CN112957038A - Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement - Google Patents
Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement Download PDFInfo
- Publication number
- CN112957038A CN112957038A CN202110137686.9A CN202110137686A CN112957038A CN 112957038 A CN112957038 A CN 112957038A CN 202110137686 A CN202110137686 A CN 202110137686A CN 112957038 A CN112957038 A CN 112957038A
- Authority
- CN
- China
- Prior art keywords
- photonic crystal
- oxygen sensor
- blood oxygen
- placing
- sensor based
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/1455—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters
- A61B5/14551—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters for measuring blood gases
- A61B5/14552—Details of sensors specially adapted therefor
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/1455—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters
- A61B5/14551—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters for measuring blood gases
- A61B5/14556—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters for measuring blood gases by fluorescence
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Medical Informatics (AREA)
- General Health & Medical Sciences (AREA)
- Biophysics (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- Pathology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A preparation method of a high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement relates to the field of fluorescent oxygen sensors, in particular to a preparation method of a blood oxygen sensor based on photonic crystal fluorescence enhancement. The method aims to solve the problems of indicator leakage and fluorescence signal attenuation when the optical oxygen sensor prepared by the existing method is used for blood oxygen detection. The method comprises the following steps: placing the polystyrene microsphere emulsion in a light-proof container, adding fluorescent dye, performing ultrasonic treatment, placing in a dark box at room temperature for swelling, centrifuging, and re-dispersing the precipitate by using pure water to obtain the dispersed microsphere emulsion; adding the polysorbate solution into the microsphere emulsion, performing ultrasonic treatment, and placing the mixture into a flat-bottom glass tube; obliquely placing a quartz plate into a flat-bottom glass tube, and placing the quartz plate and the glass tube together in a water-proof incubator until emulsion is completely evaporated to obtain a photonic crystal device; and spin-coating a layer of PDMS on the surface of the prepared photonic crystal device, and curing to obtain the blood oxygen sensor. The invention is applied to the field of sensors.
Description
Technical Field
The invention relates to the field of fluorescent oxygen sensors, in particular to a preparation method of a photonic crystal fluorescence enhancement-based blood oxygen sensor.
Background
In recent years, people's health consciousness is increased while the living standard of residents is increased, and more cardiovascular diseases attract wide attention. Blood oxygen saturation is one of the important physiological indicators directly related to this type of disease. The blood oxygen saturation is oxyhemoglobin (HbO)2) The proportion of total hemoglobin (Hb), the concentration of blood oxygen in the blood, is an important physiological parameter of the life cycle. When some organs in the organism are in an anoxic state for a long time, the physiological function of the organism can not be normally performed, tissue edema is caused, the defense function is reduced, and the blood circulation in the human body is seriously influenced. In addition, the detection of the blood oxygen content in the biological tissue can realize the early medical diagnosis of various diseases and provide a basis for the development of the subsequent medical work of patients.
The traditional oxyhemoglobin saturation measuring method is to firstly take blood from a human body, then carry out electrochemical analysis by using a blood gas analyzer and measure the partial pressure PO of blood oxygen2And calculating the blood oxygen saturation. This method is cumbersome and does not allow continuous monitoring. The finger stall type photoelectric sensor is adopted, during measurement, the sensor needs to be sleeved on a finger of a person, the finger is used as a transparent container for containing hemoglobin, red light with the wavelength of 660nm and near infrared light with the wavelength of 940nm are used as incident light sources, the passing light conduction intensity is measured, and the concentration of the hemoglobin and the blood oxygen saturation are calculated.
The existing optical oxygen sensor mainly focuses on gaseous oxygen sensing and is not suitable for detecting blood oxygen. The reason is that when dissolved oxygen sensing is performed, the oxygen sensor needs to be soaked in a solution, which easily causes leakage of an indicator, reduces fluorescence intensity, and further affects a detection result. In addition, blood is rich in red blood cells, and when the blood oxygen concentration is detected by using the optical oxygen sensor, the scattering effect of the cells on light causes a large amount of attenuation of optical signals and difficult collection, so that the existing oxygen sensor is difficult to apply to a solution and a complex liquid environment such as blood.
Disclosure of Invention
The invention aims to solve the problems of indicator leakage and fluorescence signal weakening when an optical oxygen sensor prepared by the existing method is used for blood oxygen detection, and provides a preparation method of a high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement.
