JP2004132909A - Flow-through type magnetic resonance detector - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flow-through type magnetic resonance detector causing temperature rising or reaction of a fluid sample, capable of measuring a state after an optional time from a point of time of the temperature rising or reaction, and capable of adjusting the time until measurement. <P>SOLUTION: The flow-through type magnetic resonance detector has supply pipes 11 and 12 for supplying samples, a state changing means 15 for changing states of the samples supplied from the supply pipes, a sample pipe 16 formed with a flow-through hole 17 allowing flowing through of the samples along a longitudinal direction into which the samples with states changed by the state changing means flows in from one end of the flow-through hole, and a detection coil 20 arranged in an outer side of the sample pipe for detecting a magnetic resonance signal of the samples in the sample pipe. The state changing means, the supply pipes, and the detection coil are provided so that a distance between the state changing means and the detection coil can be changed. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a magnetic resonance apparatus for measuring a magnetic resonance signal of a fluid sample, and more particularly to a flow-type magnetic resonance detector for measuring a fluid sample in a flowing state. This is a flow-through type magnetic resonance detector capable of measuring the state at an arbitrary time after the temperature or the reaction time and adjusting the time until the measurement.
[0002]
[Prior art]
For example, a method of sending a fluid sample to a magnetic resonance signal detection unit of a magnetic resonance apparatus from a line for transporting the fluid sample and measuring a magnetic resonance signal in a state where the fluid sample is circulated, automatically supplies the fluid sample. It has many advantages such as being able to perform measurement by automatic operation while being able to perform complex analysis in combination with other analyzers. The fluid sample is sent to the magnetic resonance signal detection unit, and the physical properties of various fluid samples (including supercritical fluid) or samples dissolved in various fluids can be measured.
[0003]
In addition, the inventors of the present invention have proposed a measurement cell as shown in Patent Document 1 described below. The measurement cell shown in FIG. 1 of Patent Document 1 is used as a flow-type measurement cell. The sample is supplied to the detection unit on the lower end side through the inside of the central Ti tube. The sample after the magnetic resonance signal is detected by the detection coil is discharged upward from a gap provided on the outer periphery of the spacer made of fluororesin. In this measurement cell, a highly sensitive measurement can be performed with a considerably large sample volume in the detection section, and there is no problem in mechanical strength.
[0004]
[Patent Document 1]
JP 2000-241518 A
[Problems to be solved by the invention]
In a magnetic resonance measuring apparatus using a measuring cell disclosed in Patent Document 1 and other conventional flow-type measuring cells, magnetic resonance can be performed without changing various states such as temperature, pressure, and composition of a fluid sample. Is measured. On the other hand, there is a demand that the temperature of a fluid sample be rapidly and instantaneously increased and that the physical properties of the sample be measured after a predetermined time from the time when the temperature is increased, or that the fluid sample is reacted with another substance, There is a demand to measure physical properties of a sample after a predetermined time. There has been no magnetic resonance detector capable of measuring the physical properties of a sample at any time in a transient state with high accuracy and high reproducibility.
[0006]
Accordingly, the present invention provides a magnetic resonance apparatus for measuring a magnetic resonance signal of a fluid sample, in which the temperature of the fluid sample is raised or reacted, and a state at any time after the temperature rise or the reaction time can be measured. It is an object of the present invention to provide a flow-type magnetic resonance detector capable of adjusting the time until measurement.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, a flow-type magnetic resonance detector of the present invention includes a supply pipe for supplying a sample, a state changing unit for changing a state of the sample supplied from the supply pipe, and a longitudinal direction. A flow hole through which the sample can flow is formed along, and a sample tube into which the sample whose state has been changed by the state changing means flows from one end of the flow hole, and is arranged outside the sample tube, A detection coil for detecting a magnetic resonance signal of the sample in the sample tube, wherein the state changing unit, the supply tube, and the detection coil change a distance between the state changing unit and the detection coil. It is provided as possible.
[0008]
In the above-mentioned flow-type magnetic resonance detector, it is preferable that the detection coil is provided so as to be movable in a longitudinal direction of the sample tube.
