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WO2004009677A1 - Couche d'immobilisation pour des biocapteurs - Google Patents

Couche d'immobilisation pour des biocapteurs Download PDF

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Publication number
WO2004009677A1
WO2004009677A1 PCT/EP2003/050316 EP0350316W WO2004009677A1 WO 2004009677 A1 WO2004009677 A1 WO 2004009677A1 EP 0350316 W EP0350316 W EP 0350316W WO 2004009677 A1 WO2004009677 A1 WO 2004009677A1
Authority
WO
WIPO (PCT)
Prior art keywords
immobilization layer
layer according
immobilization
polyorganosiloxane
residue
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2003/050316
Other languages
German (de)
English (en)
Inventor
Hans-Dieter Feucht
Manfred Stanzel
Jürgen STROPP
Heinrich Zeininger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to EP03753578A priority Critical patent/EP1525248A1/fr
Publication of WO2004009677A1 publication Critical patent/WO2004009677A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/001—Enzyme electrodes
    • C12Q1/002—Electrode membranes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/54353—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals with ligand attached to the carrier via a chemical coupling agent
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
    • G01N33/552—Glass or silica

Definitions

  • the present invention relates to an immobilization layer for biosensors and their use for the production of biosensory detection layers, in particular for the production of so-called DNA chips.
  • Detection systems are understood to be biological recognition molecules, such as antibodies, enzymes, nucleic acids and the like, which are bound to a carrier (transducer) via a so-called immobilization layer.
  • Detection systems are understood to be biological recognition molecules, such as antibodies, enzymes, nucleic acids and the like, which are bound to a carrier (transducer) via a so-called immobilization layer.
  • carrier transducer
  • Mainly calorimetric, piezoelectric, optical and electrochemical principles are used as transducers.
  • the detection systems or originally the immobilization layers, are usually immobilized in approximately two-dimensional layers on the transducer systems.
  • the immobilization can take place through covalent bonds, through affinity interaction but also through hydrophilic / hydrophobic interactions. For reasons of stability, covalent bonds are preferred, but the formation of stable complexes, such as Biotm / avidin, is also successfully used.
  • I. illner, E. Katz give a good overview of the structure of almost two-dimensional biological recognition layers: "Redox Protem layers on conductive supports - systems for bioelectronic applications" in Angew. CNEM. 2000, 112, 1230-69.
  • the biological function carriers ie the recognition molecules
  • alkoxysilanes which are known as contain linker groups, but are also immobilized using cyanuric chloride or carbodiide.
  • recognition molecules labeled with thioalkyl are used, which are immobilized on the transducer surface via sulfur-gold bonds in the form of so-called self-assembly layers.
  • An interesting approach to immobilizing nucleic acids on transducer surfaces is the photochemically supported synthesis of Affymetrix (Light-directed spatially addressable parallel chemical synthesis, SPA Fodor et al., Science 251, 767-773 (1991)).
  • WO 00/43539 describes the construction of a three-dimensional DNA recognition layer by immobilizing the DNA capture probes in the form of polymer brushes.
  • Timofeev et al. describes a chemically modified, radically crosslinked polyacrylamide which can be used, for example, for the immobilization of capture oligos (EN Timofeev et al., Regioselective Immobilization of Short Oligonucleotides to Acrylic Copolymer Gels, Nucleic Acids Research, 1966, Vol. 24, No. 16, 3142-3148).
  • amino or aldehyde groups are used as coupling groups in the hydrogel.
  • Aldehyde- or amino-functionalized scavenger oligos can be covalently immobilized on these coupling groups under reductive reaction conditions.
  • a radically crosslinkable polyorganosiloxane which additionally contains linker groups for coupling biological or chemical functional supports, is described by the applicant in EP 0 562 369 B1.
  • EP 0 562 372 B1 describes the production of enzyme-containing detection layers for biosensors based on the aforementioned functional polyorganosiloxanes.
  • the hydrophilicity of the immobilization layers produced in this way is subsequently increased in an additional process step by reacting part of the linker groups present in the matrix with, for example, an amino acid to such an extent that, for example, enzymes such as glucose oxidase are immobilized in the layer while maintaining their functionality can.
  • This subsequent improvement in the hydrophilicity of the immobilization layer is complex (reaction time several hours at 60 ° C., alkaline medium) and is therefore out of the question, in particular for the mass production of analytical biochips.
  • the object of the present invention is thus the generation of a radically cross-linked, i.e. three-dimensional hydrophilic immobilization layer for biosensory applications, which can be produced easily and inexpensively and can therefore also be used for the production of analytical biochips.
  • the present invention accordingly relates to an immobilization layer for bion sensors, produced from a polyorganosiloxane, optionally with the addition of reaction crosslinkers / reaction mediators on a support material, the polyorganosiloxane corresponding to the following general structure: R1 -
  • Rl lower alkyl group with preferably 1 to 4 carbon atoms
  • the polyorganosiloxanes used to build up the immobilization layer are described in the parallel German patent application (number not yet known) and carry all the functions essential for the functioning of a biochip on the polysiloxane framework, namely crosslinker groups for forming the three-dimensional layer, linker groups for linking the recognition molecules and hydrophilic ones Groups to facilitate the penetration of the recognition molecules, their binding as well as the penetration of the molecules to be recognized and thus triggering a positive recognition reaction.
