Optochemical sensor and method for production

Abstract

An optochemical sensor for measuring concentrations of analytes is provided with a reactive matrix preferably made of polymeric material capable of swelling. Further provided are a mirror layer and a layer of a plurality of discrete islands that are electrically conductive, between which layers the reactive matrix is positioned, the diameter of the islands being smaller than the wavelength of the light employed for monitoring and evaluation.

We claim:  
     
       1. Optochemical sensor system for measuring the concentration of a substance, said system comprising a light source and a sensor, said light source emitting incident light at a wavelength toward said sensor for irradiating said sensor, said sensor comprising: 
       a mirror layer,  
       an island layer consisting of a plurality of islands of electrically conductive material, said islands having a diameter smaller than the wavelength of incident light emitted from said light source and used for irradiating said sensor, and  
       a reactive matrix situated between said mirror layer and said island layer, said reactive matrix being composed of a material which is capable of swelling or shrinking in the presence of the substance to be measured depending on the concentration of the substance, wherein the shrinking or swelling of the reactive matrix causes a change in color of light reflected from said sensor, wherein the change of color can be monitored as an optical response due to swelling or shrinking of said reactive matrix.  
     
     
       2. Optochemical sensor system according to claim  1 , wherein said islands of said island layer are made of metal. 
     
     
       3. Optochemical sensor system according to claim  1 , wherein said mirror layer and said islands of said island layer are made of gold. 
     
     
       4. Optochemical sensor system according to claim  1 , wherein said island layer has a mass thickness of less than 20 nm. 
     
     
       5. Optochemical sensor system according to claim  1 , wherein said island layer has a light absorption of 40-60 percent for the particular wavelength used. 
     
     
       6. Optochemical sensor system according to claim  1 , wherein said mirror layer is formed as a second island layer consisting of a second plurality of islands of electrically conductive material, said islands of said second island layer having a diameter which is smaller than the wavelength of incident light emitted from said light source and used for irradiating said sensor. 
     
     
       7. Optochemical sensor system according to claim  1 , wherein said wavelength is in the visible light region and the diameter of said islands is smaller than 100 nm. 
     
     
       8. Optochemical sensor system according to claim  7 , wherein the diameter of said islands is smaller than 60 nm. 
     
     
       9. Optochemical sensor system according to claim  1 , wherein said reactive matrix comprises an optically transparent polymer selected from the group consisting of polyacrylic acid derivatives and polyvinylpyrrolidone derivatives. 
     
     
       10. Optochemical sensor system according to claim  9 , wherein said reactive matrix is an acrylic acid acrylamide copolymer. 
     
     
       11. Optochemical sensor system according to claim  1 , wherein the optical thickness of said reactive matrix is less than 1,000 nm. 
     
     
       12. Optochemical sensor system according to claim  11 , wherein the optical thickness of said reactive matrix is less than 100 nm and said wavelength is in the visible light region. 
     
     
       13. Optochemical sensor system for measuring the concentration of a substance, said system comprising a light source and a sensor, said light source emitting incident light at a wavelength toward said sensor for irradiating said sensor, said sensor comprising: 
       a mirror layer,  
       an island layer consisting of a plurality of islands of electrically conductive material, said islands having a diameter smaller than the wavelength of incident light emitted from said light source and used for irradiating said sensor, and  
       a matrix situated between said mirror layer and said island layer, wherein said island layer undergoes chemical destruction due to reaction processes with the substance to be measured or with reaction products of the substance depending on the concentration of the substance to be measured, wherein the chemical destruction of said island layer causes a change in color of light reflected from said sensor, wherein the change of color can be monitored as an optical response due to chemical destruction of said island layer.  
     
     
       14. Optochemical sensor system according to claim  13 , wherein said mirror layer is formed as a second island layer consisting of a second plurality of islands of electrically conductive material, said islands of said second island layer having a diameter which is smaller than the wavelength of incident light emitted from said light source and used for irradiating said sensor. 
     
