Measurement device and measurement method

The measurement device and method address the challenge of efficiently measuring radical concentrations and lifetimes by using a flow path with a radical generating unit and test light detection, achieving accurate and reproducible results across varying flow rates and conditions.

JP2025126437APending Publication Date: 2025-08-29YOKOGAWA ELECTRIC CORP
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Patent Information

Application Number
JP2024022622
Authority / Receiving Office
JP · JP
Patent Type
Applications
Current Assignee / Owner
Filing Date
2024-02-19
Publication Date
2025-08-29

AI Technical Summary

Technical Problem

Existing measurement technologies are limited in their ability to efficiently measure and analyze the concentration and lifetime of radicals in fluid streams, particularly in a way that allows for high reproducibility and flexibility in flow rates and reaction conditions.

Method used

A measurement device and method that includes a flow path with a radical generating unit to produce radicals from precursors, multiple measurement positions, and a system to measure radical concentration and lifetime using test light irradiation and detection, allowing for flexible flow rates and reaction conditions.

Benefits of technology

Enables accurate and reproducible measurement of radical concentrations and lifetimes, even with varying flow rates, and allows for simultaneous measurement of multiple substances, with a simple and cost-effective system configuration.

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Abstract

SOLUTION: The present invention provides a measurement device comprising a flow path having a main inlet and a main outlet, a pump for supplying a fluid containing radical precursors to the main inlet of the flow path, a radical generating unit for generating radicals from the radical precursors in a radical generating region of the flow path, and a measuring unit for measuring a measurement value corresponding to the concentration of the radicals in at least one measurement position on the flow path closer to the main outlet than the radical generating region, in which the radical generating unit may generate the radicals by applying at least one of voltage, heat, light, or an electron beam to the fluid containing the radical precursors.SELECTED DRAWING: Figure 1
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Description

[Technical Field]

[0001] The present invention relates to a measurement device and a measurement method. [Background technology]

[0002] Patent Document 1 describes "an apparatus for observing a transient absorption spectrum or its changes by irradiating a sample that has been photoexcited by irradiating it with pulsed light, irradiating it with probe light, and detecting changes in the intensity of the probe light with a streak camera" (Claim 1).

[0003] Patent Document 2 states, "The present invention is an apparatus for measuring transient absorption of a substance, comprising: an excitation light source that emits excitation light that excites the substance; a probe light source that emits probe light, which is stationary light, toward a sample containing the substance excited by the excitation light; a spectroscopic means that disperses the transmitted probe light that has passed through the sample and outputs it as output light; and a photodetector means that detects the output light, wherein the photodetector means comprises an avalanche photodiode (APD)" (paragraph 0010).

[0004] Patent Document 3 states, "An optical measurement device according to some embodiments includes a first irradiation unit that irradiates a first irradiation area on a movement path of a moving sample with excitation light; a second irradiation unit that irradiates a second irradiation area on the movement path that is closer to the movement direction of the sample than the first irradiation area with probe light; a detection unit that detects the probe light irradiated onto the sample by the second irradiation unit; and a control unit that calculates the optical parameters at the plurality of time points based on the detection intensities of the probe light that pass through the sample at each of the plurality of time points and are detected at different timings by the detection unit in a transient response of the optical parameters of the sample caused by excitation by the excitation light, and calculates physical parameters of the sample based on the calculated optical parameters." (paragraph 0007)

[0005] Patent Document 4 states, "FIG. 1 shows an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As shown, the gas sampling detection system 10 includes at least one plasma generator and / or radical gas generator 12 in fluid communication with at least one processing chamber 16 through at least one gas passage 14." (paragraph 0015) and "As shown in FIG. 1, at least one sampling module 32 can be in fluid communication with the radical gas generator 12 through at least one sampling conduit 30." (paragraph 0019). [Prior art document] [Patent documents] [Patent Document 1] Japanese Patent Publication No. 6-17866 [Patent Document 2] JP 2007-212145 A [Patent Document 3] Patent No. 7298746 [Patent Document 4] Special Publication No. 2021-517638 Summary of the Invention

[0006] In a first aspect of the present invention, there is provided a measurement device comprising: a flow path having a main inlet and a main outlet; a pump that supplies a fluid containing a radical precursor to the main inlet of the flow path; a radical generating unit that generates radicals from the radical precursor in a radical generating region of the flow path; and a measurement unit that measures a measurement value corresponding to the concentration of the radicals at at least one measurement position in the flow path closer to the main outlet than the radical generating region.

[0007] In the above-described measuring device, the radical generating section may generate the radicals by applying at least one of voltage, heat, light, and an electron beam to the fluid containing the radical precursor.

[0008] In any of the above measuring devices, the flow path may have a first sub-inlet, and the radical generating section may generate the radicals from the radical precursor by supplying an oxidant to the first sub-inlet.

