WO2009118271A1 - Matériaux dérivés d’un sol-gel pour une détection de ph par fluorescence optique - Google Patents

Matériaux dérivés d’un sol-gel pour une détection de ph par fluorescence optique Download PDF

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Publication number
WO2009118271A1
WO2009118271A1 PCT/EP2009/053277 EP2009053277W WO2009118271A1 WO 2009118271 A1 WO2009118271 A1 WO 2009118271A1 EP 2009053277 W EP2009053277 W EP 2009053277W WO 2009118271 A1 WO2009118271 A1 WO 2009118271A1
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sensor
sol
gel
substrate
hpts
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PCT/EP2009/053277
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Colette Mcdonagh
Dorota Wencel
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Dublin City University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • C03C1/008—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route for the production of films or coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • 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
    • 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
    • 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
    • G01N21/78—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 producing a change of colour
    • G01N21/80—Indicating pH value

Definitions

  • the present invention relates to pH sensing and in particular to a sensing material for optical fluorescent pH sensing.
  • the invention more particularly relates to a pH sensing material comprising a sol-gel material and sensors incorporating such materials.
  • Optical methods for pH measurements exhibit a number of advantages over electrochemical methods.
  • Optical fluorescence-based pH sensing is one of the most widely used optical techniques and offers advantages such as high sensitivity and versatility with respect to detection schemes.
  • unreferenced intensity- based sensing is hampered by effects such as fluctuations in excitation source, detector drift and changes in light path through the sensor film.
  • leaching and photobleaching also have an effect on the intensity reading.
  • Such optical methods typically employ an optode which is an optical sensor device that optically measures a specific substance usually with the aid of a chemical transducer.
  • an optode which is an optical sensor device that optically measures a specific substance usually with the aid of a chemical transducer.
  • One of the most attractive features of an optode is that it does not require a separate reference sensor and it does not suffer from electrical interferences, unlike electrochemical sensors.
  • Optical fibres allow transmission of optical signals over large distances and, therefore, optodes based on optical fibres, are ideal for remote sensing. Optodes are also attractive for other reasons: their ease of handling, their low energy consumption, low production cost, ease of miniaturisation and possibility of non- invasive measurements, which is of a great importance for real time measurements in industry.
  • Most optical pH sensors consist of a proton-permeable solid matrix in which the pH indicator is encapsulated such that it is accessible to the analyte while being impervious to leaching effects. pH is measured as a function of reversible changes in the fluorescence or lifetime of the indicator, which are often influenced by the matrix- indicator interaction.
  • an optical pH sensor in accordance with the present invention that comprises a sol-gel material providing a support matrix for a pH indicator dye.
  • an optical sol-gel-based pH sensor which is based on ratiometric detection of the pH-dependent fluorescence of 8- hydroxypyrene-l,3,6-trisulfonic acid trisodium salt (HPTS), which has been ion- paired with cetyltrimethylammonium bromide CTAB, (HPTS-IP) and which has been physically entrapped in a hybrid sol-gel film.
  • HPTS 8- hydroxypyrene-l,3,6-trisulfonic acid trisodium salt
  • CTAB cetyltrimethylammonium bromide CTAB
  • HPTS-IP cetyltrimethylammonium bromide CTAB
  • the microstructure of the film which is a composite of the precursors (3-glycidoxypropyl) trimethoxysilane and ethyltriethoxysilane (GPTMS/ETEOS), has been tailored to completely encapsulate the dye thereby eliminating leaching.
  • the polar GPTMS precursor provides a hydrophilic matrix which promotes proton permeability while the ETEOS precursor improves the adhesion and mechanical stability of the resulting sol-gel-derived layers. While it is not intended to limit the present teaching to any one set of experimental results such a sensor displays a reproducible and reversible response, a resolution of 0.02 pH units and a response time of less than 12 s. The response is stable for time periods in excess of 1 month.
  • Fig. 1 depicts the chemical structure of HPTS
  • Fig. 2 graphically depicts the normalised absorption spectra of HPTS in 0.15 M phosphate buffers at different pH values
  • Fig. 3 depicts the chemical structure of HPTS-IP
  • Fig. 4(a) depicts an SEM image of a pH sensor film provided in accordance with the present teaching
  • Fig. 4(b) depicts an AFM image of the pH sensor film
  • Fig. 5(a) graphically depicts normalised excitation spectra of HPTS-IP entrapped in the sol-gel matrix (GPTMS/ETEOS) at different pH values;
