WO1997047966A1 - Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree - Google Patents

Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree Download PDF

Info

Publication number
WO1997047966A1
WO1997047966A1 PCT/EP1997/003037 EP9703037W WO9747966A1 WO 1997047966 A1 WO1997047966 A1 WO 1997047966A1 EP 9703037 W EP9703037 W EP 9703037W WO 9747966 A1 WO9747966 A1 WO 9747966A1
Authority
WO
WIPO (PCT)
Prior art keywords
optical sensor
polyurethane
weight
urea
thermoplastic
Prior art date
Application number
PCT/EP1997/003037
Other languages
English (en)
Inventor
Steven Mark Barnard
Dirk Beckelmann
Joseph Berger
Marizel Rouilly
Adrian Waldner
Original Assignee
Novartis Ag
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 Novartis Ag filed Critical Novartis Ag
Priority to EP97927171A priority Critical patent/EP0906566A1/fr
Priority to AU31753/97A priority patent/AU3175397A/en
Priority to JP10501204A priority patent/JP2000512754A/ja
Publication of WO1997047966A1 publication Critical patent/WO1997047966A1/fr

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G01J3/4406—Fluorescence spectrometry
    • 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
    • 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
    • G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH

Definitions

  • the invention relates to an optical sensor for pH determination independently of the ion strength which comprises a solid polyurethane, polyurea-urethane or polyurea composition containing pH-sensitive fluorescem bound via a urethane and/or urea group in the form of a membrane on a transparent support material
  • the invention also relates to an optical fluorescence method which permits high-accuracy pH determination independently of the ion strength of the measurement solution
  • the method is particularly suitable for determining the pH of physiological solutions, in particular for determining the pH of blood
  • WO 90/00572 describes a sensor for pH determination and partial pressure determination of CO z which comprises a polyurethane hydrogel in which up to 20 % of an azo dye has been copolymerized The azo dye changes its absorption spectrum as a function of the pH, so that pH determination can be carried out via an absorption measurement The effect of the ion strength on the measurement result is not described
  • EP-A-481 740 describes in general terms polyether-polyurethanes in combination with a covalently bound fluorescence dye for pH determination, but no mention is made anywhere of the extent of the effect of ion strength on the measured signal
  • WO 94/28786 describes, for example, a composition of polyurethane acrylate prepolymer and fluorescem acrylamide which is copolymerized on a glass fibre with the aid of a photoinitiator, giving a pH-sensitive sensor whose sensitivity range can be varied within narrow limits by the prepolymer fluorescem acrylamide ratio
  • the polymer compositions allow, for example, the hydrophilicity, hydrophobicity, polarity and/or dielectric constant of the matrix to be set very precisely, which, in combination with the fluorophore concentration range selected, results in measurement independent of ion strength in a certain pH range
  • the response times and conditioning times correspond to the short periods required for optical measurement systems, these parameters being essentially dependent on the membrane thickness
  • a response time of about 10 seconds can be achieved by means of the novel sensors
  • the invention relates to an optical sensor for pH determination independently of the ion strength in the physiological range, comprising
  • the geometrical form of the support material and thus of the sensor can vary greatly, it can be, for example, a fibre, cylinder, sphere, rectangular block or cube
  • Through-flow systems in which continuous measurements or successive measurements can be carried out are also possible
  • Planar sensors are preferred They can have an area of from 0 01 to about 50 cm 2 , advantageously from 0 02 to 10 cm 2
  • the measurement region of the sensor can have an area of less than 5 mm 2 , preferably less than or equal to 2 mm 2
  • the measurement region may be identical with a fully coated surface of the support material Coating of the support material on both sides, but in a locally separated manner, is advantageous
  • the sensor can comprise one or more locally separated membrane layers; in the latter case, parallel measurements with identical or different measurement samples can be carried out
  • the support material is transparent It can be, for example, an inorganic glass, quartz or a transparent thermoplastic or crossimked plastic, such as polycarbonate, polyester, polyamide, polyacrylate or polymethacrylate
  • the dnsocyanates are preferably selected from the group consisting of 1 ,6-b ⁇ s ⁇ socyanato- hexane, 5- ⁇ socyanato-3-( ⁇ socyanatomethyl)-1,1 ,3-t ⁇ methylcyclohexane, 1 ,3-b ⁇ s[5- ⁇ so- cyanato-1 ,3,3-tr ⁇ methylphenyl]-2,4-d ⁇ oxo-1 ,3-d ⁇ azet ⁇ d ⁇ ne, 3,6-b ⁇ s[9- ⁇ socyanatononyl]-4,5-d ⁇ - ( 1 -heptenyl)cyclohexene, b ⁇ s[4- ⁇ socyanatocyclohexyl]methane, trans-1 ,4-b ⁇ s ⁇ socyanato- cyclohexane, 1 ,3-b ⁇ s[ ⁇ socyanatomethyl]benzene, 1 ,3-b ⁇ s[1-
