• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    In an opto-chemical sensor, comprising a sensor layer formed on a carrier composed of spun nanofibers doped with a luminescent dye, the emissivity of which after excitation with electromagnetic radiation is to be detected by substances such as O 2, CO 2, lactate, glucose, NH 3, SO 2, H 2 O 2, Nitrogen oxides, halogenated hydrocarbons and ions or measured variables to be determined, such as the pH, the humidity and the temperature is variable in a gas or liquid phase, the sensor layer of nanofibers with a diameter between 50 nm and 1000 nm is formed, and the Nanofibers are selected from the group of metalloporphyrins, benzoporphyrins, azabenzoporphyrins, naphthoporphyrins, phthalocyanines, polycyclic aromatic hydrocarbons, in particular perylenes, perylenedimines, pyrenes, with at least one luminescent dye; Xanthene dyes, azo dyes, bodypy dyes, azabodipy dyes, cyanine dyes, metal-ligand complex dyes, especially bipyridines, bipyridyls, phenantrolines, coumarins and acetylacetonates of ruthenium and iridium; Acridine dyes, oxazine dyes, coumarins, azaannulenes, squarines, 8-hydroxyquinolines, polymethines, luminescent nanoparticles, such as quantum dots, nanocrystals; Carbostyryls, terbium complexes, inorganic phosphors or dyes associated with ionophores (e.g., crown ethers) or derivatized in the aforementioned classes.
    公开号:AT512675A1
    申请号:T389/2012
    申请日:2012-03-30
    公开日:2013-10-15
    发明作者:
    申请人:Joanneum Res Forschungsgmbh；
    IPC主号:
    专利说明:

    The present invention relates to an opto-chemical sensor comprising a sensor layer formed on a support of spun nanofibers doped with a luminescent dye, the emissivity of which, after excitation with electromagnetic radiation, is to be detected by substances such as O 2, CO 2, lactate, glucose, NH 3 S02, H202, nitrogen oxides, halogenated hydrocarbons or measured variables to be determined, such as the pH, the humidity and the temperature in a gas or liquid phase can be changed.
    Sensors for measuring the concentration of certain substances such as gases, metabolites or ions in solutions or solids work either electrochemically, in which case they have the disadvantage that they consume a portion of the substance to be determined for a quantitative detection of the gas to be determined whereby the measurement result is falsified or else recently opto-chemical sensors have been developed, which are characterized in that they do not change the composition of the analyte over time, but that they are the quantitative detection of the concentration of the substance or of the gas to be determined only by a change in the Lumineszenzeigenschaften, such as indicate the luminescence quenching of the luminescent substance contained in the sensor. In this case, characteristic parameters, such as the luminescence intensity, the phase shift of the luminescence signal or the decay time of the luminescence are checked, and by comparing the luminescence signal with a calibration function, a quantitative detection of the substance to be measured succeeds. For opto-chemical sensors, it is necessary that the luminescent dyes be mixed into a solid matrix, such as polymers, during a measurement of a substance to be measured, this must diffuse through the polymer matrix to the dye molecules embedded therein, so that the fluorescent dyes are affected ,
    More recently, highly sensitive opto-chemical oxygen sensors have been developed in which the luminescent dyes are embedded in nanofiber membranes made by electrospinning. For example, such an oxygen sensor is known from the article by J. Wang et al., Chem. Commun., 2009, 5868 et seq., In which a dye based on a Cu (I) complex is embedded in a nanofiber membrane made of polystyrene material is which membrane was made by electrospinning. The nanofibers do not form a continuous layer, but rather a layer which consists of superimposed, disordered polymer threads. Such a layer has a porous structure and thus has an increased surface-to-volume ratio compared to continuous polymer matrices, so that such layers succeed in markedly increasing the accessibility of the analyte to the dye, thereby enabling to provide more sensitive sensors.
    In addition to the sensitivity of the sensors, however, it is necessary in a large number of applications not only to obtain an accurate measurement signal, but in particular to obtain the measured value quickly, in particular in real time, in order to further improve the significance of the measurements and the fields of application of the sensors to increase.
    The present invention now aims to provide an opto-chemical sensor which, in addition to high measurement accuracy, provides a significantly improved, in particular faster, response than conventional sensors.