[0009] In any of the above measurement devices, the flow path may have a second sub-inlet connected to the flow path between the radical-generating region and the at least one measurement position for introducing into the flow path another fluid that reacts with the radicals in the fluid.

[0010] In any of the above-mentioned measuring devices, the measuring unit may include an inspection light irradiating unit that irradiates inspection light onto the fluid at the at least one measurement position, and a detector that detects the inspection light that has passed through the fluid at the at least one measurement position of the flow path.

[0011] In any of the above measurement devices, the at least one measurement position may include a plurality of measurement positions, and the measurement unit may measure the measurement value for each elapsed time from generation of the radical corresponding to each of the plurality of measurement positions.

[0012] In any of the above-described measuring devices, the pump may change the flow rate of the fluid in the flow path, and the measuring unit may measure the measurement value at each elapsed time from the generation of the radicals corresponding to each of a plurality of different flow rates.

[0013] Any of the above measurement devices may further include a calculation unit that calculates the lifetime of the radical using the measurement values ​​at each elapsed time from the generation of the radical.

[0014] Any of the above measurement devices may include an excitation light irradiator that irradiates the fluid with excitation light between the radical-generating region and the at least one measurement position in the flow channel.

[0015] In a second aspect of the present invention, there is provided a measurement method comprising: supplying a fluid containing radical precursors to a main inlet of a flow path having a main inlet and a main outlet; generating radicals from the radical precursors in a radical generation region of the flow path; and measuring a measurement value corresponding to the concentration of the radicals at at least one measurement position in the flow path closer to the main outlet than the radical generation region.

[0016] The above summary of the invention does not list all of the features of the present invention, and subcombinations of these features may also be inventions. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows the configuration of a measurement device 10 according to this embodiment. [Figure 2] 1 shows a cross-sectional view of a first example of a flow channel 101. FIG. [Figure 3] 1 shows an operation flow in the measurement device 10 according to this embodiment. [Figure 4] 1 shows a cross-sectional view of a second example of a flow channel 101. FIG. [Figure 5] 10 shows a perspective view of a third example of a flow channel 101. FIG. [Figure 6] 10 shows a cross-sectional view of a fourth example of a flow channel 101. FIG. [Figure 7] 10 shows a perspective view of a fifth example of a flow channel 101. FIG. [Figure 8] 10 shows a cross-sectional view of a sixth example of a flow channel 101. FIG. [Figure 9] 22 illustrates an example computer 2200 in which aspects of the present invention may be embodied, in whole or in part. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the scope of the invention according to the claims. Furthermore, not all of the combinations of features described in the embodiments are necessarily essential to the solution of the invention.

[0019] FIG. 1 shows the configuration of a measurement device 10 according to this embodiment. The measurement device 10 generates radicals from radical precursors and measures the concentration of the generated radicals. Here, a radical precursor is a substance that can be converted into radicals through one or more reaction stages. The measurement device 10 includes a flow-through cell 100, a pump 120, a radical generating unit 132, a measurement unit 140, a measurement control unit 150, a calculation unit 160, a memory unit 170, and an output unit 180.

[0020] The flow cell 100 is a cell through which a fluid containing radical precursors and radicals flows. In this embodiment, the flow cell 100 has a plate-like structure. The flow cell 100 may be made of a light-transmitting material. The flow cell 100 has a flow path 101.

[0021] The flow channel 101 is a passage through which a fluid containing radical precursors and radicals flows. The flow channel 101 may have a constant cross-sectional area. The flow channel 101 may have a polygonal or circular cross-section. The flow channel 101 may have a rectangular or square cross-section. The flow channel 101 includes a main inlet 102, a main outlet 104, a radical generation region 106, and one or more measurement locations.

[0022] The main inlet 102 is an inlet through which a fluid containing radical precursors is supplied to the flow channel 101. The main outlet 104 is an outlet through which the fluid after measurement is discharged from the flow channel 101. The main outlet 104 may be connected to a discharge flow channel. Alternatively, the main outlet 104 may be connected to the main inlet 102. That is, the fluid discharged from the main outlet 104 may be repeatedly supplied from the main inlet 102. In this case, the measurement device 10 can repeatedly measure the radicals discharged from the main outlet 104. Note that in this specification, for convenience, the path in the flow channel 101 through which the fluid containing radical precursors is introduced, the radicals are measured, and the fluid after measurement is discharged is referred to as the "main path," and the inlet and outlet related to the main path are referred to as the "main inlet 102" and the "main outlet 104" for convenience of explanation. Therefore, the terms "main inlet" and "main outlet" do not limit the cross-sectional area of ​​the flow path or the confluence / division angle at the confluence / division section relative to the "secondary inlet" and "secondary outlet" described below.