  • the dnsocyanate is particularly preferably b ⁇ s[4- ⁇ socyanatophenyl]methane (4,4'-MDI), 2,4- or 2,6-b ⁇ s ⁇ socyanatotoluene (TDI), 1 ,6-b ⁇ s ⁇ socyanatohexane (HDI), 5- ⁇ socyanato-3- ⁇ so- cyanatomethyl-1 ,1 3-tr ⁇ methylcyclohexane (IPDI) or b ⁇ s[4- ⁇ socyanatocyclohexyl]methane (MDI), or a mixture of these dnsocyanates
  • Examples of C 2 -C 12 alkylenediols are ethylene glycol, 1 ,3-propanediol, 1 ,4-butaned ⁇ ol, 1 ,5-pentaned ⁇ ol, 1 ,6-hexanediol, 1 ,7-heptaned
  • the diol, component d), in the thermoplastic, randomly segmented polyurethane, polyurea or polyurethane-urea is preferably ethylene glycol, butanediol or hexanediol.
  • C 2 -C 12 alkylenediamines are 1 ,2-ethylenediamine, 1,3-d ⁇ aminopropane, 1 ,4-diaminobutane, 1 ,5-diaminopentane, 1 ,6-diaminohexane, 1 ,7-diaminoheptane, 1 ,8-diaminooctane, 1 ,9-diaminononane, 1 ,10-diaminodecane, 1 ,11-diaminoundecane and 1 , 12-diaminododecane.
  • C 3 -C 12 alkylenetriols examples include glycerol, the various positional isomers of butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, undecanetriol and dodecanetriol.
  • the amino or hydroxyl group of the fluorescein dye f) and the terminal isocyanate component a) are bonded in a urea or urethane group.
  • Component b) in the thermoplastic, randomly segmented polyurethane, polyurea or polyurethane-urea is preferably 70-85 % by weight of polyethylene glycol having a molecular weight of 600-2,000 daltons.
  • Component f) in the thermoplastic, randomly segmented polyurethane, polyurea or polyurethane-urea is preferably 0.1-1 % of a fluorescein dye which is amino- or hydroxyl- functionalized via a bridging group.
  • thermoplastic, randomly segmented polyurethane, polyurea or polyurethane-urea preferably has a molecular weight of from 10,000 to 30,000 daltons.
  • thermoplastic, randomly segmented polyurethane, polyurea or polyurethane-urea preferably includes a fluorescein of the formula (la) or (lb)
  • F ⁇ is a bridging group and is linear or branched C 1 -C 2 oalkylene, C 3 -C 2 oalkenylene, C 3 -C 20 alkynylene or CH 2 -(O-(CHR 2 ) r -CH 2 -CH 2 )n
  • R 2 is C 1 -C 4 alkyl
  • X is OH or NH 2
  • r is 0 or 1
  • n is a number from 1 to 20
  • Another preferred fluorescein is 4-am ⁇ nofluoresce ⁇ n.
  • linear or branched C r C 2 oalkyl radicals are methyl, ethyl, and the various positional isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tndecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl
  • linear or branched C 3 -C 20 alkenyl radicals are the various positional isomers of propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, t ⁇ decenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl and eicosenyl.
  • linear or branched C 3 -C 2 oalkynyl radicals are the various positional isomers of propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tndecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and eicosynyl
  • the thickness of the polymer layer B) is preferably from 0.1 to 500 ⁇ m, particularly preferably 1 to 100 ⁇ m
  • These layers can be produced in a manner known per se, for example by dissolving the composition in an organic solvent, then casting the solution to give a film, and finally removing the solvent
  • Suitable solvents are alcohols, ethers, esters, acid amides and ketones Relatively volatile solvents, in particular tetrahydrofuran, are particularly suitable
  • thermoplastic processing Besides these methods in which the composition is firstly dissolved then shaped, and the solvent is then evaporated again, hot shaping processes are also possible, since the composition is a thermoplastic material. Suitable processes are extrusion, injection moulding, compression moulding or blow moulding, as known from thermoplastic processing
  • the layer can be transparent or slightly opaque It is preferably transparent
  • the support materials can be treated in advance with adhesion promoters
  • plasma treatment of the support material in order to generate functional groups on the surface is also possible
  • the surface can also be provided with copolyme ⁇ zable groups in order to achieve particularly high adhesion
  • adhesion promoters for glasses are tnethoxyglycidyloxysilane, 3-az ⁇ dopropylt ⁇ ethoxy- silane and 3-am ⁇ nopropyltr ⁇ ethoxys ⁇ lane
  • the surfaces treated in this way can be modified further, for example by means of 0-(N-succm ⁇ m ⁇ dyl)-6-(4'-az ⁇ do-2'-n ⁇ trophenylam ⁇ no)- hexanoate It has been found particularly advantageous to treat the surfaces with silanes of ethylenically unsaturated carboxylic acid esters, for example 3-t ⁇ methoxys ⁇ lylpropyl methacrylate
  • the polymers can be prepared by methods known per se
  • the reactants can be reacted with one another as such, i e without addition of a solvent or diluent, for example in the melt
  • a solvent or diluent or a mixture of solvents is usually advantageous
  • solvents or diluents which may be mentioned are esters, such as ethyl acetate, ethers, such as diethyl ether, dipropyl ether, dnsopropyl ether, dibutyl ether, tert-butyl methyl ether, tetrahydrofuran or dioxan, ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone, amides, such as N,N-d ⁇ - methylformamide, N,N-d ⁇ ethylformam ⁇ de, N,N-d ⁇ methylacetam ⁇ de, N-methylpyrrolidone or hexamethylphospho ⁇ c tnamide,
