WO2024125678A1 - Capteur optique d'oxygène - Google Patents
Capteur optique d'oxygène Download PDFInfo
- Publication number
- WO2024125678A1 WO2024125678A1 PCT/CZ2022/050134 CZ2022050134W WO2024125678A1 WO 2024125678 A1 WO2024125678 A1 WO 2024125678A1 CZ 2022050134 W CZ2022050134 W CZ 2022050134W WO 2024125678 A1 WO2024125678 A1 WO 2024125678A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ptoep
- oxygen
- pcl
- luminescence
- oxygen sensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6434—Optrodes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/7769—Measurement method of reaction-produced change in sensor
- G01N2021/7786—Fluorescence
Definitions
- the present invention relates to detection of oxygen gas in gaseous and/or aqueous media.
- This invention presents easy to use and economic detection of gas oxygen in mixture of gases and oxygen dissolved in water stored in several containers or in several systems such as in pipelines or other duct systems and other aqueous media including cell cultures for tissue engineering. It can be also used for monitoring quality of water especially in the case of impurities or microbial contaminations in aqueous media via monitoring of attachment of these contaminants yielding to film/biofilm on the surface of the sensor and thus decreasing diffusion of oxygen to sensor.
- Art The ability to detect oxygen content in gas mixtures and localized dissolved oxygen in aqueous environments including also biological environments is greatly desired in many applications.
- Oxygen is also of vital importance for many cellular processes having great significance in biomedical applications. For instance, oxygen supply is a crucial limiting factor during three-dimensional cell culture directed toward tissue engineering. Convention Clark electrodes have dominated the oxygen sensor field thanks to their reliability and lack of heavy atom interference. However, these sensors consume oxygen during measurements, are invasive and difficult to miniaturize to provide localized information. Therefore, in recent years, the attention is devoted to optical detection of oxygen via dynamic quenching (energy transfer) of luminescence (phosphorescence) from an excited luminescent molecule in its triplet state to an oxygen molecule.
- dynamic quenching energy transfer
- luminescence phosphorescence
- Luminescent molecules used in the literature can be classified as polycyclic aromatic hydrocarbons, polypyridyl complexes, metal porphyrins and complexes with rarely used central atoms.
- the most commonly used luminescent molecules are palladium(II) and platinum(II)tetrakis(pentafluorophenyl)porphyrin (PdTFPP and PtTFPP, respectively) and tris(4,7-diphenyl- 1,10-phenanthroline) ruthenium(II) dichloride (Ru(dpp) 3+ ).
- PtOEP octaethylporphyrin
- oxygen-sensitive luminescent molecules are generally dispersed in transparent, oxygen permeable polymer matrix, generally in the form of a thin polymer film.
- PtOEP was immobilized in polystyrene, ethyl cellulose, cellulose acetate butyrate, polyvinylchloride, styrene- pentafluorostyrene copolymer and polydimethylsiloxane films.
- PtOEP was encapsulated in PVC, polystyrene, ethylcellulose, silicon RTV3140 and silicon RTV108 thin films and the effect of humidity on oxygen permeability was evaluated.
- Another study (C.M. Penso et al. PtOEP–PDMS-Based Optical Oxygen Sensor. Sensors 21 (2021) 5645–5659) used PtOEP encapsulated in polydimethylsiloxane film. The authors mentioned good sensitivity compared with other sensors.
- the sensitivity for oxygen, I 0 /I 100 values of the PtTFPP or PtOEP doped in n-octyltriethoxysilane /tetraethylorthosilane composite xerogels were estimated to be 22.31 and 47.84, respectively.
- the typical Stern–Volmer plot shows a very good linearity.
- the basic disadvantage of the above-described sensors is the fact, that luminescent molecules are immobilized in thin polymer layers, where they exhibit relatively long response & recovery time. Contrary, sensors with fast response characteristics have broad field of applications whenever a quick change in oxygen pressure has to be monitored e.g. in pulmonary medicine.
