Sensors with improved properties

• US 7,501,091 B2
• Filed: 12/29/2000
• Issued: 03/10/2009
• Est. Priority Date: 12/30/1999
• Status: Expired due to Fees

• Current Assignee: Smiths Detection (Smiths Group International Holdings Ltd.)
• Original Assignee: Smiths Detection (Smiths Group International Holdings Ltd.)
• Inventors: Munoz, Beth C., Pierce, Kenneth J., Galloway, Collin P.
• Primary Examiner(s): Sines; Brian J
• Application Number:
  US09/752,656
• Publication Number:
  US 20060099715A1
• Time in Patent Office: 2,993 Days
• Field of Search: 436/151, 436/43, 422/68.1, 422/82.01, 422/82.02, 422/50, 422/83, 422/98, 702/136, 702/22, 257/414
• US Class Current: 422/50
• CPC Class Codes: G01N 2291/02863 Electric or magnetic parameters
• CPC Class Codes: G01N 27/126 comprising organic polymers
• CPC Class Codes: G01N 33/0031 comprising two or more sensors, e.g. a sensor array electrochemical electrode arrays G01N27/27
• CPC Class Codes: Y10T 436/11 Automated chemical analysis

Abstract

A sensor or a sensor array connected to an electrical measuring apparatus is disclosed. In one embodiment, at least one sensor contains a layer of conductive modified particles which forms an electrical pathway or electrical circuit between two electrodes which are connected to an electrical measuring apparatus. In another embodiment, the first sensor contains at least one region of a nonconducting material and also a region that contains one or more modified particles. The modified particles are preferably conductive. An electrical path exists though the regions of the nonconducting material and the region containing the modified particles. The modified particles are conductive and more preferably are pigment particles such as modified carbon black, wherein the modified particles have attached at least one organic group. Alternatively, or in addition, the modified particle can be an aggregate having a carbon phase and a silicon-containing species phase and/or a metal-containing species phase wherein the aggregate optionally has attached at least one organic group. A sensor array for detecting an analyte in a fluid is also disclosed wherein each sensor emits a different response signature to an analyte wherein at least one of the sensors contains at least the modified particles as described above. Also, the present invention relates to a method for detecting the presence of an analyte in a fluid. The method involves contacting one or more sensors as described above with the analyte to generate a response and detecting the response with a detector that is operatively associated with each sensor in order to detect the presence of an analyte. Other advantages and embodiments are further described.

Claims

1. A sensor for detecting an analyte in a fluid, wherein said sensor comprises a layer comprising conductive modified particles, wherein the layer comprising conductive modified particles has a preexisting resistance that is altered in the presence of the analyte, wherein said conductive modified particles comprise carbon products or colored pigments having at least one organic group covalently bonded to the particles,

wherein the sensor includes an electrical measuring apparatus electrically connected to the layer comprising conductive modified particles that detects an alteration in the preexisting resistance of the layer in the presence of the analyte, and

wherein said conductive modified particles comprise an aggregate comprising a carbon phase and a silicon-containing species phase, wherein said aggregate optionally has attached at least one organic group.

2. The sensor of claim 1, wherein said organic group comprises at least one aromatic group, at least one C₁-C₁₀₀ alkyl group, or mixtures thereof.

3. The sensor of claim 1, wherein said organic group comprises a polymeric group.

4. The sensor of claim 1, wherein said organic group further comprises at least one ionic group, ionizable group, or both.

5. The sensor of claim 1, wherein said organic group comprises a polymer, an alkane, an alkene, an alkyne, a diene, an alicyclic hydrocarbon, an arene, a heterocyclic, an alcohol, an ether, a ketone, an aldehyde, a carbonyl, a carbanion, a polynuclear aromatic or a derivative of organic, functional group, a chiral group, a polyethylene glycol, a surfactant, a detergent, a biomolecule, a polysaccharide, a protein complex, a polypeptide, a dendrimeric material, an oligonucleotide, a fluorescent moiety, or radioactive group.

6. The sensor of claim 1, wherein said organic group comprises a 18-carbon alkyl group, a 4-carbon alkyl group, an alkyl ester, an oligoether, an anionic group, a poly(chloro-methylstyrene), or a poly(alkylacrylate).

7. The array of sensors according to claim 1, wherein said sensor array comprises two or more sensors for detecting an analyte in a fluid, wherein at least at least one of the sensors comprises the sensor of claim 1, and wherein each sensor provides a different response for the same analyte with a detector that is operatively associated with each sensor.

