and the sensing reagent is ferozine solution;

(j) the membrane is a chromium permeate membrane and the sensing reagent is selected from bis)2,4,6 trichlorophenyl) oxalate-H₂ O₂ -per-5ylene, acidified diphenycarbazide, and a lophine/KOH/H₂ O₂ mixture;

(k) the membrane is a selenium permeable membrane and the sensing reagent is selected form 2,3 napthothriazole and a 1,10 phenanthroline/eosin mixture;

(m) the membrane is a gold permeable membrane and the sensing reagent is selected form butylrodamein B/chloride mixture and 5-hydrosy-2-hydroxmethyl-1,4-pyrone;

(n) the membrane is a calcium permeable membrane and the sensing reagent is N-(4methylumbelliferone-8-methyl)-1,10-diazo-18-crown-6;

20. The sensor of claim 19 further comprising a sample preparation chamber adjacent to the modular cell body and having the semi-permeable membrane as an interface between the sample preparation chamber and the cell body.

21. The senor of claim 20 wherein the sample preparation chamber has an inlet port and an outlet port for passing sample through the chamber and an irradiation port for irradiating the sample in the chamber.

22. The senor of claim 20 further comprising a chemical bed in the chamber for producing chemical reactions of the sample in the chamber.

23. The sensor of claim 19 further comprising a lateral sensing reagent inlet port and a lateral sensing reagent outlet port formed on a lateral surface in the cell body.

24. The sensor of claim 19 for arsenic wherein the membrane is an arsenic ion permeable membrane and the sensing solution is selected from thorium-morin chelate, a luminol-(NH₄)₂ MoO₄ -NH₄ NO₃ mixture, an ammonium molybdate/stannous chloride mixture and an N-ethyl-8hydroxtetrahydroquinoline/ferric chloride mixture.

25. The sensor of claim 19 for benzene wherein the membrane is selected form high density polyethylene, high density polyproplene and fluoridated forms thereof, and the sensing reagent is a solvent for benzene with refractive index lower than benzene.

26. The sensor of claim 19 for cyanide wherein the membrane is a cyanide permeate membrane and the sensing reagent is p-benzoquinone.

27. The sensor of claim 19 for hydrazine wherein the membrane is a hydrazine permeable membrane and the sensing reagent is cupric neocuprine solution.

28. The sensor of claim 19 for cupric ion wherein the membrane is a cupric ion permeable membrane and the sensing reagent is selected for 2,2'"'"'- dipyridylketone hydrazone solution and lumpocupferron solution.

29. The sensor of claim 19 for trichloroethylene wherein the membrane is a trichloroethlene permeable silicone polymer and the sensing reagent is a solvent for trichloroethylene with refractive index lower than trichloroethylene.

30. The sensor of claim 29 wherein the solvent is ethanol or acetone.

31. The sensor of claim 19 for mercuric ion wherein the membrane is a mercuric ion permeate membrane and the sensing solution is selected form 2,2'"'"'-dipyridylketone hydrazone solution and indole-3-proionic acid.

32. The sensor of claim 19 for iron (2+) wherein the membrane is an iron (2+) permeable membrane and the sensing reagent is ferrozine solution.

33. The sensor of claim 19 for chromium wherein the membrane is a chromium permeable membrane and the sensing reagent is selected form bis(2,4,6 trichlorophenyl)oxalate-H₂ O₂ -per-5ylene, acidified diphenycarbazide, and a lophine/KOH/H₂ O₂ mixture.

34. The sensor of claim 19 for selenium wherein the membrane is a selenium permeate membrane and the sensing reagent is selected from 2,3-diaminonaphthalene, 3,3'"'"'-diaminobezidine, and dithizone.

35. The sensor of claim 19 for silver wherein the membrane is a silver permeable membrane and the sensing reagent is selected from 2,3 napthotriazole and a 1,10 phenanthroline/eosin mixture.

36. The sensor of claim 19 for gold wherein the membrane is a gold permeable membrane and the sensing reagent is selected from butylrhodamine B/chloride and 5-hydroxy-2-hydroxmehtyl-1,4-pyrone.

37. The sensor of claim 19 for calcium wherein the membrane is a calcium permeable membrane and the sensing reagent is N-(4-methylumbelliferone-8-methyl) 1,10-diazo-18-crown-6.

38. The sensor of claim 19 for aldehydes wherein the membrane is an aldehyde permeable membrane and the sensing reagent is p-nitrophenyl hydrazine.

39. The sensor of claim 19 for blood wherein the membrane is a blood permeable membrane and the sensing reagent is selected from benzidine and tetramethyldiaminotriphenylmethane.

40. The sensor of claim 19 for alcohol wherein the membrane is an alcohol permeable membrane and the sensing reagent is selected from acidified vanillin and an alcohol dehydrogenase/zinc hydroxide mixture.

41. The sensor of claim 19 for ozone wherein the membrane is an ozone permeable membrane and the sensing reagent is selected from dihydroacridane and indigo blue.

42. The sensor of claim 19 for sulfite wherein the membrane is a sulfit porous membrane and the sensing reagent is malachite green.

43. The sensor of claim 19 for sulfate wherein the membrane is a sulfate porous membrane and the sensing reagent is ed thorin-barium complex.

44. The sensor of claim 19 for creatine phosphokinase wherein the membrane is a creatine phosphokinase permeable membrane and the sensing reagent is a mixture of MM, BB monclonal antibodies and MB polyclonal antibody.

45. A reservoir chemical sensor comprising:

a modular reservoir cell body;

a sensing reagent in the cell body;

species communication means formed in the cell body for passing a species of interest into the cell body to interact with the sensing reagent and comprising a lateral sample inlet port and an opposed lateral outlet port on opposed lateral surfaces of the cell body for passing sample through the cell body;

a lateral sensing reagent inlet port on a lateral surface of the cell body for replenishing reagent in the cell body;

valves placed in the inlet and outlet ports to regulate or control flow;

a light source positioned at one end of the cell body to illuminate the interior of the cell body;

a detector positioned at an opposed end of the cell body to detect effects produced by the interaction of the species of interest with the sensing reagent;

an adapter means at each end of the cell for mounting and aligning the light source and detector to the cell body.

46. A reservoir chemical sensor comprising:

a modular reservoir cell body comprising adjacent cell body sections and a semi-permeable membrane mounted between adjacent cell body sections to form adjacent cell body chambers;

a sensing reagent in the cell body;

species communication means formed in the cell body for passing a species of interest into the cell body to interact with the sensing reagent;

a light source positioned at one end of the cell body to illuminate the interior of the cell body;

a detector positioned at an opposed end of the cell body to detect effects produced by the interaction of the species of interest with the sensing reagent;

an adapter means at each end of the cell for mounting and aligning the light source and detector to the cell body;

wherein the sensing reagent further comprises a first reagent in one cell body chamber and a second reagent in a second cell body chamber, wherein the first reagent is reactive with the species of interest to form a reaction product, and the second reagent is reactive to the reaction product, and the membrane is permeable to the reaction product and impermeable to the first and second reagents.

47. The sensor of claim 46 wherein the light source and detector are positioned in the second chamber.

48. The sensor of claim 46 wherein the species communication means are formed in the first chamber.

49. The sensor of claim 46 for arsenic wherein the first reagent is ammonium molybdate and the second reagent is stannous chloride.

50. The sensor of claim 46 for arsenic wherein the first reagent is N-ethyl-8-hydroxtetrahydroquinoline and the second reagent is ferric chloride.