- sensors utilizing silicon matrix exhibit excellent oxygen sensing properties, but display nonlinearity of Stern-Volmer plots (B.A. DeGraff et al. Luminescence-Based Oxygen Sensors. Review in Fluorescence 2005, Springer, New York, NY, 2005, pp. 125–151) and so low biocompatibility, that have to be covered by another biocompatible polymer (R. Xue et al. Polydimethylsiloxane core–polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors. Sens. Actuators, B 192 (2014) 697–707).
- the functional sensor is predisposed not only by the intrinsic properties of the selected luminescent molecule (spectral characteristics and quantum yield of luminescence) but it is also influenced by the properties of the near surroundings of the luminescent molecule.
- key parameters determining the efficacy are the oxygen permeability/diffusion coefficient and the surface to volume ratio of the used supporting matrix. Disclosure of the Invention
- the oxygen detection system according to the present invention contains an oxygen-sensitive probe (luminescent molecule) incorporated in polymer nanofibers of transparent nanofiber membrane as supporting matrix.
- Basic requirements for the luminescent molecule are the following: i) high quantum yield of triplet state and phosphorescence, ii) long lifetime of T 1 state, iii) high photostability toward photobleaching, iv) low tendency to aggregate luminescent molecules in the polymer supporting matrix v) low leaching ability of luminescent molecules from the polymer supporting material to aqueous media.
- Basic requirements for the polymer supporting matrix are the following: i) The polymer supporting materials should be transparent toward used excitation light. The wavelength of the excitation light in UV/VIS region needs to correspond to an absorption band of the used oxygen sensor molecule. ii) The supporting polymer materials should be able to bind the used luminescent molecule without leakage.
- the polymer composition must not negatively affect the photophysical characteristics of photosensitizers, especially in terms of quenching the triplet states of the sensor molecule.
- the polymer should have a high oxygen permeability and diffusion.
- the surface of supporting polymer materials should have high specific surface, if the supporting material is made from nanofiber membranes, the nanofibers should have a small diameter.
- the aqueous solutions/media must not dissolve the supporting polymer.
- the oxygen sensor material formed from luminescent molecules in polymer supporting matrix must have good mechanical properties.
- the aim of the present invention is to provide a photoactive polymer material, which would be suitable for practical use of oxygen detection, could be produced in a cost-effective manner, and would comply with all requirements for safety and effectiveness.
- a key prerequisite for a strong luminescence signal and its quenching used for oxygen sensing is high luminescence, therefore, one of the requirements enabling practical use is, as mentioned above, a high yield of triplet state photogeneration.
- An object of the present invention is an optical oxygen sensor, comprising a poly( ⁇ -caprolacton) nanofiber membrane doped with platinum (II) complex of octaethylporphyrin (Scheme 1), wherein said complex is incorporated within said membrane in an amount in the range of from 0.1 to 4 wt.
- Poly( ⁇ -caprolacton) (PCL) is a biocompatible, transparent polymer with high oxygen diffusion coefficient and low ability to quench triplet states of the sensor.
- the platinum (II) complex of octaethylporphyrin (PtOEP), encapsulated in the transparent poly( ⁇ -caprolacton) nanofiber membrane, is capable of sensing triplet oxygen upon irradiation by visible light, including excitation beam during measuring of sensor luminescence.
- Nanofiber membrane refers to a membrane composed of fibers having their diameter within the range of from 400 to 1800 nm, determined by scanning electron microscopy (SEM); the nanofiber diameters measured by NIS Elements 4.0 image analysis software. Nanofiber membranes may be produced by a variety of methods known to a person skilled in the art, including electrospinning, drawing, centrifugal spinning, thermal-induced phase separation and template synthesis. Electrospinning is the preferred method of production of nanofiber membranes in this invention.
