Sensor device containing mesoporous crystalline material

• US 5,364,797 A
• Filed: 05/20/1993
• Issued: 11/15/1994
• Est. Priority Date: 05/20/1993
• Status: Expired due to Fees

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Original Assignee: Mobil Oil Corporation (Exxon Mobil Corporation)
• Inventors: Stucky, Galen D., Vartuli, James C., Olson, David H.
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): CRAWFORD, LESLIE
• Application Number:
  US08/064,280
• Time in Patent Office: 544 Days
• Field of Search: 422/68.1, 422/82.05, 422/82.01, 422/82.08, 422/55, 422/83, 436/166, 436/169, 436/149, 436/501, 436/163, 436/527, 436/164, 436/524, 436/100, 436/103, 436/106, 436/119, 436/124, 436/127, 436/139, 436/149, 436/76, 436/73, 502/60, 502/64, 502/77, 423/326, 423/328, 423/329, 423/330-332, 423/118, 423/277, 423/328.1, 423/328.2, 423/329.1, 435/4, 435/6, 435/7.1
• US Class Current: 436/501
• CPC Class Codes: G01N 2021/7786 Fluorescence
• 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: G01N 31/221 for investigating pH value
• CPC Class Codes: G01N 31/223 for investigating presence of specific gases or aerosols G01N31/221, G01N31/222 take precedence; actuation of fire alarm by presence of smoke or gases G08B17/10
• CPC Class Codes: G01N 33/54373 involving physiochemical end-point determination, e.g. wave-guides, FETS, gratings
• CPC Class Codes: Y10T 436/15 Inorganic acid or base [e.g. , hcl, sulfuric acid, etc. ]
• CPC Class Codes: Y10T 436/16 Phosphorus containing
• CPC Class Codes: Y10T 436/17 Nitrogen containing
• CPC Class Codes: Y10T 436/18 Sulfur containing
• CPC Class Codes: Y10T 436/19 Halogen containing
• CPC Class Codes: Y10T 436/20 Oxygen containing
• CPC Class Codes: Y10T 436/21 Hydrocarbon

Abstract

A sensor device includes ultra-large pore crystalline material M41S as a selective detecting element, and a measuring element for quantifying physical, chemical or biological events which occur within the crystalline material. The crystalline material may also contain an additional selective detecting component within its pores.

Claims

1. A sensor device comprising an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units with a relative intensity of 100 and having a benzene sorption capacity of greater than 15 grams benzene per 100 grams of anhydrous crystal at 50 torr and 25°

C., and a means for detecting, the device capable of detecting an event selected from the group consisting of sorption of a gas, change in pH, presence of metal ions, reaction between co-members of a biological affinity pair, presence of Lewis acid and presence of a Lewis base, said event occurring in the crystalline material.

2. The device of claim 1 wherein the crystalline phase material has been modified by contacting with a treatment composition comprising M'"'"'X'"'"'Y'"'"'_n wherein

M'"'"' is selected from a group consisting of Periodic Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB;

X'"'"' is selected from a group consisting of halides, hydrides, alkoxides of 1 to about 6 carbon atoms alkyl of C_1-18, alkenyl of C_6-18, aryl of C_6-18, aryloxide of C_6-18, sulfonates, nitrates and acetates;

Y'"'"' is selected from a group consisting of X'"'"', amines, phosphines, sulfides, carbonyls and cyanos; and

n=1-5;

said contacting occurring under sufficient conditions so that the crystalline phase material functionalized.

3. The device of claim 2 wherein the crystalline material is contacted with the treatment composition before organics are removed by calcination or low temperature organics extraction.

4. The device of claim 2 wherein the crystalline material is contacted with the treatment composition after organics are removed by calcination or low temperature organics extraction.

5. The device of claim 1 wherein the crystalline material is as-synthesized.

6. The device of claim 1 wherein the crystalline material is calcined.

7. The device of claim 1 wherein the crystalline material has been subjected to low temperature organics extraction at less than 150°

C.