    To achieve this object, the sensor according to the invention is now characterized in that the sensor layer is formed of nanofibers with a diameter between 50 nm and 1000 nm, and that the nanofibers are selected from the group of metalloporphyrins, benzoporphyrins, azabenzoporphyrins, naphthas with at least one luminescent dye. porphyrins, phthalocyanines, polycyclic aromatic hydrocarbons, especially perylenes, perylenediimines, pyrenes; Xanthene dyes, azo dyes, bodypy dyes, azabodipy dyes, cyanine dyes, metal-ligand complex dyes, especially bipyridines, bipyridyls, phenantrolines, coumarins and acetylacetonates of ruthenium and iridium; Acridine dyes, oxazine dyes, coumarins, azaannulenes, squarines, 8-hydroxyquinolines, polymethines, luminescent nanoparticles, such as quantum dots, nanocrystals; Carbostyryle, terbium complexes, inorganic phosphors or doped with ionophores, such as crown ethers or derivatized dyes of the aforementioned classes are doped. By choosing the diameter of the nanofibers between 50 nm and 1000 nm, it is possible to provide a sensor layer which has a porous structure which has a significantly increased surface-to-volume ratio compared to a continuous sensor layer , so that during a measurement, the diffusion paths of the molecules to be measured are massively reduced and thus on the one hand the measurement accuracy is increased and on the other hand, a reduction of the response times is achieved. By further comprising the nanofibers with at least one luminescent dye selected from the group consisting of metalloporphyrins, benzoporphyrins, azabenzoporphyrins, naphthoporphyrins, phthalocyanines, polycyclic aromatic hydrocarbons, in particular perylenes, perylenedimines, pyrenes; Xanthene dyes, azo dyes, bodypy dyes, azabodipy dyes, cyanine dyes, metal-ligand complex dyes, especially bipyridines, bipyridyls, phenantrolines, coumarins and acetylacetonates of ruthenium and iridium; Acridine dyes, oxazine dyes, coumarins, azaannulenes, squarines, 8-hydroxyquinolines, polymethines, luminescent nanoparticles, such as quantum dots, nanocrystals; Carboxylates, terbium complexes, inorganic phosphors or doped with ionophilic, such as crown ethers or derivatized dyes of the aforementioned classes, it is possible in a surprising manner, the response speed of the sensor many times over conventional
    To increase sensors. This greatly reduced response time is particularly surprising since comparable sensors according to the prior art, which use other luminescent dyes, but otherwise prepared analogously, have significantly slower response times. By mixing in at least one luminescent dye selected from the group mentioned, it is possible to reduce the response times of an opto-chemical sensor, which has a sensor layer of nanofibers doped with such luminescent dyes, to well below 1 s in comparison to response times of conventional sensors in the order of at least 3 s, in particular at least 5 s.
    Unless otherwise stated, response time is generally understood to be the response time t95, which describes the duration of the signal rise from 0% to 95% of the final signal intensity or signal drop of 100% to 5%.
    Particularly short response times of well below 1 s are surprisingly achieved according to the present invention in that the at least one luminescent dye of Pd (II) octaethylporphyrin, Pt (II) octaethylporphyrin, Pd (II) tetraphenylporphyrin, Pt (II) tetraphenylporphyrin , Pd {II) meso-tetraphenyl-tetrabenzoporphyrin, Pt (II) meso-tetra-phenyl-tetrabenzoporphyrin, Pd (II) -octaethylporphyrin-ketone, Pt (II) -octaethylporphyrin-ketone, Pd (II) -mesotetra (pentafluorophenyl ) porphyrin, Pt (II) meso-tetra (pentafluorophenyl) porphyrin, Ru (II) tris (4,7-diphenyl-1,10-phenanthroline) (Ru (dpp) 3), Ru (II) tris ( 1,10-phenanthroline) (Ru (phen) 3), tris (2,2-bipyridine) ruthenium (II) chloride hexahydrate [Ru (bpy) 3], erythrosine B, fluorescein, eosin, iridium (III) ( (N-methyl-benzoimidazol-2-yl) -7- (diethylamino) -coumarin)) 2 (acetyl-acetonate), iridium {III) ((benzothiazol-2-yl) -7- (diethylamino) -coumarin)) 2 (aoetylacetonate), Lumo-genrot, lumogen yellow, Macrolex fluorescence red, Macrolex fluorescence yellow, Rho damin B, Rhodamine 6G, TAMRA, Texas Red, Sulfo-Rhodamine, m-Cresol Red (mCP), Thymol Blue (TB), Xylenol Blue (XB), Cresol Red (CR), Chlorophenol Blue, Bromcresol Green (BG), Bromcresol Red (BP), Bromothymol Blue (BTB), 4-nitrophenol (NP), alizarin, phenolphthalein (PP), o-cresolphthalein (oCP), chlorophenol red (CPR), calmagite (CG), bromoxylenol blue (BXB), methyl red (MR), phenol red (PR), Neutral red (NR), nitrazing yellow (NY), 3,4,5,6-tetrabromophenolsulfone phthalein, Congo red (CR), fluorescein, eosin, 2 ', 7'-dichlorofluorescein, 5 (6) -carboxy-fluorocecine, carboxy-pentofluorescein, 8 Hydroxypyrene-1,3,6-trisulfonic acid (HPTS), Seminaphthorhodafluors (SNARF dyes) seminaphthofluorescein (SNAFL dyes). Although this group of luminescent dyes are common luminescent dyes, by blending these luminescent dyes into the polymer material and then electrospinning the mixture to the nanofibers forming the sensor layer, a significant reduction in the response time or duration over, for example, europium based dyes could be achieved. : -4: -: »» * «· • · * · · ♦ * ·
    If, as corresponds to a further development of an invention, the opto-chemical sensor is further developed such that the nanofibers further contain an anionic, cationic or nonionic surfactant, it is surprisingly found that the response times are even further reduced to values significantly below 1 s can be. The incorporation of a surfactant into the nanofibers causes a further coarsening of the surface, in particular a further increase in the porosity of the surface of the nanofibers, so that the accessibility of the analyte is further increased to the dye.