- the term “luminescent molecule” refers in general to a compound, which is able of absorb light in visible or near UV region. After absorption of light, the luminescent molecule is excited via singlet excited state to its longer-lived excited luminescent triplet state (T 1 ). In the presence of oxygen, the energy transfer from T 1 of the luminescent molecule to the ground state triplet oxygen O2( 3 ⁇ g-) quench the luminescence. The process is coupled with spin inversion of O 2 ( 3 ⁇ g -) to singlet oxygen O 2 ( 1 ⁇ g ). The luminescent molecule then returns to its ground state and remains chemically intact until it absorbs a further quantum of energy from light.
- FIG. 1 A simplified Jablonski diagram illustrating luminescence quenching of a luminescent molecule by molecular oxygen is depicted in Figure 1.
- the term crizosin refers to anticianoxygen-sensing sensor“.
- Poly( ⁇ -caprolacton) nanofiber membrane doped with platinum (II) complex of octaaethylporphyrin means that luminescent molecules in monomeric states are encapsulated in the transparent polymer nanofiber membrane. The incorporation takes place during the synthesis of the membrane, wherein solutions of poly( ⁇ - caprolactone) and of the platinum (II) complex of octaethylporphyrin in desired ratio are electrospun or undergo any other suitable method of producing nanofibers.
- the fibers of the poly( ⁇ -caprolacton) nanofiber membrane of the optical oxygen sensor according to the present invention have diameter in the range of from 400 to 1800 nm, preferably in the range of from 400 to 950 nm, more preferably in the range of from 300 to 800 nm, even more preferably from 400 to 650 nm.
- the optical oxygen sensor according to the present invention can be prepared by electrospinning a solution of poly( ⁇ -caprolactone) and of the platinum (II) complex of octaethylporphyrin in a desired ratio, preferably the solvent is selected from THF, DMF, DCM or mixtures thereof. More preferably, the optical oxygen sensor according to the present invention can be prepared by dissolving PCL and PtOEP in a suitable solvent, preferably in a mixture of DCM/DMF (3:2 by weight). The concentration of PCL in the resulting solution is preferably in the range of from 6 to 10 wt. %. The quantity of PtOEP in the solution is in the range of from 0.1 to 4 wt.
- V 12-22 kV
- flow rate 1.0 ml/h for 15 min.
- the produced nanofibers are deposited on Al foil covering the collecting electrode to form the nanofiber membrane with incorporated PtOEP.
- the area density of the optical oxygen sensor according to the present invention is in the range of from 2 to 30 g/m 2 , preferably in the range of from 4 to 20 g/m 2 , more preferably in the range of from 5 to 15 g/m 2 , even more preferably in the range of from 5 to 10 g/m 2 , determined gravimetrically by weighing of a define area of nanofiber membrane using analytical balance.
- the thickness of the poly( ⁇ -caprolacton) nanofiber membrane doped with platinum (II) complex of octaethylporphyrin according to the present invention is in the range of from 15 to 150 ⁇ m, preferably in the range of from 22 to 138 ⁇ m, more preferably in the range of from 30 to 60 ⁇ m, even more preferably in the range of from 35 to 45 ⁇ m, determined using thickness gauge.
- the optical oxygen sensor according to the present invention comprises a poly( ⁇ -caprolacton) nanofiber membrane doped with platinum (II) complex of octaethylporphyrin, wherein said complex is incorporated within said membrane in an amount of 0.2 wt.
- the area density of the optical oxygen sensor according to the present invention is in the range of from 5 to 10 g/m 2
- the thickness of the optical oxygen sensor is in the range of from 35 to 45 ⁇ m.
- the optical oxygen sensor according to the present invention may be used for detection of oxygen gas in gaseous and/or aqueous media also when deposited on an aluminum foil, polypropylene spunbond, baking paper or any sheet supporting material. Another object of the invention is the use of the above described optical oxygen sensor for detection of oxygen gas in gaseous and/or aqueous media.
- FIG 4 Left: SEM of PtOEP in PCL nanofiber membrane (PCL(PtOEP)) illustrating nanofiber character of the matrix. Right: The statistics of relative abundance of nanofiber diameters.
