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US4894339A Expired / Lapsed US ⏱️ 0.0 years remaining

Immobilized enzyme membrane for a semiconductor sensor

Assignee: Mitsubishi Electric Corp
•
Filing: 1986-12-17
•
Granted: 1990-01-16
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Expires: 2006-12-17
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Abstract

Abstract A membrane containing an immobilized enzyme for a semiconductor sensor is prepared containing a water soluble photosensitive resin including a high molecular weight polyvinyl pyrrolidone crosslinked to 2, 5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and an enzyme. Glutaraldehyde and bovine serum albumin, polyamino acid or polyamino amino acid copolymer may also be present to provide chemical crosslinking. The enzyme may be glucose oxidase, urease or lipase. The membrane can be directly formed on ion-sensitive protions of a pH-ion sensitive field effect transistor to form a semiconductor sensor by coating an aqueous solution of the resin and enzyme on the ion-sensitive portion, drying and irradiating with light such as ultraviolet light to provide photo crosslinking.

Inventors

  • 👤 Yoshio Hanazato
  • 👤 Satoru Shiono
  • 👤 Mamiko Nakako
  • 👤 Satoshi Yamada

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 06:13
CPC Classifications
C; C12; C12Q; C12Q1/00; C12Q1/001; C12Q1/002; C12N; C12N11/00; C12N11/02; C12N11/08; C12N11/082; C12N11/089; C12N11/091; C12N11/098; Y; Y10; Y10S; Y10S435/00; Y10S435/817

