JP2007304078A - Fraction collector, its control method, and its washing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable washing of the outside of a nozzle for dripping an eluent after dispensing the eluent. <P>SOLUTION: The fraction collector includes a passage pipe 31 and the like. The eluent from a column flows into the dripping nozzle 11 for dripping the eluent through these passage pipes. A container 14 for storing a plurality of test tubes for dispensing the eluent is provided under the dripping nozzle 11. When the dripping nozzle 11 is washed, the dripping nozzle 11 is moved to a washing position (broken line). A washing nozzle 12 is set in the washing position, and a solvent supplied through a passage pipe 33 is sprayed onto the dripping nozzle 11 from the washing nozzle 12. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fraction collector, in particular, a fraction collector having a nozzle for dropping liquid, a control method thereof, and a cleaning method thereof.

  In liquid chromatography, an eluent corresponding to a mobile phase composed of a sample having a plurality of components and a plurality of solvents mixed at a predetermined mixing ratio flows through a column packed with a stationary phase. At this time, the sample flowing into the column together with the eluent moves along with the flow of the eluent while adsorbing to the stationary phase packed in the column, and is discharged from the column after a predetermined time. Here, the time required for discharging each component contained in the sample depends on the affinity with the eluent, the interaction between the stationary phase of the column and each component, etc., and differs for each component. That is, those having weak affinity with the eluent and those having strong interaction with the stationary phase stay in the column for a long time. Conversely, those having a strong affinity with the eluent and those having a weak interaction with the stationary phase quickly pass through the column. Therefore, the sample contained in the eluent is separated for each component and flows out of the column.

  The fraction collector of Patent Document 1 separates the eluent that has passed through the column into a container such as a test tube. The fraction collector has a nozzle for dropping the eluent from the column, and supports the container directly under the nozzle so as to receive the eluent dropped from the nozzle. A control device such as a personal computer connected to the fraction collector (or a control unit installed inside the fraction collector) separates the eluent into each container according to the concentration of the sample contained in the eluent from the column. To control the fraction collector. As a result, the eluent is collected for each component contained in the sample in each container.

Japanese Patent Laid-Open No. 7-140127 (FIG. 1)

  In the fraction collector as described above, it is particularly important to keep the flow path and nozzle through which the eluent passes clean. For example, when one liquid chromatography is performed and another liquid chromatography is performed, if the eluent used in the previous liquid chromatography remains in the channel or nozzle, the elution separated in the next liquid chromatography The previous eluent is mixed into the liquid. In order to solve such a problem, after liquid chromatography is performed, a solvent not containing a sample is caused to flow down to a flow path or a nozzle, and the remaining eluent is washed away.

  However, simply letting the eluent flow down using the existing flow path only cleans the inside of the nozzle, and the eluent may remain outside the nozzle.

  An object of the present invention is to provide a fraction collector capable of performing control for cleaning the outside of a nozzle, a control method thereof, and a cleaning method thereof.

Means for Solving the Problems and Effects of the Invention

  The fraction collector of the present invention is a fraction collector for liquid chromatography that separates the liquid from the column into a sorting container according to the concentration of the sample contained in the liquid from the column, and the liquid chromatography is performed. A dropping nozzle for dropping the liquid from the column, a sorting container support member for supporting the sorting container so as to receive the liquid dropped from the dropping nozzle, and cleaning for spraying the liquid onto the outer surface of the dropping nozzle And a nozzle.

  According to the fraction collector of the present invention, it is possible to control the fraction collector so as to clean not only the inside of the dropping nozzle but also the outer surface of the dropping nozzle by the cleaning nozzle that sprays liquid onto the outer surface of the dropping nozzle. Therefore, when performing liquid chromatography, it is suppressed that the component of the eluent used in the previous liquid chromatography mixes in the eluent of this liquid chromatography.

  Moreover, in this invention, it has the 1st-3rd port through which a liquid passes, The state which the said 1st port connected to the said 2nd port, and the state which connected to the said 3rd port A first three-way valve that selectively takes the liquid, an introduction flow path for introducing liquid from the column to the first port when the liquid chromatography is performed, and a second port to the dropping nozzle. A liquid sorting channel that is a liquid channel, and a liquid discharging channel that is different from the liquid sorting channel and that discharges the liquid that has passed through the third port. It is preferable. According to this configuration, a fraction collector that can perform control to discharge the eluent that does not need to be sorted into the sorting container through a flow path different from the flow path for sorting is realized.

  In the present invention, the liquid discharge channel has fourth to sixth ports through which liquid passes, and the fourth port communicates with the fifth port. A second three-way valve that selectively takes a state communicating with the second port, a first partial flow path that is a liquid flow path from the third port to the fourth port, and the fifth It is preferable to have a second partial flow path for discharging the liquid that has passed through the port, and a cleaning liquid flow path that is a liquid flow path from the sixth port to the cleaning nozzle.

  According to the above configuration, by controlling the first and second three-way valves, (1) a state in which the liquid is supplied to the dropping nozzle, (2) a state in which the liquid is discharged through the liquid discharge channel, and (3 ) A fraction collector capable of controlling three states of supplying a liquid to the cleaning nozzle is realized. That is, (A) supplying the liquid to the dropping nozzle and separating the liquid, (B) supplying the liquid to the dropping nozzle and cleaning the inside of the dropping nozzle, (C) via the liquid discharge channel It is possible to selectively control the four operations of cleaning the flow path while discharging the liquid, and (D) cleaning the outer surface of the dropping nozzle while supplying the liquid to the cleaning nozzle. Therefore, since the liquid discharge channel is used to clean the outer surface of the dropping nozzle, the configuration of the apparatus is simplified compared to the case where a channel for supplying the liquid to the cleaning nozzle is separately prepared.