- Figure 6 The dependence of sensitivity (I 0 /I max ratio) on concentration of PtOEP in PCL matrix.
- Figure 7 The dependence of sensitivity (I 0 /I max ratio) on thickness of PCL matrix doped by PtOEP.
- Figure 9 Samples of 1wt% PtOEP encapsulated in PCL, PS and PVDF-HFP nanofiber membranes. The time resolved luminescence traces at 640 nm in air fitted by double-exponential function.
- Figure 10 The time resolved luminescence traces at 640 nm in air, oxygen and vacuum fitted by double- exponential function of samples of 1wt% PtOEP encapsulated in PCL (A) PS (B) and PVDF-HFP (C) nanofiber membranes.
- Figure 11 Stern-Volmer plot from luminescence lifetimes (1/ ⁇ L ) of samples 1wt% PtOEP encapsulated in PCL, PS and PVDF-HFP nanofiber membranes at 640 nm in vacuum, air and oxygen atmosphere.
- Materials and methods Platinum (II) complex of octaethylporphyrin, PCL, PS, PVDF-HFP and TEAB were purchased from Sigma Aldrich (USA), Tecophilic HP-60D-60 was purchased from Lubrizol (USA).
- the steady- state luminescence spectra were monitored using an FLS 980 (Edinburgh Instruments, UK) spectrofluorimeter.
- Oxygen sensing FLS 980 (Edinburgh Instruments, UK) spectrofluorimeter with a flow-through luminescence cuvette equipped commercial oxygen sensor ISO OXY-2 from Word Precision Instruments (Clark electrode) and a connection to nitrogen and oxygen gas bottles was used to measure the luminescence response of the optical oxygen sensor according to this invention to gas atmosphere or dissolved oxygen/nitrogen in water.
- the sample (3 ⁇ 1 cm) of said optical oxygen sensor on quartz glass was diagonally placed in closed cuvette. The cuvette enables measuring of luminescence of said optical oxygen sensor and content of oxygen by Clark electrode in the same time.
- Time resolved luminescence All experiments were performed in vacuum, air, and oxygen atmosphere at 24 o C with a Quantel Smart 450 Nd YAG laser (excitation wavelength 355 nm, fwhm ⁇ 5 ns). Time-resolved luminescence of materials at 640 nm was measured using a LKS 20 laser kinetic spectrometer (Applied Photophysics, UK) equipped with Hamamatsu R928 photomultiplier. The luminescence kinetics of all materials exhibited deviations from single exponential decay and they were fitted by double exponential function.
- F T ( ⁇ L0 – ⁇ L )/ ⁇ T0 , where ⁇ L0 and ⁇ L are the luminescence lifetimes in vacuum and in oxygen/air, respectively.
- the materials were evacuated at least 30 min by rotary pump for measurements in vacuum.
- Example 1 Preparation of the optical oxygen sensor using different polymers
- PCL poly( ⁇ -caprolacton)
- platinum (II) complex of octaethylporphyrin (PtOEP) was prepared by electrospinning method.
- other polymer matrices were used to incorporate PtOEP.
- the general procedure for preparing the materials was as follows: A mixture of 99 wt % of a polymer (Tecophilic, PCL, PS, PVDF-HFP) and 1 wt % PtOEP were dissolved in spinning solvent(s) according to Table 1 to prepare 6-10 wt % polymer solutions for the fabrication of photoactive nanofiber materials. In some cases the conductivity of the spinning solutions was enhanced by addition of tetraethylammonium bromide (TEAB) in DMF. The solutions were electrospun using needle electrospinning technology as described in Y. Guo et al. Research progress, models and simulation of electrospinning technology: a review. J. Mater. Sci. 57 (2020) 58–104.
- TEAB tetraethylammonium bromide
- Nanofibers creating nanofiber membrane were deposited on an Al foil covering the collecting electrode. All the above described nanofiber membranes can be also produced using the modified Nanospider TM electrospinning industrial technology by the simultaneous formation of charged liquid jets on the surface of a thin wire electrode, where the number and location of the jets was set to their optimal positions, or by using any other suitable method of producing nanofibers. Table 1. Parameters used for preparation of nanofiber membranes with 1 wt% PtOEP by needle electrospinning.
