Biomimetic sensor that simulates human response to airborne toxins

• US 5,063,164 A
• Filed: 06/29/1990
• Issued: 11/05/1991
• Est. Priority Date: 06/29/1990
• Status: Expired due to Term

• Current Assignee: Quantum Group Inc.
• Original Assignee: Quantum Group Inc.
• Inventors: Goldstein, Mark K.
• Primary Examiner(s): NOT, DEFINED
• Assistant Examiner(s): Trembley, Theresa A.
• Application Number:
  US07/546,543
• Time in Patent Office: 494 Days
• Field of Search: 422/88, 422/91, 422/58, 436/120, 436/121, 436/134, 436/81, 436/902, 436/169, 436/128, 428/402.24, 252/315.2
• US Class Current: 436/169
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence
• CPC Class Codes: Y10T 436/182 Organic or sulfhydryl containing [e.g., mercaptan, hydrogen, sulfide, etc.]
• CPC Class Codes: Y10T 436/184 Only hydrogen sulfide
• CPC Class Codes: Y10T 436/200833 Carbonyl, ether, aldehyde or ketone containing
• CPC Class Codes: Y10T 436/205831 Carbon monoxide only

Abstract

The present invention relates to a biomimetic sensor for detecting the presence of airborne toxins, such as carbon monoxide, mercury, ethylene oxide, volatile organic materials, and hydrogen sulfide. The biomimetic sensor, which has a functional life of at least one year, comprises a porous, semi-transparent substrate into which is impregnated a self-regenerating chemical sensor reagent. The response of the biomimetic sensor mimics the human response to such toxins, with respect to sensitivity and affinity. The extended functional lifetime of the biomimetic sensor and the mimicking of the human response to the toxins are achieved by the use of a molecular encapsulant that encapsulates at least one component of the chemical sensor reagent.

Claims

1. A biomimetic sensor for detecting the presence of airborne toxins comprising:

a porous, semi-transparent substrate that is transmissive to light;

means for detecting light transmitted through the substrate;

a self-regenerating chemical sensor reagent for detecting airborne toxins, wherein the self-regenerating chemical sensor is able to regenerate itself for a period of at least one year at ambient conditions; and

a molecular encapsulant encapsulating at least one component, but not all the components, of the chemical sensor reagent.

2. A biomimetic sensor as claimed in claim 1, wherein the substrate is selected from the group consisting of porous silica-gel beads, porous leached borosilicate glass, and porous silicon dioxide.

3. A biomimetic sensor as claimed in claim 2, wherein the porous, semi-transparent substrate has an pore size of about 200 nm to 1000 nm.

4. A biomimetic sensor as claimed in claim 1, wherein the chemical sensor reagent is a mixture in which at least one compound is selected from each of the following groups:

Group 1;

Palladium salts selected from the group consisting of palladium sulfate, palladium sulfite, palladium pyrosulfite, palladium chloride, palladium bromide, palladium iodide, palladium perchlorate, CaPdCl₄, Na₂ PdCl₄ and K₂ PdCl₄ ;

Group 2;

Molybdenum or tungsten salts selected from the group consisting of silicomolybdic acid, salts of silicomolybdic acid, molybdenum trioxide, heteropolyacids of molybdenum, ammonium molybdate, alkali metal or alkaline earth salts of the molybdate anion or heteropolytungstenates;

Group 3;

Copper salts selected from the group consisting of copper sulfate, copper chloride, copper bromide, copper iodide, and copper perchlorate;

Group 4;

Molecular encapsulants selected from the group consisting of a α

-cyclodextrin, β

-cyclodextrin, modified β

-cyclodextrin and γ

-cyclodextrin; and

Group 5;

Soluble chloride ions selected from the group consisting of lithium chloride, sodium chloride, lithium perchlorate, magnesium perchlorate, calcium perchlorate, aluminum perchlorate, platinum chloride, inorganic acids, calcium chloride, magnesium chloride, and cobalt chloride.

5. A biomimetic sensor as claimed in claim 4, wherein the molecular encapsulant has an internal cavity with a diameter of at least 50 nm.

6. A biomimetic sensor as claimed in claim 4, wherein the compounds from Groups 1, 2, 3, 4, and 5 are present in the following ratio ranges:

Group 1;

Group 2--0.01;

1 to 0.5;

1;

Group 3;

Group 2--0.001;

1 to 0.08;

1;

Group 4;

Group 2--1;

1 to 20;

1; and

Group 5;

Group 2--0.01;

1 to 10;

1.

7. A biomimetic sensor as claimed in claim 1, wherein the sensor reagent comprises means for detecting an airborne toxin selected from the group consisting of carbon monoxide, mercury, ethylene oxide, volatile organic material or hydrogen sulfide.

8. A biomimetic sensor as claimed in claim 4, wherein the compound from Group 1 is palladium chloride, the compound from Group 2 is silicomolybdic acid, the compound from Group 3 is copper chloride, the compound from Group 4 is a modified β

-cyclodextrin, and the compound from Group 5 is calcium chloride.

