Attenuated total reflection spectroscopy device and attenuated total reflection spectroscopy method

Abstract

This ATR device is equipped with: a prism having a reflecting surface; a holding part that holds a sample containing a suspension on the reflecting surface; and an adjusting part that adjusts the flow state of the sample held on the reflecting surface. The adjusting part adjusts the flow state of the sample to a first flow state in order to acquire a first detection result relating to the sample in the first flow state, and adjusts the flow state of the sample to a second flow state in order to acquire a second detection result relating to the sample in the second flow state.

Description

[Technical Field]

[0001] The present disclosure relates to an attenuated total reflection spectroscopy apparatus and an attenuated total reflection spectroscopy method. [Background technology]

[0002] Patent Document 1 describes a drug evaluation device that evaluates a drug suspended in an evaluation liquid as an attenuated total reflection spectroscopy device. The attenuated total reflection spectroscopy device described in Patent Document 1 determines information about the sample, such as the presence or absence of crystalline particles suspended in the evaluation liquid, the presence or absence of amorphous particles suspended in the evaluation liquid, or the proportion of crystalline particles suspended in the evaluation liquid. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 5848621 Summary of the Invention [Problem to be solved by the invention]

[0004] In the above-described attenuated total reflection spectroscopy apparatus, in addition to obtaining the above-described information about the sample, there are cases where it is required to obtain more detailed information about the sample. However, obtaining detailed information about the sample requires, for example, obtaining information about each of the samples that have been prepared separately, which can make the work complicated.

[0005] Therefore, an object of the present disclosure is to provide an attenuated total reflection spectroscopy apparatus and an attenuated total reflection spectroscopy method that make it possible to easily obtain detailed information about a sample. [Means for solving the problem]

[0006] An attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure includes an optical element having a reflective surface, a holding unit that holds a sample containing a suspension on the reflective surface, and an adjusting unit that adjusts the flow state of the sample held on the reflective surface. The adjusting unit adjusts the flow state of the sample to a first flow state in order to obtain a first detection result for the sample in the first flow state, and adjusts the flow state of the sample to a second flow state in order to obtain a second detection result for the sample in the second flow state.

[0007] In this attenuated total reflection spectroscopy apparatus, a sample containing a suspension is held on the reflecting surface of an optical element. The adjustment unit adjusts the flow state of the sample to a first flow state to obtain a first detection result for the sample in a first flow state, and adjusts the flow state of the sample to a second flow state to obtain a second detection result for the sample in a second flow state. As a result, for example, by relatively strengthening the first flow state, the amount of suspended matter in the sample near the reflecting surface can be relatively reduced, and a detection result for a sample with a relatively low suspended matter content can be obtained as the first detection result. Furthermore, for example, by relatively weakening the second flow state, the amount of suspended matter in the sample near the reflecting surface can be relatively increased, and a detection result for a sample with a relatively high suspended matter content can be obtained as the second detection result. This makes it possible to obtain both a detection result that resembles the liquid in the sample and a detection result that resembles the suspended matter in the sample, for example, without separately preparing the samples. Therefore, this attenuated total reflection spectroscopy apparatus makes it possible to easily obtain detailed information about the sample.

[0008] In the attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure, the holding unit may include a holder disposed on the reflecting surface. The holder may have a recess that, together with the reflecting surface, defines a sample storage space, an inlet hole communicating with the recess and through which the sample flows when introduced into the storage space, and an outlet hole communicating with the recess and through which the sample flows when discharged from the storage space. The adjustment unit may include a pump that circulates the sample from the outlet hole to the inlet hole, and an output control unit that controls the output of the pump. This allows the pump to cause the sample held on the reflecting surface to flow. Furthermore, by controlling the output of the pump, the flow rate of the sample held on the reflecting surface can be controlled, thereby adjusting the flow state of the sample.

[0009] In the attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure, the holder may be transparent to visible light, thereby allowing the flow state of the sample held on the reflective surface to be visually observed.

[0010] The attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure may further include a light output unit that outputs light to a reflecting surface from the side opposite the sample, and a light detection unit that detects the light reflected by the reflecting surface. The adjustment unit may adjust the flow state of the sample while the light detection unit is detecting the light. This makes it possible to easily obtain first and second detection results related to the sample during the light detection period.

[0011] In the attenuated total reflection spectroscopy apparatus according to the first aspect of the present disclosure, the light output from the light output unit may be a terahertz wave, thereby enabling the first detection result and the second detection result regarding the sample to be obtained with high accuracy using the terahertz wave.

[0012] The attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure may further include an inlet pipe for supplying a sample to the holder, and a temperature adjustment unit for adjusting the temperature of the sample flowing through the inlet pipe. The inlet pipe may be connected to the holder. The temperature adjustment unit may be provided in the inlet pipe. This allows the temperature of the sample held by the holder to be maintained constant, for example, by adjusting the temperature of the sample flowing through the inlet pipe. This makes it possible to obtain detailed information about the sample with high accuracy.

[0013] In an attenuated total reflection spectroscopy apparatus according to one aspect of the present disclosure, the temperature adjustment unit may include a thermal processing unit that performs a heating or cooling process on the sample flowing through the introduction tube, a detection unit that detects the temperature of the sample flowing through the introduction tube, and a control unit that controls the output of the thermal processing unit. The thermal processing unit may be provided outside the introduction tube. The control unit may increase or decrease the output of the thermal processing unit based on the detection result by the detection unit. This allows the temperature of the sample flowing through the introduction tube to be adjusted with high precision. Therefore, the temperature of the sample held by the holding unit can be maintained with high precision, making it possible to obtain detailed information about the sample with high precision.

[0014] In the attenuated total reflection spectroscopy apparatus according to the first aspect of the present disclosure, the thermal processing unit may include a Peltier element, which makes it possible to easily and reliably adjust the temperature of the sample flowing through the introduction tube with high precision.

[0015] An attenuated total reflection spectroscopy method according to one aspect of the present disclosure includes a first step of holding a sample containing a suspension on a reflecting surface, a second step of adjusting the flow state of the sample held on the reflecting surface so that the sample is in a first flow state, a third step of obtaining a first detection result for the sample in the first flow state, a fourth step of adjusting the flow state of the sample held on the reflecting surface so that the sample is in a second flow state, and a fifth step of obtaining a second detection result for the sample in the second flow state.

[0016] In this attenuated total reflection spectroscopy method, a first detection result is obtained for a sample in a first fluid state in the third step, and a second detection result is obtained for a sample in a second fluid state in the fifth step. As a result, for example, by relatively strengthening the first fluid state in the second step, the amount of suspended matter in the sample near the reflecting surface can be relatively reduced, and in the third step, a detection result for a sample with a relatively low suspended matter content can be obtained as the first detection result. Furthermore, for example, by relatively weakening the second fluid state in the fourth step, the amount of suspended matter in the sample near the reflecting surface can be relatively increased, and in the fifth step, a detection result for a sample with a relatively high suspended matter content can be obtained as the second detection result. This makes it possible to obtain both a detection result that approximates the liquid in the sample and a detection result that approximates the suspended matter in the sample, for example, without separately preparing the samples. Therefore, this attenuated total reflection spectroscopy method makes it possible to easily obtain detailed information about the sample.

[0017] In the attenuated total reflection spectroscopy method according to the present disclosure, the first flow state may be stronger than the second flow state, thereby enabling the first and second detection results regarding the sample to be reliably obtained.

[0018] In the attenuated total reflection spectroscopy method according to one aspect of the present disclosure, the second flow state may be a stationary state, whereby suspended matter in the sample held on the reflecting surface can be precipitated in the fourth step, and a detection result relating to the precipitate constituted by the suspended matter can be obtained as the second detection result in the fifth step.