The invention relates to a preparation method of a high-sensitivity self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement, which comprises the following steps:
swelling of polystyrene microspheres
Placing the polystyrene microsphere emulsion in a light-proof container, adding a PtOEP/THF fluorescent dye, performing ultrasonic treatment at room temperature, performing ultrasonic treatment, placing in a dark box at room temperature for swelling, centrifuging, pouring out a supernatant, and re-dispersing the precipitate by using pure water to obtain the dispersed microsphere emulsion;
preparation of photonic crystal fluorescence enhanced oxygen sensor
Adding the polysorbate solution into the microsphere emulsion which is dispersed in the first step, carrying out ultrasonic treatment until the mixture is uniformly mixed, and then placing the mixture in a flat-bottom glass tube;
obliquely placing the quartz plate subjected to hydrophilization treatment into a flat-bottom glass tube, and placing the quartz plate and the glass tube together into a water-proof incubator, wherein the temperature of the incubator is set to be 60-65 ℃ until emulsion is completely evaporated, so that a photonic crystal device is obtained;
and spin-coating a layer of Polydimethylsiloxane (PDMS) on the surface of the prepared photonic crystal device, horizontally placing the photonic crystal device in a vacuum drying oven, and taking out the photonic crystal device after complete curing to obtain the blood oxygen sensor.
Further, in the first step, the mass concentration of the polystyrene microsphere emulsion is 0.4%. The polystyrene microspheres have uniform particle size and are commercially available.
Further, the preparation method of the PtOEP/THF fluorescent dye in the first step comprises the following steps: dissolving octaethylporphyrin platinum powder (PtOEP) in tetrahydrofuran, and preparing to obtain indicator concentrateDegree of 1X 10-3mol/l of PtOEP/THF fluorescent dye.
Further, in the first step, the volume ratio of the polystyrene microsphere emulsion to the PtOEP/THF fluorescent dye is 2000: (1-5).
Further, the speed of centrifugation in the first step is 7000-8000 rpm, and the centrifugation time is 5-10 min.
Furthermore, the swelling time in the step one is 1-2 h.
Further, in the second step, the Polydimethylsiloxane (PDMS) is Dow Corning Sylard184 silicon rubber, wherein the basic component and the curing agent are mixed according to the mass ratio of 10:1, and the mixture is stirred uniformly and then stands for half an hour to remove bubbles.
Further, the hydrophilization treatment method of the quartz plate in the second step is as follows: and respectively and sequentially cleaning the quartz plate by using detergent, ethanol and pure water, preparing a mixed solution of ammonia water and hydrogen peroxide, and immersing the cleaned quartz plate into the mixed solution for 4.5-5.5 hours to complete hydrophilization. Preferably, the volume ratio of the ammonia water to the hydrogen peroxide in the mixed solution of the ammonia water and the hydrogen peroxide is 7: 3.
Further, in the second step, the temperature of the vacuum drying oven is 60-65 ℃, and the heat preservation time is 10-15 hours.
The invention has the beneficial effects that:
the invention is based on the principle that photoluminescence can be enhanced multiply when the peak position of the emission peak of the fluorescent substance is partially overlapped with the peak position of the photon forbidden band of the photonic crystal. The photonic crystal has a photonic forbidden band, and electromagnetic waves cannot be transmitted in the band gap, so that the photonic crystal has a good regulation and control effect on incident light. Meanwhile, when the size of the colloidal particles falls within the visible wavelength range (400nm-760nm), light is scattered on the crystal surface, and a color enhancement effect appears visually. Based on the fluorescence enhancement effect of the photonic crystal and the fluorescence quenching principle of oxygen, the fluorescence enhancement type blood oxygen sensor with the photonic crystal microstructure is prepared.
According to the invention, PtOEP is selected as an indicator, PDMS is selected as a substrate material, the fluorescence indicator is fixed in the PS microsphere by using a swelling method, and the core-shell structure and the specific hydrophobic property of PDMS can effectively prevent the indicator from leaking. Is beneficial to the long-term stability of the monitoring of the oxygen content of the solution in practical application. And the Stern-Volmer equation has high linear correlation, and can accurately measure the blood oxygen concentration in blood.
The method introduces a photonic crystal microstructure, and the photonic crystal has a photonic forbidden band which can greatly enhance the luminous intensity of the fluorescent dye.
The unique hydrophobic property of PDMS makes the blood oxygen sensor have self-cleaning capability and improves the hydrophobicity. In addition, PDMS has good air permeability and flexibility, and can be well attached to the skin, so that the flexible wearable structure is realized.
The invention also has the advantages of simple preparation process, low cost, high sensitivity, high signal-to-noise ratio and the like.