- the general procedure for preparing the materials was as follows: A mixture of 96-99.9 wt% PCL and 4-0.1 wt% PtOEP were dissolved in DCM/DMF (3:2) according to Table 2 to prepare 0.1-4 wt % solutions for the fabrication of photoactive nanofiber materials.
- PCL Membrane concentration Solvent Voltage in solvent PCL(PtOEP 0.1 wt%) 10 % DCM/DMF 3/2 (wt.) 14 kV PCL(PtOEP 0.2 wt%) 10 % DCM/DMF 3/2 (wt.) 14 kV PCL(PtOEP 0.4 wt%) 10 % DCM/DMF 3/2 (wt.) 14 kV PCL(PtOEP 0.6wt %) 10 % DCM/DMF 3/2 (wt.) 14 kV PCL(PtOEP 1.0 wt%) 10 % DCM/DMF 3/2 (wt.) 12 kV PCL(PtOEP 4 wt%) 10 % DCM/DMF 3/2 (wt.) 8 kV
- Example 3: Preparation of the optical oxygen sensor in PCL of different thickness PCL(Mn 80 000)/ PtOEP optical oxygen sensor was prepared by needle electrospinning method.
- the general procedure for preparing the materials was as follows: A mixture of 99.8 wt% PCL and 0.2 wt% PtOEP were dissolved in DCM/DMF (3:2) according to Table 3 to prepare 0.2 wt % solutions for the fabrication of nanofiber materials.
- Example 5 Basic characterization of prepared optical oxygen sensors The morphology of the prepared optical oxygen sensors described in Examples 1 and 2 was characterized using scanning electron microscopy (SEM) - a scanning electron Quanta 200 FEG microscope (FEI, Czech Republic). The nanofiber diameters were measured by NIS Elements 4.0 image analysis software (Laboratory Imaging, Czech Republic). The area density was determine gravimetrically, weighing of a define area of nanofiber membrane using analytical balance (A&D GR 200).
- PtOEP is a sensitive oxygen luminescence sensor molecule with absorption and emission in VIS and near UV region ( Figures 2, 3), and it is highly photostable.
- PCL can be electrospun to form nanofiber membrane ( Figure 4).
- PCL does not significantly quench the luminescence of PtOEP ( Figure 3, Table 6, Figure 10), and PCL nanofiber membrane can be used as a scaffold for tissue engineering.
- the intensity ratio of sensor in oxygen-free water (I 0 ) and in water saturated with oxygen (I max ) reached the value of 30.7 (Table 8).
- the intensity ratio of sensor in gas atmosphere reached even value of 47.9 (Table 7).
- the sensitivity- quenching of PtOEP luminescence in other nanofiber membranes is less sensitive (Table 5). The sensitivity strongly depends on concentration of PtOEP in PCL.
- PCL(PtOEP) exhibit fast response and recovery time, less than 0.6 s in gas atmosphere (Table 5).
- Example 6 Oxygen sensing characterization of PtOEP encapsulated in prepared nanofiber membranes of different polymers The nanofiber polymer membranes mentioned in Examples 1, 2 and 3 were electrospun on an aluminum supporting layer. Their sensing characteristics in gas atmospheres were evaluated by luminescence and time- resolved luminescence methods (see Materials and Methods) and summarized in Table 5 and 6. All experiments were performed at 24 o C. Table 5. The sensitivity (I 0 /I max ratio), response (t 95 ) and recovery time (t 95 ⁇ ) and corresponding thickness of matrix for 1wt% PtOEP encapsulated in different polymer nanofiber membranes.
- PCL(PtOEP) utilizes the high PCL transparency and facile oxygen transport due to the high diffusion coefficient of the polymer.
- the luminescence of the sensor was monitored in H 2 O with different concentrations of dissolved oxygen that were maintained by nitrogen or oxygen gas bubbling.