[0019] The attenuated total reflection spectroscopy method according to one aspect of the present disclosure may further include a sixth step. In the sixth step, light is output to a reflecting surface from the side opposite the sample, and the light reflected by the reflecting surface is detected. The second, third, fourth, and fifth steps may be performed during the period in which the sixth step is performed. This makes it possible to easily obtain first and second detection results related to the sample during the light detection period.

[0020] In the attenuated total reflection spectroscopy method according to the aspect of the present disclosure, the light may be terahertz waves, thereby enabling the first and second detection results regarding the sample to be obtained with high accuracy using the terahertz waves.

[0021] The attenuated total reflection spectroscopy method according to the present disclosure may further include a seventh step of acquiring information about the sample based on the first and second detection results, thereby making it possible to easily acquire detailed information about the sample, as described above. [Effects of the Invention]

[0022] According to the present disclosure, it is possible to provide an attenuated total reflection spectroscopy apparatus and an attenuated total reflection spectroscopy method that make it possible to easily obtain detailed information about a sample. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 is a diagram showing the configuration of an attenuated total reflection spectroscopic device according to the first embodiment. [Figure 2] FIG. 2 is a configuration diagram of the adjustment unit of the first embodiment. [Figure 3] 3 is an exploded perspective view of the holding portion shown in FIG. 2. FIG. [Figure 4] FIG. 4 is a cross-sectional view taken along line IV-IV in FIG. [Figure 5] FIG. 5 is a flowchart of the attenuated total reflection spectroscopy method according to the first embodiment. [Figure 6] FIG. 6 is a diagram showing the results of the attenuated total reflection spectroscopy method of the first embodiment. [Figure 7] FIG. 7 is a diagram showing the results of the attenuated total reflection spectroscopy method of the second embodiment. [Figure 8] FIG. 8 is a cross-sectional view of a holding portion and an adjusting portion of a modified example. [Figure 9] FIG. 9 is a diagram showing the configuration of the attenuated total reflection spectroscopic device according to the second embodiment. [Figure 10] FIG. 10 is a configuration diagram of the temperature adjusting unit shown in FIG. [Figure 11] FIG. 11 is an exploded perspective view of the heat transfer portion shown in FIG. [Figure 12] FIG. 12 is a diagram showing the results of the comparative example and the example. [Figure 13] FIG. 13 is a configuration diagram of a temperature adjusting unit according to a modified example. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or corresponding parts are denoted by the same reference numerals, and duplicated explanations will be omitted.

[0025] [First embodiment] [ATR device] 1, the attenuated total reflection spectroscopy apparatus 1 of the first embodiment includes an optical output unit 20, a prism (optical element) 30, an optical path difference adjusting unit 40, a polarizer 50, a combining unit 60, a photodetector 70, and a processing unit 80. The attenuated total reflection spectroscopy apparatus 1 is an apparatus for acquiring information about a sample S by, for example, performing attenuated total reflection spectroscopy (ATR) using terahertz waves. Hereinafter, the "attenuated total reflection spectroscopy apparatus 1" will be referred to as the "ATR apparatus 1." The ATR apparatus 1 is used, for example, as a quality analysis tool in the manufacturing process of pharmaceuticals, foods, chemical materials, etc., or as an analysis tool in the research and development stage of pharmaceuticals, foods, chemical materials, etc.

[0026] The light output unit 20 outputs terahertz waves T as light. Specifically, the light output unit 20 has a light source 21, a branching unit 22, a chopper 23, a plurality of mirrors M1 to M3, and a terahertz wave generating element 24. The light source 21 outputs light by pulse oscillation. The light source 21 is, for example, a femtosecond pulse laser light source that outputs pulsed laser light with a pulse width of about femtoseconds. The branching unit 22 is, for example, a beam splitter. The branching unit 22 branches the light output from the light source 21 into pump light P1 and probe light P2. The chopper 23 alternately passes and blocks the pump light P1 output from the branching unit 22 at a constant period.

[0027] The mirrors M1 to M3 sequentially reflect the pump light P1 that has passed through the chopper 23. The pump light P1 that has passed through the chopper 23 is reflected sequentially by the mirrors M1 to M3, and then enters the terahertz wave generating element 24. Note that hereinafter, the optical system of the pump light P1 that reaches the terahertz wave generating element 24 from the branching unit 22 is referred to as the "pump optical system."

[0028] The terahertz wave generating element 24 outputs terahertz waves T when the pump light P1 reflected by the mirror M3 is incident thereon. The terahertz wave generating element 24 includes, for example, a nonlinear optical crystal (e.g., ZnTe), a photoconductive antenna element (e.g., an optical switch using GaAs), a semiconductor (e.g., InAs), or a superconductor. When the terahertz wave generating element 24 includes a nonlinear optical crystal, the terahertz wave generating element 24 generates terahertz waves T by a nonlinear optical phenomenon that occurs in response to the incidence of the pump light P1.

[0029] Terahertz waves T are electromagnetic waves with a frequency of approximately 0.01 THz to 100 THz, which corresponds to an intermediate region between light waves and radio waves, and have intermediate properties between light waves and radio waves. Terahertz waves T are generated at a constant repetition period and have a pulse width of approximately several picoseconds. In other words, the terahertz wave generating element 24 generates a pulsed light train including a plurality of terahertz waves T arranged at a predetermined time interval (pulse interval). Note that, hereinafter, the optical system for the terahertz waves T from the terahertz wave generating element 24 to the multiplexing unit 60 is referred to as the "terahertz wave optical system."

[0030] The prism 30 is, for example, a so-called aplanatic prism. The cross section of the prism 30 has, for example, a triangular shape. The prism 30 has an incident surface 30a, an exit surface 30b, and a reflecting surface 30c. The incident surface 30a and the exit surface 30b each intersect obliquely with the reflecting surface 30c. The reflecting surface 30c is a total internal reflection surface. A sample S is held on the reflecting surface 30c. The prism 30 is transparent to the terahertz wave T output from the terahertz wave generating element 24. The refractive index of the prism 30 is greater than the refractive index of the sample S. The material of the prism 30 is, for example, silicon.

[0031] The terahertz waves T incident on the incident surface 30a of the prism 30 are incident on the reflecting surface 30c from the side opposite the sample S, reflected by the reflecting surface 30c, and output to the outside from the exit surface 30b. Thus, by detecting the attenuated reflectance of the evanescent waves that leak out when the terahertz waves T are totally reflected by the reflecting surface 30c, it is possible to obtain information about the sample S in the terahertz waveband. The sample S includes a suspension. The sample S includes a liquid and suspended matter dispersed in the liquid. The suspended matter is not dissolved in the liquid. Examples of the liquid include pure water, distilled water, saline, blood, ethanol, methanol, acetone, ethyl acetate, isopropanol, dioxane, dimethyl sulfoxide, dimethylformamide, formamide, formic acid, butyric acid, sulfuric acid, hydrochloric acid, acetic acid, nitric acid, trifluoroacetic acid, and phosphoric acid. Examples of the suspended matter include calcium sulfate (gypsum), carbamazepine, theophylline, and nifedipine. In this embodiment, the liquid is pure water and the suspended substance is nifedipine.

[0032] The optical path length difference adjusting unit 40 has multiple mirrors M4 to M8. The probe light P2 output from the branching unit 22 is reflected in turn by each of the mirrors M4 to M8, passes through the polarizer 50, and enters the multiplexing unit 60. Note that hereinafter, the optical system of the probe light P2 from the branching unit 22 to the multiplexing unit 60 is referred to as the "probe optical system." In the optical path length difference adjusting unit 40, the mirrors M5 and M6 move to adjust the optical path length between the mirror M4 and the mirror M5 and the optical path length between the mirror M6 and the mirror M7, thereby adjusting the optical path length of the probe optical system. In this way, the optical path length difference adjusting unit 40 adjusts the difference between the "optical path of the pump optical system and the terahertz wave optical system from the branching unit 22 to the multiplexing unit 60" and the "optical path of the probe optical system from the branching unit 22 to the multiplexing unit 60."