Drawings
FIG. 1 is an electron micrograph of a photonic crystal after swelling with 5. mu.l of the dye in example 1;
FIG. 2 is a graph showing the relationship between the fluorescence enhancement factor and the amount of the indicator added in example 1;
FIG. 3 shows the fluorescence emission spectra of PtOEP in example 1 under different oxygen contents;
FIG. 4 is the Stern-Volmer curve of example 1;
FIG. 5 is a graph showing the light resistance test of the blood oxygen sensor in example 1;
FIG. 6 is a graph showing the relationship between the contact angle and the amount of dye added in example 1;
FIG. 7 is a physical diagram of the blood oxygen sensor in accordance with example 1;
fig. 8 shows the flexible wearable performance test of the blood oxygen sensor in example 1.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the high-sensitivity self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement in the embodiment comprises the following steps:
swelling of polystyrene microspheres
Placing the polystyrene microsphere emulsion in a light-proof container, adding a PtOEP/THF fluorescent dye, performing ultrasonic treatment at room temperature, performing ultrasonic treatment, placing in a dark box at room temperature for swelling, centrifuging, pouring out a supernatant, and re-dispersing the precipitate by using pure water to obtain the dispersed microsphere emulsion;
preparation of photonic crystal fluorescence enhanced oxygen sensor
Adding the polysorbate solution into the microsphere emulsion which is dispersed in the first step, carrying out ultrasonic treatment until the mixture is uniformly mixed, and then placing the mixture in a flat-bottom glass tube;
obliquely placing the quartz plate subjected to hydrophilization treatment into a flat-bottom glass tube, and placing the quartz plate and the glass tube together into a water-proof incubator, wherein the temperature of the incubator is set to be 60-65 ℃ until emulsion is completely evaporated, so that a photonic crystal device is obtained;
and spin-coating a layer of Polydimethylsiloxane (PDMS) on the surface of the prepared photonic crystal device, horizontally placing the photonic crystal device in a vacuum drying oven, and taking out the photonic crystal device after complete curing to obtain the blood oxygen sensor.
The invention aims to provide a preparation method of a photonic crystal fluorescence enhancement type oxygen sensor capable of measuring the content of dissolved oxygen. The oxygen sensor with the photonic crystal microstructure is prepared by adopting the principle that the photoluminescence of a fluorescent substance with an emission peak at a specific wavelength is enhanced by the photonic crystal. When the PtOEP coated into the microsphere is excited by a light source with a certain wavelength, the oxygen sensor can emit strong and stable fluorescence, the fluorescence signal can be effectively quenched by molecular oxygen, and the quenching ratio corresponds to the oxygen content one to one. Based on the principle, the long-acting stable photonic crystal fluorescence enhanced blood oxygen sensor with high sensitivity, high signal-to-noise ratio, good stability and good self-cleaning performance can be finally prepared.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the mass concentration of the polystyrene microsphere emulsion is 0.4%. The rest is the same as the first embodiment.
The polystyrene microspheres in this embodiment are uniform in particle size and are commercially available.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: PtOEP/THF fluorescent dye in step oneThe preparation method comprises the following steps: dissolving platinum octaethylporphyrin powder (PtOEP) in tetrahydrofuran to obtain indicator with concentration of 1 × 10-3mol/l of PtOEP/THF fluorescent dye. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the volume ratio of the polystyrene microsphere emulsion to the PtOEP/THF fluorescent dye is 2000: (1-5). The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the speed of centrifugation in the first step is 7000-8000 rpm, and the centrifugation time is 5-10 min. The others are the same as in one of the first to third embodiments.
The sixth specific implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the swelling time in the first step is 1-2 h. The others are the same as in one of the first to third embodiments.
The seventh embodiment: the difference between this embodiment mode and one of the first to third embodiment modes is: and in the second step, the PDMS is Dow Corning Sylard184 silicon rubber, wherein the basic component and the curing agent are mixed according to the mass ratio of 10:1, and the mixture is stirred uniformly and then stands for half an hour to remove bubbles. The others are the same as in one of the first to third embodiments.
In order to prevent the indicator from leaking, a layer of PDMS is coated on the surface of the prepared photonic crystal device in a spin coating mode, and the PDMS has good fluidity, so that the PDMS can penetrate into gaps among the photonic crystal microspheres.
The specific implementation mode is eight: the difference between this embodiment mode and one of the first to third embodiment modes is: the hydrophilization treatment method of the quartz plate in the second step comprises the following steps: and respectively and sequentially cleaning the quartz plate by using detergent, ethanol and pure water, preparing a mixed solution of ammonia water and hydrogen peroxide, and immersing the cleaned quartz plate into the mixed solution for 4.5-5.5 hours to complete hydrophilization. The others are the same as in one of the first to third embodiments.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: the volume ratio of the ammonia water to the hydrogen peroxide in the mixed solution of the ammonia water and the hydrogen peroxide is 7: 3. The rest is the same as the embodiment eight.
