Analytical device and analytical method
The analytical device simplifies the estimation of oxygen partial pressure by using an oxygen-bound complex film and chromaticity analysis, addressing the complexity and cost issues of existing monitors.
Patent Information
- Application Number
- JP2021080649
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2021-05-11
- Publication Date
- 2025-05-21
- Estimated Expiration
- 2041-05-11
Smart Images

Figure 0007680723000001 
Figure 0007680723000002 
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Abstract
Description
[Technical field]
[0001] The present invention relates to an analytical device and method for estimating the oxygen partial pressure in a liquid. [Background technology]
[0002] When a patient's heart is stopped during the treatment of cardiac disease, an extracorporeal circulation circuit is used to maintain the patient's life. Specifically, venous blood is drawn from the patient, and carbon dioxide is removed from the drawn venous blood and oxygen is added to turn it into arterial blood. The arterial blood is then sent to the patient, maintaining the patient's life while the heart is stopped and the heart is treated. At this time, the partial pressures of oxygen and carbon dioxide in the venous blood and arterial blood, respectively, are used as indicators to confirm that extracorporeal circulation is being performed appropriately.
[0003] As an example, Patent Document 1 describes an extracorporeal circulation system to which a blood gas monitor is connected. A blood gas monitor sensor disposed in a blood transfer tube is connected to the blood gas monitor. In the extracorporeal circulation system, pH information, carbon dioxide partial pressure information, and oxygen partial pressure information are obtained from the blood gas monitor during surgery on a patient. [Prior art documents] [Patent documents]
[0004] [Patent Document 1] International Publication No. 2019 / 026847 Summary of the Invention [Problem to be solved by the invention]
[0005] The blood gas monitor described in Patent Document 1 uses a special agent for measurement. In addition, the blood gas monitor has a complicated structure, which makes it expensive and large in size. Therefore, there is a demand for a device that measures oxygen partial pressure in a simple manner. [Means for solving the problem]
[0006] An analytical device according to one embodiment of the present invention is an analytical device that estimates the oxygen partial pressure of a liquid, and includes a contact unit that brings the liquid into contact with an oxygen-bound complex film, a detection unit that detects the color of the oxygen-bound complex film, and an analysis unit that analyzes a chromaticity point in a chromaticity diagram that corresponds to the color of the oxygen-bound complex film to estimate the oxygen partial pressure of the liquid.
[0007] Furthermore, an analytical method according to one embodiment of the present invention is an analytical method for estimating the oxygen partial pressure of a liquid, which comprises contacting the liquid with an oxygen-bound complex film, detecting the color of the oxygen-bound complex film, and analyzing a chromaticity point in a chromaticity diagram that corresponds to the color of the oxygen-bound complex film, thereby estimating the oxygen partial pressure of the liquid. Effect of the Invention
[0008] As a result, the analytical device and analytical method according to the present invention make it possible to easily estimate the oxygen partial pressure in the liquid to be analyzed.
[0009] Further characteristics of the invention will become apparent from the following description of an embodiment thereof, given by way of example only with reference to the accompanying drawings, in which: [Brief description of the drawings]
[0010] [Figure 1] FIG. [Diagram 2] FIG. 1 is a schematic diagram illustrating a method for producing a polymer ligand. [Diagram 3] FIG. 1 is a schematic diagram illustrating a method for producing an oxygen-binding complex film. [Figure 4] Schematic diagram of the xy chromaticity diagram. [Diagram 5] An enlarged portion of the xy chromaticity diagram. [Figure 6] An enlarged portion of the xy chromaticity diagram. [Figure 7] Graph showing the results of ultraviolet-visible absorption spectrum measurement. [Figure 8] Graph showing the results of ultraviolet-visible absorption spectrum measurement. [Figure 9] FIG. 2 is a partially enlarged view of the xy chromaticity diagram according to the first embodiment. [Figure 10] 4 is a table showing chromaticity points according to the first embodiment. [Figure 11] 1 is a table showing the relationship between the first angle and the oxygen concentration of the gas. [Figure 12] 11 is a table showing the relationship between the second angle and the degree of deterioration. [Figure 13] Schematic diagram of the a*b* chromaticity diagram. [Figure 14] An enlarged portion of the a*b* chromaticity diagram. [Figure 15] 11 is a table showing chromaticity points according to the second embodiment. [Figure 16] FIG. 11 is a partially enlarged view of an a*b* chromaticity diagram according to the second embodiment. [Figure 17] 1 is a table showing the relationship between the third angle and the oxygen concentration of the gas. [Figure 18] 4 is a table showing the relationship between the fourth angle and the degree of deterioration. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail with reference to the drawings. However, the dimensions, materials, shapes, and relative positions of components described in the following embodiments can be arbitrarily set and can be changed according to the configuration of the device to which the present invention is applied or various conditions. Furthermore, unless otherwise specified, the scope of the present invention is not limited to the embodiments specifically described below.
[0012] [First embodiment] FIG. 1 is a schematic diagram illustrating an analysis device 10 that estimates the oxygen partial pressure of a liquid. As shown in FIG. 1, the analysis device 10 includes a contact unit 12 that brings a liquid into contact with an oxygen-bound complex film 11. For example, the contact unit 12 is configured to accommodate the oxygen-bound complex film 11 and a liquid to be analyzed. As an example, the contact unit 12 includes a quartz cell 13 and the oxygen-bound complex film 11 formed on the inner surface of the quartz cell 13. Alternatively, the contact unit 12 may include a container that accommodates the liquid, and a film or the like on which the oxygen-bound complex film 11 is formed may be disposed in the container.
[0013] The oxygen-binding complex film 11 binds to oxygen molecules and changes color depending on the degree of binding. Therefore, the color of the oxygen-binding complex film 11 changes depending on the oxygen partial pressure of the liquid. For example, the oxygen-binding complex film 11 is at least one of a salcomine complex film, an iron porphyrin complex film, a cobalt porphyrin complex film, and a copper complex film. Note that parts of the oxygen-binding complex film 11 may be made of different materials, and in this case, the detection unit 14 may detect the colors of the parts of the oxygen-binding complex film 11 made of different materials.
[0014] The liquid is contained in the internal space of the quartz cell 13, and may be, for example, pure water, blood, blood preparations such as human red blood cell fluid, infusion, or physiological saline. In addition, when the liquid to be analyzed by the analysis device 10 is an opaque liquid, for example, blood, oxygen received from the blood may be dissolved in the liquid contained in the contact part 12. In this case, as an example, the contact part 12 further includes a hydrophobic membrane (for example, a thin film made of silicone, a silicon base material, or a fluorine-based base material) that is oxygen-permeable. The hydrophobic membrane is disposed between the liquid and the liquid to be analyzed (for example, blood). As a result, oxygen that has permeated the hydrophobic membrane from the blood dissolves in the liquid, changing the oxygen partial pressure of the liquid. Therefore, the analysis device 10 can estimate the oxygen partial pressure of the blood based on the oxygen partial pressure of the liquid. In the following description, an example in which the liquid to be analyzed is pure water will be described.