[0009]
Further, in the above-mentioned flow type magnetic resonance detector, it is preferable that a position adjusting mechanism that can adjust a position of the detection coil in a longitudinal direction of the sample tube from outside the detection container is preferable.
[0010]
Further, in the above-mentioned flow-type magnetic resonance detector, when a cavity is formed inside and a detection container for accommodating the sample tube and the detection coil in the cavity is provided, the detection container is provided with the detection coil. Can be moved in the direction opposite to the moving direction of the detection coil by the same movement amount as the detection coil. Thereby, the detection coil can always be arranged at the position of the external magnetic field most suitable for measurement.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
An embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing the overall configuration of a magnetic resonance apparatus using the flow-type magnetic resonance detector of the present invention. The magnetic resonance detector 1 is installed inside a cylindrical member 31 arranged at the center of the cylindrical magnet 3. As will be described in detail later, a sample tube 16 (see FIG. 2) through which a sample flows from above to below is installed inside the magnetic resonance detector 1, and a magnetic resonance signal of the sample is transmitted to a detection coil 20 (see FIG. 2). 2).
[0012]
The sample to be measured is pressurized to a predetermined pressure (for example, 40 MPa) by the pump 51 and supplied to the magnetic resonance detector 1 via the supply pipe 11. Further, a heating medium (for example, water) for instantaneously raising the temperature of the sample is pressurized to a predetermined pressure (for example, 40 MPa) by the pump 52, and is supplied via the supply pipe 12 to the magnetic resonance detector. 1 is supplied. The heating medium is heated to a predetermined temperature (for example, about 600 ° C.) by the heat exchanger 42 arranged in the supply path. The sample is also heated to a constant temperature by the heat exchanger 41 arranged in the supply path. The heat exchangers 41 and 42 are driven by the temperature control device 4.
[0013]
The pump 51 and the pump 52 are controlled by the pressure control device 5 so that the pressurized pressure becomes a predetermined target value, and the target values of these pressurized pressures are specified by the computer 7. Further, the temperature of the sample and the temperature raising medium is controlled by the computer 7 and the temperature controller 4.
[0014]
The sample and the heating medium are mixed in the mixer 15 (see FIG. 2), whereby the temperature of the sample is instantaneously increased. If the supply amounts of the sample and the heating medium are the same and the specific heats of the two are approximately equal, the temperature of the sample after the heating is about the average value of the temperature before mixing the sample and the heating medium. In order to measure the physical properties of the sample in the supercritical state, the sample is made to exceed the critical temperature and become a supercritical fluid by this instantaneous temperature rise. The sample whose measurement has been completed is discharged from the discharge pipe 13 through the differential pressure valve 14.
[0015]
The mixer 15 is provided with a temperature detector 43 (see FIG. 2) for detecting the temperature at the time of mixing the sample and the heating medium. As the temperature detector 43, for example, a thermocouple element can be used. The output of the temperature detector 43 is sent to the computer 7, and feedback control is performed so that the temperature of the mixed sample becomes a predetermined target temperature. That is, the temperature of the heating medium is changed and controlled by the temperature controller 4 and the heat exchanger 42 so that the temperature of the mixed sample matches the target value. The sample supplied from the supply pipe 11 is controlled to have a constant temperature. However, the temperature control is not limited to this, and the temperature of the sample supplied from the supply pipe 11 may be changed and controlled, or the temperature of both the sample and the temperature raising medium may be changed and controlled. You may do so.
[0016]
The magnetic resonance signal of the sample is detected by the detection coil 20 (see FIG. 2). The magnetic resonance signal from the detection coil 20 is sent to the spectrometer 6 for frequency analysis. The output of the spectrometer 6 is sent to a computer 7, where data processing of the measurement result, display of the processing result and analysis result, and the like are performed. The computer 7 controls the temperature and pressure of the sample via the temperature control device 4 and the pressure control device 5, and controls the entire magnetic resonance apparatus to measure the sample.
[0017]
FIG. 2 is an enlarged view showing a configuration of the magnetic resonance detector 1. The magnetic resonance detector 1 is shown as a partially cutaway sectional view. The main part of the magnetic resonance detector 1 is constituted by the sample tube 16 and the detection coil 20 arranged in the detection container 2. The detection container 2 is formed in a substantially cylindrical shape as a whole, and has a cavity 2a inside. The detection container 2 is installed at the center of a cylindrical member 31 arranged at the center of the magnet 3 (see FIG. 1). That is, it is placed on the support member 32 fixed to the cylindrical member 31, and is fixed at the center position.
[0018]
A mixer 15 is arranged at the upper end of the detection container 2. Supply pipes 11 and 12 are connected to the upper surface of the mixer 15, and a sample and a heating medium (hot water) are supplied from the supply pipes 11 and 12, respectively. An output port 151 is formed on the lower surface of the mixer 15. A sample tube 16 is connected to the lower surface of the mixer 15. Further, the mixer 15 is provided with a temperature detector 43 for detecting the temperature at the time of mixing the sample and the heating medium. The output of the temperature detector 43 is sent to the computer 7 as described above, and the feedback control is performed.
[0019]
A flow hole 17 is formed in the sample tube 16 along the central axis. The inner diameter of the flow hole 17 is constant without changing in the axial direction. Here, the flow hole 17 is formed at the center position along the center axis of the sample tube 16, but it is not always necessary to provide the flow hole 17 at the center position. The flow hole 17 may be formed in the longitudinal direction (axial direction) of the sample tube 16. The output port 151 of the mixer 15 and the flow hole 17 of the sample tube 16 are connected in a sealed state so that leakage of the sample does not occur.
[0020]
A heat insulating layer 161 made of a heat insulating material is provided on the outer periphery of the sample tube 16. The heat insulating layer 161 prevents heat from flowing out of the sample passing through the flow hole 17 and prevents the sample heated in the mixer 15 from changing its temperature while passing through the flow hole 17. . Various heat insulating materials can be used for the heat insulating layer 161. Furthermore, the heat insulating means is not limited to a single heat insulating layer, and a vacuum double tube or the like may be arranged to insulate the heat.
[0021]
The lower end of the sample tube 16 is connected to the discharge tube 13 via the bottom of the detection container 2. The sample tube 16 and the discharge tube 13 are connected in a sealed state so that leakage of the sample does not occur. The sample whose measurement has been completed is discharged from the discharge pipe 13 through the differential pressure valve 14. The sample tube 16 is attached so that the central axis thereof (the central axis of the flow hole 17) coincides with the central axis of the detection container 2.
[0022]
The sample tube 16 is made of a material that sufficiently transmits a high-frequency magnetic field applied for detecting a magnetic resonance signal and a high-frequency magnetic field induced by the sample. That is, the material of the sample tube 16 must be non-magnetic and non-conductive, and is preferably a material that does not generate a noise component that disturbs a frequency band in which a magnetic resonance signal is measured. As this material, in consideration of mechanical strength, corrosion resistance, heat resistance, pressure resistance and the like, a ceramic material obtained by sintering alumina, zirconia, silicon nitride, or the like can be used.
[0023]
An inner cylindrical member 18 is fixed to the bottom of the detection container 2, and an outer cylindrical member 19 is provided outside the inner cylindrical member 18. The outer tubular member 19 is guided by the inner tubular member 18 in the central axis direction of the sample tube 16 and is movable in the central axis direction of the sample tube 16. A detection coil 20 for detecting a magnetic resonance signal of the sample is fixed to an upper end of the outer cylindrical member 19.
[0024]
A nut 21 is fixed outside the outer tubular member 19. A screw shaft 22 screwed with the nut 21 is provided in the central axis direction of the sample tube 16. The screw shaft 22 is formed of a material such as ceramic which has little influence on the measurement of the magnetic resonance signal. A lower portion of the screw shaft 22 is provided to penetrate the bottom surface of the detection container 2, and a knob 23 is formed at a lower end of the screw shaft 22. The screw shaft 22 is provided so as to be rotatable with respect to the detection container 2 and immovable in the axial direction.
[0025]
The nut 21, the screw shaft 22, and the knob 23 function as a position adjusting mechanism that moves the detection coil 20 in the central axis direction of the sample tube 16 and adjusts the position in the central axis direction. That is, by rotating the knob portion 23 in either the forward or reverse direction, the position of the detection coil 20 can be freely adjusted from the upper end position of the stroke indicated by reference numeral 20a to the lower end position of the stroke illustrated. is there. By adjusting the position of the detection coil 20, it is possible to measure the physical properties of the sample in a state where an arbitrary time has elapsed from the time when the temperature of the sample is instantaneously increased in the mixer 15.
[0026]
This is because the sample passes through the sample tube 16 at a constant flow rate, so that the time from when the sample is heated and the position of the sample in the sample tube 16 correspond exactly. For example, assuming that the flow rate of the sample after the temperature is raised in the mixer 15 is 50 mL / min and the inner diameter (diameter) of the flow hole 17 of the sample tube 16 is 3 mm, the sample 1 second after the time of the temperature rise is obtained. Has reached a position about 120 mm from the temperature raising position. Therefore, if the center position of the detection coil 20 can be adjusted to a position 12 to 120 mm from the heating position, the physical properties of the sample 0.1 to 1 second after the heating can be measured. In the arrangement shown in FIG. 2, the time from the time when the temperature is raised to the time when the temperature is measured can be adjusted in the range of 0.4 to 1 second.
[0027]
A temperature detector 44 for detecting the temperature of the sample passing through the flow hole 17 is provided at an intermediate portion in the axial direction of the sample tube 16. As the temperature detector 44, for example, a thermocouple element can be used. The temperature detector 44 is provided at a position further below the stroke lower end position of the detection coil 20. The temperature of the sample after measurement by the detection coil 20 can be detected by the temperature detector 44. The output of the temperature detector 44 is sent to the computer 7. From the output of the temperature detector 44, the temperature of the sample at the time of measurement by the detection coil 20 can be confirmed, and it can also be confirmed whether or not a temperature change from the mixing temperature in the mixer 15 has occurred.
[0028]
Here, the case where the sample is heated instantaneously by mixing it with the heating medium in the mixer 15 has been described, but a case where the temperature is lowered instead of raising the temperature may be used. If the temperature of the sample is to be reduced, the sample is mixed with a cooler medium. In addition to this, the present invention is also applicable to a case where a reaction such as a chemical reaction is caused by mixing a sample with another sample in the mixer 15 and the physical properties of the sample are measured at an arbitrary time after the reaction. Can be used.
[0029]
Further, instead of raising the temperature of the sample instantaneously by the mixer 15, the temperature of the sample may be raised by microwave heating. That is, in place of the mixer 15, other heating means, an arbitrary means for changing the state of the sample, or the like may be provided. Then, it is possible to measure the physical properties of the sample after an arbitrary time from when the state of the sample is changed.
[0030]
In FIG. 2, the position of the detection coil 20 is adjusted by manually rotating the knob 23. However, an actuator for rotating the knob 23 is provided, and the actuator is controlled by the computer 7. This makes it possible to perform the measurement while automatically and automatically changing the time from the temperature increase or the reaction time. This makes it possible to automatically and continuously measure the physical properties of the sample at each time point in a transient state.
[0031]
Further, in the embodiment described here, the detection coil 20 is movable and the position is adjustable, but conversely, the mixer 15 and the sample tube 16 may be movable, and the detection coil and the sample tube are relatively movable. It is only necessary to be able to move to. Further, the detection coil is desirably installed so as to be position-adjustable with respect to the sample tube, but even if the position of the detection coil is fixed, it is possible to measure the physical properties of the sample at a predetermined point in time according to the fixed position. .
[0032]
In addition, the time between the mixing time of the sample and the measurement time is adjusted by changing the distance between the mixer and the detection coil. However, the flow rate (namely, the flow rate) of the sample is changed and the measurement is performed from the mixing time of the sample. You can also adjust the time to the point. In this case, even when the distance between the mixer and the detection coil is fixed, the time from the mixing time to the measurement time can be adjusted. Further, both the distance between the mixer and the detection coil and the flow rate of the sample may be changed.
[0033]
Although the arrangement in which the sample passes through the sample tube from above to below has been described, a mixer may be provided at the lower end side of the sample tube to allow the sample to pass from below to above. When the detection coil is moved relative to the detection container, the entire detection container is moved in the opposite direction by the amount of movement of the detection coil so that the position of the detection coil is kept at a constant position with respect to the external magnetic field generated by the magnet 3. Can be kept. Thereby, the detection coil can always be arranged at the position of the external magnetic field most suitable for measurement.
[0034]
As described above, according to the flow-type magnetic resonance detector of the present invention, the detection coil can be moved in the axial direction of the sample tube, and the position of the detection coil can be adjusted. Can be measured with high accuracy and high reproducibility. For example, the temperature of a fluid sample can be raised suddenly and instantaneously, and the physical properties of the sample can be measured at an arbitrary time after the temperature rise. In addition, the fluid sample can be reacted with another substance, and the physical properties of the sample can be measured at an arbitrary time after the reaction. In addition, the accuracy and reproducibility of the measurement are high.
[0035]
【The invention's effect】
The present invention is configured as described above, and has the following effects.
[0036]
Since the distance between the state changing means and the detection coil can be changed, the physical properties of the sample at any time after the state change of the sample can be measured with high accuracy and high reproducibility. That is, the temperature of the fluid sample can be raised or reacted instantaneously, and the physical properties of the sample can be measured at any time after the temperature or reaction. In addition, the accuracy and reproducibility of the measurement are high.
[0037]
Since the detection coil is movable in the axial direction of the sample tube, the position of the detection coil can be adjusted by a simple mechanism, and the cost of the magnetic resonance detector can be reduced.
[0038]
Since the position of the detection coil in the direction of the center axis of the sample tube is adjustable from the outside of the detection container, the position of the detection coil can be easily adjusted, and many measurements can be performed in a short time.
[0039]
The detection container that houses the detection coil is moved in the opposite direction by the same amount as the detection coil when the detection coil moves, so that the position of the detection coil is always maintained at the position of the external magnetic field that is most suitable for measurement I can put it.
[Brief description of the drawings]
FIG. 1 is a diagram showing an overall configuration of a magnetic resonance apparatus using a flow-type magnetic resonance detector of the present invention.
FIG. 2 is a partial cross-sectional view showing a configuration of a flow-type magnetic resonance detector of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Magnetic resonance detector 2 ... Detection container 2a ... Cavity part 3 ... Magnet 4 ... Temperature control device 5 ... Pressure control device 6 ... Spectrometer 7 ... Computer 11, 12 ... Supply pipe 13 ... Discharge pipe 14 ... Differential pressure valve 15 ... Mixer 16 Sample tube 17 Flow hole 18 Inner cylindrical member 19 Outer cylindrical member 20 Detection coil 21 Nut 22 Screw shaft 23 Knob 31 Cylindrical member 32 Support members 41 and 42 Heat Exchangers 43, 44 Temperature detectors 51, 52 Pump 151 Output port 161 Thermal insulation layer

Claims (4)

A supply pipe (11) for supplying a sample;
State changing means (15) for changing a state of the sample supplied from the supply pipe (11);
A flow hole (17) through which the sample can flow is formed along the longitudinal direction, and a sample tube into which the sample whose state has been changed by the state changing means (15) flows from one end of the flow hole (17). (16),
A detection coil (20) disposed outside the sample tube (16) for detecting a magnetic resonance signal of the sample in the sample tube (16);
The state changing means (15), the supply pipe (11) and the detection coil (20) are provided so that the distance between the state changing means (15) and the detection coil (20) can be changed. A flow-type magnetic resonance detector. A flow-type magnetic resonance detector according to claim 1,
The flow type magnetic resonance detector, wherein the detection coil (20) is provided so as to be movable in a longitudinal direction of the sample tube (16). A flow type magnetic resonance detector according to claim 2,
A flow-type magnetic resonance detector having a position adjusting mechanism (21 to 23) capable of adjusting a position of the detection coil (20) in a longitudinal direction of the sample tube (16) from outside the detection container (2). A flow type magnetic resonance detector according to claim 2,
A cavity (2a) is formed therein, and a detection container (2) for accommodating the sample tube (16) and the detection coil (20) in the cavity (2a);
The detection container (2) is moved by the same amount as the detection coil (20) in the direction opposite to the direction of movement of the detection coil (20) when the detection coil (20) moves. Type magnetic resonance detector.

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