Analyte-selective sensor

• US 6,004,442 A
• Filed: 06/16/1997
• Issued: 12/21/1999
• Est. Priority Date: 10/18/1994
• Status: Expired due to Fees

• Current Assignee: Institut Fur Chemo- Und Biosensorik Munster e.V.
• Original Assignee: Institut Fur Chemo- Und Biosensorik Munster e.V.
• Inventors: Ahlers, Benedikt, Cammann, Karl, Choulga, Alexandre
• Primary Examiner(s): Till, Terrence R.
• Assistant Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US08/817,522
• Time in Patent Office: 918 Days
• Field of Search: 204/415, 204/416
• US Class Current: 204/416
• CPC Class Codes: G01N 27/3275 Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction

Abstract

The invention concerns an analyte selective sensor for the qualitative and/or quantitative determination of ions or substances contained in solution. The proposed sensor (1) comprises at least one analyte-specific layer (3) deposited on an inert carrier (7) and in contact with the solution; this analyte-specific layer consists of a liquid, solid or semi-solid material and is in contact with at least two electrodes (5, 6). The layer (3) selectively removes the analyte from the solution so that its own electrical characteristics, such as resistance, conductivity, admittance or impedance, change as the analyte is taken up.

Claims

1. Analyte-selective sensor for at least one of qualitative and quantitative detection of at least one of ions and materials contained in solutions, wherein said sensor (1, 2) comprises at least one analyte specific layer (3, 8) of at least one of a liquid, solid and semi-solid material, in contact with the solution, applied to an inert carrier (7) and being solely ionically conductive, and which is in connection with at least two electrodes (5, 6), the layer (3, 8) containing coupling members which selectively remove the analyte from the solution, so that, by absorption of the analyte, at least one of the ionic resistance, the ionic conductivity, the ionic admittance and the ionic impedance of the layer (3, 8) is altered.

2. Analyte-selective sensor according to claim 1 wherein the electrodes (5, 6) are in direct contact with the analyte-specific layer (3, 8), and are constructed as one of two- and four-electrode arrangements.

3. Analyte-selective sensor according to claim 2 wherein the electrode materials are selected from the group consisting silver, gold, platinum, palladium, nickel, tantalum, titanium, chromium, copper, vanadium, aluminium, conductive pastes containing particles of metal or graphite, epoxy resins containing particles of metal or graphite, carbon based materials, highly doped silicon, conductive polymers and conductive polymers which contain particles of metal or graphite.

4. Analyte-selective sensor according to claim 2 wherein the electrode materials are at least one of electrical conductors, semiconductors and defect point conductors.

5. Analyte-selective sensor according to claim 2 wherein the electrodes (5, 6) are at least one of wire electrodes, disc electrodes and interdigital electrodes (IDE).

6. Analyte-selective sensor according to claim 1 wherein the electrodes (5, 6) are at least one of wire electrodes disc electrodes and interdigital electrodes (IDE).

7. Analyte-selective sensor according to claim 6 wherein the electrode materials are at least one of electrical conductors, semiconductors and defect point conductors.

8. Analyte-selective sensor according to claim 6 wherein the electrode materials are selected from the group consisting of silver, gold, platinum, palladium, nickel, tantalum, titanium, chromium, copper, vanadium, aluminium, conductive pastes containing particles of metal or graphite, epoxy resins containing particles of metal or graphite, carbon based materials, highly doped silicon, conductive polymers and conductive polymers which contain particles of metal or graphite.

9. Analyte-selective sensor according to claim 1 wherein the electrode materials are at least one of electrical conductors, semiconductors and defect point conductors.

10. Analyte-selective sensor according to claim 9 wherein the electrode materials are selected from the group consisting of silver, gold, platinum, palladium, nickel, tantalum, titanium, chromium, copper, vanadium, aluminum conductive pastes containing particles of metal or graphite, epoxy resins containing particles of metal or graphite, conductive pastes containing carbon-based materials, epoxy resins containing carbon-based materials, highly-doped silicon conductive polymers, and conductive polymers which contain particles of metal or graphite.

11. Analyte-selective sensor according to claim 10 wherein the electrode surface is roughened.

12. Analyte-selective sensor according to claims 1, 2, 6, 9, 10 or 11 wherein the electrodes (5, 6) are located directly on the carrier (7).