- the sensitivity of PCL(PtOEP) to dissolved oxygen can be expressed by the intensity ratio of PCL(PtOEP) in oxygen-free water (I 0 ) and in water saturated with oxygen (I max ).
- the data from oxygen sensing in gas atmosphere and dissolved oxygen sensing indicate in both cases the broad range, good accuracy and very high sensitivity of the PCL(PtOEP) with a reversible luminescent response (Table 5, Figures 5, 8 and 11).
- Example 10 Reversibility of oxygen sensing
- sample of PCL(PtOEP) as prepared in Example 2 with 0.2 wt. % PtOEP of was used.
- the sample was fixed on quartz glass in quartz cuvette.
- Example 11 Measuring Response and Recovery Time
- samples of 1 wt. % PtOEP in different polymers prepared in Example 1 were used.
- Example 12 Measurement of kinetics and lifetimes of PCL(PtOEP) In this experiment, polymeric membranes PCL with 1 wt % PtOEP as prepared in Example 1were used for measuring luminescence kinetics (lifetimes) in the gas atmosphere with different oxygen content.
- Example 13 Measurement of photostability of PCL(PtOEP) The sample (3 ⁇ 1 cm) of PCL nanofiber membrane with 0.2 wt% PtOEP, prepared in Example 3, (thickness 42 ⁇ m) on quartz glass was diagonally placed in closed cuvette.
- PCL(PtOEP) represents cheap, easy to prepare and robust optical oxygen sensor with fast, very sensitive, photostable, reversible luminescent response and linear Stern–Volmer quenching behavior over the whole range of oxygen content in gas atmospheres and the dissolved oxygen concentrations in aqueous media.
- the optical oxygen sensor prepared from electrospun material possesses encapsulated PtOEP molecules that are protected from the surroundings by a PCL shell. Due to the high oxygen permeability and low quenching behavior of PCL, the luminescence of PtOEP is highly sensitive to quenching by oxygen.
- PCL(PtOEP) represent excellent optical oxygen nanofiber sensor, as exhibit the best sensing properties over other sensor molecules encapsulated in other polymer nanofiber membranes known from the literature.
- PCL(PtOEP) utilizing biodegradable and biocompatible PCL for oxygen sensing represents a very sensitive method to measure the content of oxygen not only in gas atmospheres but also in aqueous (biological) media, bioreactors or in compartments where the dimensions are too small to use standard oxygen electrodes and when chemical probes are too toxic (for application in tissue engineering and other biological applications) and/or are sensitive to the surroundings. 5
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
La présente invention concerne un capteur optique d'oxygène, comprenant une membrane de nanofibres de poly (ɛ-caprolactone) dopée avec un complexe de platine (II) d'octaéthylporphyrine, ledit complexe étant incorporé à l'intérieur de ladite membrane en une quantité située dans la plage allant de 0,1 à 4 % en poids. L'invention concerne en outre son utilisation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CZ2022/050134 WO2024125678A1 (fr) | 2022-12-16 | 2022-12-16 | Capteur optique d'oxygène |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CZ2022/050134 WO2024125678A1 (fr) | 2022-12-16 | 2022-12-16 | Capteur optique d'oxygène |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024125678A1 true WO2024125678A1 (fr) | 2024-06-20 |
Family
ID=84981784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CZ2022/050134 Ceased WO2024125678A1 (fr) | 2022-12-16 | 2022-12-16 | Capteur optique d'oxygène |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024125678A1 (fr) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160041135A1 (en) * | 2013-03-15 | 2016-02-11 | Ohio State Innovation Foundation | Core-shell nanofiber-based sensors |