The detailed implementation mode is ten: the present embodiment differs from the first to eighth embodiments in that: and in the second step, the temperature of the vacuum drying oven is 60-65 ℃, and the heat preservation time is 10-15 h. The rest is the same as the first to eighth embodiments.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the preparation method of the high-sensitivity self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement comprises the following steps:
swelling of polystyrene microspheres
Dissolving platinum octaethylporphyrin powder (PtOEP) in tetrahydrofuran to obtain indicator with concentration of 1 × 10- 3mol/l of PtOEP/THF fluorescent dye;
placing 10ml of polystyrene microsphere emulsion with uniform particle size of 0.4 wt% in a light-proof container, adding 5-25 mu l of PtOEP/THF fluorescent dye, carrying out ultrasonic treatment at room temperature for 10min to uniformly disperse the dye, carrying out ultrasonic treatment, placing the sample in a dark box at room temperature for swelling for 1h, centrifuging the sample at 7000rpm for 5min after swelling, pouring out the supernatant, and re-dispersing the lower-layer precipitate with pure water to obtain the dispersed microsphere emulsion (the concentration is 0.4 wt%);
preparation of photonic crystal fluorescence enhanced oxygen sensor
Adding the polysorbate solution into the microsphere emulsion which is dispersed in the first step, carrying out ultrasonic treatment to uniformly mix the polysorbate solution and the microsphere emulsion, and then placing the mixture into a flat-bottom glass tube;
respectively and sequentially cleaning the quartz plate with detergent, ethanol and pure water, then preparing a mixed solution of ammonia water and hydrogen peroxide (wherein the volume ratio of the ammonia water to the hydrogen peroxide is 7:3), and immersing the cleaned quartz plate into the mixed solution of the ammonia water and the hydrogen peroxide for 5 hours to complete hydrophilization treatment;
obliquely placing the quartz plate subjected to hydrophilization treatment into a flat-bottom glass tube, and placing the quartz plate and the glass tube together into a water-proof incubator, wherein the temperature of the incubator is set to be 60 ℃ until emulsion is completely evaporated, so as to obtain a photonic crystal device;
in order to prevent the indicator from leaking, a layer of PDMS is coated on the surface of the prepared photonic crystal device in a spin coating mode, and the PDMS has good fluidity, so that the PDMS can penetrate into gaps among the photonic crystal microspheres. And horizontally placing the photonic crystal device in a vacuum drying oven after spin coating, setting the temperature at 60 ℃, preserving the heat for 10 hours, and taking out the photonic crystal device after complete curing to obtain the blood oxygen sensor.
The PDMS is obtained by mixing the basic components of Dow Corning Sylad 184 silicon rubber and a curing agent in a mass ratio of 10:1, uniformly stirring, and standing for half an hour to remove bubbles.
Structural characterization of oxygen sensor
And characterizing the structure of the oxygen sensor by using a scanning electron microscope.
Four, determination of fluorescence enhancement factor of oxygen sensor
And (3) concentrating the swelled polystyrene microspheres, dripping the concentrated polystyrene microspheres on a quartz plate, drying the quartz plate in a drying oven at the temperature of 60 ℃, and curing the PDMS according to the second step. The fluorescence emission intensity Q of the system was measured with a spectrophotometer model LS550And the fluorescent substance is used as a reference group for the fluorescence enhancement effect of the photonic crystal. By changing different adding amounts of the indicator during swelling, the relation between the using amount of the indicator and the fluorescence enhancement effect is explored, and the fluorescence emission intensity Q under different using amounts of the indicator is calculatedxAnd Q0As a fluorescence enhancement factor.
Fifth, oxygen sensor Stern-Volmer curve determination
And changing the flow ratio of oxygen and nitrogen entering the system to prepare dissolved oxygen standard solutions with different concentrations. Measurement of fluorescence intensity I of carrier liquid saturated with nitrogen flowing through sensing membrane0And the fluorescence intensity I under each dissolved oxygen concentration and calculating the ratio I0I, solving a linear regression equation I according to the principle of least square method0/I＝1+KSV[Q]Establishing the concentration of dissolved oxygen under the response signalQuantitative analysis model of degree.
The experimental results are as follows:
(one) influence of different swelling amounts of the indicator on the self-assembly effect of the photonic crystal:
when the polystyrene microsphere swells octaethylporphyrin platinum, the addition amount of the dye has great influence on the self-assembly of the photonic crystal. The amount of the fixed polystyrene microsphere emulsion (0.4 wt%) was 10ml, and the amount of the added PtOEP/THF fluorescent dye was adjusted to 5-20. mu.l. After swelling for 1h in the dark at room temperature, the photonic crystal is self-assembled by using a vertical deposition method, and an electron microscope image of the photonic crystal after swelling by 5 mul of dye is shown in figure 1.