[0015] The analysis device 10 also includes a detection unit 14 that detects the color of the oxygen-bound complex film 11. The detection unit 14 is configured to detect the changing color of the oxygen-bound complex film 11. As an example, the detection unit 14 is a camera that captures an image or video, or an image sensor (e.g., a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), etc.).
[0016] Furthermore, the analysis device 10 includes an analysis unit 15 that estimates the oxygen partial pressure of the liquid by analyzing the chromaticity points corresponding to the color of the oxygen-bound complex film 11 in a chromaticity diagram described later. The analysis unit 15 estimates the oxygen partial pressure of the liquid by analyzing the color detected by the detection unit 14, for example, the color of image data. For this purpose, the analysis unit 15 is configured as a computer that combines a processor that executes various arithmetic processing and operation control according to a predetermined analysis program, an internal memory required for the operation of the processor, and other peripheral devices. The detection unit 14 and the analysis unit 15 are connected wirelessly or by wire. In the following description, an example in which the detection unit 14 is a digital camera will be described. As an example of the detection unit 14, a digital camera photographs the oxygen-bound complex film 11 to detect the color of the oxygen-bound complex film 11 and acquires image data. In this case, the analysis unit 15 acquires image data from the detection unit 14 and analyzes the color contained in the acquired image data.
[0017] As an example, the analysis unit 15 has a processor (not shown) and a memory (not shown) as a storage unit that stores a control program. The processor is, for example, a CPU (Central Processing Unit) or an MPU (Micro-Processing Unit), and controls the entire device and also controls various processes in a comprehensive manner based on the program stored in the memory. The memory also includes a RAM (Random Access Memory), which is a system work memory for the processor to operate, as well as a ROM (Read Only Memory), HDD (Hard Disc Drive), SSD (Solid State Drive), and other storage devices that store programs and system software. In the following, the CPU executes various processing operations such as calculations, controls, and discriminations according to the control program stored in the ROM or HDD.
[0018] In addition, an operation unit including a keyboard or various switches for inputting predetermined commands and data is connected to the analysis unit 15 via a wired or wireless connection. In addition, a display unit 17 for displaying the input state, setting state, measurement results, and various information of the device is connected to the analysis unit 15 via a wired or wireless connection. As an example, the display unit 17 displays the oxygen partial pressure of the liquid as the analysis result by the analysis unit 15. Furthermore, the analysis unit 15 can also be controlled according to a program stored in a portable recording medium such as a CD (Compact Disc), a DVD (Digital Versatile Disc), a CF (Compact Flash) card, and a USB (Universal Serial Bus) memory, or an external storage medium such as a server on the Internet.
[0019] The analysis device 10 further includes a light source 16 (e.g., a D65 light source) such as a white light source that irradiates the oxygen-bonded complex film 11 with light. Light emitted from the light source 16 and reflected by the oxygen-bonded complex film 11 is incident on the detection unit 14. Light emitted from the light source 16 and transmitted through the oxygen-bonded complex film 11 may also be incident on the detection unit 14. For the sake of explanation, FIG. 1 illustrates the light source 16 with the transmitted light being incident thereon by a broken line. Note that a reflecting unit such as a mirror that constitutes an optical path may be disposed between the light source 16 and the detection unit 14.
[0020] [Color change behavior] The color of the oxygen-bound complex film 11 changes when it binds with oxygen molecules. For example, when the oxygen-bound complex film 11 is a polymeric salcomine complex film (P(EHMA-VPy)-CoS film), which is an example of a salcomine complex film, its color when formed is yellow. When oxygen molecules bind to the oxygen-bound complex film 11, the color of the oxygen-bound complex film 11 changes from yellow to reddish purple. The oxygen-bound complex film 11 and its color change will be described below using a polymeric salcomine complex film as an example.
[0021] [Synthesis of polymeric salcomine complex membrane] First, a polymer ligand, P(EHMA-VPy) (poly(ethylhexyl methacrylate-co-vinylpyridine)), is synthesized by the method shown in FIG. 2. This results in the synthesis of a polymer ligand with EHMA:VPy=85:15 (mol%). Furthermore, in order to prepare a polymer salcomine complex film, 42 mg of P(EHMA-VPy) and 0.3 mg of salcomine (CoS) are prepared. Then, CoS is charged so that VPy unit:CoS=40:1 (molar ratio) is obtained, and dissolved in 1 mL of dichloromethane under a nitrogen atmosphere. After that, a P(EHMA-VPy)-CoS film (film thickness: 100 μm) is formed in a quartz cell 13 by a solvent casting method (FIG. 3). The film thickness is not limited to 100 μm, and may be, for example, 50 μm or 70 μm. However, by setting the film thickness to 100 μm, the time until the oxygen binding ability of the polymer salcomine complex film is lost becomes longer.
[0022] [xy chromaticity diagram] In order to analyze the changing color, the analysis unit 15 utilizes an xy chromaticity diagram (FIG. 4) of the CIE XYZ color system (color space), which is an example of a chromaticity diagram. For example, immediately after the polymeric salcomine complex film is formed by the above-mentioned method, light is irradiated from the light source 16 (e.g., a D65 light source) at room temperature (24-26° C.) and in a nitrogen atmosphere. Then, the polymeric salcomine complex film in the quartz cell 13 is photographed using the detection unit 14 (e.g., a mirrorless digital single-lens camera "OM-D E-M1 Mark II" manufactured by Olympus Corporation). In this way, image data (hereinafter also referred to as reference image data) of the polymeric salcomine complex film in a state in which oxygen is not bonded immediately after the film formation is obtained. The light source 16 may be natural light or a white light source.
[0023] Next, oxygen (O 2 ) 3% and nitrogen (N 297% of the mixed gas (oxygen 3%) is bubbled through the pure water to prepare a liquid to be analyzed. The prepared liquid is then introduced into the quartz cell 13, which is the contact portion 12, so that the entire polymeric salcomine complex film is immersed in the mixed gas. The mixed gas (oxygen 3%) is then introduced into a position that does not contact the polymeric salcomine complex film. Then, the mixed gas is bubbled in the liquid until the oxygen binding equilibrium state is reached. Note that a part of the introduced gas is dissolved in the liquid, and the remaining part is exhausted to the outside from an exhaust port formed in the quartz cell 13. In parallel, the ultraviolet-visible absorption spectrum of the polymeric salcomine complex film is measured. Then, when the oxygen binding equilibrium state is reached, for example, when the absorbance does not change, light is irradiated from the light source 16. Then, the polymeric salcomine complex film is photographed using the detection portion 14. In this manner, image data corresponding to the mixed gas (oxygen 3%) (hereinafter also referred to as first image data) is obtained.