  • Fig. 5(b) is a pH calibration plot of GPTMS/ETEOS sensor film
  • Fig. 6(a) graphically depicts absorption spectra of pH sensor film before measurements, after 24 h, after 3 and 4 weeks in buffer solutions at pH 7.0
  • Fig. 7 graphically depicts the photostability of the pH sensor film
  • Fig. 8 graphically depicts the reversibility of the pH sensor films
  • Fig. 9 graphically depicts response time of the pH sensor film
  • Fig. 10 graphically depicts the reproducibility of pH sensor films
  • sol-gel derived materials for optical fluorescent pH sensing that offer continuous optical pH monitoring over long-term are provided.
  • the sol-gel materials according to the present disclosure also provide for high pH sensitivity and ease of miniaturisation (advantages over pH electrode). Moreover, the materials are stable, are available at low-cost and require low-maintenance. It is envisioned that the pH material according to the present disclosure may be used in a wide variety of commercial applications including, but not limited to bioprocess management, environmental analysis (capability of continuous, remote and underground sensing) and biomedical applications (for example in the continuous monitoring of blood pH or arising from its ease of miniaturisation and suitability for in vivo measurements).
  • a sol-gel is a colloidal suspension of silica particles that is gelled to form a solid.
  • the specifics of any one sol-gel formulation will differ from those of other formulations.
  • the present inventors have identified that the sol- gel-based formulation GPTMS/ETEOS is suitable for and particularly advantageous in the context of continuous pH sensing.
  • pH indicator 8- hydroxypyrene-l,3,6-trisulfonic acid trisodium salt HPTS 8- hydroxypyrene-l,3,6-trisulfonic acid trisodium salt
  • HPTS-IP precipitate of the ion pair
  • Such an indicator dye exhibits two different pH-dependent excitation bands, corresponding to the protonated (acidic, 405 nm) form and the deprotonated (basic, 460 nm) form, and a single emission band (515 nm). The presence of the dual excitation bands facilitate the use of referenced, excitation ratiometric detection.
  • HPTS-IP is more hydrophobic than HPTS and displays poor water solubility.
  • the formulation according to the present disclosure exhibits the same pH-dependent absorption and emission maxima as the unmodified HPTS indicator so, as was detailed above, it is suitable for ratiometric measurements, which are insensitive to dye concentration, leaching and photobleaching of the fluorophore, instrument fluctuations and optical alignment. Furthermore, the formulation according to the present disclosure is a robust pH sensor achieved using physical entrapment as an immobilization method and which is resistant to dye leaching.
  • the advantages of this method are its ease of implementation, low-cost reliability as the fabricated sensor films do not exhibit leaching. This method is easy and not time consuming to implement in contrast to covalent binding methods.
  • the pH dye used is compatible with low-cost LEDs and can be used with inexpensive instrumentation (for example LED light sources and photodiode detectors) to provide a pH sensor detection system.
  • the sol-gel material developed can be deposited using a wide range of printing methods which makes it suitable for low-cost mass production. Preliminary results showed that the sensor is compatible with gamma irradiation treatment, which as will be appreciated by those skilled in the art, makes it particularly useful for bioprocess monitoring applications. Heterogeneity occurred at a very fine level as shown by the AFM image in Figure 4b. The variation in height is very uniform throughout the sample area with surface roughness of 0.24 nm.
  • sol-gel materials offer numerous advantages over polymers. They exhibit higher thermal, chemical and photochemical stability, along with improved mechanical strength, and are optically transparent over a broader spectral range (down to 250 nm).
  • the present invention relates in general to (a) a fluorescent dye, modified HPTS as shown in Figure 3, (b) a sol-gel-derived material suitable for the entrapment of the fluorescent dye and continuous optical pH sensing and (c) an optical fluorescent pH sensor that comprises the pH indicator dye entrapped in the sol-gel matrix.
  • HPTS 8-hydroxypyrene-l,3,6-trisulfonic acid trisodium salt
  • HPTS Depending on the pH, HPTS exhibits two different absorption maxima, one at
  • this indicator can be used for dual excitation measurements as it exhibits pH-dependent shifts in excitation maxima.
  • the ratio of the emission intensity at two excitation wavelengths is used as a robust measure of the pH and is particularly useful in the context of ratiometric detection techniques. It has a number of advantages over unreferenced intensity measurements. It is insensitive to dye concentration, leaching and photobleaching of the fluorophore, instrument fluctuations and optical alignment.
  • a key step in the development of optical pH sensors is immobilisation of a pH sensitive dye in a suitable, solid matrix.
  • a suitable, solid matrix dictates the characteristics of the sensor.
  • a pH indicator is adsorbed, e.g., via electrostatic or hydrophobic interactions, on a solid substrate. It is simple but not very reliable, since the adsorbed indicator may leach out.