Claims Analysis

Total Claims: 59
Claim 1
Independent Claim 31 words
A membrane containing an immobilized enzyme comprising: a water soluble photosensitive resin including poly-vinyl pyrrolidone having a high molecular weight crosslinked to 2, 5-bis (4'-azide2'-sulfobenzal) cyclopentanone sodium salt; and an enzyme.
Claim 2
Dependent Claim 31 words
A membrane containing an immobilized enzyme comprising: a water soluble photosensitive resin including poly-vinyl pyrrolidone having a high molecular weight crosslinked to 2, 5-bis (4'-azide2'-sulfobenzal) cyclopentanone sodium salt; and an enzyme.
Claim 3
Dependent Claim 23 words
A membrane as set forth in claim 1 wherein said enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 4
Dependent Claim 23 words
A membrane as set forth in claim 1, further comprising; glutaraldehyde; and a material adapted to cooperate with glutaraldehyde to form chemical crosslinking.
Claim 5
Dependent Claim 23 words
A membrane as set forth in claim 3 wherein said enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 6
Dependent Claim 36 words
A membrane as set forth in claim 3 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 7
Dependent Claim 36 words
A membrane as set forth in claim 4 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 8
Dependent Claim 14 words
A membrane as set forth in claim 5 wherein said polyamino acid is poly-L-lysine.
Claim 9
Dependent Claim 14 words
A membrane as set forth in claim 6 wherein said polyamino acid is poly-L-lysine.
Claim 10
Dependent Claim 20 words
A membrane as set forth in claim 5 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosin.
Claim 11
Dependent Claim 20 words
A membrane as set forth in claim 6 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosin.
Claim 12
Dependent Claim 54 words
A membrane as set forth in claim 1 wherein said polyvinyl pyrrolidone having a high molecular weight is 2-20 weight %; and said 2, 5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt is 0.5-1.5 weight %; and said enzyme comprises glucose oxidase of 5.0-7.5 weight %; said membrane further comprising bovine serum albumin of 5-10 weight %.
Claim 13
Independent Claim 90 words
A method for producing a membrane containing an immobilized enzyme comprising the steps of: coating on a base an aqueous solution which is composed of a water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight and 2,5-bis(4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and an enzyme; drying the aqueous solution thus coated on said base so as to form a membrane containing an immobilized enzyme; and irradiating said membrane containing an immobilized enzyme with ultraviolet light to provide photo-crosslinking between said polyvinyl pyrrolidone, said cyclopentanone sodium salt, and said enzyme.
Claim 14
Independent Claim 90 words
A method for producing a membrane containing an immobilized enzyme comprising the steps of: coating on a base an aqueous solution which is composed of a water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight and 2,5-bis(4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and an enzyme; drying the aqueous solution thus coated on said base so as to form a membrane containing an immobilized enzyme; and irradiating said membrane containing an immobilized enzyme with ultraviolet light to provide photo-crosslinking between said polyvinyl pyrrolidone, said cyclopentanone sodium salt, and said enzyme.
Claim 15
Dependent Claim 27 words
A method for producing a membrane as set forth in claim 12 wherein said enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 16
Dependent Claim 31 words
A method for producing a membrane as set forth in claim 12 wherein said aqueous solution further comprises; glutaraldehyde; and a material adapted to cooperate with glutaraldehyde to form chemical crosslinking.
Claim 17
Dependent Claim 27 words
A method for producing a membrane as set forth in claim 14 wherein said enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 18
Dependent Claim 40 words
A method for producing a membrane as set forth in claim 14 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 19
Dependent Claim 40 words
A method for producing a membrane as set forth in claim 15 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 20
Dependent Claim 18 words
A method for producing a membrane as set forth in claim 16 wherein said polyamino acid is poly-L-lysine.
Claim 21
Dependent Claim 18 words
A method for producing a membrane as set forth in claim 17 wherein said polyamino acid is poly-L-lysine.
Claim 22
Dependent Claim 24 words
A method for producing a membrane as set forth in claim 16 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosin.
Claim 23
Dependent Claim 24 words
A method for producing a membrane as set forth in claim 17 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosin.
Claim 24
Dependent Claim 59 words
A method for producing a membrane as set forth in claim 12 wherein said polyvinyl pyrrolidone having a high molecular weight is 2-20 weight %; and said 2, 5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt is 0.5-1.5 weight %; and said enzyme comprises glucose oxidase of 5.0-7.5 weight %; said aqueous solution further comprising bovine serum albumin of 5-10 weight %.
Claim 25
Dependent Claim 35 words
A method for producing a membrane as set forth in claim 12 further comprising dipping said membrane after irradiation by said ultraviolet light into an aqueous solution of glutaraldehyde so as to form chemical crosslinking.
Claim 26
Dependent Claim 27 words
A method for producing a membrane as set forth in claim 23 further comprising washing the membrane containing an immobilized enzyme with a buffer solution after crosslinking.
Claim 27
Dependent Claim 22 words
A method for producing a membrane as set forth in claim 24 wherein said enzyme immobilized in said membrane is glucose oxidase.
Claim 28
Dependent Claim 51 words
A method for producing a membrane as set forth in claim 24 further comprising: dipping said membrane containing an immobilized enzyme into an aqueous solution of glycine after washing with said buffer solution; and again washing said membrane containing an immobilized enzyme with a buffer solution for removal of residual glutaraldehyde.
Claim 29
Dependent Claim 22 words
A method for producing a membrane as set forth in claim 26 wherein said enzyme immobilized in said membrane is glucose oxidase.
Claim 30
Dependent Claim 61 words
A sensor containing an enzyme comprising: a first pH-ion sensitive field effect transistor having a membrane containing a first immobilized enzyme, said membrane being composed of a first water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight crosslinked to 2,5-bis(4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and said first enzyme; a second pH-ion sensitive field effect transistor; and a reference electrode.
Claim 31
Dependent Claim 61 words
A sensor containing an enzyme comprising: a first pH-ion sensitive field effect transistor having a membrane containing a first immobilized enzyme, said membrane being composed of a first water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight crosslinked to 2,5-bis(4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and said first enzyme; a second pH-ion sensitive field effect transistor; and a reference electrode.
Claim 32
Dependent Claim 60 words