[0024] Similarly, a mixed gas (10% oxygen) consisting of 10% oxygen and 90% nitrogen is introduced, and the polymeric salcomine complex film in an oxygen-binding equilibrium state is photographed. In this way, image data corresponding to the mixed gas (10% oxygen) (hereinafter also referred to as second image data) is obtained. Furthermore, 100% oxygen gas is introduced, and the polymeric salcomine complex film in an oxygen-binding equilibrium state is photographed. In this way, image data corresponding to the gas (100% oxygen) (hereinafter also referred to as third image data) is obtained. Furthermore, gas (100% oxygen) is introduced until the oxygen-binding ability is inactivated, and then the polymeric salcomine complex film is photographed. In this way, image data in the inactivated state (hereinafter also referred to as inactivated image data) is obtained.
[0025] Similarly to photographing the polymeric salcomine complex film, a camera profile creation tool (for example, "Colorchecker Passport" manufactured by X-rite) is irradiated with light from the light source 16 to photograph the creation tool. Then, using the created camera profile, calibration is performed on the image data of the polymeric salcomine complex film obtained by photographing. As an example, the calibration of the image data is performed using "Adobe Photoshop (registered trademark)" manufactured by Adobe. Then, color information (lightness and chromaticity) of the CIE L*a*b* color system is obtained from the image data obtained by calibration. Furthermore, the obtained color information is converted into the CIE XYZ color system. Then, the x chromaticity point and the y chromaticity point are obtained and plotted on an xy chromaticity diagram of the CIE XYZ color system as shown in FIG. 4.
[0026] In this manner, the chromaticity points in the xy chromaticity diagram of the reference image data, the first image data, the second image data, the third image data, and the deactivated image data are obtained. Note that each image data may contain something other than the polymeric salcomine complex film (e.g., a part of the quartz cell 13). In this case, the analysis unit 15 obtains the chromaticity points using an image of the part of the polymeric salcomine complex film.
[0027] [Color point behavior] The behavior of the chromaticity points will be described with reference to Fig. 5 and Fig. 6. Fig. 5 and Fig. 6 are schematic explanatory diagrams enlarging a portion A surrounded by a dashed line in the xy chromaticity diagram of Fig. 4. Reference point 1, which is an example of the first reference point, corresponds to the deactivated image data and is a chromaticity point when the polymer salcomine complex film is completely deteriorated. Reference point 2, which is an example of the second reference point, corresponds to the reference image data in an oxygen-free atmosphere immediately after film formation and is a chromaticity point before deterioration of the polymer salcomine complex film begins. Furthermore, chromaticity point 100P0 corresponds to the third image data and is a chromaticity point when 100% oxygen gas is introduced to reach an oxygen bond equilibrium state. The degree of deterioration of the polymer salcomine complex film (hereinafter also referred to as the deterioration degree) will be described later.
[0028] FIG. 5 shows oxygen angle D1, which is the angle between a line connecting reference point 1 and a chromaticity point corresponding to each image data, and a line connecting reference point 1 and reference point 2. Oxygen angle D1, which is an example of a first angle, correlates with the oxygen concentration of a gas in contact with the liquid, and therefore correlates with the oxygen partial pressure of the liquid. For example, the oxygen partial pressure of the liquid can be calculated by multiplying the oxygen concentration of a gas (air) in contact with the liquid by the air pressure. Therefore, oxygen angle D1 also correlates with the oxygen partial pressure of the liquid.
[0029] Specifically, in FIG. 5, the chromaticity point 3P0 corresponds to the first image data of the undegraded polymer salcomine complex film. The chromaticity point 3P3 corresponds to the first image data of the polymer salcomine complex film degraded by 30%. The chromaticity point 3P5 corresponds to the first image data of the polymer salcomine complex film degraded by 50%. The oxygen angles D1 corresponding to the chromaticity points 3P0, 3P3, and 3P5 are all approximately equal. Therefore, by using the oxygen angle D1 at this time, the oxygen concentration of the gas in contact with the liquid can be estimated to be 3%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere can be calculated as 22.8 Torr = 760 Torr × 0.03.
[0030] 5, the chromaticity point 10P0 corresponds to the second image data of the undegraded polymer salcomine complex film. The chromaticity point 10P3 corresponds to the second image data of the polymer salcomine complex film degraded by 30%. The chromaticity point 10P5 corresponds to the second image data of the polymer salcomine complex film degraded by 50%. The oxygen angles D1 corresponding to the chromaticity points 10P0, 10P3, and 10P5 are all approximately equal. Therefore, by using the oxygen angle D1 at this time, the oxygen concentration of the gas can be estimated at 10%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere can be calculated as 76 Torr = 760 Torr × 0.10.
[0031] 5, the chromaticity point 100P0 corresponds to the third image data of the undegraded polymer salcomine complex film. The chromaticity point 100P3 corresponds to the third image data of the polymer salcomine complex film degraded by 30%. The chromaticity point 100P5 corresponds to the third image data of the polymer salcomine complex film degraded by 50%. The oxygen angles D1 corresponding to the chromaticity points 100P0, 100P3, and 100P5 are all approximately equal. Therefore, by using the oxygen angle D1 at this time, the oxygen concentration of the gas can be estimated to be 100%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere can be calculated as 760 Torr = 760 Torr × 1.00.
[0032] Next, FIG. 6 shows a deterioration angle D2, which is an angle formed by a straight line connecting the reference point 2 and the chromaticity point corresponding to each image data, and a straight line connecting the reference point 2 and the reference point 1. The deterioration angle D2, which is an example of the second angle, correlates with the deterioration degree of the polymer salcomine complex film. Specifically, in FIG. 6, the deterioration angles D2 corresponding to the chromaticity points 3P0, 10P0, and 100P0 are all approximately equal. Therefore, by using the deterioration angle D2 at this time, it is possible to estimate a deterioration degree of 0% of the polymer salcomine complex film. Similarly, the deterioration angles D2 corresponding to the chromaticity points 3P3, 10P3, and 100P3 are all approximately equal. Therefore, by using the deterioration angle D2 at this time, it is possible to estimate a deterioration degree of 30% of the polymer salcomine complex film. Furthermore, the deterioration angles D2 corresponding to the chromaticity points 3P5, 10P5, and 100P5 are all approximately equal. Therefore, by using the deterioration angle D2 at this time, it is possible to estimate that the deterioration degree of the polymer salcomine complex film is 50%.
[0033] [Deterioration of polymeric salcomine complex film] The degree of deterioration of the polymer salcomine complex film can be calculated from the results of ultraviolet-visible absorption spectrum measurement. As an example, the absorbance of the light having a wavelength of 560 nm in the polymer salcomine complex film (for example, 0.9) is subtracted from the absorbance of the light having a wavelength of 560 nm in the undegraded polymer salcomine complex film (for example, 1.2) to obtain a first value (for example, 0.3). Furthermore, the initial absorbance of the light having a wavelength of 560 nm in the polymer salcomine complex film in a state in which no oxygen is bonded immediately after film formation (for example, 0.2) is subtracted from the absorbance of the light having a wavelength of 560 nm in the undegraded polymer salcomine complex film (for example, 1.2) to obtain a second value (for example, 1.0). Furthermore, the value (for example, 0.3) obtained by dividing the first value by the second value is multiplied by 100 to calculate the degree of deterioration (for example, 30%).
