WO2022204746A9 - Capteur optique de gaz avec couche barrière - Google Patents

Capteur optique de gaz avec couche barrière Download PDF

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Publication number
WO2022204746A9
WO2022204746A9 PCT/AT2022/060099 AT2022060099W WO2022204746A9 WO 2022204746 A9 WO2022204746 A9 WO 2022204746A9 AT 2022060099 W AT2022060099 W AT 2022060099W WO 2022204746 A9 WO2022204746 A9 WO 2022204746A9
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WO
WIPO (PCT)
Prior art keywords
layer
barrier layer
matrix
substrate
polymer
Prior art date
Application number
PCT/AT2022/060099
Other languages
German (de)
English (en)
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WO2022204746A1 (fr
Inventor
Arne Sieber
Original Assignee
Oxygen Scientific GmbH
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 Oxygen Scientific GmbH filed Critical Oxygen Scientific GmbH
Publication of WO2022204746A1 publication Critical patent/WO2022204746A1/fr
Publication of WO2022204746A9 publication Critical patent/WO2022204746A9/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6434—Optrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N2021/7706—Reagent provision
    • G01N2021/773—Porous polymer jacket; Polymer matrix with indicator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

Definitions

  • the invention relates to an optode consisting of a functional layer with at least one luminescent dye which is immobilized in a matrix and a polymer substrate.
  • It also relates to a method for the production of optodes, wherein a functional layer with at least one luminescent dye is introduced into a matrix and the matrix with the functional layer is applied to a polymer plate having a plurality of polymer substrates and then the polymer substrates from the Polymer plate are separated.
  • Optical gas sensors also known as optodes, are based on special dyes that are excited to luminescence, i.e. fluorescence or phosphorescence. They are therefore luminescent dyes.
  • the gaseous analyte to be measured is oxygen
  • the intensity and the decay time of the luminescence depend on the oxygen partial pressure, since oxygen quenches the luminescence.
  • suitable dyes for example ruthenium complexes, polycyclic aromatic hydrocarbons, for example decacyclen, or platinum porphyrins. The dyes are usually immobilized and/or distributed in a matrix.
  • Suitable matrix materials are, for example, various polymers.
  • Polystyrene PS, also called polystyrene
  • silicones can also be used.
  • the matrix is usually exposed on one side to the medium in which the analyte is to be measured.
  • the matrix is arranged on the substrate on another side, usually the opposite side.
  • the measurement is carried out from this side in that light for exciting the dye penetrates through the substrate into the matrix and the reflected light of the dye is measured through the substrate. This enables a separation from the medium and the measuring electronics, but requires a substrate that is transparent at least for the wavelengths that are relevant for the dye.
  • the functional layer can be surrounded by at least one part of the matrix that contains no dye. In one embodiment, the functional layer can therefore only make up part of the matrix. Provision can also be made for the functional layer to extend essentially over the entire matrix extends. In other words, the dye can essentially be distributed throughout the entire matrix.
  • the dyes are usually first dissolved in a suitable solvent together with the matrix. Then this so-called cocktail is applied to a transparent substrate.
  • the usual processes are doctor blade coating, roll-to-roll coating, knife coating, screen printing, solenoid valve printing, piezo valve printing, etc.
  • PET polyethylene terephthalate
  • Glass is particularly suitable as a substrate because it is chemically inert and impermeable to gases.
  • the disadvantage is that the production of glass optodes is expensive, since glass can be coated but is difficult to cut.
  • the separation of large wafers into individual sensor plates, i.e. glass plates on glass substrates, is complex and therefore expensive.
  • PET films also have good chemical resistance and relatively low 02 permeability compared to other polymers, making them very suitable for coating.
  • Optodes made of PET films can be separated very easily, for example by punching, with cutting plotters or with inexpensive C02 laser cutting, also known as C02 laser cutters.
  • the production of sensor plates can be done very cheaply - a polymer plate, usually a PET film, is coated with the "cocktail" and then the sensor plates are separated.
  • Dyes can migrate from the matrix into the substrate over time. This can change the response time and/or decay time and/or signal intensity of the optode. This can result in the optode having to be recalibrated, or in the worst case, the optode becoming unusable.
  • the analyte can diffuse into the substrate, affecting the response time of the optode. For example, if the optode is exposed to high oxygen partial pressure for a long time, oxygen will diffuse into the substrate. If the oxygen optode is subsequently exposed to a low oxygen partial pressure it takes a certain amount of time for the excess oxygen to diffuse back out of the substrate into the environment, which means that the measurement signal is increased during this time.
  • WO 2016 022897 A1 describes a gas sensor which provides two sensor layers, which are arranged one above the other and contain dyes, on a glass substrate, with an oxygen-impermeable layer being arranged between the sensor layers.