[0033] When the terahertz wave T output from the exit surface 30b of the prism 30 and the probe light P2 that has passed through the polarizer 50 enter the multiplexing unit 60, the multiplexing unit 60 multiplexes the terahertz wave T and the probe light P2 and outputs the combined light coaxially to the photodetector 70. The multiplexing unit 60 is, for example, a thin, stretched film-like mirror adhered to a rigid support frame. The multiplexing unit 60 is, for example, a pellicle.

[0034] The photodetector 70 detects the terahertz wave T output from the prism 30. Specifically, the photodetector 70 has a terahertz wave detecting element 71, a quarter-wave plate 72, a polarization splitter 73, a photodetector 74a, a photodetector 74b, a differential amplifier 75, and a lock-in amplifier 76. When the terahertz wave T and the probe light P2 output from the multiplexer 60 are incident on the terahertz wave detecting element 71, the terahertz wave detecting element 71 detects the correlation between the terahertz wave T and the probe light P2.

[0035] Specifically, the terahertz wave detecting element 71 includes an electro-optic crystal. When the terahertz wave T and the probe light P2 are incident on the terahertz wave detecting element 71, birefringence is induced in the terahertz wave detecting element 71 by the Pockels effect as the terahertz wave T propagates. The polarization state of the probe light P2 changes due to the birefringence, and the probe light P2 is output from the terahertz wave detecting element 71. The amount of birefringence at this time depends on the electric field strength of the terahertz wave T. Therefore, the amount of change in the polarization state of the probe light P2 in the terahertz wave detecting element 71 depends on the electric field strength of the terahertz wave T.

[0036] The probe light P2 output from the terahertz wave detecting element 71 passes through the quarter-wave plate 72 and enters the polarization separation element 73. The polarization separation element 73 is, for example, a Wollaston prism. The polarization separation element 73 separates the incident probe light P2 into two polarized components that are orthogonal to each other and outputs them.

[0037] Each of the photodetectors 74a and 74b includes, for example, a photodiode, and detects the power of the two polarization components of the probe light P2 and outputs an electrical signal having a value corresponding to the detected power to the differential amplifier 75.

[0038] The differential amplifier 75 receives the electrical signals output from the photodetector 74a and the photodetector 74b, and outputs an electrical signal having a value corresponding to the difference between the values ​​of the electrical signals to the lock-in amplifier 76. The lock-in amplifier 76 synchronously detects the electrical signal output from the differential amplifier 75 at the repetition frequency of the passage and blocking of the pump light P1 in the chopper 23. The signal output from the lock-in amplifier 76 has a value that depends on the electric field strength of the terahertz wave T. In this way, the photodetector 70 detects the correlation between the terahertz wave T and the probe light P2, and detects the electric field amplitude of the terahertz wave T.

[0039] The processing unit 80 is electrically connected to the lock-in amplifier 76. The processing unit 80 acquires information about the sample S based on the detection results detected by the light detection unit 70. The processing unit 80 is composed of a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), etc.

[0040] [Adjustment section] Hereinafter, the first and second horizontal directions, which are orthogonal to each other, will be referred to as the X-axis direction and the Y-axis direction, respectively, and the vertical direction will be referred to as the Z-axis direction. As shown in Fig. 2, the ATR device 1 includes a holder 11 and an adjustment unit 12. These are not shown in Fig. 1. The holder 11 holds the sample S on the reflecting surface 30c of the prism 30. The adjustment unit 12 includes a pump 121, a container 122, a plurality of tubes 123, and an output control unit 124.

[0041] The pump 121 is connected to the container 122 and the holding unit 11 by a tube 123. The holding unit 11 is connected to the container 122 by a tube 123. The container 122 contains a sample S. The sample S is circulated among the pump 121, the container 122, and the holding unit 11 by suction and pressure feeding by the pump 121.

[0042] The output control unit 124 controls the output of the pump 121. When the output of the pump 121 increases, the flow rate of the sample S between the pump 121, the container 122, and the holding unit 11 increases. When the output of the pump 121 decreases, the flow rate of the sample S between the pump 121, the container 122, and the holding unit 11 decreases. The output control unit 124 is composed of a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), etc.

[0043] [Holding part] As shown in Fig. 3, the holder 11 has a substrate 13, a pair of supports 14, an attachment portion 15, a holder 16, and a sealing member 17 (see Fig. 4). The substrate 13 holds the prism 30 so that the reflecting surface 30c is perpendicular to the Z-axis direction and the incident surface 30a and the exit surface 30b intersect with the X-axis direction. The reflecting surface 30c is substantially flush with the front surface 13a of the substrate 13. The terahertz waves T can be incident on the incident surface 30a and emitted from the exit surface 30b on the back surface 13b side of the substrate 13.

[0044] Each support 14 is fixed to the surface 13a of the substrate 13. The pair of supports 14 are arranged on both sides of the prism 30 in the Y-axis direction. Each support 14 has, for example, a rectangular parallelepiped shape with its length direction in the X-axis direction. A pin 141 is provided on each mounting surface 14a of each support 14 opposite the substrate 13.

[0045] The mounting portion 15 includes a plate 151, a cylindrical body 152, and a pair of fixing members 153. The plate 151 has, for example, a rectangular plate shape. The length direction of the plate 151 is the Y-axis direction, and the thickness direction is the Z-axis direction. The width of the plate 151 in the X-axis direction is approximately the same as the width of the supports 14 in the X-axis direction. The width of the plate 151 in the Y-axis direction is approximately the same as the distance between the end faces of the pair of supports 14 in the Y-axis direction (the end faces opposite the prisms in the Y-axis direction). A through hole 15a is formed in the plate 151. When viewed from the Z-axis direction, the through hole 15a has, for example, a rectangular shape with the length direction being the X-axis direction.

[0046] The cylinder 152 is provided on one main surface of the plate 151. The cylinder 152 has, for example, a rectangular cylindrical shape. The cylinder 152 extends along the Z-axis direction. When viewed from the Z-axis direction, the length direction of the cylinder 152 is, for example, the X-axis direction. When viewed from the Z-axis direction, the cylinder 152 surrounds the through-hole 15a of the plate 151. The width of the cylinder 152 in the Y-axis direction is smaller than the distance between the pair of supports 14 in the Y-axis direction. The cylinder 152 is fixed to the plate 151.

[0047] Each fixing member 153 is provided on the opposite side of the plate body 151 from the cylindrical body 152. The pair of fixing members 153 is provided on both sides of the through-hole 15a and the cylindrical body 152 in the Y-axis direction. Each fixing member 153 penetrates the plate body 151.

[0048] The holder 16 has a rectangular parallelepiped shape with its length in the X-axis direction. The holder 16 is housed inside a cylindrical body 152. The plate body 151 of the mounting portion 15 is placed on the mounting surface 14a of each support 14 so that the cylindrical body 152 housing the holder 16 is located between the plate body 151 and the prism 30. Each fixing member 153 is fixed to a pin 141 provided on the corresponding support 14. In this way, the holder 16 is attached to the prism 30.

[0049] 4, the holder 16 has a first main surface 16a that is perpendicular to the Z-axis direction and a second main surface 16b that is opposite to the first main surface 16a. The first main surface 16a is exposed from the through-hole 15a of the plate body 151. The second main surface 16b protrudes from the end of the cylindrical body 152 that is opposite to the plate body 151.