A sensor containing an enzyme as set forth in claim 28 further comprising a third pH-ion sensitive field effect transistor having a membrane containing a second immobilized enzyme deposited thereon, said second membrane being composed of a second water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight of and 2,5-bis(4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and said second enzyme.
Claim 33
Dependent Claim 27 words
A sensor containing an enzyme as set forth in claim 28 wherein said first enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 34
Dependent Claim 27 words
A sensor containing an enzyme as set forth in claim 29 wherein said second enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 35
Dependent Claim 26 words
A sensor containing an enzyme as set forth in claim 28 further comprising; glutaraldehyde; and a material adapted to cooperate with glutaraldehyde to form chemical crosslinking.
Claim 36
Dependent Claim 26 words
A sensor containing an enzyme as set forth in claim 29 further comprising; glutaraldehyde; and a material adapted to cooperate with glutaraldehyde to form chemical crosslinking.
Claim 37
Dependent Claim 27 words
A sensor containing an enzyme as set forth in claim 31 wherein said first enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 38
Dependent Claim 27 words
A sensor containing an enzyme as set forth in claim 32 wherein said second enzyme is selected from the group consisting of glucose oxidase, urease and lipase.
Claim 39
Dependent Claim 39 words
A sensor containing an enzyme as set forth in claim 32 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking in selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 40
Dependent Claim 39 words
A sensor containing an enzyme as set forth in claim 33 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 41
Dependent Claim 39 words
A sensor containing an enzyme as set forth in claim 34 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 42
Dependent Claim 39 words
A sensor containing an enzyme as set forth in claim 35 wherein said material adapted to cooperate with glutaraldehyde to form chemical crosslinking is selected from the group consisting of bovine serum albumin, polyamino acid, and polyamino acid copolymer.
Claim 43
Dependent Claim 17 words
A sensor containing an enzyme as set forth in claim 36 wherein said polyamino acid is poly-L-lysine.
Claim 44
Dependent Claim 17 words
A sensor containing an enzyme as set forth in claim 37 wherein said polyamino acid is poly-L-lysine.
Claim 45
Dependent Claim 17 words
A sensor containing an enzyme as set forth in claim 38 wherein said polyamino acid is poly-L-lysine.
Claim 46
Dependent Claim 17 words
A sensor containing an enzyme as set forth in claim 39, wherein said polyamino acid is poly-L-lysine.
Claim 47
Dependent Claim 23 words
A sensor containing an enzyme as set forth in claim 36 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosine.
Claim 48
Dependent Claim 22 words
A semiconductor enzyme sensor as set forth in claim 37 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosine.
Claim 49
Dependent Claim 23 words
A sensor containing an enzyme as set forth in claim 38 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosine.
Claim 50
Dependent Claim 23 words
A sensor containing an enzyme as set forth in claim 39 wherein said polyamino acid copolymer is a copolymer of poly-L-lysine and poly-L-thyrosine.
Claim 51
Dependent Claim 61 words
A sensor containing an enzyme as set forth in claim 28 wherein said polyvinyl pyrrolidone having a high molecular weight is 2-20 weight %; and said 2,5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt is 0.5-1.5 weight %; and said enzyme comprises glucose oxidase of 5.0-7.5 weight %; said membrane containing a first immobilized enzyme further comprising bovine serum albumin of 5-10 weight %.
Claim 52
Dependent Claim 62 words
A sensor containing an enzyme as set forth in claim 29 wherein said polyvinyl pyrrolidone having a high molecular weight is 2-20 weight %; and said 2, 5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt is 0.5-1.5 weight %; and said enzyme comprises glucose oxidase of 5.0-7.5 weight %; said membrane containing a second immobilized enzyme further comprising bovine serum albumin of 5-10 weight %.
Claim 53
Dependent Claim 31 words
A sensor containing an enzyme as set forth in claim 28 wherein said membrane containing a first immobilized enzyme is directly coated and hardened on said pH-ion sensitive field effect transistor.
Claim 54
Dependent Claim 31 words
A sensor containing an enzyme as set forth in claim 29 wherein said membrane containing a second immobilized enzyme is directly coated and hardened on said pH-ion sensitive field effect transistor.
Claim 55
Dependent Claim 80 words
A sensor containing an enzyme as set forth in claim 28 wherein said membrane containing a first immobilized enzyme is formed by coating on a pH-ion sensitive field effect transistor a first aqueous solution containing said first water soluble photosensitive resin, glucose oxidase, bovine serum albumin, and hardening said first aqueous solution thus coated by irradiation with ultraviolet light, said membrane containing a first immobilized enzyme being dipped into a glutaraldehyde solution to form chemical crosslinking for improved mechanical strength.
Claim 56
Dependent Claim 80 words
A sensor containing an enzyme as set forth in claim 29 wherein said membrane containing a second immobilized enzyme is formed by coating on a pH-ion sensitive field effect transistor a second aqueous solution containing said second water soluble photosensitive resin, glucose oxidase, bovine serum albumin, and hardening said second aqueous solution thus coated by irradiation with ultraviolet light, said membrane containing a second immobilized enzyme being dipped into a glutaraldehyde solution to form chemical crosslinking for improved mechanical strength.
Claim 57
Dependent Claim 51 words
A sensor containing an enzyme as set forth in claim 28 wherein said first pH-ion sensitive field effect transistor has an ionsensitive surface, and said membrane containing a first immobilized enzyme is formed through patterning on the ion-sensitive surface of said first pH-ion sensitive field effect transistor by means of photolithography.
Claim 58
Dependent Claim 51 words
A sensor containing an enzyme as set forth in claim 29 wherein said third pH-ion sensitive field effect transistor has an ion-sensitive surface, and said membrane containing a second immobilized enzyme is formed through patterning on the ion-sensitive surface of said third pH-ion sensitive field effect transistor by means of photolithography.
Claim 59
Dependent Claim 64 words
A sensor containing an enzyme as set forth in claim 28 further comprising one or more pH-ion sensitive field effect transistors each having a further membrane containing an immobilized enzyme connected thereto, said further membrane being composed of a further water soluble photosensitive resin including polyvinyl pyrrolidone having a high molecular weight crosslinked to 2, 5-bis (4'-azide-2'-sulfobenzal) cyclopentanone sodium salt, and a further enzyme.

References Cited (Backward Citations)

US4464468A Cited
US4160698A Cited
US4269941A Cited
US4476005A Cited
US4631249A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1993-01-15 1993-07-17 1994-01-16 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1997-01-15 1997-07-17 1998-01-16 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2001-01-15 2001-07-17 2002-01-16 $7700.00 Window Closed / Lapsed

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