As can be seen from FIG. 1, the particle size of the microspheres is almost unchanged before and after swelling, but the microspheres after swelling are subjected to adhesion deformation due to mutual extrusion in the self-assembly process, so that the integrity of assembly is improved, cracks and linear defects are obviously reduced, and the shape is gradually changed from spherical to regular hexagon.
(II) influence of swelling amount of different indicators on fluorescence enhancement factor of photonic crystal
Detecting the fluorescence intensity of the swelled microspheres, and taking the obtained fluorescence intensity as a reference intensity Q0. Adjusting the adding amount of PtOEP fluorescent dye to 5 muL, 10 muL, 15 muL, 20 muL and 25 muL, self-assembling to obtain photonic crystal blood oxygen sensor, and measuring the fluorescence intensity to be QxIs mixing Q withx/Q0As a fluorescence enhancement factor, the relationship between the fluorescence enhancement effect and the amount of the PtOEP fluorescent dye added was examined. As shown in FIG. 2, when the amount of the PtOEP fluorescent dye added is 20 μ L, the fluorescence enhancement effect of the oxygen sensor is the best, and the fluorescence enhancement factor reaches more than 10.
(III) photonic crystal fluorescence enhanced blood oxygen sensor sensing performance test
Changing the flow ratio of oxygen and nitrogen entering the system to prepare 0-100% dissolved oxygen standard solution. Solving a linear regression equation I according to the principle of least square method0/I＝1+KSV[Q]And establishing a quantitative analysis model of the dissolved oxygen concentration under the response signal. The fluorescence emission spectra of PtOEP under different oxygen contents are shown in FIG. 3. The Stern-Volmer curve is shown in FIG. 4。
As can be seen from FIG. 3, the fluorescence intensity of the photonic crystal oxygen sensor is significantly reduced during the process of switching the oxygen volume fraction from 0% to 100%, and the peak position wavelength of the maximum fluorescence intensity peak obtained under different oxygen conditions is hardly changed. As shown in FIG. 4, the quenching constant K of the prepared photonic crystal oxygen sensor can be obtained by performing linear fitting of Stern-Volmer curve according to the obtained maximum fluorescence intensity data and the oxygen volume fractionSVAnd linear correlation coefficient R2The information of (1). Quenching constant KSVThe sensitivity of the oxygen sensor is positively correlated, so that the oxygen sensor shows different sensitivities on the premise of ensuring the accuracy. From Stern-Volmer equation data obtained by fitting in the graph, the prepared oxygen sensor has a good linear relation between the quenching ratio and the oxygen content in a measured concentration range, and the thin film has high detection accuracy. Wherein the indicator has a higher quenching constant (K) when the addition amount of the indicator is 20 μ lSV5.69) while the linear correlation coefficient R is constant2Up to 0.9999.
FIG. 5 shows the results of light fastness detection of blood oxygen sensor, in FIG. 5, curve a represents 5. mu.L PtOEP/THF, curve b represents 10. mu.L PtOEP/THF, curve c represents 15. mu.L PtOEP/THF, curve d represents 20. mu.L PtOEP/THF, and curve e represents 25. mu.L PtOEP/THF. Shows a trend chart of the fluorescence retention rate of the fluorescence indicator PtOEP after the photonic crystal blood oxygen sensor prepared by the invention is continuously excited by ultraviolet light of 380nm for 3600 s. As can be seen from the data in the figure, the fluorescence retention in the oxygen sensor was 99.11%. The method has the advantages that the PtOEP is uniformly distributed in the polystyrene microspheres, so that the self-quenching effect among PtOEP molecules is reduced, in addition, the indicator molecules can be effectively protected from being contacted with the external environment due to the crosslinking of PDMS, the indicator leakage is reduced, the photo-bleaching effect is reduced, and the light stability of the oxygen sensor is greatly improved.
FIG. 6 is a graph showing the relationship between the contact angle and the amount of dye added, and FIG. 6 shows that the contact angle varies with the amount of PtOEP/THF added, and reaches a maximum of 126 ℃ when the amount of dye added is 20. mu.l, indicating that the surface of the oxygen sensor is hydrophobic and has better self-cleaning capability.
Fig. 7 is a schematic diagram of the blood oxygen sensor, and it can be seen from fig. 7 that the blood oxygen sensor has excellent flexibility and can be stretched and bent greatly. Fig. 8 is that the prepared blood oxygen sensor is pasted on the inner side of an arm, so that the blood oxygen sensor can be well attached to the skin, and is free of discomfort and foreign body sensation, and therefore the wearable sensor is realized. The blood oxygen sensor has wide application prospect in the fields of wearable artificial skin and the like.