[0023] The radical-generating region 106 is a region where radicals are generated from radical precursors in the flow channel 101. The radical-generating region 106 is located between the main inlet 102 and the main outlet 104 in the flow channel 101.

[0024] The measurement position is a position where a measurement value corresponding to the radical concentration in the flow channel 101 is measured. The measurement position is located on the main outlet 104 side of the radical-generating region 106 in the flow channel 101. In addition, the measurement position may be located on the main inlet 102 side of the radical-generating region 106 for baseline measurement.

[0025] The pump 120 is connected to the main inlet 102. The pump 120 supplies a fluid containing radical precursors to the main inlet 102 of the channel 101. The pump 120 may be a syringe pump or a diaphragm pump, which have relatively little pulsation. The pump 120 may have a damper between the pump 120 and the main inlet 102 to reduce pulsation of the pump 120.

[0026] The radical generating unit 132 generates radicals from radical precursors in the radical-generating region 106 of the flow channel 101. The radical generating unit 132 may generate radicals by applying at least one of a voltage, heat, light, and an electron beam to a fluid containing the radical precursors. In this embodiment, the radical generating unit 132 generates radicals by applying a voltage to the radical-generating region 106 of the flow channel 101.

[0027] Alternatively, the radical generating unit 132 may generate radicals by applying heat to the fluid containing the radical precursor using at least one of a microheater, an electric heating wire, an induction heater, microwave heating, and a laser.The radical generating unit 132 may generate radicals by supplying an oxidizing agent to the fluid containing the radical precursor.

[0028] When the radical generating unit 132 applies a voltage, the measuring device 10 includes a current / voltage supply unit 134. The current / voltage supply unit 134 is connected to the radical generating unit 132. The current / voltage supply unit 134 supplies at least one of a current and a voltage to the radical generating unit 132, thereby controlling the voltage that the radical generating unit 132 applies to the fluid containing the radical precursors. The current / voltage supply unit 134 may be at least one of a potentiostat or a galvanostat.

[0029] The measurement unit 140 measures measurement values ​​corresponding to the radical concentration at one or more measurement positions. Here, the one or more measurement positions may be determined regularly or irregularly along the direction in which the fluid flows in the flow path 101. When multiple measurement positions are present, the measurement unit 140 measures measurement values ​​at each of the multiple measurement positions at each elapsed time from the generation of radicals. The measurement unit 140 may measure measurement values ​​including the test light intensity. The measurement unit 140 has a test light irradiation unit 142, a light flux adjustment unit 144, and one or more detectors 146.

[0030] The test light irradiator 142 includes any light source such as a semiconductor laser. The test light irradiator 142 irradiates the fluid with test light at one or more measurement positions. The test light irradiator 142 irradiates test light containing light of a wavelength absorbed by the radical to be measured. The test light irradiator 142 may irradiate test light containing light of one or more wavelengths. When the test light irradiator 142 irradiates test light containing multiple wavelengths, the measurement device 10 can simultaneously measure multiple substances.

[0031] The beam adjusting unit 144 is disposed on the optical path of the inspection light. The beam adjusting unit 144 is disposed between the measurement position and the inspection light irradiating unit 142. The beam adjusting unit 144 adjusts the diameter of the inspection light so that the inspection light is irradiated onto the measurement position. When the flow path 101 has multiple measurement positions, the beam adjusting unit 144 may adjust the diameter of the inspection light so that all of the multiple measurement positions are uniformly irradiated.

[0032] The detector 146 is disposed on the optical path of the test light. The detector 146 is disposed on the opposite side of the test light irradiation unit 142 with respect to the measurement position. When multiple detectors 146 are present, the multiple detectors 146 may be arranged in a row along the direction in which the fluid flows in the flow path 101. The detector 146 detects the test light that has transmitted through the fluid at at least one measurement position in the flow path 101. The detector 146 measures the light intensity of the detected test light (test light intensity). Since the test light includes light of a wavelength that is absorbed by radicals, the test light intensity decreases when the concentration of radicals in the fluid is high, and the test light intensity increases when the concentration of radicals in the fluid decreases.

[0033] The measurement control unit 150 is connected to the pump 120, the current / voltage supply unit 134, and the calculation unit 160. The measurement control unit 150 controls the operations of the pump 120 and the current / voltage supply unit 134.

[0034] The calculation unit 160 is connected to the detector 146 and the storage unit 170. The calculation unit 160 calculates the lifetime of the radicals using the measurement values ​​at each elapsed time since the generation of the radicals. The calculation unit 160 receives the measurement values ​​at the corresponding measurement positions from the detector 146. The calculation unit 160 may receive the inspection light intensity at the corresponding measurement positions from the detector 146. The calculation unit 160 receives information about the flow rate of the flow channel 101 from the measurement control unit 150. The calculation unit 160 writes measurement data including at least one of the measurement values ​​received from the detector 146, information about the flow rate received from the measurement control unit 150, or information obtained by processing this information by the measurement control unit 150, into the storage unit 170.