8. The array of sensors according to claim 1, wherein said sensor array comprises two or more sensors for detecting an analyte in a fluid, wherein at least at least one of the sensors comprises the sensor of claim 1, and wherein at least two sensors each comprise a layer comprising conductive modified particles, wherein the conductive modified particles for each sensor are different from each other.

9. The sensor according to claim 1, wherein the at least one organic group directly attached to the particles is of the chemical form —

X-Sp-[A]_p-R where X is attached to the particle and represents an aromatic or alkyl group, Sp is a spacer group, A is an alkylene oxide or polymer and R is a terminal group.

10. The sensor according to claim 1, wherein conductivity between the conductive modified particles within the layer changes due primarily to particle-to-particle distance changes between the conductive modified particles within the layer when the analyte is introduced to the sensor, and wherein the preexisting resistance of the layer changes accordingly.

11. The sensor according to claim 1, wherein the organic group is selected from the group consisting of:

—

C₆H₄—

COO⁻

X⁺, —

C₆H₄—

SO₃⁻

X⁺, —

C₆H₄—

(PO₃)<sup>−

2</sup>2X⁺, —

C₆H₂—

(COO⁻

X⁺)₃, —

C₆H₃—

(COO⁻

X⁺)₂, —

(CH₂)_z—

(COO⁻

X⁺), —

C₆H₄—

(CH₂)_z—

(COO⁻

X⁺), wherein X+ is a caton selected from the group consisting of Na⁺, H⁺, K⁺, NH₄⁺, Li⁺, Ca₂⁺, and Mg⁺, and z is an integer between 1 and 18 inclusive.

12. The sensor according to claim 1, wherein the alteration in the preexisting resistance of the layer in the presence of the analyte is a result of swelling of the layer comprising conductive modified particles.

13. An array of sensors for detecting an analyte in a fluid, said sensor array comprising:

a first and a second sensor electrically connected to an electrical measuring apparatus, wherein said first sensor comprises a region of nonconducting material and a region comprising conductive modified particles; and

an electrical path through said region of nonconducting material and said region comprising conductive modified particles, wherein the region of nonconducting material and the region comprising conductive modified particles have a preexisting resistance that is altered in the presence of the analyte, wherein said conductive modified particles comprise carbon products or colored pigments having at least one organic group covalently bonded to the particles, aggregates comprising a carbon phase and a silicon-containing species phase and optionally having attached at least one organic group, aggregates comprising a carbon phase and metal-containing species phase optionally having attached at least one organic group, silica-coated carbon blacks, or combinations thereof and wherein the electrical measuring apparatus detects an alteration in the preexisting resistance in the presence of the analyte,

wherein said conductive modified particles comprise an aggregate comprising a carbon phase and a silicon-containing species phase, wherein said aggregate optionally has attached at least one organic group.

14. The array of sensors according to claim 13, wherein said second sensor is selected from a surface acoustic wave (SAW) sensor, a quartz microbalance, an organic semiconducting gas sensor, a bulk conducting polymer sensor, a polymeric coating on an optical fiber sensor, conducting/nonconducting regions sensor conducting filler in insulating polymer sensors, dye impregnated polymeric coating on an optical fiber, a polymer composite, a micro-electro-mechanical system device, a micromachined cantilever, or a micro-opto-electromechanical system device.

15. The array of sensors according to claim 13, wherein said organic group comprises at least one aromatic group, at least one C₁-C₁₀₀ alkyl group, or mixtures thereof.

16. The array of sensors according to claim 13, wherein said organic group comprises a polymeric group.

17. The array of sensors according to claim 13, wherein said organic group further comprises at least one ionic group, ionizable group, or both.

18. The array of sensors according to claim 13, wherein said organic group comprises a polymer, an alkane, an alkene, an alkyne, a diene, an alicyclic hydrocarbon, an arene, a heterocyclic, an alcohol, an ether, a ketone, an aldehyde, a carbonyl, a carbanion, a polynuclear aromatic or a derivative of organic, functional group, a chiral group, a polyethylene glycol, a surfactant, a detergent, a biomolecule, a polysaccharide, a protein complex, a polypeptide, a dendrimeric material, an oligonucleotide, a fluorescent moiety, or radioactive group.

19. The array of sensors according to claim 13, wherein said organic group comprises a 18-carbon alkyl group, a 4-carbon alkyl group, an alkyl ester, an oligoether, an anionic group, a poly(chloro-methylstyrene), or a poly(alkylacrylate).