Claims (10)
1. A preparation method of a high-sensitivity self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement is characterized by comprising the following steps:
placing the polystyrene microsphere emulsion in a light-proof container, adding a PtOEP/THF fluorescent dye, performing ultrasonic treatment at room temperature, performing ultrasonic treatment, placing in a dark box at room temperature for swelling, centrifuging, pouring out a supernatant, and re-dispersing the precipitate by using pure water to obtain the dispersed microsphere emulsion;
secondly, adding the polysorbate solution into the microsphere emulsion which is dispersed in the first step, performing ultrasonic treatment until the mixture is uniformly mixed, and then placing the mixture into a flat-bottom glass tube;
obliquely placing the quartz plate subjected to hydrophilization treatment into a flat-bottom glass tube, and placing the quartz plate and the glass tube together into a water-proof incubator, wherein the temperature of the incubator is set to be 60-65 ℃ until emulsion is completely evaporated, so that a photonic crystal device is obtained;
and spin-coating a layer of polydimethylsiloxane on the surface of the prepared photonic crystal device, horizontally placing the photonic crystal device in a vacuum drying oven, and taking out the photonic crystal device after complete curing to obtain the blood oxygen sensor.
2. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 1, wherein the mass concentration of the polystyrene microsphere emulsion in the step one is 0.4%.
3. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 1 or 2, wherein the method comprisesCharacterized in that the preparation method of the PtOEP/THF fluorescent dye in the step one comprises the following steps: dissolving octaethylporphyrin platinum powder in tetrahydrofuran to obtain the indicator with the concentration of 1 × 10-3mol/l of PtOEP/THF fluorescent dye.
4. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 3, wherein the volume ratio of the polystyrene microsphere emulsion to the PtOEP/THF fluorescent dye in the first step is 2000: (1-5).
5. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 4, wherein the centrifugation speed in the first step is 7000-8000 rpm, and the centrifugation time is 5-10 min.
6. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 5, wherein the swelling time in the first step is 1-2 h.
7. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 1, wherein the PDMS in the step two is Dow Corning Sylard184 silicon rubber, wherein the basic component and the curing agent are mixed according to a mass ratio of 10:1, and the mixture is stirred uniformly and then kept still for half an hour.
8. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 1, wherein the hydrophilization treatment method of the quartz plate in the second step is: and respectively and sequentially cleaning the quartz plate by using detergent, ethanol and pure water, preparing a mixed solution of ammonia water and hydrogen peroxide, and immersing the cleaned quartz plate into the mixed solution for 4.5-5.5 hours to complete hydrophilization.
9. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 8, wherein the volume ratio of ammonia water to hydrogen peroxide in the mixed solution of ammonia water and hydrogen peroxide is 7: 3.
10. The method for preparing a highly sensitive self-cleaning blood oxygen sensor based on photonic crystal fluorescence enhancement as claimed in claim 1, wherein the temperature of the vacuum drying oven in the second step is 60-65 ℃ and the heat preservation time is 10-15 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137686.9A CN112957038B (en) | 2021-02-01 | 2021-02-01 | Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110137686.9A CN112957038B (en) | 2021-02-01 | 2021-02-01 | Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112957038A true CN112957038A (en) | 2021-06-15 |
| CN112957038B CN112957038B (en) | 2022-10-28 |
Family
ID=76272929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110137686.9A Active CN112957038B (en) | 2021-02-01 | 2021-02-01 | Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112957038B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260764A (en) * | 2022-08-25 | 2022-11-01 | 哈尔滨工业大学 | Preparation method of flexible oxygen sensing film based on microstructure |
| CN115595141A (en) * | 2022-09-30 | 2023-01-13 | 浙江清华柔性电子技术研究院（Cn） | Method for manufacturing oxygen sensor fluorescent film, oxygen sensor fluorescent film and oxygen sensor |