[0050] The holder 16 has a recess 16c, an inlet hole 16d, and an outlet hole 16e. The recess 16c is formed on the second main surface 16b. The recess 16c is recessed to a predetermined depth from the second main surface 16b. When viewed from the Z-axis direction, the recess 16c has, for example, a rectangular shape with its length direction aligned with the X-axis direction. The inlet hole 16d and the outlet hole 16e are aligned in the Z-axis direction.

[0051] The introduction hole 16d is in communication with the recess 16c. The introduction hole 16d extends along the Z-axis direction. The introduction hole 16d penetrates the holder 16 in the Z-axis direction. The introduction hole 16d opens to the first main surface 16a and the bottom surface of the recess 16c. When viewed from the Z-axis direction, the introduction hole 16d has, for example, a circular shape. A tube 123 is connected to the opening of the introduction hole 16d in the first main surface 16a (see FIG. 2).

[0052] The outlet hole 16e is in communication with the recess 16c. The outlet hole 16e extends along the Z-axis direction. The outlet hole 16e penetrates the holder 16 in the Z-axis direction. The outlet hole 16e opens to the first main surface 16a and the bottom surface of the recess 16c. When viewed from the Z-axis direction, the outlet hole 16e has, for example, a circular shape. A tube 123 is connected to the opening of the outlet hole 16e in the first main surface 16a (see FIG. 2).

[0053] The holder 16 is disposed on the reflecting surface 30c of the prism 30 so that the second main surface 16b faces the reflecting surface 30c. A portion of the holder 16 on the side of the first main surface 16a is held by a cylindrical body 152 of the mounting part 15. The first main surface 16a is in contact with a plate body 151 of the mounting part 15. The holder 16 is pressed against the reflecting surface 30c by the mounting part 15. The recess 16c of the holder 16 and the reflecting surface 30c define a storage space R in which the sample S is stored. The sample S is introduced into the storage space R by flowing through the introduction hole 16d. The sample is discharged from the storage space R by flowing through the discharge hole 16e.

[0054] The holder 16 is transparent to visible light. The material of the holder 16 is, for example, acrylic. The sealing member 17 is, for example, an O-ring. The sealing member 17 is disposed in the recess 16c. The sealing member 17 extends along the outer edge of the recess 16c. When viewed from the Z-axis direction, the sealing member 17 is disposed outside the introduction hole 16d and the discharge hole 16e. The sealing member 17 seals the storage space R.

[0055] [Adjustment of flow state by adjustment unit] During the period in which the optical detection unit 70 detects the terahertz waves T, the adjustment unit 12 adjusts the flow state of the sample S held on the reflecting surface 30c to a first flow state in order to obtain a first detection result regarding the sample S in the first flow state, and adjusts the flow state of the sample S to a second flow state in order to obtain a second detection result regarding the sample S in the second flow state.

[0056] The flow state of the sample S refers to the kinetic energy of the sample S held on the reflecting surface 30c of the prism 30. When the kinetic energy of the sample S is large, the flow state of the sample S is said to be strong, and when the kinetic energy of the sample S is small, the flow state of the sample S is said to be weak. For example, when the flow velocity of the sample S is large, the flow state of the sample S is strong, and when the flow velocity of the sample S is small, the flow state of the sample S is weak. Also, for example, when the sample S is strongly stirred, the flow state of the sample S is strong, and when the sample S is weakly stirred, the flow state of the sample S is weak.

[0057] When the flow state of the sample S is strong, the suspended matter in the sample S is likely to be uniformly dispersed in the sample S. When the flow state of the sample S is weak, the suspended matter in the sample S is likely to settle in the sample S. When the flow state of the sample S is strong, the amount of suspended matter at a position close to the reflecting surface 30c (in this embodiment, a position in the storage space R closer to the reflecting surface 30c than the bottom surface of the recess 16c) becomes relatively small, and the amount of liquid at a position close to the reflecting surface 30c becomes relatively large. When the flow state of the sample S is weak, the amount of suspended matter at a position close to the reflecting surface 30c becomes relatively large, and the amount of liquid at a position close to the reflecting surface 30c becomes relatively small.

[0058] The adjustment unit 12 circulates the sample S between the container 122 and the holder 16. Specifically, the output control unit 124 drives the pump 121. The pump 121 circulates the sample S from the outlet hole 16e to the introduction hole 16d. Specifically, when the pump 121 is driven, the sample S accommodated in the container 122 is supplied to the introduction hole 16d of the holder 16 via the tube 123 by suction from the pump 121. The sample S supplied to the introduction hole 16d flows through the introduction hole 16d and is introduced into the storage space R. The sample S introduced into the storage space R passes through the storage space R and flows through the outlet hole 16e, and is then discharged from the storage space R. The sample S discharged from the outlet hole 16e is supplied again to the container 122 via the tube 123 by pressure transfer from the pump 121. The sample S supplied to the container 122 is supplied again to the introduction hole 16d by suction from the pump 121. In this way, in the ATR device 1, a circulation path for the sample S is formed.

[0059] When acquiring a first detection result related to the sample S, the output control unit 124 sets the flow state of the sample S held on the reflecting surface 30c (the sample S accommodated in the accommodation space R) to a first flow state. The output control unit 124 maintains the first flow state of the sample S for a predetermined period. Specifically, the output control unit 124 increases the output of the pump 121 to increase the flow rate of the sample S in the circulation path. The output control unit 124 maintains the increased output of the pump 121 for a predetermined period, thereby maintaining the increased flow rate of the sample S in the circulation path for a predetermined period.

[0060] When acquiring a second detection result related to the sample S, the output control unit 124 changes the flow state of the sample S held on the reflecting surface 30c (the sample S accommodated in the accommodation space R) to a second flow state. The first flow state is stronger than the second flow state. The output control unit 124 maintains the second flow state of the sample S for a predetermined period. Specifically, the output control unit 124 reduces the output of the pump 121 to reduce the flow rate of the sample S in the circulation path. The flow rate of the sample S when acquiring a first detection result related to the sample S is higher than the flow rate of the sample S when acquiring a second detection result related to the sample S. The output control unit 124 maintains the reduced output of the pump 121 for a predetermined period, thereby maintaining the reduced flow rate of the sample S in the circulation path for a predetermined period.

[0061] In this embodiment, the first detection result is a detection result regarding the liquid in the sample S. The first detection result is, for example, data detected by the light detection unit 70, and is data for calculating spectroscopic information of the liquid in the sample S. In this embodiment, the second detection result is a detection result regarding suspended matter in the sample S. The second detection result is, for example, data detected by the light detection unit 70, and is data for calculating spectroscopic information of the suspended matter in the sample S.

[0062] As described above, the ATR apparatus 1 is a flow-through type apparatus that can continuously monitor, for example, parameters necessary for quality control of the sample S. Such an ATR apparatus 1 can be easily introduced into a manufacturing process.

[0063] [Actions and effects of ATR equipment] As described above, in the ATR device 1, the sample S containing a suspension is held on the reflecting surface 30c of the prism 30. The adjustment unit 12 adjusts the flow state of the sample S to a first flow state to obtain a first detection result for the sample S in the first flow state, and adjusts the flow state of the sample S to a second flow state to obtain a second detection result for the sample S in the second flow state. By relatively strengthening the first flow state, the amount of suspended matter in the sample S near the reflecting surface 30c can be relatively reduced, and a detection result for the sample S with a relatively low suspended matter content can be obtained as the first detection result. Furthermore, by relatively weakening the second flow state, the amount of suspended matter in the sample S near the reflecting surface 30c can be relatively increased, and a detection result for the sample S with a relatively high suspended matter content can be obtained as the second detection result. This makes it possible to obtain both a detection result that resembles the liquid in the sample S and a detection result that resembles the suspended matter in the sample S, for example, without separately preparing the sample S. Therefore, the ATR device 1 makes it possible to easily obtain detailed information about the sample S. For example, based on the first detection result and the second detection result, it is possible to obtain spectroscopic information about the liquid in the sample S and spectroscopic information about the suspended matter in the sample S. Therefore, by analyzing and utilizing the information about the sample S from multiple angles, it is possible to easily perform a detailed evaluation of a suspension such as the sample S.