13. Analyte-selective sensor according to claim 1 further comprising at least one further layer (11) which contains at least one substance which is capable of forming a redox pair, said at least one further layer (11) being applied between the electrodes (5, 6) and the analyte-specific layer (3, 8) so that the resistance of the phase boundary is not increased.

14. Analyte-specific sensor according to claim 1 wherein the inert carrier (7) is selected from the group consisting of glass, paper, epoxy resin, plastic, polymer, sapphire and ceramic.

15. Analyte-selective sensor according to claim 1 wherein the carrier (7) is the inner surface of at least one of a capillary of a tube and an enclosed vessel.

16. Analyte-selective sensor according to claim 1 wherein the analyte-specific layer (3, 8) is a liquid which is capable of extracting the analyte selectively out of the solution (4) into the layer (3, 8).

17. Analyte-selective sensor according to claim 11 wherein the liquid is selected from the group consisting of non-polar liquids, aromatic hydrocarbons and saturated aliphatic hydrocarbons.

18. Analytical sensor according to claim 1 wherein the analyte-specific layer (3, 8) is a liquid which contains at least one of molecule-selective coupling members and ion-selective coupling members, so that the analyte is selectively extracted out of the solution (4) into the layer (3, 8).

19. Analyte-selective sensor according to claim 1 wherein the analyte-specific layer (3, 8) is a polymer, so that the analyte is selectively extracted out of the solution (4) into the layer (3, 8).

20. Analyte-selective sensor according to claim 19 wherein the analyte-specific layer (3, 8) is selected from the group consisting of polyethylene oxide film and polymer which has cation complexing properties and properties of separating ion pairs.

21. Analyte-selective sensor according to claim 20 wherein the analyte-specific layer (3, 8) contains alkali salts as ionic additives.

22. Analyte-selective sensor according to claim 19 wherein the polymer is produced by at least one of chemical, photochemical and electrochemical polymerisation of a polymerisable monomer selected from heteroaromatic/aromatic compounds in the presence of free analyte molecules, with the analyte molecule then being washed out of the polymer so that, during membrane formation, "prints" of the analyte form on a molecular scale, which then act as coupling members with increased affinity to the analytes.

23. Analyte-selective sensor according to claim 19, wherein the polymer is a complex-forming polymer whose base polymers are selected from the group consisting polystyrols, polyacrylates, polyacrylnitrites, polyvinyl alcohols, polyethylenimines, polysiloxanes, polysaccharides, modified cellulose, starch, lignin, and chitin, the polymer being formed in the presence of at least one of complexing groups and chelate groups so that analyte-specific coupling members result.

24. Analyte-selective sensor according to claim 23 wherein the at least one of complexing groups and chelate groups are selected from the group consisting of iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxin, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl residues, cage compounds (e.g. cyclophane, crown ether, antibiotics, cyclodextrine), antigens, antibodies, natural polypeptides, synthetic polypeptides, lectins, specific bonding proteins, lipids and tensides.

25. Analyte-selective sensor according to claim 19 wherein the polymer comprises polyions which have functional groups (coupling members) which can selectively bond at least one of anions and cations, so that during the selective bonding an alteration in the morphology of the polymer occurs.

26. Analyte-selective sensor according to claim 25 wherein the polymer is selected from the group consisting of proteoglycane and glycoproteins.

27. Analyte-selective sensor according to claim 19 wherein the analyte-specific layer (3, 8) comprises a crystalline liquid phase.

28. Analytc-selective sensor according, to claim 19 wherein the analyte-specific layer (3, 8) is formed from polylonic complexes between quaternary ammonium ions and further polyions.

29. Analyte-selective sensor according to claim 19 wherein the polymer is selected from the group consisting of ion exchangers and ionic polymers.

30. Analyte-selective sensor according to claim 29 wherein the polymer is selected from the group consisting of copolymers of ethylene, acrylic acid, metacrylic acid carboxy elastomers, terpolymers, terpolymer ethylene-propylene-diene sulphonate, substituted polyvinyls, perfluropolymers, and polyampholytes.

31. Analyte-selective sensor according to claim 19 wherein the polymer further contains at least one of ion-selective coupling members and molecule-selective coupling members.

32. Analyte-selective sensor according to claim 31 wherein the coupling members are selected from the group consisting of cation exchangers, anion exchangers, complex formers for cations, complex formers for anions and complex formers for neutral particles.