8. The device of claim 1 wherein the crystalline material comprises an inorganic, porous crystalline phase material having a hexagonal arrangement of uniformly-sized pores at least about 13 Angstroms in diameter and exhibiting, after calcination, a hexagonal electron diffraction pattern that can be indexed with a d₁₀₀ value greater than 18 Angstrom Units.

9. The device of claim 1 wherein the means for detecting is selected from the group consisting of surface acoustic wave, fiber optic, electrochemical, spectroscopic, autoradiographic and semiconductor elements.

10. The device of claim 1 wherein the material has pores which have been adjusted to a predetermined shape and size.

11. The device of claim 1 wherein the material contains a selective detecting component.

12. The sensor device of claim 11 wherein the selective detecting element is supported unattached within the pores of the material.

13. The sensor device of claim 11 wherein the selective detecting component is covalently bonded within the pores of the material.

14. The device of claim 11 wherein the selective detecting component is hydrogen-bonded within the pores of the material.

15. The device of claim 11 wherein the selective detecting component is coordinatively attached within the pores of the material.

16. The device of claim 11 wherein the selective detecting component is selected from the group consisting of ionophores, Lewis bases, Lewis acids, fluorophores, dyes, M'"'"'Y'"'"'_n and a member of a biological binding pair.

17. A method for detecting a compound selected from the group consisting of a gas, hydrogen ions (pH), metal ions, a co-member of a biological affinity pair, a Lewis acid and a Lewis base comprising contacting a medium containing the compound with a sensor device which comprises an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units with a relative intensity of 100 and having a benzene sorption capacity of greater than 15 grams benzene per 100 grams of anhydrous crystal at 50 torr and 25°

C. and detecting the compound in the crystalline material with a means for detecting.

18. The device of claim 17 wherein the crystalline phase material has been modified by contacting with a treatment composition comprising M'"'"'X'"'"'Y'"'"'_n wherein

M'"'"' is selected from a group consisting of Periodic Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB;

X'"'"' is selected from a group consisting of halides, hydrides, alkoxides of 1 to about 6 carbon atoms alkyl of C_1-18, alkenyl of C_6-18, aryl of C_6-18, aryloxide of C_6-18, sulfonates, nitrates and acetates;

Y'"'"' is selected from a group consisting of X'"'"', amines, phosphines, sulfides, carbonyls and cyanos; and

n=1-5;

said contacting occurring under sufficient conditions so that the crystalline phase material functionalized.

19. The device of claim 18 wherein the crystalline material is contacted with the treatment composition before organics are removed by calcination or low temperature organics extraction.

20. The device of claim 18 wherein the crystalline material is contacted with the treatment composition after calcination.

21. The device of claim 17 wherein the crystalline material is as-synthesized.

22. The device of claim 17 wherein the crystalline material is calcined.

23. The device of claim 17 wherein the crystalline material is subjected to low temperature organics extraction at less than 150°

C.

24. The method of claim 17 wherein the means for detecting physical or chemical changes is selected from the group consisting of surface acoustic wave, fiber optic, electrochemical, spectroscopic, autoradiographic and semiconductor elements.

25. The method of claim 17 wherein the material has pores which have been adjusted to a predetermined shape and size.

26. The method of claim 17 wherein the material contains a selective detecting component.

27. The method of claim 26 wherein the selective detecting element is unattached within the pores of the material.

28. The method of claim 26 wherein the selective detecting component is covalently bonded within the pores of the material.

29. The method of claim 26 wherein the selective detecting component is hydrogen-bonded within the pores of the material.

30. The method of claim 26 wherein the selective detecting component is coordinatively attached within the pores of the material.

31. The method of claim 26 wherein the selective detecting component is selected from the group consisting of ionophores, Lewis bases, Lewis acids, fluorophores dyes, M'"'"'Y'"'"'_n and a member of a biological binding pair.