  • the epoxy-functional residue in the polyorganosiloxane used to form the immobilization layer is then preferably selected from the following groups:
  • the former being particularly preferred.
  • the photopolymerizable radical Z is preferably introduced by adding a photopolymerizable compound to an epoxy-functional radical E located on the siloxane chain.
  • the photopolymerizable compound is preferably an acrylic or methacrylic acid.
  • the hydrophilic radical H is preferably a polyalkylene glycol ether, in particular a polyethylene glycol ether compound.
  • the polyorganosiloxane used to produce the immobilization layer is selected from the following group:
  • reaction mediators such as tri (meth) acrylates
  • di- and monofunctional polyethylene glycol (meth) acrylates Radical initiators are used to start the crosslinking reaction.
  • a transducer system and subsequent thermal or photocrosslinking or photostructuring result in a water-swellable, functional polyorganosiloxane layer, into which biological or chemical recognition molecules for analytical or diagnostic applications are coupled using the existing linker groups while maintaining their functionality.
  • the mixtures can be applied with all modern coating technologies. However, spin coating and dispensing are preferred.
  • the polyorganosiloxanes or their mixture with crosslinking molecules and reaction mediators are adapted to the coating process.
  • a polymeric film former for spin coating, the additional use of a polymeric film former in the mixture can be considered. No further additives are required to produce submicron layers. It is also not necessary to add plasticizers. A solvent such as dimethylformamide or methyl ethyl ketone can be added to adjust the processing viscosity of the polyorganosiloxane mixture.
  • the polyorganosiloxane mixture is applied in solution, depending on the transducer dimensions, in drops of a size from a few ⁇ l to 1 nl and less.
  • high-boiling solvents which have a sufficiently long life for the drop at the tip of the dispensing cannula, are used in order to enable reproducible dosing and settling of the drop.
  • the boiling point of the solvent must not be too high to allow the solvent to evaporate sufficiently quickly from the settled drop. overall a tempering step to control the residual solvent content may be required.
  • dimethylformamide or 2,3-butanediol or mixtures thereof are preferably used for dispensing the mixture.
  • the polyorganosiloxane mixtures are applied in layer or spot form to transducer or carrier surfaces made of metal, glass, silicon, silicon dioxide, silicon nitride or plastic.
  • the coating of surfaces also includes the coating of inner surfaces of microchannels or nanotubes. The surfaces to be coated must always be coated with an adhesion promoter.
  • the polyorganosiloxane mixture is polymerized and crosslinked by thermal or UV initiation.
  • the layer can also be structured. Contact or proximity exposure is carried out through a mask.
  • the polyorganosiloxane mixture works here like a negative resist, i.e. polymerisation and crosslinking take place in the irradiated area. There is no reaction in the darkened areas.
  • the mixture here is detached from the substrate in a development step.
  • Auxiliary components such as polymeric film formers and non-crosslinked mixture components are removed from the crosslinked layer by extraction. Under certain circumstances, this can take place at the same time as the actual equipment step.
  • the biological or chemical recognition molecules are preferably applied to the immobilization layer from aqueous solution, from aqueous buffer solution or from mixtures of polar solvents with water. It is applied by dripping on or spotting on or dispensing.
  • the solution with the biological or chemical recognition molecules can also be brought to the crosslinked layer by transport through the fluidic system itself. Networked spots, which are surrounded by a protective ring, are advantageously used for the precise loading of measuring spots.
  • a tempering step may be necessary for the covalent coupling of the biological or chemical recognition molecules, which are provided with a coupling group that matches the linker group present in the crosslinked layer.
  • a climate chamber is used to prevent the polyorganosiloxane layer from drying out during the coupling reaction.
  • Aminoalkyl groups are particularly suitable for coupling to the epoxy linker groups.
  • the system according to the invention enables the construction of sensor arrays with biological recognition molecules in a three-dimensional matrix with a high integration density.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Urology & Nephrology (AREA)
  • Hematology (AREA)
  • Biomedical Technology (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Zoology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pathology (AREA)
  • Cell Biology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Wood Science & Technology (AREA)
  • Food Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biophysics (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

L'invention concerne une couche d'immobilisation destinée à des biocapteurs et produite à partir d'un polyorganosiloxane avec addition éventuelle de réticulants/médiateurs réactionnels sur un matériau support. Le polyorganosiloxane utilisé présente la structure générale (I), dans laquelle E représente un reste à fonction époxy ayant 4 à 20 atomes de carbone, Z représente un reste (photo)polymérisable ayant 8 à 40 atomes de carbone, H représente un reste hydrophile, R<1> représente un groupe alkyle inférieur ayant de préférence 1 à 4 atomes de carbone, R<2> représente R<1 >ou H, et m + n + o + p + r vaut 50 à 200 et est égal à la longueur de chaîne L.
PCT/EP2003/050316 2002-07-18 2003-07-17 Couche d'immobilisation pour des biocapteurs Ceased WO2004009677A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03753578A EP1525248A1 (fr) 2002-07-18 2003-07-17 Couche d'immobilisation pour des biocapteurs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10232695.9 2002-07-18
DE2002132695 DE10232695A1 (de) 2002-07-18 2002-07-18 Immobilisierungsschicht für Biosensoren