  • the covalent binding method which involves the formation of a chemical bond between the indicator dye and the matrix, is usually complicated and time-consuming but very reliable since the indicator is not likely to leach out.
  • the entrapment method involves the encapsulation of a pH indicator in a porous polymeric matrix. It is easy to implement and reliable but slow indicator leaching can be a problem depending on the efficiency of entrapment.
  • the present inventors have realised that sol-gel entrapment of a pH indicator dye provides for a very efficient entrapment of the dye with the result that the final material offers the advantages of easy implementation and reliability without significant leaching.
  • the optimum solution for the development of a robust, low-cost, easy to prepare and non-leaching optical pH sensor is to carefully tailor the sol-gel matrix to obtain efficient dye entrapment.
  • sol-gel materials exhibit better thermal, chemical, photochemical stability and mechanical strength than polymers.
  • a sol-gel-based formulation suitable for pH sensing has been developed in accordance with the present disclosure.
  • the sol is doped with a pH sensitive dye.
  • the pH sensitive dye, HPTS was ion paired with cetyltrimethylammonium bromide (CTAB), to form a HPTS derivative, HPTS-IP as shown in Figure 3.
  • CTAB cetyltrimethylammonium bromide
  • HPTS-IP is more hydrophobic than HPTS and has poor water solubility.
  • the developed pH sensor according to the present disclosure is suitable for pH determination from pH 5.0 to pH 8.0. It exhibits excellent reproducibility, reversibility, photostability, temporal stability, minimal leaching and short response time. Ratiometric dual excitation pH detection was employed to characterize the performance of the sensor.
  • the sensor films were prepared from a mixture of ETEOS- and GPTMS- derived sols combined in 1:1 molar ratio.
  • the ETEOS-based sol was prepared by mixing ETEOS, 0.1M aqueous HCl and ethanol (EtOH) in a 1 :0.007:6.25 molar ratio.
  • the GPTMS-based sol was prepared by mixing GPTMS, 1-methylimidazole, deionized water and EtOH in 1 :0.69:4:6.25 molar ratio.
  • GPTMS is (3- glycidyloxypropyl)trimethoxysilane otherwise known as 3-(2,3- epoxypropoxy)propyltrimethoxysilane or silane-Y-4087 and has a molecular formula CgH 2 QOsSi.
  • ETEOS is ethyltriethoxysilane.
  • the GPTMS/ETEOS hybrid sol was prepared by mixing the two separate sols in equal molar ratios.
  • HPTS-IP doped solutions were fabricated by mixing an ethanolic solution of HPTS-IP with the prepared hybrid sol to give a final silane/dye ratio of 10 " .
  • the precursor was combined with absolute ethanol (EtOH), followed by dropwise addition of the catalyst.
  • EtOH absolute ethanol
  • the final mixture was aged for 72 h under ambient conditions.
  • Aging time is an extremely important factor when preparing these sols.
  • Films prepared from sols aged for 24 h exhibited very low or no pH sensitivity and while it is not intended to limit the teaching of the present invention to any one time period it has been ascertained by the present inventors that at least 48 hours of ageing is important for adequate pH sensitivity.
  • CTAB 278 mg of CTAB (0.76 mmol) was dissolved in 25 ml of DI water at 50° C and mixed with a solution comprising 200 mg of HPTS (0.38 mmol) in 25 ml of DI water.
  • HPTS-IP precipitate of the ion pair
  • All films were formed by dip-coating using a dip-speed of 3mms " ' in a controlled environment using a computer-controlled dipping apparatus.
  • the glass slides were treated with 30 % HNO3 for 24 h and then rinsed with copious amount of
  • pH fluorescence measurements were acquired using a FluoroMax-2 fluorometer (Jobin Yvon, USA). All spectra were recorded from samples contained in a flow cell that was fixed at 45° with respect to the incident beam. Films on glass slides were immersed in phosphate buffer solutions that were adjusted to pH values ranging from 3.00 to 10.00. The fluorometer collected the emission intensity at 515 nm, employing excitation wavelengths of 405 nm and 460 nm. 1.5 nm passbands were used for both the excitation and emission monochromators. All measurements were performed at room temperature.
  • FIG. 5(a) depicts normalized excitation spectra of HPTS- IP entrapped in the sol-gel matrix (GPTMS/ETEOS) at various pH values and Figure 5(b) shows a pH calibration plot of GPTMS/ETEOS sensor film.
  • the pH film has a dynamic range from pH 4.0 to 9.0 with the most sensitive dynamic range occurring between pH 5 to pH 8.0 which is a particularly advantageous range for bio-processing and clinical applications.
  • Figure 8 shows the response of the sensor over 7 measurement cycles, demonstrating the reversibility of the response.
  • Figure 6 graphically depicts absorption spectra of a pH sensor film in accordance with the present teaching before measurements, after 24 h, after 3 and 4 weeks in buffer solutions at pH 7.0 (left) and fluorescence intensity after 24 h in flow- through cell (right). Pump speed was 1 mm/s.
  • the pH films showed no leaching in pH 5.0 and 7.0 (1 month soaking) as verified with UV- Vis and fluorescence measurements.
  • the pH sensor films showed very good photostability and excellent reversibility.