[0034] It has been discovered that when a gas with an oxygen concentration of 100% is supplied to pure water, the absorbance in the absorption band at a wavelength of about 560 nm increases due to the polymeric salcomine complex film bonding with oxygen. Specifically, as shown in FIG. 7, the absorption band increases at a wavelength of about 560 nm in all cases where the degree of oxygen bonding is 50%, 60%, 70%, 80%, and 90%. In FIG. 7, the vertical axis indicates the absorbance based on the results of ultraviolet-visible absorption spectrum measurement, and the horizontal axis indicates the wavelength of light. In FIG. 7, the word "initial" is added to the line indicating the absorbance of the polymeric salcomine complex film in a state where no oxygen is bonded (a state where the degree of oxygen bonding is 0%) immediately after film formation.
[0035] On the other hand, as a result of measuring the absorbance using a plurality of polymeric salcomine complex films with different degrees of deterioration, it was found that the increased absorption band subsequently decreased. Specifically, as shown in FIG. 8, in the case of 100% deterioration, the absorbance of the absorption band decreased at a wavelength of about 560 nm. Furthermore, at a wavelength of about 480 nm, there is a difference between the absorption band of a polymeric salcomine complex film that is not deteriorated immediately after film formation, i.e., has a deterioration degree of 0%, and the absorption band of a polymeric salcomine complex film corresponding to another degree of deterioration. The absorbance of the absorption band decreases irreversibly as the polymeric salcomine complex film deteriorates. In FIG. 8, the vertical axis indicates the absorbance based on the result of ultraviolet-visible absorption spectrum measurement, and the horizontal axis indicates the wavelength of light.
[0036] However, as shown in Fig. 8, when the degree of degradation is from 0% to 20%, the change in absorbance in the absorption band near the wavelength of 480 nm is small. In contrast, in the absorption band near the wavelength of 560 nm, it is relatively difficult to distinguish between the change due to the oxygen concentration and the change due to the degree of degradation.
[0037] [Example 1] Hereinafter, Example 1 will be described with reference to Figs. 9 to 12. Fig. 9 is a schematic explanatory diagram in which each chromaticity point according to Example 1 is plotted by enlarging a portion A surrounded by a dashed line in the xy chromaticity diagram of Fig. 4. Fig. 10 is a table showing each chromaticity point according to Example 1. Fig. 11 is a table showing the relationship between an oxygen angle D1, which is an example of a first angle, and the oxygen concentration of the gas. Fig. 12 is a table showing the relationship between a deterioration angle D2, which is an example of a second angle, and the deterioration degree.
[0038] In Example 1, a polymer ligand was synthesized by the above-mentioned method (FIG. 2), and then a polymer salcomine complex film was formed by the above-mentioned method (FIG. 3). Then, the polymer salcomine complex film was photographed and analyzed, and its ultraviolet-visible absorption spectrum was measured. Specifically, the polymer salcomine complex film was photographed at room temperature of 24° C. to 26° C., and image data obtained was analyzed to obtain the x chromaticity point and the y chromaticity point as shown in FIG. 9 and FIG. 10. At this time, the polymer salcomine complex film was irradiated with light from a D65 light source, and the polymer salcomine complex film was photographed with an Olympus Corporation mirrorless digital single-lens camera "OM-D E-M1 Mark II."
[0039] In addition, under the same conditions as those for photographing the polymer salcomine complex film, the image data was calibrated using a camera profile created by photographing "Colorchecker Passport" manufactured by X-rite. At this time, the calibration was performed using "Adobe Photoshop (registered trademark)" manufactured by Adobe. Then, color information in the CIE L*a*b* color system was obtained from the obtained image data, and the obtained color information was converted into the CIE XYZ color system. In this way, chromaticity points corresponding to the image data obtained by photographing and plotted on the CIE xy chromaticity diagram were obtained. Specifically, the reference point 1, the reference point 2, and the chromaticity points of x and y corresponding to each image data are as shown in FIG. 10.
[0040] Reference point 2 is a chromaticity point corresponding to the reference image data of the polymeric salcomine complex film in a state where oxygen is not bonded immediately after film formation. This reference image data was obtained by photographing the polymeric salcomine complex film in a nitrogen atmosphere. Reference point 1 is a chromaticity point corresponding to the inactivated image data of the polymeric salcomine complex film in a state where the oxygen binding ability is inactivated.
[0041] The deactivation image data was obtained by introducing pure water as the liquid to be analyzed into the quartz cell 13 in which the polymeric salcomine complex film was formed, bubbling 100% oxygen gas until the oxygen binding ability was deactivated, and then photographing the polymeric salcomine complex film. At this time, the pure water was introduced into the quartz cell 13 so that the entire polymeric salcomine complex film was immersed. The 100% oxygen gas was introduced at a position that did not contact the polymeric salcomine complex film. Note that the absorption band near the wavelength of 560 nm gradually decreased from about 15 minutes after the start of the measurement. Then, about 60 minutes after the start of the measurement, the spectrum converged and the polymeric salcomine complex film completely deactivated its oxygen binding ability.
[0042] The chromaticity points 3P0, 3P10, 3P20, 3P30, 3P40, and 3P50 are chromaticity points corresponding to image data of the polymer salcomine complex film in the degradation states of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. These image data were acquired by introducing pure water into the quartz cell 13 on which the polymer salcomine complex film was formed, bubbling a mixed gas consisting of 3% oxygen and 97% nitrogen until the oxygen bond equilibrium state was reached, and then photographing the polymer salcomine complex film. At this time, the pure water was introduced into the quartz cell 13 so that the entire polymer salcomine complex film was immersed. In addition, the mixed gas containing 3% oxygen was introduced at a position that did not contact the polymer salcomine complex film.
[0043] The chromaticity points 10P0, 10P10, 10P20, 10P30, 10P40, and 10P50 are chromaticity points corresponding to image data of the polymer salcomine complex film in the degradation states of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. These image data were acquired by introducing pure water into the quartz cell 13 in which the polymer salcomine complex film was formed, bubbling a mixed gas consisting of 10% oxygen and 90% nitrogen until the oxygen bond equilibrium state was reached, and then photographing the polymer salcomine complex film. At this time, the pure water was introduced into the quartz cell 13 so that the entire polymer salcomine complex film was immersed. In addition, the mixed gas containing 10% oxygen was introduced at a position that did not contact the polymer salcomine complex film.