    Particularly fine nanofibers and in particular readily spinnable nanofibers are obtained according to a development of the invention characterized in that the surfactant from the group consisting of anionic surfactants based on carboxylates, sulfonates and sulfates, such as alkyl carboxylates, alkylbenzenesulfonates, sodium dodecylbenzenesulfonate, secondary alkanesulfonates, sulfates such Sodium lauryl sulfate, dodecyl sulfate, nonionic surfactants based on fatty alcohol ethoxylates, fatty alcohol propoxylates, alkylglucosides, alkyl polyglucosides, octylphenol ethoxylates, nonylphenol ethoxylates, nonoxinols, block copolymer surfactants or cationic surfactants based on quaternary ammonium compounds, such as hexadecyltrimethylammonium bromide, distearyldimethylammonium chloride or fluorinated surfactants or silicone surfactants is selected. In addition to improving the spinnability by adding the specifically mentioned surfactants to the polymer mixture, it is furthermore possible to increase the sensitivity of a sensor formed therewith by further increasing the porosity of the fibers and thus further improving the surface-to-volume ratio , which in addition to the improvement of the measurement intensity also further increases the response speed. With such sensors, for example, it is possible to reliably and reliably measure concentrations of 0 to 100% of substances such as O 2, CO 2, lactate and various ions in both the gas and liquid phases of samples.
    Particularly fast-response sensors are achieved according to a development of the invention in that the surfactant is contained in an amount of 0.001 mg / ml to 10 mg / ml in the polymer solution to be spun. Higher amounts of surfactant reduce the surface tension too much and homogeneous fibers can no longer be obtained. Too small amounts of surfactant show no sufficient effect. Particularly high pore numbers in the nanofibers can be further achieved by dissolving the starting materials for the nanofibers in a low-boiling organic solvent such as C4-Ce ketones and ensuring that the solvent rapidly during and after preparation of the fibers and completely removed from the formed fibers, whereby the pore number of the fibers can be further increased and there is no lowering of the activity of the dye indicator by remaining in the polymer solvent molecules.
    Particularly preferred results are achieved according to the invention in that hexadecyltrimethylammonium bromide is used as the surfactant. By adding such a. 5 · - * f V * ·
    Surfactants, the sensitivity of the sensor can be further increased without reducing the response speed.
    Particularly uniform nanofibers, which in particular allow reproducible measurements, are achieved according to the invention by using polysaccharide-based polymers, such as cellulose, cellulose acetate (CA), hydroxyethylcellulose, chitosan, dibutyrylchitin, car-boxymethylcellulose (CMC), ethylcellulose, trimethylsilylcellulose (TMSC ), Koilagen, dextran, gelatin, gluten, hyaluronic acid; Ethyl vinyl alcohol copolymer (EVOH), poly (vinyl butyral) (PVB), polydimethylsiloxanes (PDMS), polyamides (PA), polyacrylic acid (PAA), polyacrylonitrile (PAN), polycactrolactone (PCL), polyethylene oxide (PEO), polyoxymethylene (POM ), Polyesters such as polyethylene and butylene terephthalate (PET, PBT), polybutylene succinate (PBS), polytrimethyl-terephthalate; Polylactides (PLA) and polyglycolides and their copolymers (PLGA), polyacrylic late, such as polymethyl methacrylate (PMMA), polyacrylamides, polyhydroxyethyl acrylate (poly-HEMA), polyglycols, polysulfone (PSU), polyetherimide (PEI), polythiophenes, polyaniline (PANi) , Polysilanes, polyimides, polypyrrole, ethyl vinyl acetate copolymers (EVAc), polystyrene (PS), polyurethanes (PU), polyvinyl alcohol (PVOH), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) and fluorinated copolymers, polyamines, such as polyvinylpyrrolidone ( PVP), polycarbonates (PC), polyvinyl carbazole or mixtures thereof. Of these polymers, individuals are already in use both in conventional homogeneous-layer sensors and in sensors which contain nanofibers, although it has surprisingly been found that by a combination of the preferred luminescent dyes with the known polymers a significant increase in the response rate of the Sensors can be achieved, so that trained with such polymers sensors, for example, in cardiopulmonary load tests, spiroergometry, ventilation monitoring, in clinical and emergency medicine as well as in metabolic diagnostics and pulmonary function testing, such as in sports medicine can find their application. In particular, if the sensor has a homogeneous distribution of the luminescent materials in the polymers, i. no agglomerates of the dye molecules are formed, it is possible to achieve particularly fast response times.