  • the amine- or hydroxyl-functional fluoresceins of the formula (la) or (lb) covalently bonded to the isocyanate group can be prepared by processes known per se; the starting materials are either commercial products or can be prepared by analogous processes
  • the polymer-bound fluorescem dyes have strong absorption and fluorescence In principle, both properties can be used for pH measurement
  • the invention furthermore relates to a method for the reversible, optical determination of the pH of an aqueous sample independently of the ion strength by the fluorescence method, in which an optical sensor comprising
  • the method can be carried out by, after calibration with samples of known pH, measuring the fluorescence intensity in contact with a measurement solution of unknown composition, and determining the pH for the measured fluorescence intensity directly from the calibration
  • the sensors are brought into contact with the calibration solutions or with the measurement samples This can be done by hand (for example by pipetting) or by means of a suitable automatic through-flow system, with the sensors permanently installed in a flow cell
  • suitable automatic through-flow system with the sensors permanently installed in a flow cell
  • Light sources which can be used for the fluorescence excitation are UV lamps (for example mercury vapour lamps and halogen lamps), lasers, diode lasers and light diodes It may be expedient to use filters to filter out light having the wavelength at which the fluorescent dye has an absorption maximum
  • the fluorescent light emitted by the sensors can be collected, for example using a lens system, and then directed to a detector, for example a secondary electron multiplier or a photodiode
  • the lens system can be arranged in such a way that the fluorescence radiation is measured through the transparent support, over the edges of the support or via the analyte sample
  • the radiation is advantageously directed in a manner known per se via a dichroic mirror
  • the fluorescence from the sensors is preferably measured during contact with the calibration or sample solutions
  • the measurement can be carried out under photostationary conditions with continuous exposure, or, if required, with time resolution This can be achieved, for example, by means of a time-limited laser pulse or by modulation of the intensity of the light source
  • the measurement solution preferably has a pH of from 6 7 to 7.8
  • the measurement solution can include salts of inorganic or organic acids Examples are salts of citric acid, tactic acid, acetic acid, phosphoric acid, hydrochloric acid or sulphuric
  • the ion strength of the measurement solution is preferably from 0 05 to 5 mol/l, particularly preferably from 0 05 to 1 mol/l
  • the ion strength is preferably built up essentially by 1 1 or 1 2 salts
  • Examples of 1 1 salts are LiCI, NaCl, KCI and NH 4 CI
  • Examples of 1 2 salts are CaCI 2 , MgCI 2 and K 2 S0 4 , as desc ⁇ bed, for example, in G Kortum, Lehrbuch der Eiektrochemie [Textbook of Electrochemistry], 4th Edition, Verlag Chemie 1966, page 156
  • the measurement solution preferably comprises or consists of a body fluid It particularly preferably comprises or consists of blood
  • the method can be carried out as an individual measurement or continuously
  • the invention likewise relates to the use of an optical sensor desc ⁇ bed above for optical pH determination of an aqueous measurement solution independently of the ion strength by the fluorescence method
  • Example A3 The compound from Example A3 is dissolved in MeOH, and 2 mol eq. of SnCI 2 H 2 0 are added, whereupon a gas is immediately evolved. The deep-red solution is stirred at RT for 5 hours, and aqueous ammonia is then added, whereupon a red solid precipitates. This is filtered off and dried in a high vacuum, m.p. > 270°C.
  • thermoplastic, randomly segmented polvurethanes which are soluble in organic solvents
  • PTHF polytetrahydrofuran
  • M n 1000 g/mol
  • PEG polyethylene glycol
  • BDO butanediol
  • DABCO diazabicyclooctane
  • Example C1 The procedure is as in Example C1 using the corresponding polymers for Examples B6 and
  • the sensors are installed in a flow cell
  • the calibration or sample solutions are metered in by means of pumps and passed through the cell
  • the measurement arrangement is thermostatted
  • the light from a halogen lamp (white light, excitation wavelength 480 nm) is passed through an excitation filter, reflected at a dichroic mirror and bundled onto the planar sensors by means of lenses
  • the fluorescent light (at 520 nm) emitted by the sensors is collected by the same lens system and passed through an emission filter and the dichroic mirror to a photodiode
  • the fluorescence from the sensors is recorded during exposure by means of the calibration or sample solutions
  • the pH can be determined directly from the measurement value
  • Table 1 shows the pH dependence of the ion strength of the electrolyte in the pH range from 6 7 to 8 0 obtained owing to the different membrane compositions
  • the numerical values relate to the difference in the pK a values measured once at an ion strength of 0 1 mol/l and once at an ion strength of 0 3 mol/l