-
2022
- 2022-12-16 WO PCT/CZ2022/050134 patent/WO2024125678A1/fr not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160041135A1 (en) * | 2013-03-15 | 2016-02-11 | Ohio State Innovation Foundation | Core-shell nanofiber-based sensors |
Non-Patent Citations (17)
| Title |
|---|
| B.A. DEGRAFF ET AL.: "Review in Fluorescence", 2005, SPRINGER, article "Luminescence-Based Oxygen Sensors", pages: 125 - 151 |
| C.M. PENSO ET AL.: "PtOEP-PDMS-Based Optical Oxygen Sensor", SENSORS, vol. 21, 2021, pages 5645 - 5659 |
| C.WOLF ET AL.: "Ultra-fast opto-chemical sensors by using electrospun nanofibers as sensing layers", SENSORS AND ACTUATORS B, vol. 209, 2015, pages 1064 - 1069 |
| I. DALFEN, S.M.BORISOV, S. M.: "Porous matrix materials in optical sensing of gaseous oxygen", ANAL. BIOANAL. CHEM., vol. 414, 2022, pages 4311 - 4330, XP037857673, DOI: 10.1007/s00216-022-04014-6 |
| J. NAPP ET AL.: "Targeted Luminescent Near-Infrared Polymer-Nanoprobes for in Vivo Imaging of Tumor Hypoxia", ANAL., vol. 83, 2011, pages 9039 - 9046 |
| K. EATON ET AL.: "Effect of humidity on the response characteristics of luminescent PtOEP thin film optical oxygen sensors", SENS. ACTUATORS, B, vol. 82, 2002, pages 94 - 104, XP004332518, DOI: 10.1016/S0925-4005(01)00996-0 |
| M. QUARANTA ET AL.: "Indicators for optical oxygen sensors", BIOANAL. REV., vol. 4, 2012, pages 115 - 157, XP055071464, DOI: 10.1007/s12566-012-0032-y |
| PRESLEY KAYLA ET AL: "Analysis of long-term optical performance of phosphorescent oxygen sensing polymeric nanofibers", POLYMER TESTING, ELSEVIER, AMSTERDAM, NL, vol. 80, 27 September 2019 (2019-09-27), XP085935823, ISSN: 0142-9418, [retrieved on 20190927], DOI: 10.1016/J.POLYMERTESTING.2019.106127 * |
| PRESLEY KAYLA F ET AL: "Oxygen sensing performance of biodegradable electrospun nanofibers: Influence of fiber composition and core-shell geometry", SENSORS AND ACTUATORS B: CHEMICAL, ELSEVIER BV, NL, vol. 329, 13 November 2020 (2020-11-13), XP086455452, ISSN: 0925-4005, [retrieved on 20201113], DOI: 10.1016/J.SNB.2020.129191 * |
| R. XUE ET AL.: "Microscale Sensing of Oxygen via Encapsulated Porphyrin Nanofibers: Effect of Indicator and Polymer ''Core'' Permeability", ACS APPL. MATER. INTERFACES, vol. 7, 2015, pages 8606 - 8614 |
| R. XUE ET AL.: "Polydimethylsiloxane core-polycaprolactone shell nanofibers as biocompatible, real-time oxygen sensors", SENS. ACTUATORS, B, vol. 192, 2014, pages 697 - 707, XP055666264, DOI: 10.1016/j.snb.2013.10.084 |
| RUIPENG XUE ET AL, SENSORS AND ACTUATORS B: CHEMICAL, vol. 192, 1 March 2014 (2014-03-01), NL, pages 697 - 707, XP055666264, ISSN: 0925-4005, DOI: 10.1016/j.snb.2013.10.084 * |
| S.K. LEE ET AL.: "Photoluminescent determination of oxygen using metalloporphyrin-polymer sensing systems", SPECTROCHIM. ACTA, PART A, vol. 54, 1998, pages 91 - 100 |
| T.S. YEH ET AL.: "Highly sensitive optical fiber oxygen sensor using Pt(II) complex embedded in sol-gel matrices", SENS. ACTUATORS, B, vol. 119, 2006, pages 701 - 707, XP025112371, DOI: 10.1016/j.snb.2006.01.051 |
| XU-DONG WANG ET AL: "Optical methods for sensing and imaging oxygen: materials, spectroscopies and applications", CHEMICAL SOCIETY REVIEWS, vol. 43, no. 10, 1 January 2014 (2014-01-01), UK, pages 3666 - 3761, XP055365171, ISSN: 0306-0012, DOI: 10.1039/C4CS00039K * |