    In order to make the sensor substantially insensitive to external influences and at the same time, however, not to reduce the response speed of the same, according to an embodiment of the invention, the sensor is designed so that the sensor layer is covered with a permeable cover layer.
    Particularly advantageous results, in particular no restrictions with respect to the response speed and the response intensity are achieved according to the present invention in that the permeable cover layer of porous membranes, such as polytetrafluoroethylene, polyvinylidene fluoride, cellulose acetate, cellulose nitrate or a polyamide having a pore size between 0.1 .mu.m and 2000 pm is formed. ♦ «* * -β; «· * · · • ♦« · · * * • · · · »· * · ♦» · * · ·
    A further possibility for rendering the sensors substantially insensitive to external influences and at the same time not lowering the response speed thereof is, according to a development of the invention, the sensor designed such that the sensor layer is formed from nanofibers connected to the permeable cover layer, wherein In particular, no limitations on the response speed and the response intensity are achieved according to the present invention in that the permeable cover layer of porous membranes such as polytetrafluoroethylene, polyvinylidene fluoride, cellulose acetate, cellulose nitrate or polyamide having a pore size between 0.1 pm and 2000 pm is formed.
    The combination of permeable cover layer and sensor layer can furthermore be assembled in any desired manner with sensors or sensor substrates.
    Among the large number of sensors that can be produced, an opto-chemical sensor whose sensor layer is formed from a polymer doped with Pt (II) Te-tra (pentafluorophenyl) porphyrin (PtTFPP) and admixed with hexadecyltrimethylammonium bromide has proven particularly suitable as an oxygen sensor. With such a sensor it is possible to produce a miniaturizable oxygen sensor which has response times of well below 1 s and which can be used, for example, in intensive care medicine, anesthetics, lung diagnostics and sports medicine. Such a sensor can be arranged, for example for measurements of the breathing air directly in the flow of exhaled air in the vicinity of the nose, and, as in a further development of the invention, the sensor is arranged in a mounted in a mounting cap clamping or holding element, For example, the sensor can be kept simple and can be connected, for example via glass fibers, to evaluation electronics, which can also be miniaturized on a user's belt or trouser pocket, so that a large number of measurements, such as breathing air, can be performed in real time with such a mini-sensor ,
    Furthermore, by virtue of the fact that the cover layer is adhesively bonded to the carrier in the region of the clamping and holding elements, it is also possible to protect the sensor from mechanical influences, so that a prolonged and in particular repeated use of the same is made possible.
    Due to the extremely short response times of the opto-chemical sensor and in particular due to the miniaturization thereof, the sensor is formed in such a way that the sensor layer is formed of two superimposed layers doped with mutually different luminescent nanofibers. By forming the sensor layer of two superposed layers of nanofibers doped with mutually different luminescent dyes, it is simultaneously possible to measure either two properties of one substance, such as, for example, the oxygen concentration and the pH or two different analytes. Such an arrangement is precise due to the large porosity of the layers, which allow fast diffusion rates of the respective analytes down into deep layers of the sensor, and has response times below 1 s for both measured quantities.
    According to a development of the invention, such a combination of dyes can also be realized in only one nanofiber layer, in which the sensor layer is formed from two nanofibers containing mutually different luminescent dyes. Such sensors can be used for the measurement of analytes based on the principles of DLR (Dual Luminophor Referencing, RET (Resonance Energy Transfer) and light harvesting).
    In order to ensure in particular that all analytes also reach lower-lying nanofoam layers, according to a further development of the invention, the opto-chemical sensor is designed such that nano-fiber layers doped one above the other and doped with luminescent dyes have different layer thicknesses from one another.
    Reproducible and reliable measurement results are achieved according to the present invention in that the layer thickness of each luminescent dye doped nanofiber layer is at least the simple thickness of a nanofiber, i. 50 nm to 1000 nm.
    The invention will be explained in more detail with reference to embodiments.
    example 1
    Production of an oxygen sensor
    A 15 wt% polystyrene solution is dissolved with 0.1 wt% Pt-tetra (pentafluorophenyl) porphyrin (PtPFTT) and 0.008 wt% hexadecyltrimethylammonium bromide in 2-butanone and charged at 12 kV and 12 cm distance between a metal needle, from which the solution is pressed, and a counter electrode to a fiber layer with a thickness of 20 pm on a polyethylene terephthalate (PET) film spun. The nanofiber layer is covered with a 0.22 nm pore size polyvinylidene difluoride membrane and mounted on a glass rod with the PET side and held in a clamp to resist peeling of the polyvinylidene difluoride layer. About the glass rod of the sensor thus formed is excited with light and the emitted light is derived to a photodiode.
    In a breath oxygen concentration measurement application, the sensor showed response times t95, which is the time to reach 95% of the constant end signal, of 80 ms. For comparison, a sensor which has a homogeneous sensor layer formed of the same materials, a response time of 5 s.
    Example 2
    Production of an oxygen sensor ··································································
    A 15 wt% polystyrene solution is dissolved with 0.09 wt% Pd meso-tetra (pentafluorophenyl) porphyrin and 0.1 wt% distearyl dimethyl ammonium chloride in 2-butanone and processed according to the procedure of Example 1 ,
    In a mission to measure the oxygen concentration of vacuum packed food, the sensor showed response times t95 of 75 ms. For comparison, a sensor which has a homogeneous sensor layer formed of the same materials has a response time of 5.10 s.
    Example 3
    Production of an oxygen sensor
    A 15 wt% polymethyl methacrylate (PMMA) is mixed with 0.1 wt% Ru (II) tris (4,7-diphenyl-1,10-phenanthroline) and 0.007 wt% dodecylsulfonate in 2-butanone dissolved and processed according to the method of Example 1.
    In a mission to measure the oxygen concentration of an endurance athlete, the sensor showed response times to5 of 85 ms. For comparison, a sensor which has a homogeneous sensor layer formed of the same materials, a response time of 5 s.
    Example 4
    Production of an oxygen sensor
    A 15% by weight carboxymethylcellulose solution is dissolved with 0.12% by weight of tris (2,2-bipyridine) ruthenium (II) chloride hexahydrate in 2-pentanone and processed according to the method of Example 1.
    In an application to measure the oxygen concentration of a patient suffering from COPD, the sensor showed response times tas of 80 ms. For comparison, a sensor which has a homogeneous sensor layer formed from the same materials, a response time of 5.2 s.
    Example 5
    Production of a CO Sensor
    A 15% by weight polyvinyl butyral solution is dissolved in a toluene / ethanol (80% / 20%) mixture with 0.15% cresol red and thymol blue and with 0.01% tetraoctylammonium hydroxide as ion pair former and 0.005% by weight Triton X-100 dissolved and processed according to the method of Example 1.
    When used to measure the CO 2 content of an athlete's breath, such a sensor exhibited a response time of t95 of 90 ms. In comparison, a conventional COi sensor shows a response time of 5 s. ·· 4 -9- »9 Μ # 999 9 ♦ · 9 9 9 9 · ·· 4 4 4 4 4 4 4 4 4 9999 9« 999 · 9999 »4» ··· · 4 · 44 44 ·· 4 4 4 4 4 4
    Example 6
    Production of a CO Sensor
    A 12% by weight polyvinylpyrrolidone solution is dissolved in a toluene / ethanol mixture (80% / 20%) with 0.1% 8-hydroxy-1,3,6-trisulfonic acid (HPTS) and 0.01% tetraoctylamine. dissolved as ionparabildner and processed according to the method of Example 1.
    When used to measure the CO 2 content of an athlete's breath, such a sensor exhibited a response time of t95 of 85 ms. In comparison, a conventional C02 sensor shows a response time of 5.5 s.
    Example 7
    Production of a CO Sensor
    A 12 wt% ethyl cellulose solution is dissolved in a toluene / ethanol (80% / 20%) mixture with 0.1% xylenol blue (XB) and 0.009% dodecylsulfate and processed according to the procedure of Example 1.
    In use for measuring the CO 2 content of respiratory air of a patient suffering from COPD, such a sensor showed a response time t9S of 80 ms. In comparison, a conventional C02 sensor shows a response time of 5 s.
    Example 8
    Production of a CO Sensor
    A 12% by weight polyvinyl alcohol solution is dissolved in a toluene / ethanol (80% / 20%) mixture with 0.1% m-cresol red (mCP) and 0.008% sodium lauryl sulfate and processed according to the procedure of Example 1.
    In one application for measuring the CO 2 content of respiratory air from an anesthetic patient, such a sensor demonstrated a response time t95 of 75 ms. In comparison, a conventional C02 sensor shows a response time of 5.3 s.
    Example 9
    Production of a pH sensor
    A 10% by weight polyvinyl alcohol solution is dissolved in an ethanol / H 2 O mixture (50% / 50%) with 0.2% phenol red and 0.005% dodecyl sulfate and processed according to the procedure of Example 1.
    In a blood pH measurement application, such a sensor exhibited a response time of just under 1 s. In comparison, a conventional pH sensor shows a response time of 4.9 s. ··· * ···· ♦ «·« A f ·· ♦ · · * ··· - Iu- ♦ · · «« ♦ ··· »* · ♦ · · ·» · · · M · * ·· * ·
    Example 10
    Production of a pH sensor
    A 10 wt% polystyrene solution is dissolved in an ethanol / H 2 O mixture (50% / 50%) with 0.25% 2'17'-dichlorofluorescein and 0.005% distearyldimethylammonium chloride and processed according to the procedure of Example 1.
    In a blood pH measurement application, such a sensor exhibited a response time t95 of just under 80 ms. In comparison, a conventional pH sensor shows a response time of 5.2 s.
    Example 11
    Production of a pH sensor
    A 10 wt% polyamide solution is dissolved in an ethanol / methanol (50% / 50%) mixture with 0.22% carboxynaphthofluorescein and 0.005% dodecylsulfate and processed according to the procedure of Example 1.
    In use for the measurement of the pH value, which was used via the CO 2 -carbonic acid equilibrium for determining the CO 2 partial pressure of the exhaled air of a patient suffering from asthma, such a sensor showed a response time t 95 of just under 80 ms. In comparison, a conventional pH sensor shows a response time of 5.6 s.
    Example 12
    Production of a COrSensor based on RET (Resonance Energy Transfer)
    A 15% by weight ethylcellulose solution is dissolved in a toluene / ethanol mixture (80% / 20%) with 0.19% phenol red and 5% ruthenium (diphenylphenanthroline) as nanobeads in PAN and with 0.01% tetraoctylammonium hydroxide as ion pair binder and processed according to the method of Example 1.
    When used to measure the CO 2 content of an athlete's breathing air, such a sensor exhibited a response time t 95 of 90 ms. In comparison, a conventional CO ^ sensor shows a response time of 5 s.
    Example 13
    Production of a COr sensor based on DLR (Dual Luminophor Referencing)
    A 30% by weight Eudragit RL 100 solution is dissolved in ethanol / water 9/1% with 0.1% HPTS and 0.5% ruthenium (diphenylphenanthroline) as nanobeads in PAN and with 0.01% tetraoctylammonium hydroxide as ion pair former and processed according to the method of Example 1. ♦ · »» »* ·· ··· ΛΑ« «« * * ♦ ♦ · " Μ " «« · * * ··· * ♦ · I · # «* · ♦
    When used to measure the CO 2 content of an athlete's breath, such a sensor exhibited a response time of t95 of 90 ms. In comparison, a conventional COz sensor shows a response time of 5 s.
    Example 14
    Producing an NH Sensor based on a Light Harvestinq cascade
    A 15 wt% PMMA solution is processed in acetone with 1% coumarin 545T, 2 mmol / kg eosin according to the method of Example 1.
    When used to measure the HN3 content of an athlete's breathing air, such a sensor exhibited a response time of 90 ms. In comparison, a conventional NH3 sensor shows a response time of 5 s.
    权利要求:
    Claims (17)
    [1]
    «Ft ···· ft -12-» · · · · · · · · · · · · · ft · ft · ft · ft · ft ····································································· Patent pending: 1. An opto-chemical sensor, comprising a sensor layer formed on a carrier made of spun nanofibers doped with a luminescent dye, whose emissivity after excitation with electromagnetic radiation by substances to be detected , 02, C02, lactate, glucose, NH3, SO2, H202, nitrogen oxides, halogenated hydrocarbons and ions or to be determined measured variables, such as the pH, the humidity and the temperature in a gas or liquid phase is variable, characterized in that the sensor layer is formed of nanofibers with a diameter between 50 nm and 1000 nm, and in that the nanofibers with at least one luminescent dye are selected from the group of metalloporphyrins, benzoporphyrins, azabenzoporphyrins, naphthoporphyrins, phthalall ocyanines, polycyclic aromatic hydrocarbons, especially perylenes, perylenediimines, pyrenes; Xanthene dyes, azo dyes, bodypy dyes, azabodipy dyes, cyanine dyes, metal-ligand complex dyes, especially bipyridines, bipyridyls, phe-nantrolines, coumarins and acetylacetonates of ruthenium and iridium; Acridine dyes, oxazine dyes, coumarins, azaannulenes, squarines, 8-hydroxyquinolines, polymethines, lumine-dense nanoparticles, such as quantum dots, nanocrystals; Carbostyryle, terbium complexes, inorganic phosphors or ionophores, such as crown ethers, associated or derivatized dyes of the aforementioned classes are doped.