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Hematology (AREA)
  • Urology & Nephrology (AREA)
  • Pathology (AREA)
  • Biomedical Technology (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Cell Biology (AREA)
  • Microbiology (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Biophysics (AREA)
  • Inorganic Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

Capteur optique permettant de déterminer le pH indépendamment de la force ionique, et comprenant une composition de polyuréthane, de polyurée-uréthane ou de polyurée solide contenant une fluorescéine sensible au pH liée par l'intermédiaire d'un groupe urée ou uréthane sous forme d'une membrane sur un matériau de support transparent. L'invention se rapporte également à un procédé de fluorescence optique qui permet une détermination du pH d'une précision élevée indépendante de la force ionique de la solution de mesure. Ce procédé convient particulièrement à la détermination du pH de solutions physiologiques, en particulier la détermination du pH du sang.
PCT/EP1997/003037 1996-06-12 1997-06-11 Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree WO1997047966A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97927171A EP0906566A1 (fr) 1996-06-12 1997-06-11 Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree
AU31753/97A AU3175397A (en) 1996-06-12 1997-06-11 Optical sensor system for ph determination independently of the ion strength using fluorescein bound to a polymer via urethane and/or urea group
JP10501204A JP2000512754A (ja) 1996-06-12 1997-06-11 ウレタンおよび／または尿素基を介してポリマーに結合したフルオレッセインを使用したイオン強度に無関係なｐＨ測定のための光学センサー系