9. A biomimetic sensor as claimed in claim 1, further comprising a hygroscopic agent selected from the group consisting of lithium chloride, sodium chloride, lithium sulfate, lithium perchlorate, calcium perchlorate, aluminum perchlorate, platinum chloride, an inorganic non-volatile acid, calcium chloride, cobalt chloride, and combinations thereof.

10. A biomimetic sensor as claimed in claim 9, wherein the biomimetic sensor includes a second hygroscopic agent selected from the group consisting of non-volatile halide ions at a ratio of 2:

1 to 180;

1 to the palladium ions.

11. A biomimetic sensor as claimed in claim 10, wherein the hygroscopic agent comprises a chloride ion.

12. A self-regenerating biomimetic chemical sensor system comprising:

a porous, semi-transparent substrate that is transmissive to light;

means for detecting the light transmitted through the substrate;

a self-regenerating chemical sensor reagent for detecting airborne toxins; and

means for extending the lifetime of the chemical sensor system, so that it will self-regenerate for at least one year at ambient conditions, by encapsulating at least one component, but not all the components, of the chemical sensor reagent in a molecular encapsulant.

13. A self-regenerating chemical sensor system as claimed in claim 12, wherein the molecular encapsulant is selected from the group consisting of α

-cyclodextrin, β

-cyclodextrin, modified β

-cyclodextrin, γ

-cyclodextrin, and combinations thereof.

14. A method of biomimetically detecting airborne toxins comprising:

immersing a porous, semi-transparent substrate in a chemical reagent system comprising at least one compound from each of the following groups;

Group 1;

Palladium salts selected from the group consisting of palladium sulfate, palladium sulfite, palladium pyrosulfite, palladium chloride, palladium bromide, palladium iodide, palladium perchlorate, CaPdCl₄, Na₂ PdCl₄ and K₂ PdCl₄ ;

Group 2;

Molybdenum or tungsten salts selected from the group consisting of silicomolybdic acid, salts of silicomolybdic acid, molybdenum trioxide, hetropolyacids of molybdenum, ammonium molybdate, alkali metal, or alkaline earth salts of the molybdate anion or heteropolytungstenates;

Group 3;

Copper salts selected from the group consisting of copper sulfate, copper chloride, copper bromide, copper iodide, and copper perchlorate;

Group 4;

Molecular encapsulants that encapsulate at least one but not all components of the chemical reagent system, selected from the group consisting of a α

-cyclodextrin, β

-cyclodextrin, modified β

-cyclodextrin and γ

-cyclodextrin; and

Group 5;

Soluble chloride ions selected from the group consisting of lithium chloride, sodium chloride, lithium perchlorate, magnesium perchlorate, calcium perchlorate, aluminum perchlorate, platinum chloride, inorganic acids, calcium chloride, magnesium chloride and cobalt chloride;

drying the substrate impregnated with the chemical sensor reagent to form a chemical sensor system;

exposing the chemical sensor system to airborne toxins; and

evaluating the change in the optical density of the chemical sensor system for sensing airborne toxins.

15. A method as claimed in claim 14, wherein the molecular encapsulant has an internal cavity with a diameter of at least 50 nm.

16. A method as claimed in claim 14, wherein the porous, semi-transparent substrate has a pore size of 200 nm to 1000 nm.

17. A method as claimed in claim 14, wherein the compounds from Groups 1, 2, 3, 4, and 5 are present in the following ratio ranges:

Group 1;

Group 2--0.001;

1 to 0.5;

1;

Group 3;

Group 2--0.001;

1 to 0.08;

1;

Group 4;

Group 2--1;

1 to 20;

1; and

Group 5;

Group 2--0.01;

1 to 10;

1.

18. A method as claimed in claim 14, wherein the sensor reagent is exposed to an airborne toxin selected from the group consisting of carbon monoxide, mercury, ethylene oxide, volatile organic material or hydrogen sulfide.

19. A method as claimed in claim 14, wherein the compound from Group 1 is palladium chloride, the compound from Group 2 is silicomolybdic acid, the compound from Group 3 is copper chloride, the compound from Group 4 is a modified β

-cyclodextrin, and the compound from Group 5 is calcium chloride.

20. A method as claimed in claim 14, further comprising a hygroscopic agent selected from the group consisting of lithium chloride, sodium chloride, lithium sulfate, lithium perchlorate, calcium perchlorate, aluminum perchlorate, platinum chloride, an inorganic non-volatile acid, calcium chloride, cobalt chloride, and combinations thereof.

21. A method as claimed in claim 20, wherein the method includes a second hygroscopic agent selected from the group consisting of non-volatile halide ions and is present at a ratio of 2:

1 to 180;

1 to the palladium ions.

22. A method as claimed in claim 21, wherein the hygroscopic agent comprises a chloride ion.

23. An improved biomimetic chemical sensor system having a chemical sensor reagent impregnated into a porous, semi-transparent substrate, the improvement comprising a molecular encapsulant that encapsulates at least one component but not all components of the chemical sensor reagent so that the chemical sensor system will self-regenerate for at least one year at ambient temperatures.

24. An improved chemical sensor system as claimed in claim 23, wherein the molecular encapsulant is selected from the group consisting of α

-cyclodextrin, β

-cyclodextrin, modified β

-cyclodextrin and γ

-cyclodextrin.