[0064] In the ATR device 1, the holding unit 11 includes a holder 16 disposed on the reflecting surface 30c. The holder 16 has a recess 16c that, together with the reflecting surface 30c, defines a storage space R for the sample S, an inlet hole 16d that communicates with the recess 16c and through which the sample S introduced into the storage space R flows, and an outlet hole 16e that communicates with the recess 16c and through which the sample S discharged from the storage space R flows. The adjustment unit 12 includes a pump 121 that circulates the sample S from the outlet hole 16e to the inlet hole 16d, and an output control unit 124 that controls the output of the pump 121. This allows the pump 121 to cause the sample S held on the reflecting surface 30c to flow. Furthermore, by controlling the output of the pump 121, the flow rate of the sample S held on the reflecting surface 30c can be controlled, and the flow state of the sample S can be adjusted.

[0065] In the ATR device 1, the holder 16 is transparent to visible light, which allows the fluid state of the sample S held on the reflecting surface 30c to be visually observed.

[0066] The ATR device 1 includes a light output unit 20 that outputs terahertz waves T to a reflecting surface 30c from the side opposite to the sample S, and a light detecting unit 70 that detects the terahertz waves T reflected by the reflecting surface 30c. The adjusting unit 12 adjusts the flow state of the sample S while the light detecting unit 70 is detecting the terahertz waves T. This makes it possible to easily obtain a first detection result and a second detection result regarding the sample S during the detection period of the terahertz waves T.

[0067] In the ATR device 1, the light output from the light output unit 20 is terahertz waves T. This makes it possible to accurately obtain first and second detection results related to the sample S using the terahertz waves T. Specifically, when the terahertz waves T are used, the range (range in the Z-axis direction) of the evanescent waves seeping out from the reflecting surface 30c becomes relatively large. This widens the measurable region.

[0068] [ATR method] Next, the attenuated total reflection spectroscopy method (hereinafter referred to as "ATR method") performed in the ATR device 1 to obtain information about the sample S will be described.

[0069] As shown in FIG. 5, first, the sample S is supplied to the storage space R (step S1). In step S1, after the amount of sample S stored in the container 122 is secured, the pump 121 is driven by the output control unit 124. When the pump 121 is driven, the sample S is circulated in the circulation path. The sample S flows through the storage space R. As a result, the sample S is held on the reflecting surface 30c. Step S1 corresponds to the first step.

[0070] Next, terahertz waves T are output from the side opposite to the sample S to the reflecting surface 30c, and the terahertz waves T reflected by the reflecting surface 30c are detected (step S2). In step S2, the light output unit 20 causes the terahertz waves T to be incident on the incident surface 30a of the prism 30. In step S2, the light detection unit 70 detects the correlation between the terahertz waves T output from the multiplexing unit 60 and the probe light P2, and detects the electric field amplitude of the terahertz waves T. In step S2, the terahertz waves T are continuously output to the reflecting surface 30c, and the terahertz waves T reflected by the reflecting surface 30c are continuously detected. Step S2 corresponds to the sixth step.

[0071] Next, the flow state of the sample S held on the reflecting surface 30c is adjusted so that the sample S is in a first flow state (step S3). Step S3 corresponds to the second step. Next, a first detection result regarding the sample S in the first flow state is obtained (step S4). Step S4 corresponds to the third step. Next, the flow state of the sample S is adjusted so that the sample S held on the reflecting surface 30c is in a second flow state (step S5). Step S5 corresponds to the fourth step. Next, a second detection result regarding the sample S in the second flow state is obtained (step S6). Step S6 corresponds to the fifth step. Next, information regarding the sample S is obtained based on the first detection result and the second detection result (step S7). In step S7, for example, spectroscopic information regarding each of the liquid and suspended matter in the sample S is calculated. Step S7 corresponds to the seventh step.

[0072] Steps S3 to S6 are performed during the period in which step S2 is performed, that is, during the period in which the terahertz waves T are output to the reflecting surface 30c and the terahertz waves T reflected by the reflecting surface 30c are detected.

[0073] [Action and effect of the ATR method] As described above, in the ATR method, in step S4, a first detection result is obtained for the sample S in the first fluid state, and in step S6, a second detection result is obtained for the sample S in the second fluid state. Thus, in step S3, by relatively strengthening the first fluid state, the amount of suspended matter in the sample S near the reflecting surface 30c can be relatively reduced, and in step S4, a detection result for the sample S with a relatively low suspended matter content can be obtained as the first detection result. Furthermore, in step S5, by relatively weakening the second fluid state, the amount of suspended matter in the sample S near the reflecting surface 30c can be relatively increased, and in step S6, a detection result for the sample S with a relatively high suspended matter content can be obtained as the second detection result. This makes it possible to obtain both a detection result that approximates the liquid in the sample S and a detection result that approximates the suspended matter in the sample S, for example, without separately preparing the sample S. Therefore, this ATR method makes it possible to easily obtain detailed information about the sample S.

[0074] In the ATR method, the first flow state is stronger than the second flow state, which allows the first and second detection results for the sample S to be reliably obtained.

[0075] The ATR method includes step S2. In step S2, terahertz waves T are output to reflecting surface 30c from the side opposite to sample S, and the terahertz waves T reflected by reflecting surface 30c are detected. Steps S3 to S6 are performed during the period in which step S2 is performed. This makes it possible to easily obtain first and second detection results related to sample S during the period in which terahertz waves T are detected.

[0076] In the ATR method, the light is terahertz waves T. This makes it possible to use the terahertz waves T to obtain the first detection result and the second detection result regarding the sample S with high accuracy.

[0077] The ATR method includes step S7 of acquiring information about the sample S based on the first detection result and the second detection result. This makes it possible to easily acquire detailed information about the sample S, as described above.

[0078] [Example] FIG. 6 shows the results of the ATR method of the first embodiment. In the first embodiment, information on each of samples A, B, and C was obtained as sample S. Each of samples A, B, and C is a suspension in which nifedipine (suspended substance) is dispersed in pure water (liquid). The concentration of nifedipine in sample A is approximately 2.5 mg / ml. The concentration of nifedipine in sample B is approximately 5.0 mg / ml. The concentration of nifedipine in sample C is approximately 10.0 mg / ml.

[0079] FIG. 6(a) shows the absorption spectra obtained from the first detection results of samples A, B, and C in the first fluidization state. FIG. 6(b) shows the absorption spectra obtained from the second detection results of samples A, B, and C in the second fluidization state. As shown in FIG. 6(a), the absorption spectra of samples A, B, and C in the first fluidization state increase smoothly with increasing frequency and nearly overlap. As shown in FIG. 6(b), the absorption spectra of samples A, B, and C in the second fluidization state have peaks (specific peaks due to suspended matter) at predetermined frequencies (1.1 to 1.3 THz) that are separated from each other. Thus, in the first example, it was confirmed that when sample S is in the first fluidization state, it is possible to obtain detection results related to the liquid in sample S, and when sample S is in the second fluidization state, it is possible to obtain detection results related to suspended matter in sample S.

[0080] FIG. 7 shows the results of the ATR method of the second embodiment. In the second embodiment, a suspension in which gypsum (suspended matter) is dispersed in pure water (liquid) was used as the sample S, and the fluidity of the sample S was adjusted so that the fluidity of the sample S alternated between a first fluidity state and a second fluidity state. FIG. 7 shows the time change in the absorption spectrum of the sample S corresponding to a predetermined frequency (e.g., approximately 0.5 THz). In FIG. 7, line L1 shows the absorption spectrum corresponding to the liquid of the sample S, i.e., the liquid (pure water in this embodiment) in which suspended matter is not dispersed in the sample S, and line L2 shows the time change in the absorption spectrum corresponding to the sample S. As shown in FIG. 7, the absorption spectrum of the portion of line L2 corresponding to the first fluidity state (e.g., 50 to 55 min) substantially coincides with the absorption spectrum of the liquid of the sample S. The portion of line L2 corresponding to the second fluidity state (e.g., 55 to 60 min) is separated from line L1. Thus, in the second embodiment, it was confirmed that when the sample S is in the first flow state, it is possible to obtain detection results regarding the liquid in the sample S, and when the sample S is in the second flow state, it is possible to obtain detection results regarding the suspended matter in the sample S.

[0081] [Variations] The present disclosure is not limited to the above-described first embodiment. As shown in Fig. 8, the ATR apparatus 1A may include a holding unit 18 instead of the holding unit 11. The ATR apparatus 1A may include an adjustment unit 19 instead of the adjustment unit 12. The other configurations of the ATR apparatus 1A are the same as those of the ATR apparatus 1, and therefore detailed description thereof will be omitted.

[0082] The holder 18 includes a holder 180. The holder 180 has a side wall 181 and a bottom wall 182. The side wall 181 is cylindrical. The bottom wall 182 seals one opening of the side wall 181. The other opening of the side wall 181 is open. The holder 180 is disposed on the reflecting surface 30c of the prism 30 so that an end face 18a of the side wall 181 opposite the bottom wall 182 faces the reflecting surface 30c of the prism 30. The inner surface 18b of the holder 180, together with the reflecting surface 30c, defines a storage space R for storing the sample S.

[0083] The adjustment unit 19 has a shaft 191, a plurality of propellers 192, a motor 193, and an output control unit 194. The shaft 191 extends along the Z-axis direction. The shaft 191 penetrates the bottom wall portion 182 and extends to the accommodation space R. Each propeller 192 is fixed to the shaft 191 in the accommodation space R. The motor 193 is provided on the shaft 191 outside the accommodation space R. The motor 193 rotates the shaft 191. The output control unit 194 controls the output of the motor 193. The output control unit 194 is composed of a CPU (Central Processing Unit), ROM (Read Only Memory), RAM (Random Access Memory), etc.

[0084] The adjustment unit 19 can adjust the flow state of the sample S. The adjustment unit 19 agitates the sample S in the storage space R. Specifically, the output control unit 194 drives the motor 193. When the motor 193 is driven, a shaft 191 to which multiple propellers 192 are fixed rotates. The sample S stored in the storage space R is agitated by each of the propellers 192.

[0085] When acquiring a first detection result related to the sample S, the output control unit 194 sets the fluid state of the sample S held on the reflecting surface 30c (the sample S accommodated in the accommodation space R) to a first fluid state. The output control unit 194 maintains the first fluid state of the sample S for a predetermined period. Specifically, the output control unit 194 increases the output of the motor 193 to increase the rotation speed of the shaft 191. The output control unit 194 maintains the increased output of the motor 193 for a predetermined period, thereby maintaining the increased rotation speed of the shaft 191 for a predetermined period.

[0086] When acquiring a second detection result related to the sample S, the output control unit 194 changes the fluid state of the sample S held on the reflecting surface 30c (the sample S accommodated in the accommodation space R) to a second fluid state. The output control unit 194 maintains the second fluid state of the sample S for a predetermined period. Specifically, the output control unit 194 reduces the output of the motor 193 to reduce the rotation speed of the shaft 191. The rotation speed of the shaft 191 when acquiring a first detection result related to the sample S is higher than the rotation speed of the shaft 191 when acquiring a second detection result related to the sample S. The output control unit 194 maintains the reduced output of the motor 193 for a predetermined period, thereby maintaining the reduced rotation speed of the shaft 191 for a predetermined period.

[0087] According to the ATR apparatus 1A, like the ATR apparatus 1, detailed information about the sample S can be easily obtained.

[0088] In the first embodiment, an example was shown in which the output control unit 124 increased or decreased the output of the pump 121. However, the output control unit 124 may stop the flow of the sample S in the circulation path by stopping the pump 121. In other words, the second flow state may be a stationary state. This allows suspended matter in the sample S held on the reflecting surface 30c to settle, and a detection result regarding the precipitate formed by the suspended matter can be obtained as the second detection result. The output control unit 194 in the modified example may also stop the motor 193 to stop the rotation of each propeller 192.

[0089] In the first embodiment, the sample S contains nifedipine. However, the sample S may contain multiple types of suspended solids having different specific gravities. For example, the sample S may contain a first suspended solid having a first specific gravity, a second suspended solid having a second specific gravity, and a third suspended solid having a third specific gravity. The output control unit 124 may adjust the flow state of the sample S held on the reflecting surface 30c so that the sample S is in various flow states (e.g., a first flow state, a second flow state, and a third flow state). This allows the flow state of the sample S to be changed depending on the specific gravity of the suspended solid to be measured, among the first suspended solids, the second suspended solids, and the third suspended solids. In other words, the dispersion state or precipitation state of the various suspended solids in the sample S near the reflecting surface 30c can be adjusted. Therefore, for example, multiple detection results for the sample S containing multiple types of suspended solids can be easily obtained without separately preparing samples S containing the suspended solids to be measured among the multiple types of suspended solids.

[0090] In the first embodiment, an example was shown in which the holder 16 is transparent to visible light, but the holder 16 does not have to be transparent to visible light. The material of the holder 16 may be, for example, a fluororesin such as Teflon (registered trademark). The material of the holder 16 may be, for example, aluminum.

[0091] In the first embodiment, an example has been shown in which the light output unit 20 outputs the terahertz wave T as light, but the light output unit 20 may also output ultraviolet light or infrared light (near infrared light, mid infrared light, or far infrared light). In other words, the ATR device 1 may be a device that uses light in the ultraviolet or infrared region, rather than just the terahertz band.

[0092] In the ATR method, step S1 may also be performed during the period in which step S2 is performed, and steps S3 and S4 may be performed after steps S5 and S6 are performed.

[0093] In the first embodiment, the prism 30 is exemplified as an optical element, but the optical element may be, for example, a plate-shaped optical member such as a glass slide, or an optical fiber.

[0094] In the first embodiment, an example was shown in which the output control unit 124 drives the pump 121 in one direction to cause the sample S to flow in one direction both when obtaining the first detection result regarding the sample S and when obtaining the second detection result regarding the sample S. However, the output control unit 124 may, for example, drive the pump 121 in one direction to cause the sample S to flow in one direction when obtaining the first detection result regarding the sample S, and may drive the pump 121 in the direction opposite to the one direction to cause the sample S to flow in the direction opposite to the one direction when obtaining the second detection result regarding the sample S. In other words, the flow direction of the sample S may be different in each of the first flow state and the second flow state of the sample S.

[0095] In the modified example, the output control unit 194 drives the motor 193 in one direction to rotate the shaft 191 in one direction both when obtaining a first detection result regarding the sample S and when obtaining a second detection result regarding the sample S. However, the output control unit 194 may, for example, drive the motor 193 in one direction to rotate the shaft 191 in one direction when obtaining a first detection result regarding the sample S, and may drive the motor 193 in the direction opposite to the one direction to rotate the shaft 191 in the direction opposite to the one direction when obtaining a second detection result regarding the sample S. That is, the rotation direction of the shaft 191 may be different in the first flow state and the second flow state of the sample S. Furthermore, the adjustment unit 19 may adjust the flow state of the sample S by independently controlling each propeller 192.

[0096] [Second embodiment] 9, the attenuated total reflection spectroscopy apparatus 1B (hereinafter referred to as "ATR apparatus 1B") of the second embodiment differs from the ATR apparatus 1 of the first embodiment in that it further includes a temperature adjustment unit 90. The other configuration of the ATR apparatus 1B is the same as that of the ATR apparatus 1, and therefore detailed description thereof will be omitted.

[0097] The temperature adjustment unit 90 is provided between the container 122 and the holding unit 11. The temperature adjustment unit 90 is provided in a tube 123 that connects the pump 121 and the holding unit 11. Hereinafter, the tube 123 that connects the pump 121 and the holding unit 11 will be referred to as the "inlet pipe 123." In other words, the inlet pipe 123 is a tube for supplying the sample S to the holding unit 11. The temperature adjustment unit 90 is provided in a position on the inlet pipe 123 that is closer to the holding unit 11 than the pump 121.

[0098] The temperature adjustment unit 90 adjusts the temperature of the sample S flowing through the introduction pipe 123. Specifically, as shown in Fig. 10, the temperature adjustment unit 90 has a heat treatment unit 91, a detection unit 92, and a controller (control unit) 93. The heat treatment unit 91 is provided outside the introduction pipe 123. The heat treatment unit 91 performs a heating treatment or a cooling treatment on the sample S flowing through the introduction pipe 123.

[0099] Specifically, the heat treatment unit 91 has a heat transfer unit 94, a Peltier element 95, a heat sink 96, and a cooling fan 97. The heat transfer unit 94 surrounds the inlet pipe 123. The heat transfer unit 94 is thermally connected to the inlet pipe 123. As shown in FIG. 11 , the heat transfer unit 94 has a pair of plate members 94a, 94b. Each of the plate members 94a, 94b is made of a material with a relatively high thermal conductivity. The material of each of the plate members 94a, 94b is, for example, aluminum, copper, gold, silver, nickel, platinum, or the like. In this embodiment, the material of each of the plate members 94a, 94b is aluminum.

[0100] Each plate member 94a, 94b has a groove 94c. Each groove 94c extends in a serpentine shape. The inlet pipe 123 is disposed in each groove 94c and sandwiched between the pair of plate members 94a, 94b. This configuration increases the contact area between the inlet pipe 123 and the heat transfer unit 94, thereby improving the heat transfer efficiency of the heat transfer unit 94. This allows the temperature of the sample S flowing through the inlet pipe 123 to be more effectively adjusted. Note that, for example, thermally conductive grease is filled between each groove 94c and the inlet pipe 123. As shown in FIG. 10 , a Peltier element 95 is provided on the surface of the heat transfer unit 94. The Peltier element 95 includes an element portion including a heat absorption area and a heat generation area. The Peltier element 95 is thermally connected to the heat transfer unit 94. The Peltier element 95 performs a heating or cooling process on the heat transfer unit 94.

[0101] The heat sink 96 is provided on the opposite side of the Peltier element 95 from the heat transfer section 94. The heat sink 96 is thermally connected to the Peltier element 95. A refrigerant flows through the heat sink 96. The heat sink 96 promotes heat dissipation from the Peltier element 95. The cooling fan 97 is provided on the opposite side of the heat sink 96 from the Peltier element 95. The cooling fan 97 is thermally connected to the heat sink 96. The cooling fan 97 cools the heat sink 96.

[0102] The detection unit 92 detects the temperature of the sample S flowing through the introduction pipe 123 (hereinafter referred to as "the temperature of the sample S"). The detection unit 92 has a temperature sensor 98 and a sealing member 99. The tip of the temperature sensor 98 is inserted into the introduction pipe 123 between the heat transfer unit 94 and the holding unit 11. The temperature sensor 98 is, for example, a thermocouple or a resistance temperature detector. The sealing member 99 is provided at the portion of the introduction pipe 123 into which the temperature sensor 98 is inserted. The sealing member 99 covers the introduction pipe 123 and a portion of the temperature sensor 98. The sealing member 99 prevents the sample S flowing through the introduction pipe 123 from leaking outside the introduction pipe 123.

[0103] The controller 93 controls the output of the thermal processing unit 91. The controller 93 is electrically connected to each of the temperature sensor 98 and the Peltier element 95. The controller 93 receives a signal from the temperature sensor 98. The controller 93 performs feedback control on the Peltier element 95 based on the detection result of the temperature sensor 98. The controller 93 increases or decreases the output of the Peltier element 95 based on the detection result of the temperature sensor 98. When the temperature of the sample S exceeds an upper threshold, the controller 93 sends a cooling signal to the Peltier element 95, causing the Peltier element 95 to cool the heat transfer unit 94. When the temperature of the sample S falls below a lower threshold, the controller 93 sends a heating signal to the Peltier element 95, causing the Peltier element 95 to heat the heat transfer unit 94. The upper threshold and the lower threshold may be different from each other or may be the same. The controller 93 includes a CPU (Central Processing Unit), a ROM (Read Only Memory), a RAM (Random Access Memory), and the like.

[0104] The controller 93 has a monitor 93a and a plurality of switches 93b. The monitor 93a displays, for example, the temperature of the sample S and an upper or lower threshold value. In the example shown in FIG. 10, the temperature of the sample S is 25.8°C, and the upper and lower threshold values ​​are 25.0°C. Each switch 93b has a function of instructing the ON / OFF operation of the heat treatment unit 91, heating processing by the Peltier element 95, cooling processing by the Peltier element 95, or display on the monitor 93a. The transmission of a cooling signal and a heating signal to the Peltier element 95 may be performed automatically by the controller 93 or manually by the switch 93b.

[0105] As described above, the ATR instrument 1B includes an inlet pipe 123 for supplying the sample S to the holder 11 and a temperature adjustment unit 90 for adjusting the temperature of the sample S flowing through the inlet pipe 123. By adjusting the temperature of the sample S flowing through the inlet pipe 123, the temperature of the sample S held by the holder 11 can be maintained constant. This reduces the effect of temperature changes in the sample S on the measurement results. Furthermore, the temperature adjustment unit 90 performs a heating or cooling process on the relatively small volume of sample S flowing through the inlet pipe 123, thereby quickly adjusting the temperature of the sample S in real time. This makes it possible to obtain detailed information about the sample S with high accuracy. A change in the temperature of the sample S may also change the measurement results. In such cases, it may be difficult to determine whether the change in the measurement results is due to a change in the temperature of the sample S or a change in the physical properties of the sample S. In other words, information derived from the physical properties of the sample S may be obscured by changes in the measurement results caused by temperature changes in the sample S, which may make it difficult to accurately measure information about the sample S. As described above, the ATR device 1B can suitably solve such problems.

[0106] The temperature adjustment unit 90 has a heat treatment unit 91 that performs heating or cooling treatment on the sample S flowing through the introduction pipe 123, a detection unit 92 that detects the temperature of the sample S flowing through the introduction pipe 123, and a controller 93 that controls the output of the heat treatment unit 91. The controller 93 increases or decreases the output of the heat treatment unit 91 based on the detection result by the detection unit 92. This makes it possible to adjust the temperature of the sample S flowing through the introduction pipe 123 with high precision. Therefore, the temperature of the sample S held by the holding unit 11 can be maintained with high precision, making it possible to obtain detailed information about the sample S with high precision.

[0107] The temperature adjustment unit 90 is provided in the introduction pipe 123, and further, the temperature sensor 98 is provided between the heat transfer unit 94 and the holding unit 11. With this configuration, the temperature of the sample S can be detected at a position relatively close to the holding unit 11. As a result, even if the temperature of the sample S changes between the heat transfer unit 94 and the holding unit 11 due to a temperature change in the environment in which the ATR apparatus 1B is placed, the temperature of the sample S held by the holding unit 11 can be detected with higher accuracy. Moreover, the temperature adjustment unit 90 is provided in a position on the introduction pipe 123 closer to the holding unit 11 than the pump 121. With this configuration, the temperature of the sample S can be detected at a position even closer to the holding unit 11, and the temperature of the sample S held by the holding unit 11 can be detected with higher accuracy.

[0108] The heat treatment unit 91 includes a Peltier element 95. This makes it possible to easily and reliably adjust the temperature of the sample S flowing through the introduction pipe 123 with high precision.

[0109] FIG. 12 shows the results of a comparative example and an example. In each of the comparative example and the example, the change over time in the refractive index of the sample S held by the holding unit 11 was measured. In each of the comparative example and the example, heating of the sample S held in the container 122 by the heater began about 25 minutes after the start of the measurement, and heating of the sample S held in the container 122 by the heater was stopped about 40 minutes after the start of the measurement. The ATR device of the comparative example differs from the ATR device 1B of the example in that it does not include a temperature adjustment unit 90. In other words, in the comparative example, the temperature of the sample S flowing through the introduction tube 123 was not adjusted.

[0110] As shown in FIG. 12, the refractive index L1 of the comparative example gradually increases after about 25 minutes have elapsed since the start of measurement, and gradually decreases after about 40 minutes have elapsed since the start of measurement. This result is thought to be due to the fact that the sample S contained in the container 122 was heated, causing a change in the temperature of the sample S held by the holder 11. In contrast, no significant change over time was observed in the refractive index L2 of the example. This result is thought to be due to the fact that the temperature of the sample S flowing through the inlet tube 123 was adjusted by the temperature adjustment unit 90, so that the temperature of the sample S held by the holder 11 was maintained constant despite the heating of the sample S contained in the container 122.

[0111] 13, the heat treatment section 91 of the ATR apparatus 1B may have a heat transfer section 94A instead of the heat transfer section 94. The heat transfer section 94A may have, for example, a rod shape. The introduction pipe 123 may be wound spirally around the heat transfer section 94A.

[0112] The temperature adjustment unit 90 may have a plurality of heat treatment units 91. The heat treatment units 91 may be adjacent to each other outside the introduction pipe 123. The temperature adjustment unit 90 may have one detection unit 92 corresponding to the plurality of heat treatment units 91. The temperature adjustment unit 90 may have a plurality of detection units 92 corresponding to the respective heat treatment units 91. In the temperature adjustment unit 90, a single controller 93 may control the plurality of heat treatment units 91 and the plurality of or one detection unit 92.

[0113] The temperature sensor 98 may be provided at any position in the flow path of the sample S as long as it can detect the temperature of the sample S. The tip of the temperature sensor 98 may be inserted into the inlet pipe 123, for example, between the heat transfer unit 94 and the pump 121. The tip of the temperature sensor 98 may be inserted into the tube 123, for example, between the pump 121 and the container 122, or between the container 122 and the holder 11. In these cases, the temperature of the sample S can be detected flexibly as needed, thereby improving the degree of freedom in designing the ATR instrument 1B.

[0114] The sample S may not include a suspension, may not include suspended matter dispersed in a liquid, or may include only a liquid. [Explanation of symbols]

[0115] 1, 1A, 1B...ATR device (attenuated total reflection spectroscopy device), 11, 18...holding section, 12, 19...adjustment section, 16...holding body, 16c...recess, 16d...inlet hole, 16e...outlet hole, 20...light output section, 30...prism (optical element), 30c...reflecting surface, 70...light detection section, 90...temperature adjustment section, 91...heat treatment section, 92...detection section, 93...controller (control section), 95...Peltier element, 121...pump, 124...output control section, 123...inlet tube, R...accommodation space, S...sample, T...terahertz wave (light).

Claims

1. an optical element having a reflective surface; a holder that holds a sample containing a suspension on the reflecting surface; an adjusting unit that adjusts the flow state of the sample held on the reflecting surface, The adjustment unit adjusting the flow state of the sample to a first flow state to obtain a first detection result for the sample in the first flow state; adjusting the flow state of the sample to a second flow state to obtain a second detection result for the sample in the second flow state; An attenuated total reflection spectroscopy apparatus, wherein the first detection result in the first flow state and the second detection result in the second flow state are detection results of the same sample.

2. the holding unit includes a holding body disposed on the reflecting surface, the holder has a recess that, together with the reflecting surface, defines a storage space for the sample, an introduction hole that communicates with the recess and through which the sample flows when introduced into the storage space, and an outlet hole that communicates with the recess and through which the sample flows when discharged from the storage space, 2. The attenuated total reflection spectroscopy apparatus according to claim 1, wherein the adjustment unit includes: a pump that circulates the sample from the outlet hole to the inlet hole; and an output control unit that controls an output of the pump.

3. 3. The attenuated total reflection spectroscopy apparatus according to claim 2, wherein the holder is transparent to visible light.

4. a light output unit that outputs light to the reflecting surface from the side opposite to the sample; a light detection unit that detects the light reflected by the reflecting surface, 4. The attenuated total reflection spectroscopy apparatus according to claim 1, wherein the adjusting section adjusts the flow state of the sample during a period in which the light detecting section detects the light.

5. 5. The attenuated total reflection spectroscopy apparatus according to claim 4, wherein the light output from the light output section is a terahertz wave.

6. an introduction tube connected to the holding unit for supplying the sample to the holding unit; 6. The attenuated total reflection spectroscopy apparatus according to claim 1, further comprising: a temperature adjusting unit provided in the inlet pipe to adjust the temperature of the sample flowing through the inlet pipe.

7. The temperature adjustment unit is a heat treatment unit provided outside the introduction pipe and performing a heating treatment or a cooling treatment on the sample flowing through the introduction pipe; a detection unit for detecting the temperature of the sample flowing through the introduction pipe; a control unit that controls the output of the heat treatment unit, The attenuated total reflection spectroscopy apparatus according to claim 6 , wherein the control unit increases or decreases the output of the heat processing unit based on the detection result of the detection unit.

8. 8. The attenuated total reflection spectroscopy apparatus according to claim 7, wherein the heat treatment section includes a Peltier element.

9. a first step of holding a sample containing a suspension on a reflective surface; a second step of adjusting the fluidity state of the sample held on the reflecting surface so that the sample is in a first fluidity state; a third step of obtaining a first detection result for the sample in the first flow state; a fourth step of adjusting the fluidity state of the sample held on the reflecting surface so that the sample is in a second fluidity state; and a fifth step of obtaining a second detection result regarding the sample in the second flow state; The attenuated total reflection spectroscopy method, wherein the first detection result in the first flow state and the second detection result in the second flow state are detection results of the same sample.

10. 10. The method of claim 9, wherein the first flow state is stronger than the second flow state.

11. 11. The method of claim 10, wherein the second flow state is a quiescent state.

12. a sixth step of outputting light to the reflecting surface from a side opposite to the sample and detecting the light reflected by the reflecting surface; The attenuated total reflection spectroscopy method according to any one of claims 9 to 11, wherein the second step, the third step, the fourth step, and the fifth step are performed during a period in which the sixth step is performed.

13. The attenuated total reflection spectroscopy method according to claim 12 , wherein the light is a terahertz wave.

14. The attenuated total reflection spectroscopy method according to any one of claims 9 to 13, further comprising a seventh step of acquiring information about the sample based on the first detection result and the second detection result.

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