    [2]
    2. Opto-chemical sensor according to claim 1, characterized in that the least one luminescent dye is selected from: Pd (II) octaethylporphyrin, Pt (II) octaethylporophyrin, Pd (II) tetraphenylporphyrin, Pt (II) -Tetraphenylporphyrin, Pd (II) meso-tetraphenyl-tetra-benzoporphyrin, Pt (II) meso-tetraphenyi-tetrabenzoporphyrin, Pd (II) -octaethylporphyrin-ketone, Pt (II) -octaethylporphyrin-ketone, Pd (II) -meso-tetra ( pentafluorophenyl) porphyrin, Pt (II) meso-T etra (pentafluorophenyl) porphyrin, Ru (II) -Tris (4,7-diphenyl-1,10-phenanthroline) (Ru {dpp) 3), Ru (II) Tris (1,10-phenanthroline) (Ru (phen) 3), tris (2,2-bipyridine) ruthenium (II) chloride hexahydrate [Ru (bpy) 3], erythrosine B, fluorescein, eosin, iridium (HI) ((N-methyl-benzoimidazol-2-yl) -7- (di-ethylamino) coumarin)) 2 (acetylacetonate), iridium (III) ((benzothiazol-2-yl) -7- (diethylamino) -co- marin)) 2 (acetylacetonate), Lumogen red, Lumogen yellow, Macrolex fluorescence red, Macrolex fluorescence yellow, Rhodamine B, Rhodamine 6G, TAMRA, Texas Red, Sulfo-Rhodam in, m-cresol red (mCP), thymol blue (TB), xylenol blue (XB), cresol red (CR), chlorophenol blue, bromcresol green (BG), bromcresol red (BP), bromothymol lau (BTB), 4-nitrophenol (NP), alizarin , Phenolphthalein (PP), o-cresolphthalein (oCP), chlorophenol red (CPR), calmagite (CG), bromoxylenol blue (BXB), methyl red (MR), phenol red (PR), neutral red (NR), nitrazing yellow (NY), 3, 4,5,6-tetrabromophenol-sulfonphtalein, Congo red (CR), fluorescein, eosin, 2 ', 7'-dichlorofluorenocecine, 5 (6) -carboxy-fluorescein, carboxynaphthofluorescein, B-hydroxypyrene-1,3,6-trisulfonic acid (HPTS), Semi «« ··· * ··· ··· JA ·· * · · · · I t - I o "♦ ♦ · ♦ * ♦ · * * ·» »· * ·« ΜΦ » Naphthorhodafluors (SNARF dyes) seminaphthofluorescein (SNAFL dyes) or from ionophores (eg Crown ether) verbundne or derivatized previously mentioned dyes.
    [3]
    3. Opto-chemical sensor according to claim 1 or 2, characterized in that the nanofibers further contain an anionic, cationic or nonionic surfactant.
    [4]
    4. Opto-chemical sensor according to claim t, 2 or 3, characterized in that the surfactant from the group consisting of anionic surfactants based on carboxylates, sulfonates and sulfates, such as alkyl carboxylates, alkylbenzenesulfonates, sodium dodecylbenzenesulfonate, secondary alkanesulfonates, sulfates such Sodium lauryl sulfate, dodecyl sulfate, nonionic surfactants based on fatty alcohol ethoxylates, fatty alcohol propoxylates, alkylglucosides, alkyl polyglucosides, octylphenol ethoxylates, nonylphenol ethoxylates, nonoxinols, block copolymer surfactants or cationic surfactants based on quaternary ammonium compounds, such as hexadecyltrimethylammonium bromide, distearyldimethylammonium chloride or fluorinated surfactants or silicone surfactants.
    [5]
    5. Opto-chemical sensor according to claim 3 or 4, characterized in that the surfactant is contained in an amount of 0.001 mg / ml to 10 mg / ml in the polymer solution to be spun.
    [6]
    6. Opto-chemical sensor according to claim 3, 4 or 5, characterized in that hexadecyltrimethylammonium bromide is used as the surfactant.
    [7]
    7. Opto-chemical sensor according to one of claims 1 to 6, characterized in that as a base material for the nanofibers, which form the sensor layer, polysaccharide-based polymers, such as cellulose, cellulose acetate (CA), hydroxyethyl cellulose, chitosan, dibutyrylchitin, Carboxymethylcellulose (CMC), ethylcellulose, trimethylsilylcellulose (TMSC), collagen, dextran, gelatin, gluten, hyaluronic acid; Ethyl vinyl alcohol copolymer (EVOH), poly (vinyl butyral) (PVB), polydimethylsiloxanes (PDMS), polyamides (PA), polyacrylic acid (PAA), polyacrylonitrile (PAN), polycaprolactone (PCL), polyethylene oxide (PEO), polyoxymethylene (POM ), Polyesters such as polyethylene and butylene terephthalate (PET, PBT), polybutylene succinate (PBS), poly-trimethylene terephthalate; Polylactides (PLA) and polyglycolides and their copolymers (PLGA), polyacrylates such as polymethyl methacrylate (PMMA), polyacrylamides, polyhydroxyethyl acrylate (poly-HEMA), polyglycols, polysulfone (PSU), polyetherimide (PEI), polythiophenes, polyaniline (PANi), polysilanes , Polyimides, polypyrrole, ethyl vinyl acetate copolymers (EVAc), polystyrene (PS), polyurethanes (PU), polyvinyl alcohol (PVOH), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) and fluorinated copolymers, polyamines, such as polyvinylpyrrolidone (PVP) , Polycarbonates (PC), polyvinylcarbazole or mixtures thereof.