  • Figure 9 depicts the response time of the pH sensor film.
  • tgo time the time taken for the intensity to achieve 90% of the final value when the pH is changed from pH 5.0 to pH 7.0.
  • pH values were chosen as they are on either side of the pKa' value of 6.49.
  • the response time is dependent on film thickness and the flow rate/injection time of the buffer solutions. In order to eliminate the fill time of the flow cell, buffer solutions at pH 5.0 and 7.0 were injected directly into the flow cell through a short section of tubing.
  • the pH film according to the present disclosure also shows good temporal stability as is depicted below in Table 1.
  • IS ionic strength
  • the sensor is reproducible and reversible, has a resolution of 0.02 pH units in the pH range from 5.0 to 8.0, a response time of 12s for a film thickness of l ⁇ m and displays temporal stability of at least 1 month.
  • Self-referenced ratiometric detection ensures that the sensor is immune to drifts such as photobleaching effects.
  • the dynamic range of the sensor is from pH 5.0 to 8.0 and the dye is completely encapsulated in the sol-gel matrix.
  • the dynamic range and performance of the sensor are compatible with a range of applications such as bio-processing and clinical measurements. While many reported optical pH sensor studies present optimum sensor performance for selected parameters, a sol-gel based pH sensing material in accordance with the present teaching provides high performance in all of the key sensor parameters, namely, reproducibility, resolution, stability, response time and leaching characteristics.
  • pH indicators 8- hydroxypyrene-l,3,6-trisulfonic acid sodium salt (HPTS), fluorescein derivatives, seminaphthorhodafluor (SNARF) and seminaphtho fluoresceins (SNAFL) dyes and hydroxycoumarines. While these could therefore be used instead of the HPTS of the preferred arrangements, Fluoresceins, SNARF and SNAFL dyes are not as photostable as HPTS. In addition, SNARF and SNAFL indicators are extremely expensive and most coumarins are excitable in the range from 300 to 400 nm. HPTS, and more particularly its ion paired formulation, is therefore a desirable preferred dye for use in the context of the present teaching.
  • one or more other dyes could be used in order to extend the working range of the HPTS-IP-based sensor. This can be accomplished by using indicators with two pKa values or by using a group of similar dyes with different pKa values.
  • tuning of the pKa can be achieved by co- immobilisation of surfactants in the sol-gel matrix. Therefore, one can cover different range of pH by judicious selection of appropriate indicators dyes for immobilisation in the sol-gel matrix.
  • the pH sensitive material in a sol-gel form it may be applied onto a substrate in one or more techniques such as for example spin-coating, dip-coating, spray-coating, gravure and screen printing, knife coating, ink-jet printing, pin-printing, micro-array deposition and stamp printing.
  • pH sensor material has been described in an exemplary arrangement as being provided as a film it will be appreciated that the teaching of the present invention should not be construed as so limited. For example discrete spots, strips or other patterns of the sensor material could be provided depending on the specific application requirements.
  • Suitable substrate materials include those formed from glass, plastics e.g. zeonor, zeonex, polycarbonate.
  • the substrate By providing the substrate with an adhesive surface such as for example in the form of an adhesive label it is possible to adhere the pH sensor to a vertical or horizontal surface within the test environment.
  • the pH sensor could also be provided as a coating on an optical fiber.
  • the geometric form of the substrate could be modified to be for example one or more of the following: planar, curved, rigid and flexible substrates.
  • a pH sensor such as that described heretofore can be used in a variety of different applications including for example:
  • Bioprocess in head-space or in liquid phase, as free-standing demountable, probe-based sensor or printed on inside of transparent bioprocessor e.g. small volume disposable bioprocessors; Biomedical: blood, saliva, other body fluids, cell diagnostics as above, point of care;
  • Food quality/freshness food packs, food processing.
  • a particularly advantageous sensing device comprises one or more LEDs and one or more photodiodes, which may be arranged relative to the sol-gel material to capture any generated fluorescence resultant from excitation of the pH indicator dye.
  • a sensing system may be configured to solely provide an output in response to pH fluctuations, such a system may be modified to provide a multi- analyte sensor having additional sensing platforms configured to provide outputs based on one or more of an O 2 sensor, a CO 2 sensor, a temperature sensor, a humidity sensor.
  • the individual outputs of the dedicated sensors could be cross referenced to one another or could be provided as independent assessments of specific criteria that are being sensed.
  • the material comprises a combination of a sol-gel matrix with a pH indicator dye.
  • a pH sensitive sol-gel based material comprises a combination of a sol-gel matrix with a pH indicator dye.