Publications (1)

Publication Number Publication Date
WO2004009677A1 true WO2004009677A1 (fr) 2004-01-29

Family

ID=30010179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/050316 Ceased WO2004009677A1 (fr) 2002-07-18 2003-07-17 Couche d'immobilisation pour des biocapteurs

Country Status (3)

Country Link
EP (1) EP1525248A1 (fr)
DE (1) DE10232695A1 (fr)
WO (1) WO2004009677A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2653923A1 (fr) * 2004-08-11 2013-10-23 Dow Corning Corporation Méthode pour la fabrication des membranes semi-perméables pour l'application aux capteurs utilisant des matériaux silicone photopolymérisables
US10695744B2 (en) 2015-06-05 2020-06-30 W. R. Grace & Co.-Conn. Adsorbent biprocessing clarification agents and methods of making and using the same
WO2020156631A1 (fr) * 2019-01-28 2020-08-06 Wacker Chemie Ag Capteurs à base de couches de silicone diélectriques
US11229896B2 (en) 2014-01-16 2022-01-25 W.R. Grace & Co.—Conn. Affinity chromatography media and chromatography devices
US11389783B2 (en) 2014-05-02 2022-07-19 W.R. Grace & Co.-Conn. Functionalized support material and methods of making and using functionalized support material
US11529610B2 (en) 2012-09-17 2022-12-20 W.R. Grace & Co.-Conn. Functionalized particulate support material and methods of making and using the same
US11628381B2 (en) 2012-09-17 2023-04-18 W.R. Grace & Co. Conn. Chromatography media and devices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004021904B4 (de) * 2004-05-04 2011-08-18 Carl Zeiss Microlmaging GmbH, 07745 Verfahren und Vorrichtung zur Erzeugung einer Analyseanordnung mit diskreten, separaten Messbereichen zur biologischen, biochemischen oder chemischen Analyse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468270B1 (fr) * 1990-07-21 1994-02-23 Th. Goldschmidt AG Utilisation d'époxypolysiloxanes modifiés par des groupes étheroxy-alkényléniques comme revêtements durcissables
WO1996030431A1 (fr) * 1995-03-27 1996-10-03 Minimed Inc. Compositions de polyurethane/polyuree contenant de la silicone pour membranes de biodetecteurs
EP0562369B1 (fr) * 1992-03-23 1997-09-10 Siemens Aktiengesellschaft Polysiloxanes
EP0562372B1 (fr) * 1992-03-23 1997-11-26 Siemens Aktiengesellschaft Biocapteur
EP0562371B1 (fr) * 1992-03-23 1997-12-17 Siemens Aktiengesellschaft Immobilisation de substances biochimiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468270B1 (fr) * 1990-07-21 1994-02-23 Th. Goldschmidt AG Utilisation d'époxypolysiloxanes modifiés par des groupes étheroxy-alkényléniques comme revêtements durcissables
EP0562369B1 (fr) * 1992-03-23 1997-09-10 Siemens Aktiengesellschaft Polysiloxanes
EP0562372B1 (fr) * 1992-03-23 1997-11-26 Siemens Aktiengesellschaft Biocapteur
EP0562371B1 (fr) * 1992-03-23 1997-12-17 Siemens Aktiengesellschaft Immobilisation de substances biochimiques
WO1996030431A1 (fr) * 1995-03-27 1996-10-03 Minimed Inc. Compositions de polyurethane/polyuree contenant de la silicone pour membranes de biodetecteurs

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2653923A1 (fr) * 2004-08-11 2013-10-23 Dow Corning Corporation Méthode pour la fabrication des membranes semi-perméables pour l'application aux capteurs utilisant des matériaux silicone photopolymérisables
US11529610B2 (en) 2012-09-17 2022-12-20 W.R. Grace & Co.-Conn. Functionalized particulate support material and methods of making and using the same
US11628381B2 (en) 2012-09-17 2023-04-18 W.R. Grace & Co. Conn. Chromatography media and devices
US11229896B2 (en) 2014-01-16 2022-01-25 W.R. Grace & Co.—Conn. Affinity chromatography media and chromatography devices
US11389783B2 (en) 2014-05-02 2022-07-19 W.R. Grace & Co.-Conn. Functionalized support material and methods of making and using functionalized support material
US10695744B2 (en) 2015-06-05 2020-06-30 W. R. Grace & Co.-Conn. Adsorbent biprocessing clarification agents and methods of making and using the same
WO2020156631A1 (fr) * 2019-01-28 2020-08-06 Wacker Chemie Ag Capteurs à base de couches de silicone diélectriques

Also Published As

Publication number Publication date
EP1525248A1 (fr) 2005-04-27
DE10232695A1 (de) 2004-02-05

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