  • This oxygen-impermeable layer is made of glass or plastic and prevents the passage of gas to the underlying sensor layer. This enables an independent temperature measurement using this sensor layer, but represents a complex structure that is difficult to produce.
  • DE 10 2017 118 504 A1 describes a gas sensor which has a sensor layer with a plurality of adjacent protective and diffusion layers.
  • These protective and diffusion layers are of gel-like origin, ie mostly formed from gels or dispersions, and serve to chemically stabilize the dyes or inhibit the diffusion of pollutants, but are permeable to the gaseous analyte, e.g. oxygen. In this way, chemical decomposition of the dyes by reactive pollutants can be reduced, but the problems described above remain unsolved.
  • DE 10 2014 112 972 A1 describes a sensor in which a measuring membrane is embedded in a matrix that is at least partially permeable to the analyte and is arranged on a substrate.
  • the measuring membrane inside the matrix can comprise further layers such as pH buffer layers or holding layers.
  • this cannot prevent the analyte or dyes from diffusing through the matrix in the direction of the substrate and being able to accumulate there.
  • US 2011 086418 A1 discloses a cell culture arrangement with an oxygen sensor in a first layer containing dye, which is separated from a third layer containing the cells by a second layer.
  • the second layer reduces the passage of the dye, which is sometimes harmful to the cells, into the third layer, but is permeable to oxygen.
  • the object of the present invention is therefore to provide an optical gas sensor which has an extended service life and the response time is reduced.
  • the barrier layer is preferably arranged between the substrate and the matrix.
  • Gas barrier means that the barrier layer is impermeable to the analyte, ie the gas to be measured.
  • the gaseous analyte can therefore not or only insignificantly penetrate through the barrier layer.
  • the gaseous analyte can be prevented from penetrating into the substrate or being able to attach to it.
  • the barrier layer can thus simultaneously achieve a quality and long-term stability similar to that of optodes on a glass substrate.
  • cost-effective production is possible, since polymer plates, which comprise several substrates, can be easily cut after the barrier layer and the matrix have been applied.
  • the substrate is a solid polymeric substrate suitable to support and support the functional layer.
  • Typical polymers in this area of application are mostly organic polymers, such as plastics.
  • PET polyethylene terephthalate substrates
  • films, or other solid materials which are transparent to light at least for the wavelengths of the luminescence and the excitation of the dye are used as the substrate.
  • the polymer substrates usually represent subareas of the polymer plate.
  • the polymer plate is usually a homogeneous plate. This usually results in each polymer substrate being separated from the remaining parts of the polymer plate by cutting or punching out or some other suitable method.
  • the optode is preferably designed to measure oxygen. Provision can also be made for the optode to be designed to measure CO 2 or metabolites such as glucose, lactate, urea, glutamate and creatinine, insofar as they are measured via a gas measurement.
  • an optically transparent barrier layer can be applied to the polymer film as a gas barrier.
  • Such films with gas barriers can be produced inexpensively.
  • the luminescent dye comprises fluorescent color pigments.
  • the color pigments can all be of the same type, or they can also be of different types, for example excited at different wavelengths. It can also be provided instead or additionally that the luminescent dye also includes at least one dye dissolved in the matrix.
  • the barrier layer preferably has at least one solid layer.
  • Solid means a non-liquid, non-gaseous and therefore also non-gel-like layer. Solid layers are particularly good at preventing the movement of gas towards the substrate.
  • the barrier layer preferably has at least one layer which consists at least predominantly of inorganic materials, particularly preferably inorganic oxides.
  • the inorganic materials preferably comprise salts or oxides of elements from group 13 and/or 14 of the periodic table, ie for example silicon, indium, tin or aluminum.
  • the barrier layer can also be made for the barrier layer to have at least one layer which consists at least predominantly of organic materials, particularly preferably at least one polymer.
  • This is preferably at least one polymer, polyvinylidene chloride (PVDC) or ethylene-vinyl alcohol copolymer (EVOH).
  • Suitable materials for such a barrier layer are, for example, SiOx (ie silicates such as silicon dioxide or silicon tetraoxide), ITO (indium tin oxide), AlOx or clay or mixtures thereof. Accordingly, it can be provided that the arrangement of the barrier layer between the functional layer and the polymer plate includes the arrangement of a layer between the functional layer and the polymer plate, which consists of SiOx, ITO, AlOx and/or clay or at least one of these materials. In particularly simple embodiments it can be provided that the barrier layer is made of SiOx, ITO, AlOx or clay.
  • barrier layer in particular fillers, i.e. insoluble additives, which must be essentially inert to the matrix and its ingredients, impermeable to the gaseous analyte and transparent to the relevant wavelengths for excitation and emission of the dye .