| WO2023246200A1 (en) * | 2022-06-24 | 2023-12-28 | 公安部物证鉴定中心 | Octogen photonic crystal sensor, preparation method therefor and application thereof |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0368481A2 (en) * | 1988-10-14 | 1990-05-16 | Medex, Inc. | Immobilized fluorophores for oxygen sensors |
| US6207961B1 (en) * | 1996-10-15 | 2001-03-27 | American Research Corporation Of Virginia | Loss compensation using digital-signal processing in fiber-optic fluorescence sensors |
| US20030099574A1 (en) * | 2001-08-22 | 2003-05-29 | Bentsen James G. | Fluorescence based oxygen sensor systems |
| US20050037512A1 (en) * | 2003-08-12 | 2005-02-17 | Ming-Hsiung Yeh | Microencapsulation of oxygen-sensing particles |
| US20080278722A1 (en) * | 2007-05-07 | 2008-11-13 | The Board Of Trustees Of The University Of Illinois | Fluorescence detection enhancement using photonic crystal extraction |
| CN101620184A (en) * | 2009-07-30 | 2010-01-06 | 上海电力学院 | Plastic optical fiber sensing system for simultaneously measuring blood sugar concentration and blood oxygen concentration |
| US20100047839A1 (en) * | 2008-08-19 | 2010-02-25 | National Taipei University Of Technology | Latent fluorimetric indicator for biological analytes determination and the preparation method thereof |
| EP2461154A1 (en) * | 2010-12-03 | 2012-06-06 | Honeywell International Inc. | Fluorescence quenching based oxygen sensor |
| CN102650597A (en) * | 2012-04-28 | 2012-08-29 | 浙江工业大学 | Oxygen sensing film based on fluorescence quenching principle |
| US20120220841A1 (en) * | 2011-02-24 | 2012-08-30 | Nellcor Puritan Bennett Llc | Medical sensor using photonic crystal led |
| US20140106468A1 (en) * | 2011-03-14 | 2014-04-17 | Arjen Boersma | Photonic crystal sensor |
| CN104262811A (en) * | 2014-09-19 | 2015-01-07 | 哈尔滨工业大学 | Preparation method and application of polystyrene fluorescent microspheres |
| CN105352894A (en) * | 2015-10-28 | 2016-02-24 | 哈尔滨工业大学 | Preparation method of fast high-sensitivity photonic crystal humidity sensor |
| CN105352921A (en) * | 2015-10-13 | 2016-02-24 | 北京科技大学 | Preparation and application of mercury ion sensor based on photonic crystal enhanced fluorescence |
| CN106990088A (en) * | 2017-06-08 | 2017-07-28 | 厦门大学 | A kind of photon crystal humidity sensor and preparation method thereof |
| CN108084366A (en) * | 2017-12-18 | 2018-05-29 | 哈尔滨工业大学 | Colorimetric fluorescent microsphere emulsion preparation method based on octaethylporphyrin platinum and the application in optical oxygen sensing micro-fluidic detection chip |
| US20180271411A1 (en) * | 2015-10-21 | 2018-09-27 | A-Scan Llc | Depth Scanning Oxygen Sensor |
| CN110183703A (en) * | 2019-04-11 | 2019-08-30 | 厦门大学 | A kind of photonic crystal composite type pressure sensor and preparation method thereof and optical detecting method |
-
2021
- 2021-02-01 CN CN202110137686.9A patent/CN112957038B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0368481A2 (en) * | 1988-10-14 | 1990-05-16 | Medex, Inc. | Immobilized fluorophores for oxygen sensors |
| US6207961B1 (en) * | 1996-10-15 | 2001-03-27 | American Research Corporation Of Virginia | Loss compensation using digital-signal processing in fiber-optic fluorescence sensors |
| US20030099574A1 (en) * | 2001-08-22 | 2003-05-29 | Bentsen James G. | Fluorescence based oxygen sensor systems |
| US20050037512A1 (en) * | 2003-08-12 | 2005-02-17 | Ming-Hsiung Yeh | Microencapsulation of oxygen-sensing particles |
| US20080278722A1 (en) * | 2007-05-07 | 2008-11-13 | The Board Of Trustees Of The University Of Illinois | Fluorescence detection enhancement using photonic crystal extraction |
| US20100047839A1 (en) * | 2008-08-19 | 2010-02-25 | National Taipei University Of Technology | Latent fluorimetric indicator for biological analytes determination and the preparation method thereof |
| CN101620184A (en) * | 2009-07-30 | 2010-01-06 | 上海电力学院 | Plastic optical fiber sensing system for simultaneously measuring blood sugar concentration and blood oxygen concentration |
| EP2461154A1 (en) * | 2010-12-03 | 2012-06-06 | Honeywell International Inc. | Fluorescence quenching based oxygen sensor |
| US20120220841A1 (en) * | 2011-02-24 | 2012-08-30 | Nellcor Puritan Bennett Llc | Medical sensor using photonic crystal led |
| US20140106468A1 (en) * | 2011-03-14 | 2014-04-17 | Arjen Boersma | Photonic crystal sensor |
| CN102650597A (en) * | 2012-04-28 | 2012-08-29 | 浙江工业大学 | Oxygen sensing film based on fluorescence quenching principle |
| CN104262811A (en) * | 2014-09-19 | 2015-01-07 | 哈尔滨工业大学 | Preparation method and application of polystyrene fluorescent microspheres |
| CN105352921A (en) * | 2015-10-13 | 2016-02-24 | 北京科技大学 | Preparation and application of mercury ion sensor based on photonic crystal enhanced fluorescence |