[0044] The chromaticity points 100P0, 100P10, 100P20, 100P30, 100P40, and 100P50 are chromaticity points corresponding to image data of the polymer salcomine complex film in the deterioration degree state of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. These image data were acquired by introducing pure water into the quartz cell 13 in which the polymer salcomine complex film was formed, bubbling 100% oxygen gas until the oxygen bond equilibrium state was reached, and then photographing the polymer salcomine complex film. At this time, the pure water was introduced into the quartz cell 13 so that the entire polymer salcomine complex film was immersed. In addition, the 100% oxygen gas was introduced at a position that did not contact the polymer salcomine complex film.
[0045] Then, the oxygen angle D1 was calculated from the reference point 1 and the chromaticity point corresponding to each image data. As a result, it was discovered that the oxygen concentration of the gas can be estimated from the oxygen angle D1 as shown in FIG. 11. That is, the oxygen concentration of the gas can be estimated based on the oxygen angle D1 and the oxygen angle range, which is a predetermined range from the reference oxygen angle, which is the average value of the oxygen angles D1. The oxygen angle range is, for example, the maximum deviation or standard deviation, and the maximum deviation is used in FIG. 11. Specifically, when the oxygen angle D1 is included in the oxygen angle range of plus or minus 4.66 degrees from the reference oxygen angle of 89.36 degrees, the oxygen concentration of the gas is estimated to be 3%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere is estimated to be 22.8 Torr. Also, when the oxygen angle D1 is included in the oxygen angle range of plus or minus 4.72 degrees from the reference oxygen angle of 100.56 degrees, the oxygen concentration of the gas is estimated to be 10%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere is estimated to be 76 Torr.
[0046] Furthermore, the deterioration angle D2 was calculated from the reference point 2 and the chromaticity point corresponding to each image data. As a result, it was discovered that the deterioration degree of the polymer salcomine complex film can be estimated from the deterioration angle D2 as shown in FIG. 12. Specifically, when the oxygen concentration of the estimated gas is 3%, if the deterioration angle D2 is 55.51 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 0%. Similarly, when the oxygen concentration of the estimated gas is 3%, if the deterioration angle D2 is 52.81 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 10%. Also, when the oxygen concentration of the estimated gas is 10%, if the deterioration angle D2 is 53.35 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 0%. Similarly, when the oxygen concentration of the estimated gas is 10%, if the deterioration angle D2 is 53.18 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 10%.
[0047] In the first embodiment described above, the analysis unit 15 estimates the oxygen partial pressure of the liquid from the oxygen angle D1. Specifically, the analysis unit 15 calculates the oxygen angle D1 formed by a line connecting the reference point 1 and the reference point 2 in an xy chromaticity diagram of the XYZ color system, which is an example of a chromaticity diagram, and a line connecting the reference point 1 and a chromaticity point corresponding to the color of the oxygen-bonded complex film 11 detected by the detection unit 14. Here, the reference point 1 is a chromaticity point in the xy chromaticity diagram corresponding to the color of the oxygen-bonded complex film 11 in a state in which the oxygen-binding ability is inactivated. Furthermore, the reference point 2 is a chromaticity point in the xy chromaticity diagram corresponding to the color of the oxygen-bonded complex film 11 in a state in which oxygen is not bonded. Furthermore, the analysis unit 15 estimates the oxygen partial pressure of the liquid by referring to a table that associates the color of the oxygen-bonded complex film 11 with the oxygen partial pressure of the liquid. For example, the analysis unit 15 estimates the oxygen concentration of the gas from the oxygen angle D1 by referring to the table shown in FIG. 11 as a table.
[0048] The analysis unit 15 also estimates the degree of deterioration of the oxygen-bonded complex film 11 from the deterioration angle D2. Specifically, the analysis unit 15 calculates the deterioration angle D2 formed by a line connecting the reference point 1 and the reference point 2 in the xy chromaticity diagram and a line connecting the reference point 1 and the chromaticity point corresponding to the color of the oxygen-bonded complex film 11 detected by the detection unit 14. Here, the reference point 1 is a chromaticity point in the xy chromaticity diagram corresponding to the color of the oxygen-bonded complex film 11 in a state in which the oxygen-bonding ability is deactivated. The reference point 2 is a chromaticity point in the xy chromaticity diagram corresponding to the color of the oxygen-bonded complex film 11 in a state in which oxygen is not bonded. Furthermore, the analysis unit 15 refers to the table shown in FIG. 12 as a table to estimate the degree of deterioration of the oxygen-bonded complex film 11 from the deterioration angle D2.
[0049] According to the first embodiment described above, the oxygen partial pressure of the liquid to be analyzed can be measured using a relatively inexpensive spectrum analyzer or digital camera. That is, in the xy chromaticity diagram, the oxygen partial pressure can be estimated based on the reference point 1 corresponding to the deactivated image data of the oxygen-bound complex film 11 in a state where the oxygen-binding ability is deactivated, the reference point 2 corresponding to the reference image data of the oxygen-bound complex film 11 in a state where no oxygen is bound, and the chromaticity point corresponding to the image data of the oxygen-bound complex film 11 in contact with the liquid.
[0050] Furthermore, the degree of deterioration of the oxygen-bonded complex film 11 can be estimated based on the reference point 1, the reference point 2, and each chromaticity point. As a result, when the degree of deterioration reaches, for example, 50%, it is possible to take measures such as replacing the oxygen-bonded complex film 11.
[0051] [Second embodiment] The second embodiment will be described with reference to Figs. 13 to 18. Fig. 13 is an a*b* chromaticity diagram of the CIE L*a*b* color system. Fig. 14 is a schematic explanatory diagram in which a portion B surrounded by a dashed line in the a*b* chromaticity diagram of Fig. 13 is enlarged. Fig. 15 is a table showing each chromaticity point according to the second embodiment. Fig. 15 is a schematic explanatory diagram in which a portion B surrounded by a dashed line in the a*b* chromaticity diagram of Fig. 13 is enlarged and each chromaticity point according to the second embodiment is plotted. Fig. 16 is a table showing the relationship between the oxygen angle D3, which is an example of the third angle, and the oxygen concentration of the gas. Fig. 17 is a table showing the relationship between the deterioration angle D4, which is an example of the fourth angle, and the deterioration degree.
[0052] The second embodiment differs from the first embodiment in that filtering is performed. Furthermore, the analysis unit 15 uses an a*b* chromaticity diagram of the CIE L*a*b* color system (FIG. 13), which is an example of a chromaticity diagram, in order to analyze the changing color. In the explanation of the second embodiment, differences from the first embodiment will be explained, and components already explained will be given the same reference numbers and their explanation will be omitted. Except as otherwise explained, components given the same reference numbers perform substantially the same operations and functions, and have substantially the same effects.
[0053] In the second embodiment, a polymer ligand is synthesized by the same method as in the first embodiment (FIG. 2), and then a polymer salcomine complex film is formed by the same method as in the first embodiment (FIG. 3). Then, the polymer salcomine complex film is photographed and analyzed, and its ultraviolet-visible absorption spectrum is measured. Specifically, the polymer salcomine complex film is photographed at room temperature of 24° C. to 26° C. to obtain image data. At this time, the polymer salcomine complex film is irradiated with light from a D65 light source as the light source 16. The polymer salcomine complex film is photographed using an Olympus Corporation mirrorless digital single-lens camera "OM-D E-M1 Mark II" as the detection unit 14.
[0054] Thereafter, the analysis unit 15 filters a predetermined color from the image data obtained by photographing to obtain filtered image data. Then, the analysis unit 15 analyzes the chromaticity point corresponding to the color of the oxygen-bound complex film 11 based on the filtered image data. As an example, the analysis unit 15 filters a predetermined color (e.g., yellow) using the lens filter function of Adobe Photoshop (registered trademark) manufactured by Adobe. For this purpose, the analysis unit 15 applies a blue lens filter (e.g., #3E30C0) with an L* value of 30 to the image data. As a result, the polymer salcomine complex film is reddish purple in the image data of the oxygen-unbound state immediately after the film formation, but becomes black in the filtered image data of the oxygen-bound equilibrium state after the introduction of 100% oxygen gas. Also, the polymer salcomine complex film is black in the oxygen-bound equilibrium state after the introduction of 100% oxygen gas, but becomes blue-purple in the filtered image data of the state in which the oxygen-binding ability is deactivated. It is preferable that the color (color code) of the lens filter includes a complementary color of the oxygen-bound complex film 11 in the oxygen-unbound state immediately after the film formation.
[0055] From the filtered image data thus obtained, color information (lightness and chromaticity) of the CIE L*a*b* color system is obtained. Furthermore, the obtained color information is plotted on an a*b* chromaticity diagram (FIG. 13) obtained by cutting the CIE L*a*b* color space at a predetermined lightness (L* value 50 in the example of FIG. 13), and the a* chromaticity point and the b* chromaticity point on the a*b* chromaticity diagram are obtained. Specifically, the white point, which is reference point 3, which is an example of the third reference point, has an a* chromaticity point of 0 and a b* chromaticity point of 0. Furthermore, reference point 2 and the chromaticity points corresponding to each filtered image data are as shown in FIG. 15. And reference point 2, which is an example of the second reference point, is a chromaticity point corresponding to the reference image data of the polymeric salcomine complex film in a state in which oxygen is not bonded immediately after film formation. This reference image data is obtained by photographing the polymeric salcomine complex film under a nitrogen atmosphere.
[0056] In Fig. 14 and Fig. 15, chromaticity points 23P0, 23P10, 23P20, 23P30, 23P40, and 23P50 are chromaticity points corresponding to the filtered image data of the polymer salcomine complex film with degradation levels of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. The image data that is the source of these filtered image data is obtained by introducing pure water into the quartz cell 13 in which the polymer salcomine complex film is formed, bubbling a mixed gas consisting of 3% oxygen and 97% nitrogen until the oxygen bond equilibrium state is reached, and then photographing the polymer salcomine complex film. At this time, the pure water is introduced into the quartz cell 13 so that the entire polymer salcomine complex film is immersed. The mixed gas containing 3% oxygen is introduced at a position that does not contact the polymer salcomine complex film.
[0057] Moreover, the chromaticity points 20P0, 20P10, 20P20, 20P30, 20P40, and 20P50 are chromaticity points corresponding to the filtered image data of the polymer salcomine complex film with the degradation levels of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. The image data that is the source of these filtered image data is obtained by introducing pure water into the quartz cell 13 in which the polymer salcomine complex film is formed, bubbling a mixed gas consisting of 10% oxygen and 90% nitrogen until the oxygen bond equilibrium state is reached, and then photographing the polymer salcomine complex film. At this time, the pure water is introduced into the quartz cell 13 so that the entire polymer salcomine complex film is immersed. Moreover, the mixed gas containing 10% oxygen is introduced at a position that does not contact the polymer salcomine complex film.
[0058] Moreover, the chromaticity points 200P0, 200P10, 200P20, 200P30, 200P40, and 200P50 are chromaticity points corresponding to the filtered image data of the polymer salcomine complex film with the degradation levels of 0%, 10%, 20%, 30%, 40%, and 50%, respectively. The image data that is the source of these filtered image data is obtained by introducing pure water into the quartz cell 13 in which the polymer salcomine complex film is formed, bubbling 100% oxygen gas until the oxygen bond equilibrium state is reached, and then photographing the polymer salcomine complex film. At this time, the pure water is introduced into the quartz cell 13 so that the entire polymer salcomine complex film is immersed in the pure water. Moreover, the 100% oxygen gas is introduced at a position that does not contact the polymer salcomine complex film.
[0059] As a result, as shown in the a*b* chromaticity diagram of FIG. 14, the lines connecting the chromaticity points corresponding to the different deterioration levels for each oxygen concentration have similar slopes for different oxygen concentrations by filtering. That is, the lines connecting the chromaticity points corresponding to the deterioration levels of the polymeric salcomine complex film in contact with liquids of different oxygen partial pressures have similar slopes for different oxygen partial pressures. This is considered to be because the color of the polymeric salcomine complex film in a state where no oxygen is bonded immediately after film formation and the color of the polymeric salcomine complex film in a state where the oxygen binding ability is deactivated are yellow. That is, since filtering is performed using a lens filter of a blue system (for example, L* value 30), which is the complementary color of yellow, the change in brightness, which is the largest change among the three elements of color (hue, saturation, and brightness), is suppressed. As a result, it is considered that the change in brightness during deterioration of the polymeric salcomine complex film is suppressed in the filtered image data, and the color change on the a*b* chromaticity diagram is large. Furthermore, since the change in brightness is suppressed by filtering, the color change can be grasped on a two-dimensional chromaticity diagram.
[0060] In addition, as shown in the a*b* chromaticity diagram in Figure 14, the line connecting each chromaticity point corresponding to the different deterioration levels for each oxygen partial pressure converges roughly to the white point by filtering. This is thought to be because the lens filter color code #3E30C0 is closer to black (#000000) than to white (#FFFFFF). In other words, it is thought that the application of a lens filter with a color close to black caused excessive color mixing, making the color of the polymer salcomine complex film in the image data closer to black.
[0061] By utilizing this, an oxygen angle D3 shown in Fig. 16 is calculated from the reference point 3 and the chromaticity points corresponding to each filtered image data. The oxygen angle D3 is the angle formed by a line connecting the white point and the chromaticity points corresponding to each filtered image data, and a line connecting the white point and the reference point 2. In addition, a deterioration angle D4 shown in Fig. 16 is calculated from the reference point 2 and the chromaticity points corresponding to each filtered image data. The deterioration angle D4 is the angle formed by a line connecting the reference point 2 and the chromaticity points corresponding to each filtered image data, and a line connecting the reference point 2 and the white point. Alternatively, instead of the white point, an arbitrary point in the vicinity of the white point may be set as the reference point 3.
[0062] Then, as shown in FIG. 17, the oxygen partial pressure of the liquid can be estimated from the oxygen angle D3. That is, the oxygen partial pressure can be estimated based on the oxygen angle D3 and an oxygen angle range, which is a predetermined range from a reference oxygen angle, which is the average value of the oxygen angle D3. The oxygen angle range is, for example, a maximum deviation or a standard deviation, and the maximum deviation is used in FIG. 17. Specifically, when the oxygen angle D3 is within an oxygen angle range of plus or minus 1.18 degrees from the reference oxygen angle of 27.02 degrees, the oxygen concentration of the gas is estimated to be 3%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere is estimated to be 22.8 Torr. Also, when the oxygen angle D3 is within an oxygen angle range of plus or minus 2.31 degrees from the reference oxygen angle of 32.64 degrees, the oxygen concentration of the gas is estimated to be 10%, and the oxygen partial pressure of the liquid in an environment of 1 atmosphere is estimated to be 76 Torr.
[0063] Furthermore, as shown in FIG. 18, the deterioration degree of the polymer salcomine complex film can be estimated from the deterioration angle D4. That is, the deterioration degree can be estimated based on the deterioration angle D4 and a deterioration angle range that is a predetermined range from a reference deterioration angle that is an average value of the deterioration angle D4. The deterioration angle range is, for example, a maximum deviation and a standard deviation, and the maximum deviation is used in FIG. 18. Specifically, when the deterioration angle D4 is included in a deterioration angle range of plus or minus 0.98 degrees from the reference deterioration angle of 14.84 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 0%. Similarly, when the deterioration angle D4 is included in a deterioration angle range of plus or minus 0.97 degrees from the reference deterioration angle of 20.50 degrees, the deterioration degree of the polymer salcomine complex film is estimated to be 10%. Similarly, the deterioration degrees of 20%, 30%, 40%, and 50% can be estimated from the deterioration angle D4.
[0064] In the second embodiment described above, the analysis unit 15 estimates the oxygen partial pressure of the liquid from the oxygen angle D3. Specifically, the analysis unit 15 calculates the oxygen angle D3 formed by a line connecting the reference point 2 and the reference point 3 in the a*b* chromaticity diagram and a line connecting the chromaticity point corresponding to the color of the oxygen-bonded complex film 11 detected by the detection unit 14 and the reference point 3. Here, the reference point 2 is a chromaticity point corresponding to the color of the oxygen-bonded complex film 11 in a state in which oxygen is not bonded in the a*b* chromaticity diagram. Furthermore, the analysis unit 15 estimates the oxygen partial pressure of the liquid by referring to a table that associates the color of the oxygen-bonded complex film 11 with the oxygen partial pressure of the liquid. For example, the analysis unit 15 estimates the oxygen concentration of the gas from the oxygen angle D3 by referring to the table shown in FIG. 17 as a table.
[0065] The analysis unit 15 also estimates the degree of deterioration of the oxygen-bonded complex film 11 from the deterioration angle D4. Specifically, the analysis unit 15 calculates the deterioration angle D4 formed by a line connecting the reference point 2 and the reference point 3 in the a*b* chromaticity diagram and a line connecting the reference point 2 and the chromaticity point corresponding to the color of the oxygen-bonded complex film 11 detected by the detection unit 14. Here, the reference point 2 is a chromaticity point corresponding to the color of the oxygen-bonded complex film 11 in a state in which oxygen is not bonded in the a*b* chromaticity diagram. The reference point 3 is a chromaticity point at or near the white point in the a*b* chromaticity diagram. Furthermore, the analysis unit 15 refers to the table shown in FIG. 18 as a table to estimate the degree of deterioration of the oxygen-bonded complex film 11 from the deterioration angle D4.
[0066] According to the second embodiment described above, the oxygen partial pressure of the liquid to be analyzed can be measured using a relatively inexpensive spectrum analyzer or digital camera. That is, in the a*b* chromaticity diagram, the oxygen partial pressure can be estimated based on the reference point 3 corresponding to the white point, the reference point 2 corresponding to the filtered image based on the reference image data of the oxygen-bound complex film 11 in a non-oxygen-bound state, and the chromaticity point corresponding to the image data of the oxygen-bound complex film 11 in contact with the liquid.
[0067] Furthermore, the deterioration degree of the oxygen-bonded complex film 11 can be estimated based on the reference point 3 corresponding to the white point, the reference point 2, and each chromaticity point. As a result, when the deterioration degree reaches, for example, 50%, it is possible to take measures such as replacing the oxygen-bonded complex film 11.
[0068] The filtering may be performed by an optical filter that filters light corresponding to a predetermined color from the reflected light reflected by the oxygen-bonded complex film 11 or the transmitted light transmitted through the oxygen-bonded complex film 11. Specifically, an optical filter that filters out and removes yellow may be interposed between the light source 16 and the contact unit 12. Alternatively, an optical filter that filters out and removes yellow may be interposed between the contact unit 12 and the detection unit 14. As an example, the color code of the optical filter is #3E30C0. In this case, the detection unit 14 can directly obtain filtered image data. In addition, the color (color code) of the optical filter used for the image data is not limited to #3E30C0. For example, the color of the optical filter may be #704CBC (blue-purple), #000080, #0000FF (blue), #0080FF, #8000FF, or #FF00FF. Similarly, the color of a virtual lens filter used in filtering image data may be #704CBC (blue-purple), #000080, #0000FF (blue), #0080FF, #8000FF, or #FF00FF.
[0069] [Variations] In the modified example, methyl methacrylate or perfluorobutylethyl methacrylate is introduced into the ligand of the oxygen-bonded complex film 11. According to the oxygen-bonded complex film 11 of the modified example, the time required until the oxygen-bonded complex film 11 needs to be replaced (for example, the time required for the deterioration level of the oxygen-bonded complex film 11 to reach 50%) can be made longer.
[0070] Specifically, the oxygen-bonded complex film 11 may be a P(EHMA-MMA-VPy)-CoS film in which methyl methacrylate (MMA), which is inexpensive and highly soluble, is introduced into the ligand. In this case, for example, P(EHMA-MMA-VPy), which is a polymer ligand in which methyl methacrylate (MMA) is introduced into the ligand, is synthesized. This results in the synthesis of a polymer ligand in which EHMA-MMA:VPy=85:15 (mol%). Furthermore, in the synthesized polymer ligand P(EHMA-MMA-VPy), CoS is charged so that VPy:CoS=40:1 (molar ratio), and is dissolved in 1 mL of dichloromethane under a nitrogen atmosphere. Thereafter, a P(EHMA-MMA-VPy)-CoS film (film thickness: 100 μm) is formed in a quartz cell 13 by a solvent casting method.
[0071] Furthermore, in a modified example, the oxygen-bonded complex film 11 may be a P(EHMA-FBEMA-VPy)-Co(oF)S film. The P(EHMA-FBEMA-VPy)-Co(oF)S film has a salcomine complex Co(oF)S having a highly water-repellent fluorine moiety and perfluorobutylethylmethacrylate (FBEMA), a compound having a long fluorine-carbon moiety, introduced into the polymer ligand. However, by using a polymer salcomine complex film, it is possible to provide an oxygen-bonded complex film 11 that is less expensive and has low solubility.
[0072] Although the present invention has been described above with reference to each embodiment, the present invention is not limited to the above embodiment. The present invention also includes inventions that have been modified without going against the present invention, and inventions equivalent to the present invention. In addition, each embodiment and each modified form can be appropriately combined without going against the present invention.
[0073] For example, instead of a virtual lens filter or optical filter, the light source 16 may be configured not to emit light corresponding to a predetermined color. [Explanation of symbols]
[0074] 10: Analytical device, 11: Oxygen-binding complex membrane, 12: Contact section, 14: Detection section, 15: Analysis section
Claims
1. 1. An analytical apparatus for estimating oxygen partial pressure in a liquid, comprising: a contact portion for contacting the liquid with the oxygen-binding complex film; A detection unit for detecting the color of the oxygen-bound complex film; an analysis unit that analyzes a chromaticity point corresponding to the color of the oxygen-bound complex film in a chromaticity diagram to estimate the oxygen partial pressure of the liquid; the analysis unit calculates a first angle between a line connecting a first reference point and a second reference point on the chromaticity diagram and a line connecting a chromaticity point corresponding to the color of the oxygen-bonded complex film detected by the detection unit and the first reference point, and estimates the oxygen partial pressure of the liquid from the first angle; the first reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-binding complex film in a state in which the oxygen-binding ability is inactivated; The second reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-bound complex film in an oxygen-unbound state.
2. An analytical apparatus for estimating oxygen partial pressure in a liquid, comprising: a contact portion for contacting the liquid with the oxygen-binding complex film; A detection unit for detecting the color of the oxygen-bound complex film; an analysis unit that analyzes a chromaticity point corresponding to the color of the oxygen-bound complex film in a chromaticity diagram to estimate the oxygen partial pressure of the liquid; the analysis unit calculates a second angle between a line connecting the first reference point and the second reference point on the chromaticity diagram and a line connecting the first reference point and a chromaticity point corresponding to the color of the oxygen-bonded complex film detected by the detection unit, and estimates a deterioration degree of the oxygen-bonded complex film from the second angle; the first reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-binding complex film in a state in which the oxygen-binding ability is inactivated; The second reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-bound complex film in an oxygen-unbound state.
3. An analytical apparatus for estimating oxygen partial pressure in a liquid, comprising: a contact portion for contacting the liquid with the oxygen-binding complex film; A detection unit for detecting the color of the oxygen-bound complex film; an analysis unit that analyzes a chromaticity point corresponding to the color of the oxygen-bound complex film in a chromaticity diagram to estimate the oxygen partial pressure of the liquid; the analysis unit calculates a third angle formed by a line connecting the second reference point and the third reference point on the chromaticity diagram and a line connecting the third reference point and a chromaticity point corresponding to the color of the oxygen-bonded complex film detected by the detection unit, and estimates the oxygen partial pressure of the liquid from the third angle; the second reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-bound complex film in a state in which oxygen is not bound; The third reference point is a white point on the chromaticity diagram or a chromaticity point near the white point.
4. An analytical apparatus for estimating oxygen partial pressure in a liquid, comprising: a contact portion for contacting the liquid with the oxygen-binding complex film; A detection unit for detecting the color of the oxygen-bound complex film; an analysis unit that analyzes a chromaticity point corresponding to the color of the oxygen-bound complex film in a chromaticity diagram to estimate the oxygen partial pressure of the liquid; the analysis unit calculates a fourth angle between a line connecting the second reference point and the third reference point on the chromaticity diagram and a line connecting the second reference point and a chromaticity point corresponding to the color of the oxygen-bonded complex film detected by the detection unit, and estimates a deterioration degree of the oxygen-bonded complex film from the fourth angle; the second reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-bound complex film in a state in which oxygen is not bound; The third reference point is a white point on the chromaticity diagram or a chromaticity point near the white point.
5. 5. The analysis device according to claim 1, wherein the chromaticity diagram is an xy chromaticity diagram of an XYZ color system or an a*b* chromaticity diagram of an L*a*b* color system.
6. The analyzer according to claim 1 , wherein the analysis unit estimates the oxygen partial pressure of the liquid by referring to a table.
7. the detection unit photographs the oxygen-bound complex film to obtain image data in order to detect the color of the oxygen-bound complex film; 7. The analysis device according to claim 1, wherein the analysis unit obtains filtered image data by filtering a predetermined color from the image data, and analyzes a chromaticity point corresponding to a color of the oxygen-bound complex film based on the filtered image data.
8. The analytical device according to claim 1 , further comprising an optical filter that filters light corresponding to a predetermined color from the reflected light reflected by the oxygen-binding complex film or the transmitted light transmitted through the oxygen-binding complex film.
9. The analytical device according to claim 1 , wherein the oxygen-binding complex film is at least one of a salcomine complex film, an iron porphyrin complex film, a cobalt porphyrin complex film, and a copper complex film.
10. An analytical apparatus for estimating oxygen partial pressure in a liquid, comprising: a contact portion for contacting the liquid with the oxygen-binding complex film; A detection unit for detecting the color of the oxygen-bound complex film; an analysis unit that analyzes a chromaticity point corresponding to the color of the oxygen-bound complex film in a chromaticity diagram to estimate the oxygen partial pressure of the liquid; An analytical device, wherein methyl methacrylate or perfluorobutylethyl methacrylate is introduced into the ligand of the oxygen-binding complex film.
11. The analyzer according to claim 1 , wherein oxygen absorbed from blood as a liquid to be analyzed is dissolved in the liquid.
12. The analytical device according to claim 1 , wherein the contact portion further comprises an oxygen-permeable hydrophobic membrane disposed between the liquid and a liquid to be analyzed.
13. 1. An analytical method for estimating oxygen partial pressure in a liquid, comprising the steps of: contacting the liquid with the oxygen-binding complex film; detecting the color of the oxygen-binding complex film; calculating a first angle between a line connecting a first reference point and a second reference point on a chromaticity diagram and a line connecting a chromaticity point corresponding to the detected color of the oxygen-bonded complex film and the first reference point, and estimating the oxygen partial pressure of the liquid from the first angle; the first reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-binding complex film in a state in which the oxygen-binding ability is inactivated; The analysis method, wherein the second reference point is a chromaticity point on the chromaticity diagram that corresponds to the color of the oxygen-bound complex film in a state in which oxygen is not bound.
14. An analytical method for estimating oxygen partial pressure in a liquid, comprising the steps of: contacting the liquid with the oxygen-binding complex film; detecting the color of the oxygen-binding complex film; analyzing a color point on a color diagram that corresponds to the color of the oxygen-bound complex film to infer the oxygen partial pressure of the liquid; An analytical method, wherein methyl methacrylate or perfluorobutylethyl methacrylate is introduced into the ligand of the oxygen-binding complex film.
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