[0035] The measurement data is stored in the storage unit 170. The storage unit 170 may be an electronic storage medium, a magnetic storage medium, an optical storage medium, an electromagnetic storage medium, or a semiconductor storage medium.

[0036] The output unit 180 is connected to the calculation unit 160. The output unit 180 outputs the radical lifetime calculated by the calculation unit 160. At least one of the measurement control unit 150, calculation unit 160, storage unit 170, and output unit 180 may be a computer such as a personal computer (PC), tablet computer, smartphone, workstation, server computer, or general-purpose computer, or may be a computer system in which multiple computers are connected. Such a computer system is also considered a computer in a broad sense. Furthermore, at least one of the measurement control unit 150, calculation unit 160, storage unit 170, and output unit 180 may be implemented by one or more virtual computer environments executable within a computer. Alternatively, at least one of the measurement control unit 150, calculation unit 160, storage unit 170, and output unit 180 may be a dedicated computer designed for measuring radical concentrations, or may be dedicated hardware realized by dedicated circuits.

[0037] FIG. 2 shows a cross-sectional view of a first example of the flow channel 101. In this example, a radical generating unit 132 having a pair of a first electrode 200 and a second electrode 202 is disposed in the radical-generating region 106 of the flow channel 101. The first electrode 200 is disposed on the inner wall surface of the flow channel 101, and the second electrode 202 is disposed on the inner wall surface of the flow channel 101 facing the first electrode 200. The pair of the first electrode 200 and the second electrode 202 is connected to a current / voltage supply unit 134 and receives at least one of a current and a voltage from the current / voltage supply unit 134. The first electrode 200 and the second electrode 202 have opposite polarities, with one serving as an anode and the other as a cathode. The radical generating unit 132 may apply a voltage to the radical precursors to accelerate them and cause them to collide with each other, resulting in ionization, thereby generating radicals.

[0038] 3 shows an operation flow of the measurement device 10 according to this embodiment. In S302 (step 302), the measurement control unit 150 turns on the pump 120 to start the operation of the pump 120. As a result, the pump 120 continuously supplies a fluid containing radical precursors to the flow channel 101. The pump 120 may supply a fluid containing radical precursors at a predetermined ratio to the flow channel 101.

[0039] In S304, the test light irradiation unit 142 irradiates test light onto one or more measurement positions in the flow path 101. The measurement control unit 150 controls the current / voltage supply unit 134 not to supply current and voltage to the radical generating unit 132. In this case, no voltage is applied to the radical generating region 106, and therefore the fluid at the measurement positions does not contain radicals. In S306, one or more detectors 146 detect the intensity of the test light that has passed through the fluid at each of the one or more measurement positions. The calculation unit 160 writes the test light intensities detected by the one or more detectors 146 into the memory unit 170 as a baseline.

[0040] In S308, the measurement control unit 150 instructs the current / voltage supply unit 134 to supply a current or a voltage to the radical generating unit 132, thereby applying a voltage to the fluid in the radical generating region 106. This causes the radical generating unit 132 to generate radicals from radical precursors contained in the fluid.

[0041] In S310, the test light irradiator 142 irradiates the flow path 101 with test light. One or more detectors 146 detect the intensity of the test light that has passed through the fluid at the corresponding measurement positions. The calculator 160 receives the intensity of the test light detected by each detector 146 from the one or more detectors 146.

[0042] The calculation unit 160 acquires position information of each measurement position, the test light intensity at each measurement position, and the flow rate of the fluid in the flow channel 101. Here, the calculation unit 160 may store the position information of each measurement position in advance, or may read the position information of each measurement position from the storage unit 170. The position information may be the distance from the end of the radical-generating region 106 on the main outlet 104 side to the measurement position.

[0043] The calculation section 160 receives information about the flow rate of the fluid from the measurement control section 150. The flow rate may indicate the volume of the fluid flowing per unit time.

[0044] The calculation unit 160 calculates the elapsed time from when the radicals are generated until when the fluid reaches each measurement position from the radical-generating region 106, that is, the elapsed time from when the radicals are generated until when the measurement is performed, based on the distance from the radical-generating region 106 to each measurement position and the flow rate. For example, if the flow rate indicates the volume of fluid flowing per unit time, the calculation unit 160 may calculate the elapsed time by calculating (cross-sectional area of ​​the flow path 101) × (distance from the radical-generating region 106 to the measurement position) / (flow rate of the fluid). The calculation unit 160 stores measurement data including the inspection light intensity, the flow rate of the fluid, and the elapsed time at one or more measurement positions in the storage unit 170.