  Further, in the present invention, the cleaning container that receives the liquid dropped from the dropping nozzle, the sorting position where the sorting container receives the liquid dropped from the dropping nozzle, and the liquid dropped from the dropping nozzle. Nozzle moving means for moving the dropping nozzle between the cleaning position received by the cleaning container, and when the dropping nozzle is in the cleaning position, a position to spray liquid onto the dropping nozzle, It is preferable that the washing nozzle is arranged. According to this configuration, since the cleaning container receives the liquid when cleaning the dropping nozzle, the liquid at the time of cleaning is prevented from being mixed into the sorting container.

  Moreover, in this invention, when the said dripping nozzle exists in the said washing | cleaning position, the said container for washing | cleaning has a side surface surrounding the front-end | tip of the said dripping nozzle in planar view, and the said dripping nozzle exists in the said washing | cleaning position In this case, it is preferable that the side surface is disposed on an extended line of the spray nozzle of the cleaning nozzle along the direction in which the cleaning nozzle sprays the liquid. According to this configuration, since the liquid is sprayed from the cleaning nozzle to the dropping nozzle toward the side surface of the cleaning container, it is possible to prevent the liquid from being scattered around the fraction collector.

  Further, the present invention includes a storage container that stores liquid and has a stored liquid discharge port, and a cleaning liquid channel that is a liquid channel from the discharge port to the cleaning nozzle. The storage container may be arranged so that the outlet is located above the washing nozzle when used in the liquid chromatography. According to this, the structure which supplies a liquid to a washing nozzle is implement | achieved easily.

  In the fraction collector having the first and second three-way valves, the fraction collector control method according to the present invention includes the first port and the third port within a period when the liquid chromatography is not performed. Is connected to the first three-way valve, and the second three-way valve is connected to the fourth port and the sixth port. According to this, after completion of the liquid chromatography, control is performed so as to ensure a liquid flow path to the washing nozzle via the first and second three-way valves. Therefore, it is possible to control such that the liquid from the liquid chromatograph is introduced to the washing nozzle and the outer surface of the dropping nozzle is washed.

  In the fraction collector control method according to the present invention, in the fraction collector having the first and second three-way valves, a state in which the first port and the third port communicate with each other is referred to as the first three-way valve. And a discharge flow path selection step for causing the second three-way valve to take a state where the fourth port and the fifth port communicate with each other, and after the discharge flow path selection step is performed, A flow path cleaning step for cleaning the liquid flow path by discharging the liquid from the liquid discharge flow path via the first and third to fifth ports; and the first port and the third port. A washing flow path selecting step for causing the first three-way valve to take a communicating state, and causing the second three-way valve to take a state where the fourth port communicates with the sixth port; and the washing Channel selection step is performed After the said first, third, and the liquid through the fourth and the sixth port and the cleaning nozzles of a nozzle cleaning step of blowing the dropping nozzles. According to this, (C) it is possible to clean the flow path while discharging the liquid through the liquid discharge flow path, and (D) to clean the outer surface of the dropping nozzle while supplying the liquid to the cleaning nozzle. .

  The following is a description according to the first to fourth embodiments, which is an example of a preferred embodiment according to the present invention.

[First Embodiment]
FIG. 1 is a diagram illustrating an arrangement of devices including a fraction collector 10 according to the first embodiment in liquid chromatography. The devices used in the liquid chromatography are the liquid chromatograph 100, the detector 26, the control device 27, and the fraction collector 10.

  The liquid chromatograph 100, the detector 26, and the fraction collector 10 are connected to each other by a tube or the like so that a liquid flow path from the liquid chromatograph 100 to the fraction collector 10 through the detector 26 is formed. Each of the liquid chromatograph 100, the detector 26, and the fraction collector 10 and the control device 27 are connected by an interface for transmitting and receiving signals.

The control device 27 includes a general-purpose information processing device such as a personal computer and various peripheral devices such as a display. Personal computers include a central processing unit (CPU), various storage devices such as memory and hard disks, and input / output (I / O).
) Interface etc. are provided. The personal computer and the fraction collector 10 are connected via an I / O interface. The storage device stores a program for operating a personal computer as a control device for controlling the fraction collector 10 and the like. When hardware such as a CPU executes information processing based on such a program, operations of the liquid chromatograph 100, the detector 26, and the fraction collector 10 are controlled via an interface including an I / O interface. . The control device 27 is not realized using a general-purpose information processing device, but may be realized as a device specialized for controlling the fraction collector 10 and the like.

  The liquid chromatograph 100 includes a pump 23, an injector 24, and a column 25. The liquid chromatograph 100 is provided with a solvent container 22 containing the solvent L. The injector 24 contains a sample containing a plurality of components. Column 25 is packed with silica gel as a stationary phase. In the liquid chromatograph 100, a solvent flow path from the solvent container 22 to the column 25 is formed.

  The pump 23 pumps up the solvent L from the solvent container 22. The solvent L pumped up flows into the injector 24. The solvent L flowing into the injector 24 flows out of the injector 24 together with the sample accommodated in the injector 24. The eluent composed of the solvent and the sample flowing out from the injector 24 flows into the column 25. From the column 25, the eluent flows out for each component contained in the sample as time elapses.

  The detector 26 detects the concentration of the sample contained in the eluent from the liquid chromatograph 100 while allowing the eluent from the column 25 to flow out to the fraction collector 10. The detector 26 measures the absorbance in the eluent, and derives the concentration of the sample contained in the eluent based on the known relationship between the concentration of the sample contained in the eluent and the absorbance. And the detection signal which shows the density | concentration of the derived | led-out sample is sequentially transmitted to the control apparatus 27 with progress of time. The eluent flowing out of the detector 26 flows into the fraction collector 10.

  FIG. 2 is a graph showing the change over time of the concentration of the sample contained in the eluent from the liquid chromatograph 100. The horizontal axis of the graph in FIG. 2 indicates time, and the vertical axis indicates concentration. As shown by the curve 99 in FIG. 2, the change in the concentration of the sample over time includes a plurality of peaks C1 to C3 that are separated from each other in time. These peaks C1 to C3 indicate the concentration peak of each component included in the sample. That is, the eluent from the liquid chromatograph 100 includes a sample that is temporally separated for each component included in the material.

  FIG. 3 is a schematic configuration diagram showing a main configuration of the fraction collector 10. The fraction collector 10 includes a dripping nozzle 11, a washing nozzle 12, flow path pipes 31 to 35 through which a liquid such as an eluent passes, and electromagnetic valves 41 and 42 (first and second three-way valves). The eluent that has flowed out from the column 25 of the liquid chromatograph 100 flows into the one end of the channel tube 31 through the detector 26. The other end of the flow channel 31 is connected to the electromagnetic valve 41.

  The solenoid valve 41 has three ports 41a to 41c (first to third ports) through which the eluent passes, and the flow path pipe 31 is connected to the port 41a. . The port 41a of the solenoid valve 41 communicates with either the port 41b or the port 41c. In other words, the solenoid valve 41 has two ports 41a and 41b communicating with each other and the port 41c closed, and two ports 41a and 41c communicating with each other and the port 41b closed. One state can be taken selectively. The state of the electromagnetic valve 41 is switched by the control device 27 connected to the fraction collector 10.

  One end of the flow path pipe 32 is connected to the port 41 b of the electromagnetic valve 41. The other end of the channel tube 32 is connected to the dropping nozzle 11. One end of the flow path pipe 33 is connected to the port 41 c of the electromagnetic valve 41. The other end of the flow channel 33 is connected to the electromagnetic valve 42. The solenoid valve 42 has three ports 42a to 42c (fourth to sixth ports) similarly to the solenoid valve 41, and the flow path pipe 33 is connected to the port 42a. The electromagnetic valve 42 has two states: a state in which the ports 42a and 42b communicate with each other and the port 42c is closed, and a state in which the ports 42a and 42c communicate with each other and the port 42b is closed. Can be taken selectively. The state of the electromagnetic valve 42 is switched by the control device 27 connected to the fraction collector 10.

  One end of the flow path pipe 35 is connected to the port 42 c of the electromagnetic valve 42. The other end of the flow channel pipe 35 is connected to the cleaning nozzle 12. One end of the flow path pipe 34 is connected to the port 42 b of the electromagnetic valve 42. From the other end of the channel tube 34, a liquid such as an eluent is discharged to the outside of the fraction collector 10 in a region not shown. Instead of being discharged to the outside, the liquid may be stored in a discharge container or the like installed inside the fraction collector 10.

  The fraction collector 10 has an arm 51 (nozzle moving means). The arm 51 is moved in the directions of D1 to D4 in FIG. 3 (left, right, front, and rear in FIG. 3) by a drive mechanism (not shown). The movement of the arm 51 is controlled by a control device 27 connected to the fraction collector 10 via an interface. A flow path pipe 31 is fixed in the vicinity of the tip of the arm 51. When the arm 51 moves, the solenoid valve 41, the flow channel pipe 32, and the dropping nozzle 11 connected to the flow channel pipe 31 move in conjunction with the flow channel pipe 31.

  The fraction collector 10 has a test tube container 14 (container support member). The test tube container 14 accommodates a plurality of test tubes 9 (sorting containers). The test tube container 14 is configured such that the test tubes 9 accommodated therein are arranged at predetermined positions in the front-rear and left-right directions in FIG. Further, the test tube container 14 is installed in the fraction collector 10 so that the test tube 9 can be positioned below the dropping nozzle 11 by moving the dropping nozzle 11 to the arm 51. Has been. That is, each test tube 9 is installed so as to be within the movement range of the arm 51 in the front-rear and left-right directions.

  Further, the fraction collector 10 has a cleaning container 15 installed below the cleaning nozzle 12. The cleaning container 15 is a container that contains a liquid having a substantially cylindrical shape, and the upper part of the container opens upward. A cutout 15 b is formed in the side surface 15 a of the cleaning container 15. The notch 15b is formed about 1/3 above the side surface of the cleaning container 15 from the opening at the top of the cleaning container 15 downward. A discharge channel 16 is connected to the side surface of the cleaning container 15 near the bottom. The liquid stored in the cleaning container 15 is discharged to the outside of the fraction collector 10 through the discharge flow channel 16. Instead of being discharged to the outside, the liquid may be stored in a discharge container or the like installed inside the fraction collector 10.

  The cleaning container 15 is installed so as to be within the moving range of the arm 51 in the front-rear and left-right directions. That is, the arm 51 moves the dripping nozzle 11 between a sorting position where the test tube 9 accommodated in the test tube container 14 is below and a cleaning position where the cleaning container 15 is below. It is possible to make it. The sorting position corresponds to the position of the dripping nozzle 11 represented by the solid line in FIG. 3, and the cleaning position corresponds to the position of the dripping nozzle 11 represented by the broken line.

  Further, the cleaning container 15 is arranged so that the elution port formed at the tip of the dropping nozzle 11 is surrounded by the side surface 15a when the dropping nozzle 11 is at the cleaning position. That is, when the cleaning container 15 is viewed from above in FIG. 3, the dropping port of the dropping nozzle 11 is disposed so as to be surrounded by the side surface 15a. On the other hand, the notch 15b of the cleaning container 15 is formed so as to be disposed in the middle of the movement path when the dropping nozzle 11 moves between the sorting position and the cleaning position. That is, the dropping nozzle 11 passes through the notch 15b when moving between the sorting position and the cleaning position. Thereby, the dripping nozzle 11 can smoothly move between the sorting position and the cleaning position without being caught by the side surface 15 a of the cleaning container 15.

  The cleaning nozzle 12 is installed such that the liquid spray port formed at the tip is directed obliquely downward. The spray nozzle 12 is adjusted so that the liquid sprayed from the cleaning nozzle 12 reaches the vicinity of the tip of the dropping nozzle 11 at the cleaning position, and the direction of spraying from the cleaning nozzle 12. The side surface 15a is adjusted so as to hit the extended line of the tip of the cleaning nozzle 12 along (direction A in FIG. 3). Thus, when the liquid is sprayed from the cleaning nozzle 12, it is difficult for the splash of the liquid that has jumped beyond the dropping nozzle 11 to splash outside the cleaning container 15. In addition, it is preferable that the cleaning nozzle 12 has a configuration in which liquid is sprayed as widely as possible within a range that does not scatter to the outside of the cleaning container 15. As a result, the liquid is sprayed over a wide range of the dropping nozzle 11.

  With the above configuration, the fraction collector 10 separates the eluent from the liquid chromatograph 100 in the liquid chromatography as follows. Note that the control device 27 always holds the electromagnetic valve 42 in a state where the ports 42a and 42b are in communication with each other during a period in which liquid chromatography is performed.

  When the eluent from the liquid chromatograph 100 passes through the detector 26, a detection signal indicating the concentration of the sample contained in the eluent (see FIG. 2) is transmitted from the detector 26 to the control device 27. The control device 27 compares the sample concentration with the reference concentration based on the detection signal from the detector 26. When the concentration of the sample is smaller than the reference concentration, the control device 27 keeps the state of the electromagnetic valve 41 in a state where the port 41a and the port 41c are in communication. On the other hand, when the concentration of the sample contained in the eluent becomes equal to or higher than the reference concentration, the control device 27 switches the state of the electromagnetic valve 41 to a state in which the port 41a and the port 41b are in communication. Then, during the period when the concentration of the sample contained in the eluent is equal to or higher than the reference concentration, the above state is always maintained. When the concentration of the sample contained in the eluent falls below the reference concentration, the control device 27 switches the state of the electromagnetic valve 41 to a state where the port 41a and the port 41c are in communication.

  That is, the port 41a and the port 41c are connected in the period from the time t2 to t3, the time t4 to t5, and the time t6 until the time t1 when the concentration of the sample is lower than the reference concentration in FIG. The electromagnetic valve 41 is held. At this time, the eluent from the liquid chromatograph 100 is discharged through the channel tube 31, the ports 41 a and 41 c, the ports 42 a and 42 b, and the channel tube 34 in FIG. 3. On the other hand, during the period from time t1 to t2, t3 to t4, and t5 to t6 where the concentration of the sample is equal to or higher than the reference concentration, the solenoid valve 41 is held in a state where the port 41a and the port 41b are in communication. . At this time, the eluent from the liquid chromatograph 100 is supplied to the dropping nozzle 11 via the flow channel tube 31, ports 41 a and 41 b, and the flow channel tube 32 in FIG. 3. The dropping nozzle 11 drops the eluent downward. The eluent dropped from the dropping nozzle 11 is received by a test tube below the dropping nozzle 11.

  In addition, the control device 27 repeats the above control and moves the arm 51 so that the eluent is separated into separate test tubes 9 each time the sample concentration peaks C1 to C3 appear in FIG. Control. In other words, the control device 27 operates the dropping nozzle within the period of time t2 to t3 from the time when the eluent is received by a certain test tube 9 during the period of time t1 to t2 until the time t3 when the eluent reaches the reference concentration or higher. 11, the arm 51 is moved so that another test tube 9 is located below the arm 11. Then, the arm 51 is moved so that another test tube 9 is positioned below the dropping nozzle 11 within a period from time t4 to time t5 after the peak C2 is reached and next to the reference concentration or more. The control device 27 repeats such control of the arm 51 and the electromagnetic valve 41. As a result, the eluent is collected for each component contained in the sample in the plurality of test tubes accommodated in the test tube container 14.

  By the way, when liquid chromatography is performed, the eluent containing the sample remains on the dropping nozzle 11 and the channel tube 31 and the like. When the next liquid chromatography is performed with the previous eluent remaining, the previous eluent is mixed into the collected eluent. In order to avoid such a situation, the following cleaning process is performed in the fraction collector 10 until the next liquid chromatography is performed.

  First, the washing process of the dropping nozzle 11 is as follows. The control device 27 holds the dripping nozzle 11 at the cleaning position (the position of the broken line in FIG. 3) and holds the electromagnetic valve 41 in a state where the ports 41a and 41b communicate with each other. Then, the solvent is caused to flow from the liquid chromatograph 100 to the fraction collector 10 in a state where the sample is not accommodated in the injector 24. That is, before starting the cleaning process, it is necessary to remove the sample remaining in the injector 24 in advance and cause the control device 27 to control the cleaning process.

  At this time, the solvent flows into the dropping nozzle 11 via the flow channel 31, the ports 41 a and 41 b, and the flow channel 32. Then, the solvent is dropped from the dropping nozzle 11 to the lower cleaning container 15. As a result, the eluent remaining inside the dropping nozzle 11 is washed away by the solvent not containing the sample through the flow channel tube 31, the ports 41a and 41b, and the flow channel tube 32.

  Next, the cleaning process for the channel tube 33 and the like is as follows. The control device 27 holds the electromagnetic valve 41 in a state where the ports 41a and 41c are in communication with each other, and holds the electromagnetic valve 42 in a state in which the ports 42a and 42b are in communication with each other. Then, the solvent is caused to flow from the liquid chromatograph 100 to the fraction collector 10 in a state where the sample is not accommodated in the injector 24.

  At this time, the solvent is discharged through the flow channel 31, the ports 41 a and 41 c, the flow channel 33, the ports 42 a and 42 b, and the flow channel 34. As a result, the eluent remaining in the flow channel tube 31, the ports 41a and 41c, the flow channel tube 33, the ports 42a and 42b, and the flow channel tube 34 is washed away by the solvent not containing the sample.

  By the way, only the cleaning process of the dropping nozzle 11 described above does not clean the outer surface of the dropping nozzle 11 even if the inside of the dropping nozzle 11 is cleaned. The following is a cleaning process for the outer surface of the dropping nozzle 11.

  The control device 27 holds the dropping nozzle 11 at the cleaning position. At the same time, the electromagnetic valve 41 is held in a state where the ports 41a and 41c are in communication with each other, and the electromagnetic valve 42 is held in a state in which the ports 42a and 42c are in communication with each other. Then, the solvent is caused to flow from the liquid chromatograph 100 to the fraction collector 10 in a state where the sample is not accommodated in the injector 24.

  At this time, the solvent is sprayed to the outer surface of the dropping nozzle 11 through the flow channel 31, the ports 41 a and 41 c, the flow channel 33, the ports 42 a and 42 c, the flow channel 35, and the cleaning nozzle 12. . As a result, the eluent remaining on the outer surface of the dropping nozzle 11 is washed away by the solvent not containing the sample.

The control of the fraction collector 10 in the liquid chromatography and the washing process as described above is performed by the control device 27. As described above, the control device 27 is realized by performing information processing in cooperation with a general-purpose information processing device and a program stored in the information processing device. That is, the program stored in the control device 27 causes the information processing device to perform the above-described control relating to liquid chromatography and cleaning processing. This program is recorded on a removable recording medium such as a CD-ROM (Compact Disc Read Only Memory) disk, flexible disk (FD), or MO (Magneto Optical) disk, or a fixed recording medium such as a hard disk. In addition to being able to be recorded and distributed, it can be distributed via a communication network such as the Internet by wired or wireless telecommunication means. Further, this program is not limited to a general-purpose information processing apparatus, and may be configured to be used in a control apparatus specialized for controlling the fraction collector 10 and the like.

[Second Embodiment]
The following is a description of the second embodiment. Since the second embodiment and the first embodiment have many common parts, description of these common parts will be omitted below as appropriate. FIG. 4 is a schematic configuration diagram showing a cleaning nozzle 72 and a cleaning liquid supply unit 80 that supplies a liquid to the cleaning nozzle 72 according to the second embodiment.

  The structure of the cleaning nozzle 72 according to the second embodiment is the same as that of the cleaning nozzle 12 of the first embodiment. Accordingly, the direction in which the liquid is sprayed from the cleaning nozzle 72 is adjusted in the same manner as the cleaning nozzle 12.

  The cleaning liquid supply unit 80 includes a storage container 81, an electromagnetic valve 82, and a flow path pipe 83. The storage container 81 stores the liquid supplied to the cleaning nozzle 72. As the liquid stored in the storage container 81, the same solvent L as that used in liquid chromatography is used. The storage container 81 is installed above the cleaning nozzle 72. One end of a channel pipe 83 is connected to the lower part of the storage container 81. The other end of the flow channel 83 is connected to the cleaning nozzle 72. An electromagnetic valve 82 is installed in the middle of the flow path pipe 83. The electromagnetic valve 82 switches between a state in which the liquid passes through the flow path pipe 83 and a state in which the passage of the liquid is stopped. The electromagnetic valve 82 is controlled by the control device 27 connected to the fraction collector.

  The control device 27 controls the electromagnetic valve 82 to stop the passage of the solvent L in the flow path pipe 83 during the period when the liquid chromatography is performed. When the liquid chromatography is finished, the control device 27 moves the dropping nozzle 11 to the cleaning position as shown in FIG. 4 and opens the electromagnetic valve 82. As a result, the solvent L passes through the flow path pipe 83 and is supplied to the cleaning nozzle 72, sprayed from the cleaning nozzle 72 to the outer surface of the dropping nozzle 11, and the outer surface of the dropping nozzle 11 is cleaned.

  The liquid stored in the storage container 81 may be supplied by the user of the fraction collector. Alternatively, the fraction collector may have a configuration in which a part of the solvent flowing from the column 25 into the fraction collector is supplied to the storage container 81.

[Third Embodiment]
The following is a description of the third embodiment. Since the third embodiment and the first embodiment have many common parts, description of these common parts will be omitted below as appropriate. FIG. 5 is a schematic configuration diagram of the fraction collector 110 according to the third embodiment.

  The fraction collector 110 has a cleaning nozzle 112 corresponding to the cleaning nozzle 12 of the first embodiment. The cleaning nozzle 112 is fixed to a nozzle fixing base 161, and the nozzle fixing base 161 is fixed to the arm 51 via a fixing plate 162. A liquid flow path is formed inside the nozzle fixing base 161 (not shown). In addition, an opening at one end and the other end of the flow path is formed on the surface of the nozzle fixing base 161. The cleaning nozzle 112 is connected to one of the openings of the flow path. Furthermore, the attachment angle of the cleaning nozzle 112 to the nozzle fixing base 161 is set so that the dropping nozzle 11 exists on the extended line at the tip of the cleaning nozzle 112 along the direction in which the liquid is sprayed from the cleaning nozzle 112 to the dropping nozzle 11. It has been adjusted. Further, when the test tube exists below the dropping nozzle 11 as shown in FIG. 5, the inner surface of the test tube is adjusted to exist on the extended line.

  Similarly to the first embodiment, the fraction collector 110 includes an electromagnetic valve 42. The flow path pipe 33 is connected to the port 42a of the electromagnetic valve 42, and the flow path pipe 34 is connected to the port 42b. ing. On the other hand, one end of a channel pipe 135 is connected to the port 42c. The other end of the flow channel 135 is connected to the other of the openings of the flow channel formed on the surface of the nozzle fixing base 161. Thus, the liquid from the column 25 to the cleaning nozzle 112 through the flow path 31, the electromagnetic valve 41, the flow path pipe 33, the electromagnetic valve 42, the flow path pipe 135, and the flow path inside the nozzle fixing base 161. The flow path is formed.

  Further, the fraction collector 110 has a test tube container 114 (array container). In addition to the test tube 9 that receives the liquid dropped from the dropping nozzle 11, the test tube container 114 accommodates a test tube 109 having an inner diameter larger than that of the test tube 9. It is preferable that the test tube container 114 is configured such that each of the test tube 9 and the test tube 109 having different sizes can be accommodated depending on the application.

  For example, as shown in FIG. 5, a test tube support 114 a is provided on the upper portion of the test tube container 114. A plurality of circular holes 152 as viewed from above are formed in the test tube support 114a. The holes 152 are arranged in a grid pattern in the horizontal direction as shown in FIG. 5, and one test tube for each hole 152 is supported in the hole 152. Thereby, the test tube support 114a supports a plurality of test tubes while arranging them in the horizontal direction.

  The diameter of the circular hole 152 is adjusted so that the test tube 109 can pass through the inside of the hole 152. On the other hand, an adapter 151 that is installed inside the hole 152 is prepared in the test tube container 114. The adapter 151 is a cylindrical member having a substantially cylindrical shape. Further, the outer shape of the adapter 151 is adjusted so as to be just inside the hole 152, and the inner diameter of the adapter 151 is adjusted so that the test tube 9 can pass through the inside of the adapter 151.

  When the adapter 151 is accommodated in the hole 152, the inside of the adapter 151 can be passed through the test tube 9. When the adapter 151 is not accommodated in the hole 152, the test tube 109 is inserted into the hole 152. Can be passed. Thereby, the test tube container 114 can accommodate each of the test tubes 9 and 109 according to the use.

  As described above, in the fraction collector 110 of the present embodiment, it is possible to clean the outer surface of the dropping nozzle 11 without moving the dropping nozzle 11 to the cleaning position.

  The test tube container 114 has a configuration that can accommodate not only the test tube 9 but also the test tube 109 having an inner diameter larger than that of the test tube 9. Therefore, when the liquid dropped from the dropping nozzle 11 is collected, the test tube 9 is accommodated in the test tube container 114, and when the outer surface of the dropping nozzle 11 is washed, the test tube 109 is stored in the test tube container 114. Can be accommodated. Since the test tube 109 has an inner diameter larger than that of the test tube 9, when the test tube 109 is accommodated, the liquid sprayed from the cleaning nozzle 112 to the dropping nozzle 11 is larger than when the test tube 9 is accommodated. Is less likely to splash out of the test tube. In order to prevent liquid from splashing out of the test tube, it is more preferable that the test tube 109 is longer than the test tube 9. According to this, as shown in FIG. 5, the position of the upper end of the test tube is higher than that of the test tube 9 when accommodated in the test tube container 114. Therefore, it is possible to more effectively avoid the liquid splashing out of the test tube.

  As described above, the third embodiment has a configuration in which the cleaning liquid is received by the test tube disposed below the dropping nozzle 11 when the dropping nozzle 11 is cleaned. Therefore, unlike the first and second embodiments, a means for moving the dropping nozzle 11 to the cleaning position, a cleaning container, and the like are unnecessary. For this reason, the structure of an apparatus is simpler than the 1st and 2nd embodiment.

[Fourth Embodiment]
The following is a description of the fourth embodiment. Since the fourth embodiment and the third embodiment have many common parts, description of these common parts will be omitted below as appropriate. FIG. 6 is a schematic configuration diagram of a fraction collector 210 according to the fourth embodiment.

  In the fourth embodiment, unlike the third embodiment, the arm 51 can reciprocate along the direction A, and the direction B is fixed. A dropping nozzle moving unit 52 is installed below the arm 51. A nozzle fixing base 163 is installed in the dropping nozzle moving unit 52 so as to be able to reciprocate along the direction B. The dropping nozzle moving unit 52 moves the nozzle moving table 163 along the direction B in accordance with an instruction from the control unit of the fraction collector 210 (not shown).

  The fraction collector 210 includes the cleaning nozzle 112 and the electromagnetic valve 42 as in the third embodiment. The cleaning nozzle 112 is fixed to the nozzle fixing base 163 via the nozzle fixing base 161 and the fixing plate 162. The electromagnetic valve 42 and the electromagnetic valve 41 are connected via the flow path pipe 33, and the electromagnetic valve 42 and the opening of the nozzle fixing base 161 are connected via the flow path pipe 135. Further, similarly to the third embodiment, one end of a flow channel pipe 34 is connected to the electromagnetic valve 42, and a liquid discharge port is provided at the other end of the flow path tube 34. As a result, a liquid flow path from the column 25 to the cleaning nozzle 112 through the flow path pipe 31, the electromagnetic valve 41, the flow path pipe 33, the electromagnetic valve 42, the flow path pipe 135, and the nozzle fixing base 161 is formed.

  In the fraction collector 210 of the fourth embodiment having the above-described configuration, the arm 51 and the dropping nozzle moving unit 52 move the dropping nozzle 11 along each of the direction A and the direction B. Thereby, the dropping nozzle 11 moves above each test tube 9 accommodated in the test tube container 14 below the dropping nozzle 11. And the liquid from the column 25 is dripped at each test tube 9 in order.

  On the other hand, the cleaning nozzle 112 is fixed to the nozzle fixing base 163 so that the tip of the cleaning nozzle 112 faces the tip of the dropping nozzle 11. Therefore, no matter where the dropping nozzle 11 is located, the liquid can be sprayed to the outer surface near the tip of the dropping nozzle 11. When the dropping nozzle 11 is actually cleaned, it is preferable to use a test tube 109 having a diameter and height larger than the test tube 9 below the dropping nozzle 11 as in the third embodiment. . The angle of attachment of the cleaning nozzle 112 to the nozzle fixing base 161 is such that the inner surface of the dropping test tube 109 is on the extended line of the tip of the cleaning nozzle 112 along the direction in which the liquid is sprayed from the cleaning nozzle 112 to the dropping nozzle 11. It is preferably adjusted to exist.

<Modification>
In addition to the above-described embodiments, the present invention includes those having various configurations within the scope of the configurations described in the means for solving the problems. For example, although various electromagnetic valves are used in the first and second embodiments described above, any valve may be used as long as the control device 27 can control opening and closing and switching.

  In the first and second embodiments described above, the fraction collector 10 and the control device 27 are separate, but the control device 27 may be housed inside the fraction collector 10. That is, control means for controlling the electromagnetic valves 41, 42 and 83, the arm 51, etc. may be built inside the control device 27.

  In the first embodiment described above, the flow path for supplying the solvent to the cleaning nozzle 12 is constructed by branching the flow path pipe in the fraction collector 10 with an electromagnetic valve. That is, the flow path leading to the dropping nozzle 11 and the flow path reaching the cleaning nozzle 12 partially share the flow path pipe. However, a flow path to the completely different washing nozzle 12 that does not share the flow path pipe with the flow path to the dropping nozzle 11 may be constructed. Alternatively, the fraction collector 10 may have a channel tube that directly connects the pump 23 of the liquid chromatograph 100 and the cleaning nozzle 12.

  In the second embodiment described above, it is assumed that the cleaning liquid supply unit 80 and the cleaning nozzle 72 are integrally included in the fraction collector. However, a separate cleaning device having a configuration for supplying a liquid to the cleaning nozzle and the cleaning nozzle may be used. For example, when cleaning the dropping nozzle, a cleaning device having a pump that pumps the solvent from a storage container that stores the solvent and flows the solvent into the cleaning nozzle may be used.

  In the first and second embodiments described above, liquid chromatography is assumed in which the eluent is fractionated into a plurality of test tubes 9 when the concentration of the sample contained in the eluent is equal to or higher than a predetermined reference concentration. Has been. However, the present invention may be applied to liquid chromatography in which the eluent is sequentially collected into a plurality of test tubes 9 at predetermined time intervals. In the former liquid chromatography, since the eluent is dropped from the dropping nozzle 11 only when the concentration of the sample is equal to or higher than the reference concentration, the eluent containing the sample having a higher concentration than the latter liquid chromatography is subjected to the liquid chromatography. Remaining in the dropping nozzle 11. Therefore, the case of performing the former liquid chromatography is particularly meaningful in applying the present invention capable of controlling the cleaning of the outer surface of the dropping nozzle 11 than the case of performing the latter liquid chromatography.

  In the third embodiment, as in the first embodiment, the cleaning liquid is introduced to the cleaning nozzle 112 through the electromagnetic valves 41 and 42, the flow channel pipe 33, and the like. However, a cleaning solution may be introduced to the cleaning nozzle 112 by the cleaning liquid supply unit 80 or the like as in the second embodiment.

  In the third embodiment described above, the electromagnetic valve 42 that branches the flow channel pipe for introducing the cleaning liquid into the cleaning nozzle 112 may be installed at another position. For example, it may be installed in the immediate vicinity of the solenoid valve 41, like the solenoid valve 42 'of FIG. Alternatively, it is provided in the middle of the flow path pipe 31 like the electromagnetic valve 42 ″ of FIG. 7B, and the flow path pipe 335 branches off from the electromagnetic valve 42 ″ to the opening of the nozzle fixing base 161. It may be connected. As a result, a flow path from the column 25 to the cleaning nozzle 112 through the electromagnetic valve 42 ″, the flow path pipe 235, and the nozzle fixing base 161 is formed.

It is a schematic block diagram which shows the structure of each apparatus used in the liquid chromatography using the fraction collector which is one Embodiment of this invention. It is a graph which shows the time change of the density | concentration of the sample contained in the eluent which flows out from the column of FIG. It is a schematic block diagram which shows the structure of the fraction collector shown by FIG. It is a schematic block diagram which shows the partial structure of the fraction collector which concerns on embodiment different from the fraction collector shown by FIG. FIG. 5 is a schematic configuration diagram showing a configuration of a fraction collector according to another embodiment different from those in FIGS. 3 and 4. It is a side view which shows the structure of the fraction collector which concerns on another embodiment different from FIGS. It is a schematic block diagram which shows partially the structure of the fraction collector which is one modification of this invention.

Explanation of symbols

9, 109 Test tube 10, 110 Fraction collector 11 Drop nozzle 12, 72, 112 Cleaning nozzle 14, 114 Test tube container 15 Cleaning container 15a Side surface 16 Discharge flow path 31-35, 83, 135, 235 Flow path pipe 41, 42, 42 ', 82 Solenoid valve 41a-41c Port 42a-42c Port 51 Arm 80 Cleaning liquid supply unit 81 Storage container 100 Liquid chromatograph

Claims (9)

A fraction collector for liquid chromatography that dispenses the liquid from the column into a collection container according to the concentration of the sample contained in the liquid from the column,
A dropping nozzle for dropping the liquid from the column when the liquid chromatography is performed;
A sorting container support member that supports the sorting container so as to receive liquid dropped from the dropping nozzle;
A fraction collector comprising: a cleaning nozzle that sprays liquid onto an outer surface of the dripping nozzle. A first port through a third port through which the liquid passes; a state in which the first port communicates with the second port; and a state in which the first port communicates with the third port. A first three-way valve to take selectively;
An introduction flow path for introducing liquid from the column to the first port when the liquid chromatography is performed;
A liquid fractionation flow path that is a liquid flow path from the second port to the dropping nozzle;
2. The fraction collector according to claim 1, further comprising a liquid discharge flow path that is different from the liquid sorting flow path and discharges the liquid that has passed through the third port. . The liquid discharge channel is
A fourth port through a sixth port through which the liquid passes; a state in which the fourth port communicates with the fifth port; and a state in which the fourth port communicates with the sixth port. A second three-way valve to take selectively;
A first partial flow path that is a liquid flow path from the third port to the fourth port;
A second partial flow path for discharging the liquid that has passed through the fifth port;
The fraction collector according to claim 2, further comprising a cleaning liquid flow path that is a liquid flow path from the sixth port to the cleaning nozzle. A cleaning container for receiving liquid dropped from the dropping nozzle;
Nozzle moving means for moving the dropping nozzle between a sorting position at which the sorting container receives the liquid dropped from the dropping nozzle and a cleaning position at which the cleaning container receives the liquid dropped from the dropping nozzle; With
The fraction collector according to claim 3, wherein the cleaning nozzle is disposed at a position where the liquid is sprayed onto the dropping nozzle when the dropping nozzle is at the cleaning position. The cleaning container has a side surface surrounding the tip of the dropping nozzle in a plan view when the dropping nozzle is in the cleaning position;
The said side surface is arrange | positioned on the extension line of the spraying opening of the said cleaning nozzle along the direction in which the said cleaning nozzle sprays a liquid when the said dripping nozzle exists in the said washing | cleaning position, The Claim 4 characterized by the above-mentioned. Fraction collector. A storage container for storing liquid and having an outlet for stored liquid;
A cleaning liquid flow path that is a liquid flow path from the discharge port to the cleaning nozzle,
The fraction collector according to claim 1 or 2, wherein the storage container is arranged so that the discharge port is located above the washing nozzle when used in the liquid chromatography. The sorting container support member has an array container in which a plurality of the sorting containers are arranged,
The arm in which the dropping nozzle is fixed, the liquid that is dropped from the dropping nozzle, and the liquid that is dropped from the dropping nozzle moves along the direction in which the plurality of sorting containers are arranged in the arrangement container. Arm moving means for moving the arm from a position where the sorting container receives the liquid dropped from the dropping nozzle to a position where another liquid is received by the sorting container;
The cleaning nozzle is fixed to the arm so that the dripping nozzle is positioned on an extension line of the spray nozzle of the cleaning nozzle along a direction in which the cleaning nozzle sprays the liquid. 4. The fraction collector according to any one of 3 above. A method for controlling a fraction collector according to any one of claims 3-5,
The first three-way valve takes a state where the first port and the third port communicate with each other within a period when the liquid chromatography is not performed, and the fourth port and the sixth port A method for controlling a fraction collector, wherein the second three-way valve is allowed to communicate with a port. A method for cleaning the fraction collector according to any one of claims 3 to 5,
The first three-way valve is in a state where the first port and the third port communicate with each other, and the state where the fourth port and the fifth port communicate with each other is in the second three-way state. A discharge flow path selection step to be taken by the valve;
A flow path cleaning step for cleaning the liquid flow path by discharging the liquid from the liquid discharge flow path via the first and third to fifth ports after the discharge flow path selecting step is performed;
The first three-way valve allows the first port and the third port to communicate with each other, and the fourth port and the sixth port communicate with each other as the second three-way valve. A washing flow path selection step to be taken by the valve;
A nozzle cleaning step of spraying liquid onto the dropping nozzle through the first, third, fourth, and sixth ports and the cleaning nozzle after the cleaning flow path selecting step is performed. A method for cleaning the fraction collector.

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