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1475/96 1996-06-12
CH147596 1996-06-12

Publications (1)

Publication Number Publication Date
WO1997047966A1 true WO1997047966A1 (fr) 1997-12-18

Family

ID=4211359

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/003037 WO1997047966A1 (fr) 1996-06-12 1997-06-11 Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree

Country Status (4)

Country Link
EP (1) EP0906566A1 (fr)
JP (1) JP2000512754A (fr)
AU (1) AU3175397A (fr)
WO (1) WO1997047966A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10239204B3 (de) * 2002-08-21 2004-06-09 Frank Dipl.-Ing. Zahn Ionenstärke-Sensor
EP1565505A2 (fr) * 2002-11-08 2005-08-24 Leatech, LLC Matiere sensible a la pression
WO2006007209A2 (fr) * 2004-06-25 2006-01-19 Leatech, Llc Materiau sensible a la pression et a la temperature
ITMO20110327A1 (it) * 2011-12-19 2013-06-20 Rand Srl Una membrana di rilevamento per rilevare parametri di un fluido oragnico durante lo scorrimento in un circuito extracorporeo
DE102019124795A1 (de) * 2019-09-16 2021-03-18 Abberior GmbH Optischer pH-Sensor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000572A1 (fr) * 1988-07-11 1990-01-25 Nellcor Incorporated Elements de detection composes de films de colorant sous forme d'hydrogel et leur preparation
WO1994028786A1 (fr) * 1993-06-10 1994-12-22 Optical Sensors Incorporated CAPTEURS OPTIQUES POUR LA MESURE DU pH DANS DES FLUIDES
WO1995030148A1 (fr) * 1994-05-02 1995-11-09 Ciba-Geigy Ag SYSTEME DE DETECTION OPTIQUE DETERMINANT LES VALEURS DE pH ET LES FORCES IONIQUES
WO1997015832A1 (fr) * 1995-10-23 1997-05-01 Novartis Ag SYSTEME DE CAPTEUR OPTIQUE DESTINE A DETERMINER DES VALEURS DE pH INDEPENDAMMENT DE LA FORCE IONIQUE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000572A1 (fr) * 1988-07-11 1990-01-25 Nellcor Incorporated Elements de detection composes de films de colorant sous forme d'hydrogel et leur preparation
WO1994028786A1 (fr) * 1993-06-10 1994-12-22 Optical Sensors Incorporated CAPTEURS OPTIQUES POUR LA MESURE DU pH DANS DES FLUIDES
WO1995030148A1 (fr) * 1994-05-02 1995-11-09 Ciba-Geigy Ag SYSTEME DE DETECTION OPTIQUE DETERMINANT LES VALEURS DE pH ET LES FORCES IONIQUES
WO1997015832A1 (fr) * 1995-10-23 1997-05-01 Novartis Ag SYSTEME DE CAPTEUR OPTIQUE DESTINE A DETERMINER DES VALEURS DE pH INDEPENDAMMENT DE LA FORCE IONIQUE