[0045] In S312, the measurement control unit 150 determines whether or not measurement has been completed for all flow rates at which the test light intensity should be measured. If the measurement control unit 150 determines that measurement has not been completed for all flow rates (No in S312), the measurement device 10 proceeds to S314. In S314, the measurement control unit 150 controls the pump 120. The pump 120 changes the flow rate of the fluid in the flow path 101 to set the flow rate of the fluid to a value corresponding to the flow rate to be measured next.

[0046] In S310, which returns from S314, the test light irradiation unit 142 irradiates the flow path 101 through which the fluid whose flow rate has changed flows with test light. One or more detectors 146 detect the intensity of the test light that has passed through the fluid at the corresponding measurement positions. The calculation unit 160 receives the intensity of the test light detected by each detector 146 from the one or more detectors 146. The calculation unit 160 receives information about the changed flow rate of the fluid from the measurement control unit 150 and calculates the elapsed time at one or more measurement positions. The calculation unit 160 stores measurement data in the memory unit 170, including the test light intensity, the fluid flow rate, and the elapsed time at one or more measurement positions.

[0047] If the measurement control unit 150 determines that measurements have been completed for all flow rates (Yes in S312), the measurement device 10 proceeds to S316. In this case, the measurement unit 140 has measured the measurement values ​​for each elapsed time from the generation of radicals corresponding to each of a plurality of different flow rates. In S316, the calculation unit 160 calculates the optical density from the test light intensity stored in the memory unit 170. The calculation unit 160 obtains a two-dimensional plot of the calculated optical density versus elapsed time.

[0048] In S318, the calculation unit 160 calculates the radical lifetime based on the two-dimensional plot obtained in S316. The calculation unit 160 may calculate a time constant, which is the radical lifetime, by fitting an optimal function representing the two-dimensional plot to the two-dimensional plot obtained in S316. The optimal function may be an exponential function. When an exponential function is fitted to the two-dimensional plot, the time constant may be calculated based on the obtained exponential function. For example, when an exponential function expressed by x = x0exp(-t / τ) (x0 is an arbitrary constant) with respect to time t is obtained by fitting, the radical time constant is τ. Alternatively, the calculation unit 160 may calculate the radical half-life as the radical lifetime. In S320, the output unit 180 outputs the radical lifetime calculated by the calculation unit 160.

[0049] The measuring device 10 described above calculates the lifetime of radicals based on the test light intensity at different elapsed times, allowing for lifetime measurement of radicals with long lifetimes in a short time. Furthermore, the measuring device 10 described above has a simple system configuration, allowing for highly reproducible experiments. Furthermore, the measuring device 10 described above allows for the flow rate of the fluid to be changed, so that even if only one measurement position and one corresponding detector 146 are provided, radicals with different elapsed times can be measured by changing the flow rate. In this case, the measuring device 10 has only one detector 146, resulting in an inexpensive configuration.

[0050] FIG. 4 shows a cross-sectional view of a second example of the flow channel 101. In this example, multiple pairs of first electrodes 200 and second electrodes 202 are arranged in the radical-generating region 106 of the flow channel 101 along the direction of fluid flow in the flow channel 101. The first electrodes 200 and second electrodes 202 of each pair may be arranged and configured similarly to the first electrodes 200 and second electrodes 202 of FIG. 2. The first electrodes 200 and second electrodes 202 are each connected to a current / voltage supply unit 134, and each pair receives at least one of a current and a voltage from the current / voltage supply unit 134. The measuring device 10 including the flow channel 101 of this figure can control the amount of radical generation by changing the number of pairs of first electrodes 200 and second electrodes 202 to which the current / voltage supply unit 134 supplies at least one of a current and a voltage.

[0051] FIG. 5 shows a perspective view of a third example of the flow channel 101. In this example, the measurement device 10 further includes an excitation light irradiation unit 500, and includes one or more detectors 510 instead of the one or more detectors 146. The excitation light irradiation unit 500 irradiates the fluid with excitation light between the radical-generating region 106, in which the first electrode 200 and the second electrode 202 are disposed, and one or more measurement positions in the flow channel 101. The excitation light irradiation unit 500 may irradiate ultraviolet light as the excitation light. A substance (measurement substance) irradiated with the excitation light becomes excited and emits light in the process of returning to the ground state. The measurement substance may be a radical contained in the fluid, or may be a substance other than a radical that has interacted with a radical contained in the fluid.

[0052] The detector 510 is connected to the calculation unit 160. The detector 510 detects luminescence from the analyte. The detector 510 may be provided at a location other than on the optical path of the excitation light so as not to detect the excitation light. Alternatively, a filter capable of separating the excitation light and the luminescence may be provided between the detector 510 and the measurement position in the flow channel 101 so as not to detect the excitation light. In this case, the detector 510 may be provided on the optical path of the excitation light. When multiple detectors 510 are present, the multiple detectors 510 may be arranged in a line along the direction in which the fluid flows in the flow channel 101. In the example shown in this figure, the detector 510 detects luminescence perpendicular to the optical path of the excitation light.