20. The array of sensors according to claim 13, wherein the alteration in the preexisting resistance of the layer in the presence of the analyte is a result of swelling of the layer comprising conductive modified particles.

21. A sensor for detecting an analyte in a fluid, wherein said sensor comprises a layer comprising conductive modified particles, wherein the layer comprising conductive modified particles has a preexisting resistance that is altered in the presence of the analyte, wherein said conductive modified particles comprise carbon products or colored pigments having at least one organic group directly attached to the particles,

wherein the sensor includes an electrical measuring apparatus electrically connected to the layer comprising conductive modified particles that detects a change in the preexisting resistance of the layer in the presence of the analyte, and

wherein the change in the preexisting resistance is due to a change in the electrical properties across more than one of the conductive modified particles within the layer,

wherein each of the conductive modified particles is an aggregate comprising a carbon phase and a silicon-containing species phase having attached at least one organic group.

22. The sensor according to claim 21, wherein the at least one organic group is covalently attached to the particles.

23. The sensor according to claim 21, wherein the at least one organic group directly attached to the particles is of the chemical form —

X-Sp-[A]_p-R where X is attached to the particle and represents an aromatic or alkyl group, Sp is a spacer group, A is an alkylene oxide or polymer and R is a terminal group.

24. The sensor according to claim 21, wherein the organic group is selected from the group consisting of:

—

C₆H₄—

COO⁻

X⁺, —

C₆H₄—

SO₃⁻

X⁺, —

C₆H₄—

(PO₃)<sup>−

2</sup>2X⁺, —

C₆H₂—

(COO⁻

X⁺)₃, —

C₆H₃—

(COO⁻

X⁺)₂, —

(CH₂)_z—

(COO⁻

X⁺), —

C₆H₄—

(CH₂)_z—

(COO⁻

X⁺), wherein X⁺is a caton selected from the group consisting of Na⁺, H⁺, K⁺, NH₄⁺, Li⁺, Ca₂⁺, and Mg⁺, and z is an integer between 1 and 18 inclusive.

25. A method for detecting the presence of an analyte in a fluid, said method comprising:

providing a sensor array comprising at least two sensors, wherein at least one sensor comprises a layer comprising conductive modified particles wherein the layer comprising conductive modified particles has a preexisting resistance that is altered in the presence of the analyte and wherein the at least one sensor includes an electrical measuring apparatus electrically connected to the layer comprising conductive modified particles that detects an alteration in the preexisting resistance of the layer in the presence of the analyte;

each sensor having an electrical path through the sensor;

contacting said sensor array with said analyte to generate a response; and

detecting said response with a detector that is operatively associated with each sensor, and thereby detecting the presence of said analyte, wherein said conductive modified particles comprise carbon products or colored pigments having at least one organic group directly attached to the particles,

wherein the change in the preexisting resistance is due to a change in the electrical properties across more than one of the conductive modified particles within the layer,

wherein each of the conductive modified particles is an aggregate comprising a carbon phase and a silicon-containing species phase having attached at least one organic group.

26. The method according to claim 25, wherein the at least one organic group is covalently attached to the particles.

27. The method according to claim 25, wherein the at least one organic group directly attached to the particles is of the chemical form —

X-Sp-[A]_p-R where X is attached to the particle and represents an aromatic or alkyl group, Sp is a spacer group, A is an alkylene oxide or polymer and R is a terminal group.

28. The method according to claim 25, wherein the organic group is selected from the group consisting of:

—

C₆H₄—

COO⁻

X⁺, —

C₆H₄—

SO3⁻

X⁺, —

C₆H₄—

(PO₃)<sup>−

2</sup>2X⁺, —

C₆H₂—

(COO⁻

X⁺)₃, —

C₆H₃—

(COO⁻

X⁺)₂, —

(CH₂)_z—

(COO⁻

X⁺), —

C₆H₄—

(CH₂)_z—

(COO⁻

X⁺), wherein X+ is a caton selected from the group consisting of Na⁺, H⁺, K⁺, NH₄⁺, Li⁺, Ca₂⁺, and Mg⁺, and z is an integer between 1 and 18 inclusive.

29. The method according to claim 25, wherein the change in the preexisting resistance of the layer is due to a changed separation distance between adjacently-positioned ones of the conductive modified particles within the layer, caused by swelling of the layer.