     
       15. Method for preparing an optochemical sensor system for measuring the concentration of a substance, said method comprising the steps of: 
       a) providing a light source which emits incident light at a wavelength;  
       b) providing a substrate layer;  
       c) applying a mirror layer to said substrate layer;  
       d) applying a reactive matrix layer to said mirror layer, said reactive matrix layer being composed of a material which is capable of swelling or shrinking in the presence of said substance to be measured depending on the concentration of the substance to be measured, wherein the shrinking or swelling of the reactive matrix causes a change in color of light reflected therefrom; and  
       e) applying an island layer to said reactive matrix layer, said island layer having islands with a diameter smaller than the wavelength of incident light emitted from said light source.  
     
     
       16. Method according to claim  15 , wherein the island layer is vapor-deposited on said reactive polymer matrix in step e). 
     
     
       17. Method according to claim  15 , wherein said island layer is prepared or modified by the attachment of metallic particles or islands to said reactive matrix in step e). 
     
     
       18. Method according to claim  15 , within the islands of said island layer are produced, or their number or size is changed, by removing excess metal from said reactive polymer matrix. 
     
     
       19. Method according to claim  15 , wherein enzymes or catalysts are immobilized in said reactive matrix. 
     
     
       20. Method according to claim  15  wherein polyvinylpyrrolidone with a molecular weight of 280,000 to 2,000,000 is cross-linked with bisazides belonging to a group consisting of Na-4,4′-diacidostilbene-2,2′-disulphonatetetrahydrate, and 2,6-bis-(4-acidobenzylidenemethylcyclohexanone), and cured by ultraviolet radiation, in order to prepare said reactive polymer matrix of step d). 
     
     
       21. Optochemical sensor system for measuring the concentration of a substance, said system comprising a light source and an optochemical sensor, said light source emitting incident light at a wavelength toward said sensor for irradiating said sensor, said sensor comprising: 
       an island layer consisting of a plurality of islands of electrically conductive material, said islands having a diameter smaller than the wavelength of incident light emitted from said light source, and  
       a reactive matrix situated on one side of said island layer, said reactive matrix being composed of a material which is capable of swelling or shrinking in the presence of the substance to be measured depending on the concentration of the substance, wherein shrinking or swelling of the reactive matrix causes a change in color of light reflecting from said sensor, wherein the change of color can be monitored as an optical response due to swelling or shrinking of said reactive matrix, and wherein said reactive matrix includes a first surface adjacent said island layer and a second surface opposite said first surface and which forms an interface with ambient air, said second surface providing a mirror layer realized by Fresnel reflection occurring at said interface.  
     
     
       22. An optochemical sensor, comprising: 
       
         a mirror layer;  
       
       
         a film layer comprising a plurality of islands of electrically conductive material, and  
       
       
         a reactive matrix situated between said mirror layer and said film layer, wherein said reactive matrix comprises a material capable of swelling or shrinking in the presence of a substance to be measured depending on the concentration of the substance.  
       
     
     
       23. An optochemical sensor according to claim  22 , wherein said islands are made of metal.  
     
     
       24. An optochemical sensor according to claim  22 , wherein said islands comprise a microcolloidal particle.  
     
     
       25. An optochemical sensor according to claim  22 , wherein said mirror layer and said islands are made of gold.  
     
     
       26. An optochemical sensor according to claim  22 , wherein said film layer has a mass thickness of less than  20  nm.  
     
     
       27. An optochemical sensor according to claim  22 , wherein said film layer has a mass thickness of less than  15  nm.  
     
     
       28. An optochemical sensor according to claim  22 , wherein said film layer has a light absorption of  40 - 60  percent for a particular wavelength of light.  
     
     
       29. An optochemical sensor according to claim  22 , wherein said mirror layer is formed as a second film layer consisting of a second plurality of islands of electrically conductive material.  
     
     
       30. An optochemical sensor according to claim  22 , wherein the diameter of said islands is less than  100  nm.  
     
     
       31. An optochemical sensor according to claim  22 , wherein the diameter of said islands is less than  60  nm.  
     
     
       32. An optochemical sensor according to claim  22 , wherein said reactive matrix comprises an optically transparent polymer selected from the group consisting of polyacrylic acid derivatives and polyvinylpyrrolidone derivatives.  
     