  • fillers i.e. insoluble additives
  • insoluble additives which must be essentially inert to the matrix and its ingredients, impermeable to the gaseous analyte and transparent to the relevant wavelengths for excitation and emission of the dye .
  • montmorillonite or zeolites ie aluminosilicates (AlOxSiOx) are also conceivable.
  • An example of a gas barrier is a mixture of 90% silicate, 5% clay and 5% polymer emulsion.
  • the barrier layer is made of glass.
  • Clay means clay.
  • Clay is a material composed predominantly of at least one clay mineral. It can be provided that the barrier layer comprises a layer of fired clay, ie a ceramic.
  • the barrier layer can have a thickness of less than 1 ⁇ m, preferably a thickness of 10-100 nm. It has been found that in this way the gas permeability, particularly in the case of an SiOx layer, can be reduced by about two powers of ten.
  • the barrier layer is coated with the cocktail. This is preferably followed by a drying process.
  • the sensors are separated, where preferably cost-effective methods such as punching or cutting are used.
  • the diffusion of O2 into the substrate is greatly reduced. Although it may not be possible to completely avoid a diffusion of O2 into the underlying substrate, the diffusion is significantly reduced, usually by at least two or three powers of ten. The measured value falsification after a step response is correspondingly lower and no longer significant.
  • barrier layer is impermeable to the dye. Migration of dyes from the matrix into the substrate can thus be further prevented by the barrier layer. This prevents the associated changes in the optical properties of the sensor and extends its service life.
  • the barrier layer is arranged directly on the substrate. In this way, diffusion into the substrate can be prevented in a targeted manner and the substrate can be covered over a large area so that no analyte can penetrate, even via detours.
  • an optically transparent barrier layer is applied to the polymer plate as a gas barrier. At the same time, it can be applied to the substrate very easily, quickly and inexpensively.
  • the barrier layer is directly adjacent to the matrix. This is particularly advantageous since it prevents the analyte from escaping Matrix can be prevented in the direction of the substrate and so the further Be movement is prevented in the direction of the substrate.
  • the barrier layer is particularly good at preventing dye from escaping from the matrix and thus reducing the amount of dye in the matrix. This also applies when the matrix with the functional layer is applied directly to the barrier layer.
  • the further layer can have an adhesion promoter, for example at least one adhesion promoter comprising silane, which enables better bonding of the barrier layer to the matrix.
  • a further coating is applied at least partially to the barrier layer before the matrix is applied, preferably an adhesion-promoting coating, which particularly preferably comprises at least one silane, and/or that at least part of the surface of the barrier layer is applied is subjected to a surface treatment, preferably plasma treated or corona treated.
  • the barrier layer is directly adjacent to the functional layer. In this way, the dye can be prevented particularly well from moving out of the functional layer.
  • Direct arrangement on the substrate means that the barrier layer is immobilized on the substrate. There is therefore a fixed connection which cannot be detached without being destroyed.
  • the substrate has a coating on at least part of its surface and/or is treated on part of the surface.
  • the substrate can have an adhesion promoter, for example at least one adhesion promoter comprising silane, which enables a better connection of the barrier layer to the substrate.
  • a further coating is applied at least partially to the polymer sheet before the barrier layer is applied, preferably with an adhesion-promoting coating, which particularly preferably comprises at least one silane, and/or that at least part of the surface of the Polymer plate is subjected to a surface treatment, preferably plasma treated or corona treated.
  • the matrix preferably has a thickness of less than 10 ⁇ m, particularly preferably less than 5 ⁇ m and particularly preferably less than 3 ⁇ m.
  • a matrix that is as thin as possible further reduces the response time of the sensor to changes in the amount of analyte.
  • FIG. 1 shows an embodiment of an optode according to the invention in a schematic sectional view.
  • a light source 4 in this case an LED, emits light which comprises the wavelength or wavelengths to which the luminescent dye of the optode is sensitive, ie those wavelengths with which the dye can be excited to luminescence.
  • the light is passed to the dye through a substrate 3 of the PET optode (arrow 5).
  • a barrier layer 2 is arranged, which lies directly against the substrate and is connected to it, ie which is arranged on the substrate. It is also translucent, so that the light can propagate further to an oxygen-permeable matrix 1, which is arranged directly on the barrier layer 2.
  • a dye is distributed uniformly in the matrix 1 and changes its luminescent properties depending on the oxygen partial pressure.
  • the entire matrix 1 thus represents a functional layer.
  • the dye fluoresces or phosphoresces and emits light of at least one specific wavelength. This emitted light passes through the barrier layer 2 and the substrate 2 (arrow 6) and is detected by a photosensor 7. Its signal provides information about the oxygen partial pressure.