    [8]
    8. Opto-chemical sensor according to one of claims 1 to 7, characterized in that the sensor layer is covered with a permeable cover layer. -14- ··· + «« • 0 «t · · 4« · ♦ ·
    [9]
    9. Opto-chemical sensor according to one of claims 1 to 7, characterized in that the sensor layer is formed from connected to the permeable cover layer nanofibers.
    [10]
    10. Opto-chemical sensor according to claim 8 or 9, characterized in that the permeable cover layer of porous membranes, polytetrafluoroethylene, polyvinylidene fluoride TF, cellulose acetate, cellulose nitrate or polyamide having a pore size between 0.1 μηη and 2000 pm is formed.
    [11]
    11. Opto-chemical sensor according to one of claims 1 to 10, characterized in that the sensor layer of Pt (II) -Tetra (pentafluorophenyl) porphyrin (PtPFTT) doped and hexadecyltrimethylammonium bromide added polymer is formed.
    [12]
    12. Opto-chemical sensor according to one of claims 1 to 11, characterized in that the sensor layer is formed of two superimposed layers doped with each other different luminescent nanofibers.
    [13]
    13. Opto-chemical sensor according to one of claims 1 to 11, characterized in that the sensor layer is formed of two mutually different luminescent nanoparticles nanofibers.
    [14]
    14. Opto-chemical sensor according to one of claims 1 to 13, characterized in that the layer thickness of each doped with a luminescent, consisting of nanofibers layer is at least the simple thickness of a nanofiber, ie 50 nm to 1000 nm.
    [15]
    15. Opto-chemical sensor according to one of claims 1 to 14, characterized in that superimposed, doped with luminescent nanofiber layers have mutually different layer thicknesses.
    [16]
    16. Opto-chemical sensor according to one of claims 1 to 15, characterized in that the sensor is arranged in a arranged in a mounting cap clamping or holding element.
    [17]
    17. Opto-chemical sensor according to one of claims 1 to 16, characterized in that the cover layer is adhesively bonded to the carrier in the region of the clamping or holding element. Vienna, March 30, 2012 Joanneum Research Forschungsgesellsphäft m.b.H by: Cunow Patentanwe
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2000016074A1|1998-09-15|2000-03-23|Joanneum Research Forschungsgesellschaft Mbh|Opto-chemichal sensor and corresponding production method|
    WO2005100957A1|2004-04-16|2005-10-27|Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH|Luminescence sensor for determining and/or monitoring an analyte that is contained in a fluidic process medium|
    DE102009005162A1|2009-01-15|2010-07-29|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Optic fiber sensor has a recess at the fiber end, on the optical axis, for a micro ball coated with sensor dyestuff to be bonded in place by an adhesive|DE102016119810A1|2016-10-18|2018-04-19|Hamilton Bonaduz Ag|Layers for the detection of oxygen|
    AT521072A1|2018-04-12|2019-10-15|Joanneum Res Forschungsgmbh|Method and device for detecting gas leaks|
    CN110684531A|2019-10-09|2020-01-14|浙江理工大学|Preparation method of photosensitive sensing material with molybdenum disulfide quantum dots loaded with tetraphenyl zirconium porphyrin nanosheets|
    DE102019132489A1|2019-11-29|2021-06-02|Endress+Hauser Conducta Gmbh+Co. Kg|Process for oxygen measurement and device for oxygen measurement|
    EP3383876A4|2015-12-02|2019-08-14|University of Utah Research Foundation|Chemical self-doping of one-dimensional organic nanomaterials for high conductivity application in chemiresistive sensing gas or vapor|
    CN106706591B|2017-02-27|2019-05-10|中南民族大学|A kind of reversible nanometer porphyrin fluorescence sensor recognition quantitative chiral amino acid method|
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    CN109481696B|2018-12-22|2020-10-02|吉林大学|Medicine for cancer photodynamic therapy and chemotherapy and preparation method thereof|
    DE102019116397A1|2019-06-17|2020-12-17|Endress+Hauser Conducta Gmbh+Co. Kg|Optochemical sensor, sensor cap and method for producing an analyte-sensitive layer|
    CN112147113A|2019-06-26|2020-12-29|西南交通大学|Application of coumarin derivative in quantitative detection of sulfur dioxide|
    DE102019124795A1|2019-09-16|2021-03-18|Abberior GmbH|Optical pH sensor|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA389/2012A|AT512675B1|2012-03-30|2012-03-30|Opto-chemical sensor|ATA389/2012A| AT512675B1|2012-03-30|2012-03-30|Opto-chemical sensor|
    EP13720744.5A| EP2872876B1|2012-03-30|2013-03-27|Opto-chemical sensor and its use|
    PCT/AT2013/000051| WO2013142886A1|2012-03-30|2013-03-27|Opto-chemical sensor|
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