33. Analyte-selective sensor according to claim 31 or 32 wherein the complex formers are selected from the group consisting of crown ether, natural antibiotics, dicarboxylic acid diamides, tridodecylamine, guanidinium compounds, derivates of boric acid, calixarenes, cyclophanes, lipids, and tensides.

34. Analytc-selective sensor according to claim 19 wherein the polymer additionally contains a plasticiser.

35. Analyte-selective sensor according to claim 34 wherein the plasticiser is selected from the group consisting of ethers, ester plasticisers, diesters of phosphoric acid and diesters of phosphonic acid.

36. Analyte-selective sensor according to claim 1 wherein the analyte-specific layer (3, 8) is a polymer, which contains at least one of molecule-selective coupling members and ion-selective coupling members, so that the analyte is selectively extracted out of the solution (4) into the layer (3, 8).

37. Analyte-selective sensor according to claim 19 or 36 wherein the polymer comprises at least one of a homopolymerisate with an aliphatic main chain with low-polar or non-polar substituents and a copolymerisate with an aliphatic main chain with low-polar or non-polar substituents.

38. Analyte-selective sensor according to claim 37 wherein the substituents are selected from the group consisting of hydrogen, halogen, NO₂, COR, COOR, carboxylic acid nitrite groups, carboxylic acid amide groups, aliphatic/aromatic ether groupings and aromatic/heteroaromatic residues.

39. Analyte-selective sensor according to claim 19 or 36 wherein the polymer is selected from the group consisting of homopolymerisates, copolymerisates and monomer units, which originate from a halogenated alkene.

40. Analyte-selective sensor according to claim 39 wherein the substituents are selected from the group consisting of hydrogen, halogen, NO₂, COR, COOR, carboxylic acid nitrile groups, carboxylic acid amide groups, aliphatic ether groupings, aromatic ether groupings, aromatic residues and heteroaromatic residues.

41. Analyte-selective sensor according to claim 19 or 36 wherein the polymer is selected from the group consisting of substituted polyolefins, polysilanes, polysiloxanes, polyphosphazenes, polyesters, polyamides, polyurethanes and cellulose derivates.

42. Analyte-selective sensor according to claim 1 wherein the analyte-specific layer (3, 8) has a thickness of 1μ

to 1 mm.

43. Analyte-selective sensor according to claim 1 wherein the analyte-specific layer (3, 8) consists of 20 to 80% by weight polymer, 20 to 80% by weight plasticiser and 1 to 60% by weight of at least one of ion-selective components and molecule-selective components.

44. Analyte-selective sensor according to claim 1 wherein, in order to stabilise the analyte-specific layer (3, 8), a porous carrier/matrix (e.g. filter papers, textiles, glass) is used.

45. Analyte-selective sensor according to claim 1 wherein at least one further enzyme-containing layer (9) is applied to the analyte-specific layer (3, 8).

46. Analyte-selective sensor according to claim 45 wherein the layer (9) is selected from the group consisting of cross-linked proteins, natural polymers and their derivates, and synthetic polymers.

47. Analyte-selective sensor according to claim 46 wherein the enzymes are immobilized in the layer.

48. Analyte-selective sensor according to claim 45 wherein the proportion of enzyme to matrix component lies in the region of 5 to 100% by weight.

49. Analyte-selective sensor according to claim 1 further comprising an additional layer (11) between the analyte-specific layer (3, 8) and the enzyme-containing layer (9), said additional layer (11) selected from the group consisting of derivates of cellulose and vinyl polymers, and having functional groups, so that an improved bond formation is achieved.

50. Analyte-selective sensor according to claim 1 further comprising an additional layer (12) on at least one of the analyte-specific layer (3, 8) and the enzymatic layer (9), said additional layer being selected from the group consisting of copolymers of ethylene, acrylic acid, metacrylic acid, carboxy elastomers, terpolymers, terpolymer ethylene-propylene-diene sulphonate, substituted polyvinyls, perfluoropolymers and polyampholytes.

51. Analyte-selective sensor according to claim 1 wherein the electrode materials are selected from the group consisting of silver, gold, platinum, palladium, nickel, tantalum, titanium, chromium, copper, vanadium, aluminium, conductive pastes containing particles of metal or graphite, epoxy resins containing particles of metal or graphite, carbon based materials, highly doped silicon, conductive polymers and conductive polymers which contain particles of metal or graphite.