[0053] The calculation unit 160 receives the luminescence intensity detected by each detector 510 from one or more detectors 510. The calculation unit 160 receives position information of each measurement position from the storage unit 170. The position information of each measurement position may be the distance from the position where the excitation light is irradiated in the flow channel 101 by the excitation light irradiation unit 500 to each measurement position. The calculation unit 160 calculates the elapsed time based on the position information of each measurement position and information about the flow rate of the fluid. The calculation unit 160 may calculate the elapsed time using a method similar to S310 in FIG. 3. The measurement control unit 150 may perform processing similar to S312 in FIG. 3. The calculation unit 160 obtains a two-dimensional plot of the luminescence intensity versus the elapsed time. The calculation unit 160 calculates the lifetime of the excited state of the analyte based on the two-dimensional plot of the luminescence intensity versus the elapsed time. The calculation unit 160 may calculate the lifetime of the excited state of the analyte using a method similar to S318 in FIG. 3. According to the measuring device 10 having the flow channel 101 described above, it is possible to measure the lifetime of the excited state of the analyte based on a change in the luminescence from the analyte.

[0054] FIG. 6 shows a cross-sectional view of a fourth example of the flow channel 101. In this example, the flow channel 101 has a bent shape. The measurement device 10 also includes a microheater 600 instead of the radical generating unit 132 and the current / voltage supply unit 134 shown in FIG. 1. The microheater 600 is connected to and controlled by the measurement control unit 150. The microheater 600 generates radicals by applying heat to a fluid containing radical precursors present in the radical-generating region 106 of the flow channel 101. By setting the angle θ between the inflow and outflow directions of the fluid at the bent portion of the flow channel 101 close to 180°, the pressure loss caused by the fluid colliding with the wall surface of the flow channel 101 can be reduced.

[0055] 7 shows a perspective view of a fifth example of the flow path 101. In the example shown in this figure, the flow path 101 is formed in a Y-shape and has a main inlet 102 and a first sub-inlet 700. The radical generating unit 132 generates radicals from radical precursors by supplying an oxidant to the first sub-inlet 700. The radical generating unit 132 may supply the oxidant to the first sub-inlet 700 and mix the oxidant with the fluid containing the radical precursors supplied from the main inlet 102 in the radical-generating region 106 to oxidize the radical precursors. The radical generating unit 132 may supply hydrogen peroxide or hydrogen peroxide bromide as the oxidant.

[0056] 8 shows a cross-sectional view of a sixth example of the flow channel 101. In the example shown in this figure, the flow channel 101 has a second sub-inlet 800 between the radical-generation region 106 and one or more measurement positions. The second sub-inlet 800 can introduce another fluid that reacts with the radicals in the fluid into the flow channel 101. The second sub-inlet 800 may introduce a fluid containing a substance that reacts with the radicals in the fluid into the flow channel 101 as the other fluid that reacts with the radicals in the fluid.

[0057] The measuring device 10 equipped with the flow path 101 shown in this figure obtains a two-dimensional plot of optical density versus elapsed time by the method shown in S310 to S316 in Fig. 3. Here, the position information for each measurement position may be the distance from the connection position between the flow path 101 and the second sub-inlet 800 to each measurement position. According to the measuring device 10 equipped with the flow path 101 shown above, radicals generated in the radical-generating region 106 can be reacted with another fluid introduced from the second sub-inlet 800, and the concentration of radicals can be measured for each elapsed time from the start of the reaction, thereby enabling analysis of reactions using radicals.

[0058] Various embodiments of the present invention may be described with reference to flowcharts and block diagrams, where the blocks may represent (1) stages of a process in which operations are performed or (2) sections of an apparatus responsible for performing the operations. Particular stages and sections may be implemented by dedicated circuitry, programmable circuitry provided with computer-readable instructions stored on a computer-readable medium, and / or a processor provided with computer-readable instructions stored on a computer-readable medium. Dedicated circuitry may include digital and / or analog hardware circuitry, and may include integrated circuits (ICs) and / or discrete circuits. Programmable circuitry may include reconfigurable hardware circuitry, including logical AND, OR, XOR, NAND, NOR, and other logical operations, flip-flops, registers, memory elements such as field programmable gate arrays (FPGAs), programmable logic arrays (PLAs), and the like.