     
       33. An optochemical sensor according to claim  22 , wherein said reactive matrix is an acrylic acid acrylamide copolymer.  
     
     
       34. An optochemical sensor according to claim  22 , wherein the optical thickness of said reactive matrix is less than  1 , 000  nm.  
     
     
       35. An optochemical sensor according to claim  32 , wherein the optical thickness of said reactive matrix is less than  100  nm.  
     
     
       36. A method of detecting the presence of a chemical species, comprising the steps of: 
       ( A )  applying light to a sensor comprising    
       ( i )  a mirror layer,    
       ( ii )  a film layer comprising a plurality of islands of electrically conductive material, and    
       ( iii )  a reactive matrix situated between said mirror layer and said film layer    
       ( B )  contacting said sensor with a substance containing said chemical species, whereby the chemical species causes a swelling or shrinking of said reactive matrix; and    
       ( C )  detecting a change in the distance between the film layer and mirror layer by a change in the optical behavior of said light.    
     
     
       37. A method according to claim  36 , wherein said islands are made of metal.  
     
     
       38. A method according to claim  36 , wherein said islands comprise a microcolloidal particle.  
     
     
       39. A method according to claim  36 , wherein said mirror layer and said islands are made of gold.  
     
     
       40. A method according to claim  36 , wherein said film layer has a mass thickness of less than  20  nm.  
     
     
       41. A method according to claim  36 , wherein said film layer has a mass thickness of less than  15  nm.  
     
     
       42. A method according to claim  36 , wherein said film layer has a light absorption of  40 - 60  percent for a particular wavelength of light.  
     
     
       43. A method according to claim  36 , wherein said mirror layer is formed as a second film layer consisting of a second plurality of islands of electrically conductive material.  
     
     
       44. A method according to claim  36 , wherein the diameter of said islands is less than  100  nm.  
     
     
       45. A method according to claim  36 , wherein the diameter of said islands is less than  60  nm.  
     
     
       46. A method according to claim  36 , wherein said reactive matrix comprises an optically transparent polymer selected from the group consisting of polyacrylic acid derivatives and polyvinylpyrrolidone derivatives.  
     
     
       47. A method according to claim  36 , wherein said reactive matrix is an acrylic acid acrylamide copolymer.  
     
     
       48. A method according to claim  36 , wherein the optical thickness of said reactive matrix is less than  1 , 000  nm.  
     
     
       49. A method according to claim  36 , wherein the optical thickness of said reactive matrix is less than  100  nm.  
     
     
       50. A method of detecting the presence of a chemical species, comprising the steps of: 
       ( A )  applying light to a sensor comprising:    
       ( i )  a mirror layer, and    
       ( ii )  a plurality of islands of electrically conductive material positioned above said mirror layer, wherein the distance between said electrically conductive material and said mirror layer can vary depending upon the presence of absence of said chemical species;    
       ( B )  contacting said sensor with a substance that may contain said chemical species; and    
       ( C )  detecting the presence or absence of a change in the distance between said electrically conductive material and mirror layer by the presence or absence of a change in the optical behavior of said light.    
     
     
       51. A method according to claim  50 , wherein said electrically conductive material is made of metal.  
     
     
       52. A method according to claim  50 , wherein said electrically conductive material comprises a microcolloidal particle.  
     
     
       53. A method according to claim  50 , wherein said mirror layer and said electrically conductive material are made of gold.  
     
     
       54. A method according to claim  50 , wherein said electrically conductive material has a mass thickness of less than  20  nm.  
     
     
       55. A method according to claim  50 , wherein said electrically conductive material has a mass thickness of less than  15  nm.  
     
     
       56. A method according to claim  50 , wherein said electrically conductive material has a light absorption of  40 - 60  percent for a particular wavelength of light.  
     
     
       57. An method according claim  50 , wherein said mirror layer is formed as a second layer of electrically conductive material.  
     
     
       58. A method according to claim  50 , wherein the diameter of said islands of electrically conductive material is less than  100  nm.  
     
     
       59. A method according to claim  50 , wherein the diameter of said islands of electrically conductive material is less than  60  nm.