32. The method of claim 17 wherein the method detects a gas, the means for detecting comprises a piezoelectric crystal and the gas is selected from the group consisting of pyridine, thiophenes, mercaptans, furans, benzene, methane, carbon dioxide, carbon monoxide, NO_x and SO_x.

33. The method of claim 17 wherein the method detects a gas, the means for detecting comprises a fiber optic cable and the gas is selected from the group consisting of NH₃, HCN, CO₂, CO, SO₂, NO_x, O₂, H₂ O₂, formaldehyde, organoamines, thiophenes, pyridine, piperidine and pyrrolidine.

34. The method of claim 17 wherein the method detects hydrogen ions (pH), the means for detecting comprises a fiber optic cable and the crystalline material contains a pH indicator dye.

35. The method of claim 17 wherein the method detects metal ions, the means for detecting the presence of metal ions comprises potentiometric electrodes or spectroscopy and the crystalline material contains an ionophore selected from the group consisting of phenanthroline, porphyrins, salens, salophens, cryptands, cyclams, crown ethers and dimethylgloxine.

36. The method of claim 17 wherein the method detects a co-member of a biological affinity pair, the means for detecting comprises a member of the group consisting of potentiometric electrodes, autoradiography and fiber optic cable and one co-member of a biological affinity pair selected from the group consisting of antigen-antibody, hapten-antibody, polysaccharide-receptor, monosaccharide-receptor, glycoprotein-receptor, glycolipid-lectin, enzyme-substrate, enzyme-cofactor, enzyme inhibitor-enzyme, neurotransmitter-neuroreceptor, hormone-neural receptor and single strand nucleic acid complementary strand nucleic acid.

37. The method of claim 17 wherein the method detects a Lewis acid or base, the means for detecting comprises spectroscopy and the crystalline material contains sites selected from the group consisting of Lewis acids aluminum, copper, cobalt and transition metals and Lewis bases which are nitrogen-containing polymer pyrroles or amines.

38. A sensor device for sensing a gas selected from the group consisting of pyridine, thiophenes, mercaptans, furans, benzene, methane, carbon dioxide, carbon monoxide, NO_x and SO_x comprises M41S crystalline phase material and a detecting means comprising a piezoelectric crystal.

39. A sensor device for sensing a gas selected from the group consisting of NH₃, HCN, CO₂, CO, SO₂, NO_x, O₂, H₂ O₂, formaldehyde, organoamines, thiophenes, pyridine, piperidine and pyrrolidine comprises M41S crystalline phase material functionalized with an indicator molecule and a detecting means comprising a fiber optic cable.

40. A sensor device for sensing a change in pH comprises M41S crystalline phase material functionalized with a pH indicator dye and a detecting material means comprising a fiber optic cable.

41. A sensor device for sensing the presence of metal ions comprises M41S phase material containing an ionophore selected from the group consisting of phenanthroline, porphyrins, salen, salophen, cryptand, cyclam, crown ether and dimethylgloxine and a detecting means comprising potentiometric electrodes or spectroscopy.

42. A sensor device for sensing a reaction between co-members of a biological affinity pair comprises M41S crystalline phase material containing one co-member of the biological pair, the pair selected from the group consisting of antigen-antibody, hapten-antibody, polysaccharide-receptor, monosaccharide-receptor, glycoprotein-receptor, glycolipid-lectin, enzyme-substrate, enzyme-cofactor, enzyme inhibitor-enzyme, neurotransmitter-neuroreceptor, hormone-neural receptor and single strand nucleic acid-complementary strand nucleic acid;

and a detecting means comprising a member of the group consisting of electrochemical, autoradiographic and fiber optic measuring components.

43. A sensor device for detecting Lewis acids or Lewis bases comprises M41S crystalline phase material functionalized with sites selected from the group consisting of Lewis acids which are aluminum, copper, cobalt and transition metals and Lewis bases which are nitrogen-containing polymer polypyrroles and amines, and a detecting means comprising spectroscopy.