| XUE RUIPENG ET AL: "Rapid response oxygen-sensing nanofibers", MATERIALS SCIENCE AND ENGINEERING C, ELSEVIER SCIENCE S.A, CH, vol. 33, no. 6, 22 April 2013 (2013-04-22), pages 3450 - 3457, XP028553370, ISSN: 0928-4931, DOI: 10.1016/J.MSEC.2013.04.030 * |
| Y. GUO ET AL.: "Research progress, models and simulation of electrospinning technology: a review", J. MATER. SCI., vol. 57, 2020, pages 58 - 104, XP037661115, DOI: 10.1007/s10853-021-06575-w |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chu et al. | Review on recent developments of fluorescent oxygen and carbon dioxide optical fiber sensors | |
| Lee et al. | Photostable optical oxygen sensing material: platinum tetrakis (pentafluorophenyl) porphyrin immobilized in polystyrene | |
| Stepanidenko et al. | Influence of the solvent environment on luminescent centers within carbon dots | |
| Feng et al. | Ratiometric optical oxygen sensing: a review in respect of material design | |
| Amao | Probes and polymers for optical sensing of oxygen | |
| Ongun et al. | Enhanced stability of ruthenium complex in ionic liquid doped electrospun fibers | |
| EP1889050B1 (fr) | Membrane d'oxyde metallique avec un compose a selectivite gazeuse | |
| Banerjee et al. | Solid-state oxygen sensors based on phosphorescent diiodo-borondipyrromethene dye | |
| Hu et al. | A fluorescent and colorimetric sensor based on a porphyrin doped polystyrene nanoporous fiber membrane for HCl gas detection | |
| Fernández-Sánchez et al. | Novel nanostructured materials to develop oxygen-sensitive films for optical sensors | |
| Arunkumar et al. | Fluorinated meso-tetraaryl Pt (II)-porphyrins: Structure, photophysical, electrochemical, and phosphorescent oxygen sensing studies | |
| Amao et al. | An oxygen sensing system based on the phosphorescence quenching of metalloporphyrin thin film on alumina plates | |
| Borisov et al. | A versatile approach for ratiometric time-resolved read-out of colorimetric chemosensors using broadband phosphors as secondary emitters | |
| Aguayo-López et al. | Optical sensor for carbon dioxide gas determination, characterization and improvements | |
| Ongun et al. | Synthesis, characterization and oxygen sensitivity of cyclophosphazene equipped-iridium (III) complexes | |
| WO2024125678A1 (fr) | Capteur optique d'oxygène | |
| Fernández-Ramos et al. | NIR optical carbon dioxide gas sensor based on simple azaBODIPY pH indicators | |
| EP2371925B1 (fr) | Matériau capteur et utilisations associées pour détecter simultanément deux analytes | |
| Kacmaz et al. | Emission based sub-nanomolar silver sensing with electrospun nanofibers | |
| Sábio et al. | Near-infrared/visible-emitting nanosilica modified with silylated Ru (II) and Ln (III) complexes | |
| Amao et al. | Novel optical oxygen sensing material: platinum porphyrin–styrene–pentafluorostyrene copolymer film | |
| Kim et al. | Preparation and characterization of electrospun fluorescent fiber mats as temperature sensors using various polymers | |
| Akram et al. | Morphological effect of fabricated surfaces obtained from fluorinated porphyrin based copolymer for oxygen and pressure sensing applications | |
| Lv et al. | Porphyrinic polymers for gas sensing: An overview | |
| Holmes-Smith et al. | Characterization of an electropolymerized Pt (II) diamino phenyl porphyrin polymer suitable for oxygen sensing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22844020 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 22844020 Country of ref document: EP Kind code of ref document: A1 |