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Abstract

La présente invention concerne un matériau à base de sol-gel sensible au pH. Le matériau comprend une combinaison d’une matrice de sol-gel comportant un colorant indicateur du pH.
PCT/EP2009/053277 2008-03-25 2009-03-19 Matériaux dérivés d’un sol-gel pour une détection de ph par fluorescence optique WO2009118271A1 (fr)

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NL1038939C2 (nl) * 2011-07-12 2013-01-15 Innovation Desk Inrichting voor het aangeven van een verlopen tijdsperiode en het gebruik daarvan.
WO2015058778A1 (fr) * 2013-10-24 2015-04-30 Københavns Universitet Matrice à base de sol-gel
WO2016051217A1 (fr) 2014-09-30 2016-04-07 Pécsi Tudományegyetem P-nitrophénol-formaldéhyde polycondensé aux fins de mesure, procédé de production et utilisation
EP3184994A1 (fr) 2015-12-21 2017-06-28 CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement Capteur optique pour détecter une espèce chimique, le système comprenant ce capteur et son procédé de fabrication
KR20180083806A (ko) * 2017-01-13 2018-07-23 에스에프씨 주식회사 pH 검출용 염료 화합물, 이를 이용한 필름 및 키트
CN112730358A (zh) * 2020-12-17 2021-04-30 中国科学院南京地理与湖泊研究所 一种监测沉积物中pH二维动态分布的光学传感膜

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WO2015058778A1 (fr) * 2013-10-24 2015-04-30 Københavns Universitet Matrice à base de sol-gel
DK201370617A1 (en) * 2013-10-24 2015-05-11 Københavns Uni Sol-gel based matrix
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US20160251516A1 (en) * 2013-10-24 2016-09-01 Københavns Universitet Sol-Gel Based Matrix
US11236233B2 (en) 2013-10-24 2022-02-01 Københavns Universitet Sol-gel based matrix
WO2016051217A1 (fr) 2014-09-30 2016-04-07 Pécsi Tudományegyetem P-nitrophénol-formaldéhyde polycondensé aux fins de mesure, procédé de production et utilisation
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US10656091B2 (en) 2015-12-21 2020-05-19 Csem Centre Suisse D'electronique Et De Microtechnique Sa—Recherche Et Developpement Optical sensor for detecting a chemical species
KR20180083806A (ko) * 2017-01-13 2018-07-23 에스에프씨 주식회사 pH 검출용 염료 화합물, 이를 이용한 필름 및 키트
KR102513508B1 (ko) * 2017-01-13 2023-03-23 에스에프씨 주식회사 pH 검출용 염료 화합물, 이를 이용한 필름 및 키트
CN112730358A (zh) * 2020-12-17 2021-04-30 中国科学院南京地理与湖泊研究所 一种监测沉积物中pH二维动态分布的光学传感膜

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