| US20180271411A1 (en) * | 2015-10-21 | 2018-09-27 | A-Scan Llc | Depth Scanning Oxygen Sensor |
| CN105352894A (en) * | 2015-10-28 | 2016-02-24 | 哈尔滨工业大学 | Preparation method of fast high-sensitivity photonic crystal humidity sensor |
| CN106990088A (en) * | 2017-06-08 | 2017-07-28 | 厦门大学 | A kind of photon crystal humidity sensor and preparation method thereof |
| CN108084366A (en) * | 2017-12-18 | 2018-05-29 | 哈尔滨工业大学 | Colorimetric fluorescent microsphere emulsion preparation method based on octaethylporphyrin platinum and the application in optical oxygen sensing micro-fluidic detection chip |
| CN110183703A (en) * | 2019-04-11 | 2019-08-30 | 厦门大学 | A kind of photonic crystal composite type pressure sensor and preparation method thereof and optical detecting method |
Non-Patent Citations (4)
| Title |
|---|
| ZHANG BIAO; WU PENGJUN; ZHENG HUADAN: "Experimental research on fiber optic oxygen sensor based on fluorescence quenching principle", 《JOURNAL OF APPLIED OPTICS》 * |
| ZHANG, K., LUO, L., LI, W., ZHANG, H., ZHANG, Y.: "High-performance dissolved oxygen sensors based on platinum(ii) porphyrin embedded in polystyrene beads", 《NEW JOURNAL OF CHEMISTRY》 * |
| 何平: "基于荧光猝灭的溶解氧传感器研究", 《中国优秀硕士学位论文全文数据库》 * |
| 赵伟: "BTESE/TFP-TriMOS薄膜制备及其氧传感性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023246200A1 (en) * | 2022-06-24 | 2023-12-28 | 公安部物证鉴定中心 | Octogen photonic crystal sensor, preparation method therefor and application thereof |
| CN115260764A (en) * | 2022-08-25 | 2022-11-01 | 哈尔滨工业大学 | Preparation method of flexible oxygen sensing film based on microstructure |
| CN115595141A (en) * | 2022-09-30 | 2023-01-13 | 浙江清华柔性电子技术研究院（Cn） | Method for manufacturing oxygen sensor fluorescent film, oxygen sensor fluorescent film and oxygen sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112957038B (en) | 2022-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112957038B (en) | Preparation method of high-sensitivity self-cleaning type blood oxygen sensor based on photonic crystal fluorescence enhancement | |
| Yu et al. | A novel optical fiber glucose biosensor based on carbon quantum dots-glucose oxidase/cellulose acetate complex sensitive film | |
| Weigl et al. | Optical triple sensor for measuring pH, oxygen and carbon dioxide | |
| Lee et al. | Measurement of pH and dissolved oxygen within cell culture media using a hydrogel microarray sensor | |
| US9410970B2 (en) | Cellarium: thin-film sensor with microarray seal | |
| CN110760086B (en) | Polymer gel flexible film and sweat glucose visual detection method based on same | |
| Youssef et al. | Recent advances in biosensors for real time monitoring of pH, temperature, and oxygen in chronic wounds | |
| Xu et al. | Simultaneous color sensing of O2 and pH using a smartphone | |
| Huang et al. | A subcutaneously injected SERS nanosensor enabled long-term in vivo glucose tracking | |
| Hussain et al. | Glucose sensing based on the intrinsic fluorescence of sol-gel immobilized yeast hexokinase | |
| Hsu et al. | A serological point-of-care test for Zika virus detection and infection surveillance using an enzyme-free vial immunosensor with a smartphone | |
| CN105462590B (en) | A kind of boration quantum dot ratio fluorescent probe and its preparation method and application | |
| Tsukada et al. | Development of catheter-type optical oxygen sensor and applications to bioinstrumentation | |
| Pasic et al. | Miniaturized fiber-optic hybrid sensor for continuous glucose monitoring in subcutaneous tissue | |
| US20040171094A1 (en) | Oxygen sensors disposed on a microtiter plate | |
| Wang et al. | A water-sprayable, thermogelating and biocompatible polymer host for use in fluorescent chemical sensing and imaging of oxygen, pH values and temperature | |
| Zhu et al. | A fully integrated and handheld electrochemiluminescence device for detection of dopamine in bio-samples | |
| US20150253333A1 (en) | Cellarium: glucose, ph, and oxygen triple sensor | |
| Su et al. | Ratiometric glucose sensing based on fluorescent oxygen films and glucose oxidase | |
| JP3109740B2 (en) | Microorganism detector | |
| Yan et al. | Optical biosensing systems for a biological living body | |
| CN114705869B (en) | Photonic crystal biochip and protein detection method thereof | |
| Katayama et al. | Development of a patch-type flexible oxygen partial pressure sensor | |
| Badugu et al. | Development and application of an excitation ratiometric optical pH sensor for bioprocess monitoring | |
| CN104330393A (en) | Method for determining glucose by using gold nano-cluster as fluorescence probe |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |