JP6796550B2 - Automatic sample changer for NMR - Google Patents

Description

The present invention relates to an automatic sample exchange device used in a nuclear magnetic resonance device.

As a magnetic resonance device, a nuclear magnetic resonance (NMR) device and an electron spin resonance (ESR) device are known. As an apparatus similar to an NMR apparatus, a magnetic resonance imaging (MRI) apparatus is also known. Hereinafter, the NMR apparatus will be described.

The NMR apparatus irradiates a sample placed in a static magnetic field with a high-frequency signal, then detects a minute high-frequency signal (NMR signal) emitted from the sample, and extracts molecular structure information contained in the NMR signal to obtain molecules. It is a device that analyzes the structure.

In an NMR apparatus, an automatic sample exchange apparatus that automatically puts in and takes out a sample may be used in order to improve the efficiency of the work of continuously setting and taking out a sample (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-234539

By the way, the conventional automatic sample exchange device does not have a sample temperature control function. Therefore, when measuring a sample that requires temperature adjustment (for example, when measuring a sample whose physical properties change unless the temperature is maintained at a certain temperature), for example, a device having a temperature control function such as a refrigerator. It is necessary for the operator to take out the sample from the device and install it in the automatic sample exchange device at the time of measurement by storing the sample separately. As described above, when measuring a sample that requires temperature adjustment, human work is required. In addition, there is a problem that the temperature of the sample changes while the sample is moved from the device having the temperature control function to the automatic sample exchange device.

An object of the present invention is to enable the temperature of a sample to be adjusted in an automatic sample exchange device for NMR.

The automatic sample exchange device for NMR of the present invention is a hollow sleeve row accommodating a plurality of sample units for nuclear magnetic resonance measurement, and includes a sleeve row having a plurality of introduction holes formed at the bottom and the sleeve row. A hollow manifold tube provided at a position facing the bottom and having a plurality of blowout holes, and a temperature control gas introduced into the manifold tube was formed in the sleeve row from the plurality of blowout holes. It is characterized in that it is introduced into the inside of the sleeve row through the plurality of introduction holes.

According to the above configuration, the temperature of the sample in the sample unit housed in the sleeve is adjusted by the temperature control gas introduced into the sleeve. As the temperature control gas, a gas for cooling the sample may be used, or a gas for heating the sample may be used.

The manifold tube may have an annular shape. For example, when an annular sleeve row is used, an annular manifold tube is used according to the shape. For example, the annular manifold tube is provided with one introduction port, and the temperature control gas is introduced into the manifold tube from the introduction port. The temperature control gas introduced into the manifold tube branches from the introduction port and flows through the manifold tube. As another example, a linear manifold tube may be used. For example, when a linear sleeve row is used, a linear manifold tube is used according to the shape.

The sizes of the plurality of blowout holes may be different from each other. For example, the size of each blowout hole changes according to the distance from the introduction port formed in the manifold tube.

In the manifold tube, the diameter of the blowout hole may gradually increase from the upstream side to the downstream side of the temperature control gas. For example, the introduction port formed in the manifold tube corresponds to the upstream side. On the downstream side, the pressure and flow rate of the temperature control gas are lower than on the upstream side, and as a result, a temperature difference is likely to occur between the sample units. However, by adopting the above configuration, the diameter of each outlet hole The temperature difference can be reduced as compared with the case where the above are the same.

A discharge hole for discharging the temperature control gas introduced into the sleeve to the outside of the sleeve may be formed in the middle portion of each sleeve included in the sleeve row. By providing the discharge hole in the intermediate portion, it is possible to suppress or prevent the temperature control gas introduced into the sleeve from the bottom of the sleeve from reaching the upper part of the sleeve.

A dummy sample may be arranged on the sleeve in which the sample unit is not housed in the sleeve row. For example, the upper part of the sleeve has an opening for accommodating the sample unit, and a dummy sample is arranged in the opening in the sleeve where the sample unit is not accommodated. As a result, it is possible to prevent the temperature control gas introduced into the sleeve from being discharged to the outside of the sleeve through the opening at the upper portion thereof.

The automatic sample exchange device for NMR of the present invention may further include a heat insulating material provided around the sleeve row. By using a heat insulating material, the occurrence of dew condensation can be suppressed or prevented.

Each sample unit may be taken out from the upper part of each sleeve by inserting a projecting rod into the introduction hole formed at the bottom of each sleeve included in the sleeve row. According to this configuration, the introduction hole serves both as a hole for supplying the temperature control gas into the sleeve and a hole for taking out the sample unit from the sleeve. By doing so, it is not necessary to separately provide another configuration for supplying the temperature control gas or another configuration for taking out the sample unit.

The automatic sample exchange device for NMR of the present invention may further include a turntable portion that moves the sleeve to be taken out included in the sleeve row to the sampling position by mounting and rotating the sleeve row. At the sampling position, the protruding rod is inserted into the introduction hole formed at the bottom of the sleeve, so that the sample unit is taken out from the upper part of the sleeve, and the manifold tube is held at the sampling position. The protruding rod may be provided so as to avoid a position where it protrudes from the bottom surface of the sleeve.

According to the present invention, it is possible to adjust the temperature of a sample in an automatic sample exchange device for NMR.

It is a perspective view which shows the NMR system which concerns on this embodiment. It is a perspective view which shows the carousel device. It is a perspective view which shows the manifold. It is a perspective view which shows the sample unit. It is a perspective view which shows the sample unit and the sample sleeve. It is sectional drawing which shows the sample unit and the sample sleeve. It is a perspective view which shows the dummy sample. It is a perspective view which shows a dummy sample and a sample sleeve. It is sectional drawing which shows the gas introduction part for temperature control of a carousel apparatus. It is sectional drawing which shows the turntable part of a carousel device.

Hereinafter, the NMR system according to the embodiment of the present invention will be described. FIG. 1 shows an example of an NMR system according to the present embodiment. The NMR system 10 includes an NMR device 12, an automatic sample exchange device 14, and a temperature control gas supply device 16.

The NMR apparatus 12 is an apparatus for measuring an NMR signal generated by an observation nucleus in a sample. The NMR apparatus 12 includes a static magnetic field generator 18 and an NMR probe (not shown). Further, an apparatus including a host computer and an NMR spectrometer may be referred to as an NMR apparatus. The static magnetic field generator 18 includes, for example, a superconducting electromagnet (SCM) and is a device that forms a static magnetic field. The NMR probe includes a transmission / reception coil and is inserted into a tubular cavity formed in the static magnetic field generator 18. When an RF transmission signal is supplied to the transmission / reception coil, an electromagnetic wave is generated there, and a resonance absorption phenomenon occurs in the observation nucleus. After that, the NMR signal (RF reception signal) induced in the transmission / reception coil is sent from the NMR probe to the NMR spectrometer, and the spectrum of the NMR signal is analyzed.

The automatic sample exchange device 14 is an device corresponding to an example of an automatic sample exchange device for NMR, and is a device having a function of accommodating a plurality of sample units and adjusting the temperature of a sample. The automatic sample exchange device 14 includes a carousel device 20. The carousel device 20 is, for example, a device that accommodates a plurality of sample units by a turntable method. Of course, a plurality of sample units may be housed in the automatic sample exchange device 14 by a method other than the turntable method. The configuration of the carousel device 20 will be described in detail later. As will be described later, the sample to be measured is included in the sample unit.

The temperature control gas supply device 16 is a device that supplies a gas for adjusting the temperature of the sample (hereinafter, referred to as “temperature control gas”) to the automatic sample exchange device 14. The automatic sample exchange device 14 adjusts the temperature of the sample by the temperature control gas supplied from the temperature control gas supply device 16. The temperature of the temperature control gas is, for example, −40 ° C. to 100 ° C. Of course, a temperature control gas having a temperature of less than −40 ° C. may be used, or a temperature control gas having a temperature higher than 100 ° C. may be used. Air may be used as the temperature control gas, or argon gas, nitrogen gas, or the like may be used. Further, the temperature control gas supply device 16 can control the supply pressure of the temperature control gas and the flow rate of the temperature control gas. This makes it possible to supply the temperature control gas at a desired flow rate at a desired pressure.

A guide rail 22 for transporting the sample unit is provided between the static magnetic field generator 18 and the automatic sample exchange device 14. The guide rail 22 is provided with a manipulator 24 that can move along the guide rail 22. The manipulator 24 has a function of gripping a sample unit housed in the carousel device 20.

At the time of introducing the sample into the NMR apparatus 12, the sample unit containing the sample to be measured is grasped by the manipulator 24 and taken out from the carousel apparatus 20. As the manipulator 24 moves from the automatic sample exchange device 14 side to the upper part of the static magnetic field generator 18 along the guide rail 22, the sample unit is held by the manipulator 24 and the static magnetic field is moved from the automatic sample exchange device 14. It is transported above the generator 18. Above the static magnetic field generator 18, an opening (sample introduction port) leading to the cavity formed in the static magnetic field generator 18 is formed. The manipulator 24 conveys the sample unit to a position directly above the sample introduction port, and releases the sample unit at the position directly above the sample unit. As a result, the sample unit is lowered into the cavity through the sample introduction port, and is arranged in the NMR probe installed in the cavity while being controlled by the air blowing up in the cavity.

At the time of sample removal, the sample unit is raised from the NMR probe to the sample introduction port in the cavity of the static magnetic field generator 18 by the supply of air. Therefore, the manipulator 24 grabs the sample unit, moves along the guide rail 22 from above the static magnetic field generator 18 toward the automatic sample exchange device 14, and conveys the sample unit to a position directly above the carousel device 20. The sample unit is lowered by the manipulator 24 and housed in the carousel device 20.

Hereinafter, the carousel device 20 will be described in detail with reference to FIG. FIG. 2 is a perspective view showing the carousel device 20. FIG. 2 shows the carousel device 20 with the cover removed. Further, the heat insulating material and the like described later are not shown.

The carousel device 20 includes a turntable unit 26, a motor 28, a manifold 30, and a temperature control gas introduction unit 32.

The turntable unit 26 functions as a turntable mechanism on which a plurality of sample units are placed and rotated. The turntable portion 26 includes an upper table 34, a lower table 36, and a plurality of pillars 40.

The upper table 34 is a member having a disk-like shape as a whole. The lower table 36 is a member having an annular (doughnut-shaped) shape as a whole. The drum 38 is a member having a columnar shape as a whole. The upper surface of the drum 38 has a slight clearance with the upper table 34. The diameter of the drum 38 is smaller than the diameter of the hole of the lower table 36 (inner diameter of the ring), and the drum 38 is provided so as to penetrate the hole portion of the lower table 36 (the hole portion of the ring). Has been done. A motor 28 is installed below the turntable portion 26, that is, below the lower table 36, and the drum 38 is connected to the motor 28 through the hole portion of the lower table 36. As will be described later, the sample sleeve 52 is installed on the upper table 34 and the lower table 36 in a region radially outside the drum 38.

The plurality of pillars 40 are installed between the upper table 34 and the lower table 36 along the circumferential direction at intervals of predetermined distances from each other in the circumferential direction. The upper end of each pillar 40 is fixed to the upper table 34, and the lower end of each pillar 40 is fixed to the lower table 36. The upper table 34 and the lower table 36 are connected (fixed) to each other by a plurality of pillars 40.

Further, a plurality of holes 42 are formed in the upper table 34 along the circumferential direction, and a plurality of holes 44 are formed in the lower table 36 at positions corresponding to the plurality of holes 42 along the circumferential direction. Has been done. The sample sleeve 52 is inserted into the plurality of holes 42 and 44. As an example, 30 holes 42 and 30 holes 44 corresponding to them are formed.

As described above, the motor 28 is connected to the drum 38, and the drum 38 rotates about the rotation center 46 as the rotation axis by the driving force of the motor 28. When the drum 38 rotates, the upper table 34 fixed to the drum 38 and the lower table 36 connected (fixed) to the upper table 34 by a plurality of pillars 40 rotate about the rotation center 46 as a rotation axis.

Below the lower table 36, a support base 49 having an annular shape as a whole is set in a state where a gap is secured between the lower table 36 and the lower table 36. The support base 49 is provided with a manifold 30 on the upper surface facing the lower table 36. The manifold 30 is a member having an annular shape as a whole. The manifold 30 includes a sheet metal base 48 and a manifold tube 50 provided on the sheet metal base 48. The manifold tube 50 is installed at a position facing the plurality of holes 44 formed in the lower table 36. The manifold tube 50 is connected to the temperature control gas introduction unit 32. The temperature control gas introduction unit 32 is connected to the temperature control gas supply device 16 by a tube. As shown by the arrow A, the temperature control gas supplied from the temperature control gas supply device 16 is introduced into the temperature control gas introduction section 32 from the connection port 32a of the temperature control gas introduction section 32, and the temperature control gas introduction section is introduced. It is introduced into the manifold tube 50 via 32. Further, the manifold tube 50 is formed with a plurality of blowout holes in a portion facing the lower table 36, and the temperature control gas introduced into the manifold tube 50 is discharged from the plurality of blowout holes to the outside of the manifold tube 50. Squirt into. Each blowout hole of the manifold tube 50 is formed at a position corresponding to each hole 44 formed in the lower table 36. The manifold 30 will be described in detail later. The rotation shaft of the motor 28 and the rotation shaft of the drum 38 are connected to each other through the holes (ring holes) of the support base 49.

A sample sleeve 52 is inserted into each hole 42 formed in the upper table 34 and each hole 44 formed in the lower table 36, and in that state, the sample sleeve 52 is supported by the upper table 34. The sample sleeve 52 is a hollow member that houses the sample unit 54. The sample unit 54 is a member for accommodating a sample, and includes a sample rotor 56 and a sample tube 58. The sample is housed in the sample tube 58. The sample sleeve 52 and the sample unit 54 will be described in detail later. By inserting the sample sleeve 52 into each of the plurality of holes 42 and 44, the plurality of sample sleeves 52 are installed in the turntable portion 26. By accommodating the sample unit 54 in each sample sleeve 52, a plurality of sample units 54 are installed in the turntable portion 26.

When the upper table 34 and the lower table 36 are rotated by the driving force of the motor 28, the sample sleeve 52 supported by the upper table 34 moves, whereby the sample unit 54 housed in the sample sleeve 52 moves. The turntable unit 26 can move the desired sample unit 54 to a sampling position (predetermined rotation position) by such a rotation operation. At the sampling position, a rod-shaped Z-axis actuator mechanism (a member corresponding to an example of a protruding rod) (not shown) is arranged below the carousel device 20. The Z-axis actuator mechanism is a member that can move in the vertical direction at the sampling position. As will be described later, an introduction hole connected to the hollow inside is formed at the bottom of each sample sleeve 52, and the Z-axis actuator mechanism is inserted into the introduction hole of the sample sleeve 52 moved to the sampling position. Then, the sample unit 54 housed in the sample sleeve 52 is pushed upward. At the time of introducing the sample into the NMR apparatus 12, the manipulator 24 grasps the pushed-up sample unit 54 and moves to the upper part of the static magnetic field generator 18 along the guide rail 22 as described above, thereby statically. The sample unit 54 is conveyed to a position directly above the sample introduction port formed above the magnetic field generator 18, and the sample unit 54 is released at that position. As a result, the sample unit 54 is arranged in the NMR probe installed in the static magnetic field generator 18. At the time of sample extraction, as described above, the manipulator 24 grasps the sample unit 54 raised to the sample introduction port of the static magnetic field generator 18, and automatically exchanges the sample from above the static magnetic field generator 18 along the guide rail 22. It moves to the device 14 side and lowers the sample unit 54 at the sampling position. As a result, the sample unit 54 is housed in the sample sleeve 52 arranged at the sampling position. When measuring the next sample, the turntable unit 26 rotates so that the sample unit 54 containing the sample to be measured next is placed at the sampling position. As a result, the next sample unit 54 is arranged at the sampling position, and the same operation as described above is performed.

In the present embodiment, the temperature control gas ejected from the blowout hole formed in the manifold tube 50 is introduced into the inside of the sample sleeve 52 through the introduction hole formed in the bottom of the sample sleeve 52. As a result, the temperature of the sample in the sample unit 54 housed in the sample sleeve 52 is controlled. A discharge hole 60 connected to the hollow inside is formed in the middle portion of the side surface of the sample sleeve 52 (the portion between the upper part and the lower part of the sample sleeve 52), and is used for temperature control introduced inside the sample sleeve 52. The gas is discharged to the outside through the discharge hole 60.

Hereinafter, the manifold 30 will be described in detail with reference to FIG. FIG. 3 is a perspective view showing the manifold 30.

The manifold 30 includes a sheet metal base 48 having an annular shape as a whole, and a manifold tube 50 attached to the sheet metal base 48. The sheet metal base 48 is provided with an inwardly recessed portion 62 (for example, a portion having a U-shape). The position of this portion 62 is a position corresponding to the sampling position, and the Z-axis actuator mechanism moves in the vertical direction (Z direction) through this portion 62. When the Z-axis actuator mechanism moves upward, the sample unit 54 arranged at the sampling position is pushed upward. A portion 62 is provided on the sheet metal base 48 in order to avoid interference between the Z-axis actuator mechanism and the manifold 30. Further, the manifold tube 50 is provided along the sheet metal base 48, and the manifold tube 50 is also recessed inward in the portion 62 as shown by reference numeral 64. Since the manifold tube 50 is arranged in the recessed portion 62 so as to avoid the Z-axis actuator mechanism, the temperature control gas is not supplied into the sample sleeve 52 arranged in the recessed portion 62.

The manifold tube 50 is provided with an introduction port 66 for introducing a temperature control gas from the outside to the inside of the manifold tube 50. The introduction port 66 leads to the inside of the manifold tube 50, and as shown by an arrow B, the temperature control gas is introduced into the inside of the manifold tube 50 from the introduction port 66. For example, the introduction port 66 is provided at a position facing the recessed portion 62, and the temperature control gas introduced into the manifold tube 50 from the introduction port 66 is on the upstream side along the directions of arrows C1 and C2. Flows from the introduction port 66 toward the downstream portion 62.

Further, the manifold tube 50 is formed with a plurality of blowout holes 68 (orifice holes) in a portion facing the lower table 36. Each blowout hole 68 is formed at a position corresponding to each hole 44 formed in the lower table 36. As an example, 29 blowout holes 68 are formed. The manifold tube 50 has a loop-shaped piping structure in order to suppress the pressure loss and supply the temperature control gas to the downstream side with the introduction port 66 as the upstream side. The manifold 30 is installed on the support 49 so that each blowout hole 68 is arranged at a position corresponding to the lower end of the sample sleeve 52. To avoid heat loss, the manifold tube 50 is attached to the sheet metal base 48 so as to avoid contact with the sheet metal base 48. For example, the manifold tube 50 is attached to the sheet metal base 48 in contact with only a plurality of resin cable clips 70.

The manifold tube 50 is made of a fluororesin (for example, Teflon (registered trademark)) having a small heat loss and a wide heat resistant temperature range. Of course, the manifold tube 50 may be made of another material.

The size of the blowout hole 68 (for example, the size of the diameter of the hole) gradually increases from the upstream side to the downstream side. For example, the diameter of the blowout hole 68 gradually increases from 0.6 mm from the upstream side to the downstream side. Normally, the pressure of the temperature control gas is lower and the flow rate is lower toward the downstream, so that the pressure of the temperature control gas ejected from the blowout hole 68 is lower and the flow rate is likely to be lower toward the downstream. As a result, the pressure of the temperature control gas supplied into the sample sleeve 52 becomes lower and the flow rate becomes smaller toward the downstream side, and the temperature of the sample in the sample unit 54 arranged on the downstream side and the sample arranged on the upstream side The difference between the temperature of the sample in the unit 54 and the temperature of the sample tends to be large. In order to deal with this, the size of the blowout hole 68 is gradually increased from the upstream side to the downstream side. By doing so, the flow rate of the temperature control gas ejected from the outlet holes 68 on the downstream side increases as compared with the case where the sizes of the outlet holes 68 are made the same. As a result, the difference between the temperature of the sample in the sample unit 54 arranged on the downstream side and the temperature of the sample in the sample unit 54 arranged on the upstream side can be reduced. It is also possible to minimize the temperature difference by determining the size of the blowout hole 68 by experiment or simulation.

The temperature difference when the diameter of the blowout hole 68 was increased toward the downstream side (Example) and the temperature difference when the diameter of each blowout hole 68 was made the same (Comparative Example) were measured. In the example, the diameter of the blowout hole 68 was changed in the range of 0.6 mm to 1.3 mm. That is, the diameter of the most upstream outlet hole 68 is the minimum 0.6 mm, the diameter of the most downstream outlet hole 68 is the maximum 1.3 mm, and the diameter of each outlet hole 68 between the most upstream and the most downstream. Was made larger toward the downstream. In the comparative example, the diameter of all the blowout holes 68 is 0.7 mm. In this measurement, a temperature control gas having a temperature of −20 ° C. was introduced into the manifold tube 50. The flow rate of the temperature control gas at the time of introduction is 40 L / min. In the examples, the temperature difference between the sample tubes 58 was about 4 ° C., and in the comparative example, the temperature difference was about 10 ° C. In this way, by increasing the blowout hole 68 toward the downstream side, it is possible to reduce the temperature difference of each sample.

Hereinafter, the sample unit 54 will be described in detail with reference to FIG. FIG. 4 is a perspective view showing the sample unit 54. The sample unit 54 includes a sample rotor 56 and a sample tube 58. The sample tube 58 has, for example, a cylindrical elongated shape in which one end 58a is open and the other end 58b is closed. A sample (for example, a solution sample) is housed in the sample tube 58 from one end 58a, and then one end 58a is sealed. The sample tube 58 penetrates the sample rotor 56 as a holding member and is held by the sample rotor 56. The sample tube 58 is made of, for example, glass.

Hereinafter, the sample unit 54 and the sample sleeve 52 will be described in detail with reference to FIGS. 5 and 6. FIG. 5 is a perspective view showing the sample unit 54 and the sample sleeve 52. FIG. 6 is a cross-sectional view showing the sample unit 54 and the sample sleeve 52, and is an IV-IV cross-sectional view of FIG. FIG. 6 shows the sample unit 54 and the sample sleeve 52 installed on the turntable portion 26, and a part of the turntable portion 26 is also shown.

An insertion hole leading to the internal space 72 in the sample sleeve 52 is formed in the upper part of the sample sleeve 52, and the sample unit 54 is inserted into the sample sleeve 52 through the insertion hole and accommodated in the sample sleeve 52. To. As a result, a portion including the other end 58b of the sample tube 58 is arranged in the internal space 72 of the sample sleeve 52. The sample to be measured is housed in that part. The sample sleeve 52 is made of, for example, ABS resin.

An introduction hole 74 leading into the internal space 72 is formed at the bottom of the sample sleeve 52. The turntable portion 26 rotates so that the introduction hole 74 is arranged at a position facing the blowout hole 68 formed in the manifold tube 50. Although the cross section (circular shape) of the manifold tube 50 is shown in FIG. 6, the blowout hole 68 is not shown due to the cross-sectional position. The temperature control gas ejected from the blowout hole 68 is supplied to the internal space 72 from the introduction hole 74 as shown by an arrow D. For example, the temperature control gas supplied to the internal space 72 directly contacts the sample tube 58 and circulates in the sample sleeve 52 to exchange heat with the sample tube 58. As a result, the temperature of the sample tube 58 arranged in the internal space 72, that is, the temperature of the sample arranged in the sample tube 58 is controlled by the temperature control gas. When the temperature control gas for cooling is used, when the temperature control gas reaches one end 58a of the sample tube 58, the turntable portion 26 is cooled and dew condensation may occur. In order to deal with this, a discharge hole 60 is formed at an intermediate position of the sample sleeve 52 (a position corresponding to a position between one end 58a and the other end 58b of the sample tube 58), and the temperature is increased. The mixing gas is discharged to the outside through the discharge hole 60. Thereby, it is possible to suppress or prevent the temperature control gas from reaching one end 58a.

As shown in FIG. 5, the sample sleeve 52 is composed of a main body portion 52a having a relatively small diameter and an upper portion 52b provided on the upper portion of the main body portion 52a and having a relatively large diameter. There is. The diameter of the main body 52a is smaller than the diameter of the holes 42 and 44 of the upper table 34 and the lower table 36, and the diameter of the upper 52b is larger than the diameter of the holes 42 and 44. As a result, as shown in FIGS. 2 and 6, the main body 52a passes through the holes 42 and 44, the upper portion 52b does not pass through the holes 42, and the sample sleeve 52 is held by the upper table 34. The main body portion 52a and the upper portion 52b may be integrally formed, or may be formed as separate bodies and integrated.

Further, as shown in FIG. 6, from the upper table 34 to the lower table 36, in the region outside the position where the sample sleeve 52 is installed, the aluminum plate 76, the heat insulating material 78, the mesh material 80, and the mesh material 80 are arranged in this order from the inside. , An outer cover 82 is provided. The aluminum plate 76 is a member used as a reinforcing material. The heat insulating material 78 is made of, for example, urethane. The mesh material 80 is provided to form an air layer as a heat insulating layer, and is made of, for example, polyester or the like. The outer cover 82 is made of, for example, an aluminum plate.

The dummy sample will be described below. If there is a portion of the turntable portion 26 in which the sample unit 54 is not loaded, only the sample sleeve 52 will be arranged at that portion. As described above, an insertion hole for inserting the sample unit 54 is formed in the upper part of the sample unit 54. Therefore, if the sample unit 54 is not housed in the sample sleeve 52, outside air enters the internal space 72 from the upper part of the sample sleeve 52. That is, the outside air enters the inside of the carousel device 20. As a result, the temperature inside the carousel device 20 fluctuates depending on the outside air. In order to deal with this, a dummy sample is installed on a sample sleeve 52 installed at a place where the sample unit 54 is not loaded.

7 and 8 show an example of a dummy sample. FIG. 7 is a perspective view showing a dummy sample 84. FIG. 8 is a perspective view showing a dummy sample 84 and a sample sleeve 52.

As shown in FIG. 7, the dummy sample 84 includes a columnar main body 86 having a relatively small diameter, a columnar upper 88 provided above the main body 86 and having a relatively large diameter, and the like. It is composed of. The diameter of the main body 86 is smaller than the diameter of the insertion hole formed in the upper part of the sample sleeve 52. The diameter of the top 88 is larger than the diameter of its insertion hole. As a result, as shown in FIG. 8, the main body 86 of the dummy sample 84 is inserted into the insertion hole formed in the upper part of the sample sleeve 52, and the dummy sample 84 is housed in the sample sleeve 52. The dummy sample 84 functions as a lid for the sample sleeve 52, and can prevent outside air from entering the inside through the insertion hole formed in the upper part of the sample sleeve 52. As a result, it is possible to suppress or prevent temperature fluctuations in the carousel device 20 due to outside air.

The automatic sample exchange device 14 is provided with a sensor for detecting the presence or absence of the sample unit 54, but the dummy sample 84 is configured so as not to be detected by the sensor due to its shape and color. For example, the height of the dummy sample 84 when installed on the sample sleeve 52 may be a height at which the sensor does not react, or when a reflective photoelectric sensor is used, light is not reflected from the dummy sample 84. The color of the dummy sample 84 may be black.

Further, the diameter of the upper portion 88 of the dummy sample 84 may be made larger than the size of the object that can be grasped by the chuck mechanism portion (the portion having the function of grasping the object) of the manipulator 24. As a result, even if a malfunction occurs in the sensor or the like and the dummy sample 84 is erroneously detected as a sample to be measured, it is possible to prevent the dummy sample 84 from being grasped by the manipulator 24. As a result, it is possible to prevent the introduction of the dummy sample 84 into the NMR apparatus 12.

Hereinafter, the heat insulating structure of the carousel device 20 will be described.

First, with reference to FIG. 9, the heat insulating structure in the temperature control gas introduction unit 32 will be described. FIG. 9 is a cross-sectional view showing a temperature control gas insertion portion. A pipe 90 is provided in the temperature control gas introduction unit 32 to connect the connection port 32a and the introduction port 66 provided in the manifold tube 50. The temperature control gas supplied from the temperature control gas supply device 16 is introduced into the pipe 90 from the connection port 32a, passes through the pipe 90, and is introduced into the manifold tube 50 from the introduction port 66. Further, a heat insulating material 92 for preventing dew condensation is wound around the pipe 90. A drain pan 94 is installed on the lower side of the heat insulating material 92, and another drain pan 96 is installed on the lower side of the drain pan 94. The drain pans 94 and 96 have, for example, a dish-shaped or box-shaped shape. By installing the double drain pan in this way, even if dew condensation occurs, the generated water will be accumulated in the drain pan 94 or the drain pan 96.

Next, with reference to FIG. 10, the heat insulating structure in the turntable portion 26 will be described. FIG. 10 is a cross-sectional view showing the turntable portion 26. As described with reference to FIG. 6, from the upper table 34 to the lower table 36, the aluminum plate 76, the heat insulating material 78, and the mesh material 80 are arranged in the area outside the sample sleeve 52 where the sample sleeve 52 is installed. An outer cover 82 is provided. An aluminum plate 98, a heat insulating material 100, and an epoxy plate 102 are provided on the upper part of the drum 38 in this order from the drum 38 side, and an upper table 34 is provided on the epoxy plate 102. An air layer 104 is formed between the upper table 34 and the epoxy plate 102. For example, in the upper table 34, an engraving is formed on the surface facing the epoxy plate 102, and the engraved portion serves as a gap to form the air layer 104. Further, a heat insulating material 106 is provided in a region outside the hole 42 of the upper table 34. As described above, the sample sleeve 52 is inserted into the holes 42 and 44.

As described above, the occurrence of dew condensation can be suppressed or prevented by installing a member having a heat insulating effect on the portion where the temperature control gas is introduced or on the turntable portion 26. Further, by installing a member having a heat insulating effect around the sample sleeve 52, it is possible to suppress or prevent a temperature change of the sample.

Hereinafter, the operation of the automatic sample exchange device 14 according to the present embodiment will be described. The automatic sample exchange device 14 and the temperature control gas supply device 16 are connected to supply the temperature control gas from the temperature control gas supply device 16 to the automatic sample exchange device 14. As a result, the temperature control gas flows in the manifold tube 50, is ejected from the blowout hole 68 formed in the manifold tube 50, and is supplied to the internal space 72 of the sample sleeve 52 from the introduction hole 74 formed in the lower part of the sample sleeve 52. Will be done. The temperature control gas directly contacts the sample tube 58 installed in the internal space 72 and circulates in the internal space 72 to exchange heat with the sample tube 58. As a result, the temperature of the sample becomes the target temperature. The temperature control gas that has completed heat exchange is discharged into the carousel device 20 through the discharge hole 60 of the sample sleeve 52, and mainly from the recessed portion 62 (see FIG. 3) through which the Z-axis actuator mechanism passes. It is discharged to the outside of the device 20.

According to this embodiment, the temperature of the sample is adjusted by supplying the temperature control gas to the automatic sample exchange device 14. As a result, the sample tube is stored in another device for temperature control, and the operator does not have to move the sample tube from the device to the automatic sample exchange device 14 at the time of measurement. In addition, it is possible to prevent the temperature of the sample from changing while the operator is moving the sample tube.

Further, the temperature control gas is introduced into the sample sleeve 52 through the introduction hole 74 into which the Z-axis actuator is inserted, that is, the introduction hole 74 is used as a hole for inserting the Z-axis actuator and for temperature control. By also using the gas introduction hole, it is not necessary to provide another configuration for introducing the temperature control gas into the sample sleeve 52.

Further, by using the ring-shaped manifold tube 50 as a tube for supplying the temperature control gas into the sample sleeve 52, it is possible to supply the pressure leveled temperature control gas from the upstream side to the downstream side. Therefore, it is possible to suppress the occurrence of pressure loss.

Further, in the manifold tube 50, by gradually increasing the blowout holes 68 from the upstream side to the downstream side, the size of each blowout hole 68 is the same even on the downstream side where the pressure and flow rate of the temperature control gas tend to decrease. It is possible to reduce the temperature difference between the samples as compared with the case of.

Further, by forming the manifold tube 50 with a fluorine-based resin, the heat-resistant temperature range can be widened, and the usable temperature range can be widened. Further, since the thermal conductivity is lower than that of the metal pipe, heat leakage can be suppressed and a manifold with less heat loss can be provided.

Further, not only the temperature control gas is brought into direct contact with the sample tube 58, but also the internal space 72 is circulated, so that heat exchange can be performed efficiently.

Further, by installing the dummy sample 84 on the sample sleeve 52 in which the sample unit 54 is not installed, it is possible to prevent outside air from entering the sample sleeve 52. As a result, the temperature change in the carousel device 20 due to the outside air can be suppressed or prevented. Since the dummy sample 84 has a color and a shape that are difficult to be detected by the sensor, it is difficult to be detected as a sample. Even if the dummy sample 84 is detected as a sample, since the dummy sample 84 has a structure that is difficult to be grasped by the manipulator 24, it is possible to prevent the dummy sample 84 from being conveyed to the NMR apparatus 12. Can be done.

Further, by arranging a member (heat insulating material or air layer) having a heat insulating effect in the carousel device 20, the occurrence of dew condensation can be suppressed or prevented. Even if dew condensation occurs, water collects in the drain pans 94 and 96, so that water leakage to the outside of the apparatus can be prevented.

10 NMR system, 12 NMR device, 4 automatic sample exchange device, 16 temperature control gas supply device, 20 carousel device, 26 turntable section, 30 manifold, 50 manifold tube, 52 sample sleeve, 54 sample unit, 58 sample tube, 60 Discharge hole, 68 outlet hole, 72 internal space, 74 introduction hole.

Claims (6)

A hollow sleeve row that accommodates multiple sample units for nuclear magnetic resonance measurement, with a sleeve row having multiple introduction holes at the bottom.
A hollow manifold tube provided at a position facing the bottom of the sleeve row and having a plurality of blowout holes,
Including
The temperature control gas introduced into the manifold tube is introduced into the sleeve row from the plurality of blowout holes through the plurality of introduction holes formed in the sleeve row .
The manifold tube has an annular shape and has an annular shape.
The sizes of the plurality of blowout holes are different from each other,
In the manifold tube, the diameter of the blowout hole gradually increases from the upstream side to the downstream side of the temperature control gas.
An automatic sample exchange device for NMR. In the automatic sample exchange device for NMR according to claim 1 .
A discharge hole for discharging the temperature control gas introduced into the sleeve to the outside of the sleeve is formed in the middle portion of each sleeve included in the sleeve row.
An automatic sample exchange device for NMR. In the automatic sample exchange device for NMR according to claim 1 or 2 .
A dummy sample is arranged in the sleeve in which the sample unit is not housed in the sleeve row.
An automatic sample exchange device for NMR. In the automatic sample exchange device for NMR according to any one of claims 1 to 3 .
Further comprising insulation provided around the sleeve row,
An automatic sample exchange device for NMR. In the automatic sample exchange device for NMR according to any one of claims 1 to 4 .
Each sample unit is taken out from the upper part of each sleeve by inserting a projecting rod into the introduction hole formed at the bottom of each sleeve included in the sleeve row.
An automatic sample exchange device for NMR. In the automatic sample exchange device for NMR according to claim 5 .
A turntable portion for moving the sleeve to be taken out included in the sleeve row to the sampling position by mounting and rotating the sleeve row is further included.
At the sampling position, the protruding rod is inserted into the introduction hole formed in the bottom of the sleeve, so that the sample unit is taken out from the upper part of the sleeve.
The manifold tube is provided at the sampling position so as to avoid the position where the protruding rod protrudes from the bottom surface of the sleeve.
An automatic sample exchange device for NMR.