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Pathology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une optrode constituée d'une couche fonctionnelle avec au moins un colorant luminescent qui est immobilisé dans une matrice (1), et un substrat polymère (3). L'objectif de fournir un capteur de gaz qui a une durée de vie accrue et qui réduit le temps de réponse est résolu en ce qu'une couche barrière optiquement transparente (2) qui est disposée directement sur le substrat (3) est appliquée comme barrière aux gaz entre la couche fonctionnelle et le substrat polymère (3).
PCT/AT2022/060099 2021-04-01 2022-03-30 Capteur optique de gaz avec couche barrière WO2022204746A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT601002021A AT524917A2 (de) 2021-04-01 2021-04-01 Optode mit Gasbarriereschicht
ATA60100/2021 2021-04-01

Publications (2)

Publication Number Publication Date
WO2022204746A1 WO2022204746A1 (fr) 2022-10-06
WO2022204746A9 true WO2022204746A9 (fr) 2022-12-22

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Application Number Title Priority Date Filing Date
PCT/AT2022/060099 WO2022204746A1 (fr) 2021-04-01 2022-03-30 Capteur optique de gaz avec couche barrière

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AT (1) AT524917A2 (fr)
WO (1) WO2022204746A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6689438B2 (en) * 2001-06-06 2004-02-10 Cryovac, Inc. Oxygen detection system for a solid article
AU2006350626B2 (en) * 2006-11-06 2013-09-19 Agency For Science, Technology And Research Nanoparticulate encapsulation barrier stack
US8398922B2 (en) 2009-10-08 2013-03-19 The United States of America as represented by the Secretary of Commerce, the National Institute of Standards and Technology Highly sensitive oxygen sensor for cell culture
US9274060B1 (en) * 2011-01-13 2016-03-01 Mocon, Inc. Methods for transmembrane measurement of oxygen concentration and monitoring changes in oxygen concentration within a space enclosed by a membrane employing a photoluminescent transmembrane oxygen probe
DE102014112972A1 (de) 2013-09-12 2015-03-12 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Messmembran für einen optochemischen oder amperometrischen Sensor
WO2016022897A1 (fr) 2014-08-07 2016-02-11 Teleflex Medical Incorporated Capteur optique, système de capnographie et procédés d'utilisation
DE102017118504A1 (de) 2017-08-14 2019-02-14 Endress+Hauser Conducta Gmbh+Co. Kg Schutzvorrichtung für einen optochemischen Sensor und entsprechender optochemischer Sensor

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Publication number Publication date
WO2022204746A1 (fr) 2022-10-06
AT524917A2 (de) 2022-10-15

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