[0059] A computer-readable medium may include any tangible device capable of storing instructions that are executed by an appropriate device, such that the computer-readable medium having instructions stored thereon comprises an article of manufacture containing instructions that can be executed to create means for performing the operations specified in the flowcharts or block diagrams. Examples of computer-readable media may include electronic, magnetic, optical, electromagnetic, and semiconductor storage media. More specific examples of computer-readable media may include floppy disks, diskettes, hard disks, random access memory (RAM), read-only memory (ROM), erasable programmable read-only memory (EPROM or flash memory), electrically erasable programmable read-only memory (EEPROM), static random access memory (SRAM), compact disc read-only memory (CD-ROM), digital versatile disc (DVD), Blu-ray disc, memory stick, integrated circuit card, and the like.

[0060] The computer readable instructions may include either assembler instructions, Instruction Set Architecture (ISA) instructions, machine instructions, machine-dependent instructions, microcode, firmware instructions, state-setting data, or source or object code written in any combination of one or more programming languages, including object-oriented programming languages ​​such as Smalltalk®, JAVA®, C++, etc., and conventional procedural programming languages ​​such as the “C” programming language or similar programming languages.

[0061] The computer-readable instructions may be provided to a processor or programmable circuitry of a programmable data processing apparatus, such as a general-purpose computer, special-purpose computer, or other computer, either locally or over a wide-area network (WAN) such as a local area network (LAN), the Internet, etc., which executes the computer-readable instructions to create means for performing the operations specified in the flowcharts or block diagrams. Examples of processors include computer processors, processing units, microprocessors, digital signal processors, controllers, microcontrollers, etc.

[0062] 9 illustrates an example of a computer 2200 in which aspects of the present invention may be embodied, in whole or in part. Programs installed on the computer 2200 may cause the computer 2200 to function as or perform operations associated with an apparatus or one or more sections of the apparatus according to embodiments of the present invention, and / or to perform a process or steps of a process according to embodiments of the present invention. Such programs may be executed by the CPU 2212 to cause the computer 2200 to perform specific operations associated with some or all of the blocks of the flowcharts and block diagrams described herein.

[0063] A computer 2200 according to this embodiment includes a CPU 2212, a RAM 2214, a graphics controller 2216, and a display device 2218, which are interconnected by a host controller 2210. The computer 2200 also includes input / output units such as a communication interface 2222, a hard disk drive 2224, a DVD-ROM drive 2226, and an IC card drive, which are connected to the host controller 2210 via an input / output controller 2220. The computer also includes legacy input / output units such as a ROM 2230 and a keyboard 2242, which are connected to the input / output controller 2220 via an input / output chip 2240.

[0064] The CPU 2212 operates according to programs stored in the ROM 2230 and RAM 2214, thereby controlling each unit. The graphics controller 2216 acquires image data generated by the CPU 2212 into a frame buffer or the like provided in the RAM 2214 or into the graphics controller 2216 itself, and causes the image data to be displayed on the display device 2218.

[0065] The communications interface 2222 communicates with other electronic devices via a network. The hard disk drive 2224 stores programs and data used by the CPU 2212 in the computer 2200. The DVD-ROM drive 2226 reads programs or data from the DVD-ROM 2201 and provides the programs or data to the hard disk drive 2224 via the RAM 2214. The IC card drive reads programs and data from an IC card and / or writes programs and data to an IC card.

[0066] The ROM 2230 stores therein a boot program or the like that is executed by the computer 2200 upon activation, and / or programs that depend on the hardware of the computer 2200. The input / output chip 2240 may also connect various input / output units to the input / output controller 2220 via a parallel port, a serial port, a keyboard port, a mouse port, etc.

[0067] The programs are provided by a computer-readable medium such as a DVD-ROM 2201 or an IC card. The programs are read from the computer-readable medium, installed in the hard disk drive 2224, RAM 2214, or ROM 2230, which are also examples of computer-readable media, and executed by the CPU 2212. Information processing described in these programs is read by the computer 2200, and brings about cooperation between the programs and the various types of hardware resources described above. An apparatus or method may be configured by realizing information manipulation or processing in accordance with the use of the computer 2200.

[0068] For example, when communication is performed between the computer 2200 and an external device, the CPU 2212 may execute a communication program loaded into the RAM 2214 and instruct the communication interface 2222 to perform communication processing based on the processing described in the communication program. Under the control of the CPU 2212, the communication interface 2222 reads transmission data stored in a transmission buffer processing area provided in the RAM 2214, the hard disk drive 2224, the DVD-ROM 2201, or a recording medium such as an IC card, and transmits the read transmission data to the network, or writes reception data received from the network to a reception buffer processing area or the like provided on the recording medium.

[0069] The CPU 2212 may also cause all or a necessary portion of a file or database stored on an external recording medium such as the hard disk drive 2224, the DVD-ROM drive 2226 (DVD-ROM 2201), an IC card, etc. to be read into the RAM 2214, and perform various types of processing on the data on the RAM 2214. The CPU 2212 then writes back the processed data to the external recording medium.