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10239204B3 (de) * 2002-08-21 2004-06-09 Frank Dipl.-Ing. Zahn Ionenstärke-Sensor
EP1565505A2 (fr) * 2002-11-08 2005-08-24 Leatech, LLC Matiere sensible a la pression
US7176272B2 (en) * 2002-11-08 2007-02-13 Leatech, Llc Pressure sensitive material
EP1565505A4 (fr) * 2002-11-08 2008-04-09 Leatech Llc Matiere sensible a la pression
WO2006007209A2 (fr) * 2004-06-25 2006-01-19 Leatech, Llc Materiau sensible a la pression et a la temperature
WO2006007209A3 (fr) * 2004-06-25 2008-12-04 Leatech Llc Materiau sensible a la pression et a la temperature
ITMO20110327A1 (it) * 2011-12-19 2013-06-20 Rand Srl Una membrana di rilevamento per rilevare parametri di un fluido oragnico durante lo scorrimento in un circuito extracorporeo
WO2013093792A1 (fr) * 2011-12-19 2013-06-27 Rand S.R.L. Membrane de détection pour l'analyse des paramètres d'un fluide organique pendant son écoulement dans un circuit extracorporel
DE102019124795A1 (de) * 2019-09-16 2021-03-18 Abberior GmbH Optischer pH-Sensor

Also Published As

Publication number Publication date
AU3175397A (en) 1998-01-07
EP0906566A1 (fr) 1999-04-07
JP2000512754A (ja) 2000-09-26

Similar Documents

Publication Publication Date Title
Gao et al. A self-assembled fluorescent organic nanoprobe and its application for sulfite detection in food samples and living systems
EP0758451B1 (fr) SYSTEME DE DETECTION OPTIQUE DETERMINANT LES VALEURS DE pH ET LES FORCES IONIQUES
Yang et al. Thiol–chromene click chemistry: A coumarin-based derivative and its use as regenerable thiol probe and in bioimaging applications
Werner et al. Novel optical pH-sensor based on a boradiaza-indacene derivative
US5162525A (en) Fluorogenic and chromogenic three-dimensional ionophores as selective reagents for detecting ions in biological fluids
JP3869855B2 (ja) イオン強度非依存性のｐＨ値測定光センサーシステム
EP0746757A1 (fr) Procede quotientmetrique de mesure d'oxygene par fluorescence
WO1996015443A1 (fr) POLYURETHANNES THERMOPLASTIQUES SEGMENTES DE FACON ALEATOIRE EN TANT QUE MATRICE D'ANALYSE ELECTROCHIMIQUE D'IONS Ca?++¿
EP0894261B1 (fr) Fluoro-ionophores immobilises de maniere covalente, utiles en tant que capteurs d'ions optiques
WO1997047966A1 (fr) Systeme de capteur optique pour determiner le ph independamment de la force ionique, au moyen d'une fluoresceine liee a un polymere par un groupe urethane et/ou uree
KR102513508B1 (ko) pH 검출용 염료 화합물, 이를 이용한 필름 및 키트
CN109438426B (zh) 一种基于半花菁的反应型Hg2+荧光探针Cy-PT及其制备方法和应用
US6635759B2 (en) Luminescent 4-trifluoromethyl 1-2-quinolones with long wave UV absorption and the use thereof
CN111518107A (zh) pH比率型荧光探针SP-DCCH的制备方法及生物成像应用
CN113548981B (zh) 三苯胺酚类化合物及其制备方法与其检测色氨酸的应用
JP4408452B2 (ja) フルオロイオノホア、および光学的イオンセンサーにおけるそれらの使用
CN104122243B (zh) 一种检测微量Zn2+、F‑ 或AcO‑的荧光光谱分析法
CN115340517B (zh) 一种极性敏感阳离子荧光染料及其制备方法和应用
CN109627188B (zh) 一种偶氮苯的脲类衍生物及其制备方法和应用
CN111349069B (zh) 一种检测巯基的近红外有机小分子探针、其制备方法及应用
Konstantinov et al. The polycondensation of dimethyl terephthalate and ethylene glycol in the presence of dye derivatives of 1, 3, 5‐sym‐triazine
Sugimoto et al. Complexation of cobalt ion with copolypeptide containing tryptophan treated with nitric acid
CN115710259A (zh) 靶向脂滴检测h2s的开启型荧光探针及制备方法和应用
CN118359558A (zh) 一类检测亚硫酸氢根的半菁染料荧光探针及其制备方法、检测方法以及在溶液及生物体系中的应用
Viswanathamurthi et al. A Simple Selective Probe for Lysine Detection in Tablets, Food Samples and Cells

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997927171

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1997927171

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1997927171

Country of ref document: EP