[0070] Various types of information, such as various types of programs, data, tables, and databases, may be stored on the recording medium and may undergo information processing. The CPU 2212 may perform various types of processing on data read from the RAM 2214, including various types of operations, information processing, conditional judgment, conditional branching, unconditional branching, information search / replacement, etc., as described throughout this disclosure and specified by the instruction sequences of the programs, and write the results back to the RAM 2214. The CPU 2212 may also search for information in a file, database, etc. on the recording medium. For example, if multiple entries each having an attribute value of a first attribute associated with an attribute value of a second attribute are stored on the recording medium, the CPU 2212 may search for an entry that matches a condition specified by the attribute value of the first attribute from among the multiple entries, read the attribute value of the second attribute stored in the entry, and thereby obtain the attribute value of the second attribute associated with the first attribute that satisfies a predetermined condition.

[0071] The above-described programs or software modules may be stored in a computer-readable medium on or near the computer 2200. A recording medium such as a hard disk or RAM provided in a server system connected to a dedicated communication network or the Internet can also be used as a computer-readable medium, thereby providing the programs to the computer 2200 via the network.

[0072] Although the present invention has been described above using embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications and improvements can be made to the above embodiments. It is clear from the claims that such modifications and improvements can also be included within the technical scope of the present invention.

[0073] It should be noted that the execution order of each process, such as operations, procedures, steps, and stages, in the devices, systems, programs, and methods shown in the claims, specifications, and drawings is not specifically stated as "before," "prior to," etc., and that the processes can be performed in any order unless the output of a previous process is used in a subsequent process. Even if the operational flow in the claims, specifications, and drawings is described using "first," "next," etc. for convenience, this does not mean that the processes must be performed in this order. [Explanation of symbols]

[0074] 10. Measuring equipment 100 Flow Cell 101 Flow path 102 Main Inlet 104 Main Outlet 106 Radical generation region 120 Pump 132 Radical generation unit 134 Current / Voltage Supply Unit 140 Measuring section 142 Inspection light irradiation unit 144 Luminous flux adjustment section 146 detector 150 Measurement control section 160 Calculation Unit 170 Storage section 180 Output section 200 1st electrode 202 2nd electrode 500 Excitation light irradiation unit 510 detector 600 Microheater 700 1st Sub-inlet 800 Secondary Inlet 2200 Computer 2201 DVD-ROM 2210 host controller 2212 CPU 2214 RAM 2216 Graphics Controller 2218 Display Device 2220 Input / Output Controller 2222 communication interface 2224 hard disk drive 2226 DVD-ROM drive 2230 ROM 2240 I / O chip 2242 keyboard

Claims

1. a flow path having a main inlet and a main outlet; a pump for supplying a fluid containing a radical precursor to the main inlet of the flow path; a radical generating section that generates radicals from the radical precursor in a radical generating region of the flow channel; a measurement unit that measures a measurement value corresponding to the concentration of the radicals at at least one measurement position on the main outlet side of the radical-generating region in the flow path; A measuring device comprising:

2. The measuring device according to claim 1 , wherein the radical generating section generates the radicals by applying at least one of a voltage, heat, light, and an electron beam to the fluid containing the radical precursors.

3. the flow path has a first secondary inlet; The radical generating unit generates the radicals from the radical precursor by supplying an oxidant to the first sub-inlet. The measuring device according to claim 1 .

4. 2. The measurement device according to claim 1, wherein the flow path has a second sub-inlet connected to the flow path between the radical-generating region and the at least one measurement position for introducing into the flow path another fluid that reacts with the radicals in the fluid.

5. The measurement unit an inspection light irradiator that irradiates inspection light onto the fluid at the at least one measurement position; a detector for detecting the interrogation light transmitted through the fluid at the at least one measurement location in the flow path; 2. The measuring device of claim 1, further comprising:

6. the at least one measurement location includes a plurality of measurement locations; The measurement unit measures the measurement value at each elapsed time from the generation of the radicals at each of the plurality of measurement positions. The measuring device according to claim 1 .

7. The pump changes the flow rate of the fluid in the flow path, The measurement unit measures the measurement value for each elapsed time from the generation of the radicals corresponding to each of a plurality of flow rates different from one another. The measuring device according to claim 1 .

8. The measuring device according to claim 6 or 7, further comprising a calculation unit that calculates a lifetime of the radical using the measured value for each elapsed time from the generation of the radical.

9. The measuring device according to claim 1 , further comprising an excitation light irradiator that irradiates the fluid with excitation light between the radical-generating region and the at least one measurement position in the flow channel.

10. supplying a fluid containing a radical precursor to a main inlet of a flow path having a main inlet and a main outlet; generating radicals from the radical precursor in a radical generation region of the flow channel; measuring a measurement value corresponding to the concentration of the radicals at at least one measurement position on the main outlet side of the radical-generating region in the flow path; A measurement method comprising: