JPH01132964A - Fraction collector - Google Patents

Abstract

PURPOSE:To make it possible to prepare each component separately in correspondence with the change in retention time, by inputting a peak judging level and a file, which specifies a peak on a chromatograph exceeding said level, into a control unit. CONSTITUTION:A liquid chromatograph device is composed of a solvent container 1, in which eluate solution 2 is contained, a column 10, a detector 12, a fraction collector 14, and the like. In this device, the fraction collector 14 inputs a peak judging level and a file, which specifies a peak on a chromatograph exceeding said level, into a control unit. The preparation operation can be performed at the specified peak based on the file. Therefore, an arbitrary peak can be separately taken out. Thus rotational analysis can be performed. The peak judging level and a file, which specifies a specific peak on the chromatogram exceeding said level as a preparing starting condition, are inputted into the control unit. The preparation operation can be performed at the specified peak based on the file. Thus, the change in retention time can be compensated.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention makes it possible to reliably and safely separate each component according to changes in retention time, as well as easily set up various preparative methods to perform optimal analysis. Regarding the fraction collector designed to

(Prior art) In the analysis process using a liquid chromatograph, the retention time often changes due to changes in the structure of the carrier, liquid leakage, or changes in conditions such as temperature. Even if this is done, it is difficult to expect accurate analytical results because the fractionation is not performed correctly or the wrong components are fractionated.

Conventionally, as a countermeasure against such changes in retention time, there is a technique disclosed in, for example, Japanese Unexamined Patent Publication No. 58-41352. In other words, this publication states that when the baseline of the chromatogram recorded on the recorder changes, by detecting the increase in the differential change in the rise of the preparative peak, accurate peak determination is performed and the target component is separated. An automatic preparative separation device is shown.

(Problems to be Solved by the Invention) However, although such conventional fractionation devices have a useful means of peak determination, the actual state of fractionation is mechanically biased,
In response to changes in retention time, which tend to reduce the reliability of analysis results, it is not possible, for example, to change the start of preparative collection or to collect only target components that fall within a specific peak or time range. There are problems such as requiring a large number of component collection containers and prolonging the cycle time for fractionation.

On the other hand, the above-mentioned request for preparative separation is not only effective as a countermeasure against changes in retention time, but also in general in the analysis process by separating only the desired components using the minimum amount of collection containers, and in this type of analysis. This will be essential in promoting rationalization and speeding up the process.

In view of these points, the present invention makes it possible to reliably and safely separate each component according to changes in retention time, and also facilitates the rationalization and speeding up of this type of analysis by easily setting various preparative methods. The purpose of this invention is to provide a fraction collector that is optimal and can be used for a variety of analyses.

(Means for Solving the Problem) For this reason, the fraction collector of the present invention inputs a file specifying a peak determination level and a predetermined peak on a chromatogram that exceeds the level into the control unit, and inputs the file to the control unit. It is characterized by making it possible to fractionate the above-mentioned designated peaks based on the method, and also to fractionate arbitrary peaks, thereby enabling rational analysis.

Furthermore, the fraction collector of the present invention inputs into the control unit a file specifying a peak determination level and a specific peak on the chromatogram exceeding the level as preparative start conditions, and performs fractionation from the specified peak based on the file. This feature is characterized in that it is made possible to compensate for changes in retention time.

Furthermore, the fraction collector of the present invention combines two or more files specifying a peak determination level and a predetermined peak on a chromatogram exceeding the level, or a combination of two or more files specifying a fractionation time interval, Alternatively, input a combination file consisting of multiple files combining one or more of these files into the control unit, enable preparative separation based on the file, and perform multiple preparative separations in the same or different modes continuously. It is characterized by being able to perform the following tasks.

(Example) Below, an illustrated example in which the present invention is applied to a liquid chromatograph will be explained.
is a solvent storage container containing an elution solvent 2 therein, one end of a conduit 3 is inserted into the container 1, and a main pump 4 capable of pumping up the solvent 2 is inserted in the conduit 3. .

An injector 5 capable of injecting the solvent 2 and a sample to be described later into the column is connected to the conduit 3 downstream of the pump 4, and one end of a sampling tube 6 is connected to the injector 5. The other end of the tube 6 is inserted into a sample container 8 containing a sample 7 such as an organic substance, and a sampling pump 9 capable of pumping up the sample 7 is inserted into the conduit of the tube 6 .

The column 10 is filled with a predetermined packing material, and the column 1
A detector 12 capable of detecting the amount of each component flowing out from the column 10 by appropriate means is connected to a conduit 11 communicating with the column 10,
The detection result is converted into an electrical signal and output to the recorder 13, so that the recorder 13 can record the detection result. The other end of the conduit 11 is a fraction collector 14
It is held in a tube holder, which will be described later, and allows the effluent in the tube 11 to drip into a test tube 15, which is a component collection container.

The fraction collector 14 is formed into a substantially box shape as shown in FIG. 2, and has side plates 1 erected at both ends of a bottom plate 16.
7 and 17 have a pair of L-shaped fittings with spacers 18 and 18 in between.

19 are fixed in the upper and lower positions. Above metal fittings 18.18
A shaft 20.20 is rotatably supported vertically at the tip of the motor, and one of the shafts 20 is connected to a drive shaft 23 of a first pulse motor 22 via a coupling 21.

The first pulse motor 22 is fixed to the upper part of a support holder 24.24 installed upright at the end of the bottom plate 16, and its operation is controlled by a control unit, which will be described later. Direction (hereinafter referred to as Y direction)
It is possible to move to.

A timing pulley 25.25 is fixed to the shaft 20.20, and a timing belt 26 is inserted between the pulleys 25.25.
is wound around the belt 26, and a guide block 27 is fixed at a proper position on the belt 26 so as to be able to move together with the belt 26. A base plate 28 is fixed to the upper surface of the guide block 27, and a pair of rollers 2 are installed directly below the plate 28.
9 and 29 are rotatably supported, and a slide block 30 is fixed behind them.

Guide rods 32 and 33 are accommodated in the rollers 29 and the groove 31 of the slide block 30, and guide the movement of the base plate 28.
．． Both ends of 33 are fixedly installed between the side plates 17, 17.

The base of an arm plate 35 is fixed on the base plate 28 via a pin 34, the tip of which protrudes from a horizontally long opening window 37 formed in the upper part of the front plate 36.
It's sticking out to the front. A second pulse motor 38 whose operation is controlled by a control unit to be described later is attached to the base end of the arm plate 35, and a timing pulley 40 is fixed to the lower end side of the drive shaft 39 of the second pulse motor 38.

Further, a timing pulley 41 is rotatably supported directly below the tip of the arm plate 35, and a timing belt 42 is wound between the pulley 41 and the pulley 40.

A guide block 4 is placed at the appropriate position of the timing belt 42.
3 is fixed, and the aforementioned tube holder 45 is fixed to an L-shaped metal fitting 44 screwed to the lower surface of the block 43. The tube holder 45 has a through hole (not shown) communicating in the vertical direction, and allows the conduit 11 to be inserted into and removed from the hole.

On the other hand, a pair of guide rods 46, 46 are installed directly under the front half of the arm plate 35 along its longitudinal direction, and the guide blocks 43
is movable in a direction perpendicular to the axial direction of the guide rods 32 and 33 (hereinafter referred to as the X direction). 4
Reference numeral 7 denotes an arm whose outer contour is divided into a rod shape by an arm cover, 48 is a slope plate formed forward from the front edge of the top plate 49 to the upper end of the front plate 36, and the chain plate 48 has a horizontally elongated operation panel. 50 are provided.

The panel 50 is provided with a horizontally elongated preparative mode display section 51, on which a plurality of preparative mode display lamps can be blinked.

The display section 51 can display manual mode, time mode, peak mode, and external mode, which will be described later, and one of these can be selected by operating the mode selection key described later and lighting the corresponding display lamp. It is made displayable.

Reference numeral 52 denotes a display section that has approximately the same shape as the preparative mode display section 51, and is capable of displaying two types of information groups alternately.One of the information groups includes, for example, the elapsed time since the start of preparative separation. TIME; ○ hours ○ minutes ○ seconds and the current number of preparative separation repetitions CY#; ○ times and the current signal value S from the detector 12
IG, -〇~○ can be displayed.

In addition, the other information group includes, for example, the file number FILE where the fractionation is being performed, ○, the position of the test tube 15 where the fractionation has now been completed TIJBE; 0, and the peak number PEAK determined so far; O is enabled to be displayed.

Reference numeral 53 denotes an operation key consisting of a plurality of keys, including, for example, a key for instructing execution and stopping of a preparative separation program input to a control unit, which will be described later, and a key for instructing the operation of the tube holder 45 and the arm when using a predetermined rack in manual mode. 47 in one step at a time, a key to control the opening/closing of the solenoid valve attached to the tube holder 45 as an option and its step operation, a key to temporarily stop the above program being executed, and a key to the optional printer. It is equipped with keys that output the progress of preparative separation in real time.

The function keys 54 are made up of a plurality of function keys, including, for example, the mode selection key described above, a key for calling files in each mode except for the combination file described later, a key for calling the above-mentioned combination file, and a key for initializing file contents. It is provided with a key for setting and changing the contents of a file, a key for copying or printing the contents of a file to another file, a key for returning the arm 47 to its home position, and the like.

55 is a numeric keypad that allows input to the display section 52, and the keys 55 include the display section 5.
2. It is equipped with keys for correcting each parameter of the called file or inputting new data.

Among the preparative separation modes, the manual mode is the recorder 1.
The content is to perform arbitrary preparative separation by operating the above-mentioned keys while viewing the chromatogram recorded in 3.

In this case, the parameter input to the control unit is RACK# of the rack number to be used as shown in Figure 5.
, the required time DELAY (see) from the flow cell (path shown) of the detector 12 to the outlet of the conduit 11, and whether or not fractionation is started by an external signal such as an autosampler.

5TART (0, 1), which can be changed by operating a predetermined key of the function keys 54.

In addition, the time mode is a method of performing preparative collection based on a predetermined time table, and there are two methods: one is to repeat draining and fractionation at regular time intervals, and the other is to perform these at an arbitrary set time. It is selectable. In this case, by setting the safety peak or start peak in the above mode, it is possible to detect a shift in retention time and stop the subsequent preparative collection, or to start the preparative collection from when the specified peak is determined. It becomes possible.

In other words, the above safety peak assumes that the specified peak appears within the specified time, and if the specified peak does not appear within the specified time and the retention deviates as shown by the broken line in Figure 7, an alarm and error display will occur. At the same time, the subsequent fractionation is not performed, so that when the above-mentioned peak appears, the subsequent sequence can be executed regardless of the fractionation of the component concerned.

Therefore, when setting the safety peak, 5A
It is necessary to input parameters such as FE, PEAK, designated peak number, and appearance time T, MIN, T, MAX of the peak based on, for example, a chromatogram obtained in a preliminary experiment. In this case, when the baseline of the chromatogram is parallel to the time axis as shown in FIG.
EVEL) or above, and when the baseline exhibits a slope shape with respect to the time axis,
), the peak is determined based on the slope value at the PEAK detection point where the rise of the peak is detected.

Therefore, operate the numeric keypad 55 to input the setting level LA as an integer parameter, and also input the slope (SLOPE) parameter.
), the slope setting value (1 to 9) for the rise slope value created in advance and the 5AFE LEVEL, which starts fractionation when the rise of the set value is recognized in a predetermined section from the PEAK detection point, are set. Parameters are entered numerically.

On the other hand, the start peak is such that the preparative separation is started when the specified peak is determined, and in that case, 5TA
It is sufficient to input RT, PK, and the peak number as parameters.

Therefore, if the retention time of the first peak is slightly delayed, in actual chromatograms where the peaks that appear later are generally delayed by a long time, starting the preparative separation with the peak that appears in the middle of the analysis allows for more accurate separation. It becomes possible to take FIG. 8 shows an example in which the first peak is set as the safety peak and the second peak is set as the start peak.

Note that the peak determination in this case can be executed at the set level LA or the rising level of the slope.

In addition, in time mode, in addition to the above parameter input, a fifth
As shown in the figure, the time required for one cycle of fractionation is END.
TIME and the number 1 of the test tube 15 to start fractionation.
TtJB, number of test tubes 15 for preparative collection C0LL, TU
B. Data smoothing constant TM, C0N5T#, number of automatic repetitions CYCLES, 5TEP when fractionating at regular intervals, C0N5T and interval time, and T# when fractionating at arbitrary intervals DRA I N C0LL and each time interval of drain and collection, EXT and EVENT when controlling the time sequence of external equipment.
#, time from start, TIME, etc. are input as parameters.

On the other hand, the peak mode is a method of performing fractionation while performing peak determination, and the set level L depends on the peak determination method.
There are two methods: the A and slope level methods, the all-peak method in which fractionation is performed from each determined peak, the method in which arbitrary peaks are designated and fractionated, or even negative peaks can be fractionated, and the peak width There are methods of peak division when the range is wide.

Among these, for peak division, as shown in Figure 9, specify the peak you want to divide by its PEAK number, and set the preparative time to T#PEA for each section of the peak divided into multiple parts.
This is made possible by inputting the parameter as K TIME. In this case, in order to input the peak mode parameters, in addition to sharing some of the time mode parameters as shown in Figure 5, MASK input is performed for an interval in which no peak determination is performed, and the mask start time and end time are input. are input as parameters as T, MIN and T, MAX, PEAK and WIDTH are set to limit the fractionation time for one peak and input that time, and NEG and PEAK are used when fractionating a negative peak. and ALL when all peaks determined to be peaks are fractionated.

It has PEAK (0,1).

External mode EXT is a method of performing fractionation using an external controller, and is suitable for systemization using a personal computer, etc., and the parameter input at that time is R as shown in Figure 5.
ACK# and DELAY(see) and EX, 5TAR
It is specified in T.

The combination file mode is a method of sequentially fractionating a plurality of combinations of time or peak modes of a single or multiple files, and is configured by sequentially specifying file numbers for each time or peak mode.

On the other hand, the file N [L
At the same time, by operating the specified keys of the function keys 49 used for setting and changing files, the above-mentioned parameters necessary for the mode are sequentially called up on the display section 52, and the desired numerical values are inputted therein. has been created. The information for each file is stored in a microcomputer built into a control unit housed in the fraction collector 14, and the fraction collector 14 automatically performs batch processing one after another based on this data.

Among the parameters stored in the microcomputer in this way, mainly 1. TUB input and C0LL, T
Based on the UB input, the above-mentioned first
A control signal is output to the second pulse motors 22 and 38 to control the movement position of the arm 47.

In this case, the movement of the arm 47 or the tube holder 45 is such that when a drain piece, which will be described later, is used, the test tube 15 can be moved one pitch at a time in the X direction and the Y direction, as shown in FIG. When moving in the direction, it moves directly above the drain groove described below, while when stopping the sorting during the separation process, it stands still on the drain groove corresponding to the step position, and is always in its original position at the base end of the drain groove. It is positioned.

Also, arm 47 when the above drain piece is not used.
Alternatively, the tube holder 45 can be moved in a meandering manner in the order in which the test tubes 15 are arranged, as shown in FIG. 11, for example.

56. 56 is a hanging tool protruding from the lower part of the front plate 36,
Tongue pieces 58, 58, which are integral with a tray 57 made of stainless steel plate, are hooked to the tip thereof, and five racks made of synthetic resin are housed within the tray 57. The rack 59 has a substantially U-shaped rack frame 6° with open front and rear sides, and has a large number of locking holes 61 formed at the bottom thereof, and a large number of through holes 62 formed on its upright side wall.
The test tubes 15 (
It accommodates.

The above-mentioned drain pieces 65 are housed in two rows in the X direction on the partition plate 64, and the pieces 65 are made of Teflon resin or the like in the shape of an elongated gutter.
is open.

The drain 7s66 is formed in a substantially key shape as shown in FIG. 10, and the groove 66 is gradually formed at a deeper bottom toward a drain hole, which will be described later, as shown in FIG.
7 is formed. A tubular adapter 68 made of synthetic resin is removably screwed into the drain hole 67, and one end of a drain tube 70 communicating with a drain container 69 is attached to the lower end of the adapter 68.

In the figure, 71 is a lahar groove formed at the bottom of the drain groove 66;
Reference numerals 72 and 72 are retaining protrusions protruding from both ends of the lower surface of the drain piece 65, which can be inserted into the through hole 62 formed in the partition plate 64.

(Function) When analyzing a predetermined sample using the fraction collector configured in this way, first create a program file that is optimal for analyzing the sample.

To create the above file, first turn on the power to the fraction collector 14 and initialize it, then operate the mode selection key of the function key 54 to select one of the plurality of fractionation modes displayed on the display section 52, and select the corresponding fraction collection mode. After selecting the mode, input the appropriate file name for the mode. In this case, when selecting the combination file mode, the setting is made with all mode display lamps on the display section 52 blinking.

The selection of the above-mentioned preparative separation mode is made depending on the purpose of analysis and the properties of the sample, but when performing arbitrary preparative separation while viewing the chromatogram recorded on the recorder 13, for example, the manual mode is selected, and the set time When performing fractionation using a table, for example, time mode is selected.

Furthermore, when extracting components with a predetermined concentration or higher while performing peak determination for each component that appears in the chromatogram,
For example, when peak mode is selected and different types of samples are repeatedly collected using an autosampler, etc.,
For example, combination file mode is selected.

After selecting a predetermined preparative separation mode in this way, by operating a predetermined key of the function key 54, the parameters necessary for the mode are displayed in sequence on the display section 52, and by operating the numeric keypad 55 for each parameter. Enter the specified value.

The parameter input for each mode in this case is as shown in Figure 5, where the rack magnet to be used is numerically input into RACK# and linked to the dimensions of the rack, the maximum capacity of the test tubes 15, and the address of the chain tube 15. . DELAY(
see) is the time required from the flow cell of the detector 12 to the outlet of the conduit 11, which is obtained by dividing the flow rate by the volume of the conduit 11 between them, and EX and 5TART start fractionation by an external signal such as an autosampler. If so, enter the presence/absence as a value of 0.1.

In addition to the parameters common to each mode, unique parameters are input in the time mode, peak mode, and combination file mode. Among these modes, the following parameters are common to these modes.

In other words, END defines the time for one cycle of fractionation.
1. for specifying TIME and the position of the test tube 15 to start fractionation. It has a TUB number. Therefore, this means starting the preparative collection from any time range and any peak, with the intention of draining unnecessary components and collecting only the necessary components. C0LL the number of 15.

Defined as TUB input. Therefore, for example, the settings for test tubes N [L5 to 11 are 1. TUB 5, C0
LL, TUB 7.

Furthermore, as a data smoothing constant, numbers 1 to 9 are TM
, C0N5T#, ABSO, LEVEL as the reference value for peak determination, and an integer value from 0 to 99 as the percentage value of the detection sensitivity with respect to the full scale. The absolute values of negative peaks in the peak mode, ie, NEC and PEAK, are also input.

In addition, in SL○PE, which is another method of peak determination, when the baseline of the chromatogram fluctuates, the slope setting value corresponding to the rising slope value (mV/5ee) of the peak is set to a value of, for example, 1 to 9. This is done by inputting the 5AFE and LEVE settings that are paired with the 5LOPE settings above.
Enter the value of L when the full scale is 100.

Therefore, in the case of 5LOPE setting, fractionation is started when 5AFE exceeds the LEVEL setting value from the peak judgment value. In addition, it can be linked with an auto sampler, etc., or in the case of automatic preparative collection, the number of automatic repetitions CYCLES can be adjusted.
Enter 5AFE as a safety function in case the retention time fluctuates.

When setting PEAK, for example, based on the chromatogram from a preliminary experiment, specify one or more peaks by peak number, and also specify the appearance time of each peak by T, MI.
N and T.

MAX, and the peak determination method at that time is specified by AB.
Specify either SO, LEVEL or 5LOPE.

In addition to these common parameters, in time mode, 5TART is another safety function when retention time fluctuates.

You can set PK. In this case, specify the specific peak by peak number, and select the peak determination method as ABSO,
Specify with LEVEL or 5LOPE.

Therefore, 5AFE, PEAK and 5TART, PK are different in that the former specifies the stop conditions for preparative separation, and the latter specifies the start conditions for preparative separation.Therefore, the former specifies multiple arbitrary peaks and sets them. However, the latter differs in that it can be set only to one arbitrary peak.

In this case, the former is when the peak is determined within a predetermined time,
Therefore, even if 5AFE and PEAK do not actually function, the continuation of the sequence is simply allowed, and the separation of the peak is performed only if the parameters have been input in advance, regardless of the separation of the peak. . This is also true for the latter, and if the specified peak is 5T
Even if ART PEAK functions, it will not be fractionated unless the peak in question has been input as a parameter in advance as a fractionation condition. Therefore, both can be set in the same time mode, an example of which is shown in FIG.

On the other hand, if you want to perform preparative collection at fixed time intervals in time mode, enter 5TEP and C0N5T. If you want to perform preparative collection at arbitrary time intervals, enter the intervals between drain and collection, and also add the above 5AFE P to these preparative methods.
When setting EAK, 5TART, and PK, input the specified parameters.

On the other hand, as a parameter unique to the peak mode, there is MASK, which sets the time for the section in which no peak judgment is performed and therefore no fractionation is performed.Input the presence or absence of this with 0.1, and also set the start and end times of the mask section. Enter each. In addition, if the peak width is wide and you want to limit the collection time of the peak, set PEAK, WI DTH,
Enter the peak number and its preparative time. Therefore, even if a peak is being determined, the fractionation of the peak is stopped at the above value.

In addition, in peak mode, you can select whether or not to collect negative peaks.
G, PEAK (0, 1), and enter the presence/absence of fractionation for all peaks judged as ALL, PEAK (0, 1).
Enter in step 1). Furthermore, if the peak width is wide and the sample is divided into a plurality of test tubes 15 for fractionation, input the fractionation time for each divided section of the peak magnetic field.

When all parameter input for each mode is completed in this way, the registration key of the function key 54 is operated, and file creation for each mode is completed.

When creating a combination file mode file, operate the combination key of the function key 54 to initialize it, and then specify one or more of the created time mode or beak mode files using the file number. After arranging them in the sorting order, the process is completed by operating the registration key.

Therefore, in this case, the combined files constitute one combination file, and fractionation is performed continuously based on the contents of the file. 1st
Figure 9 shows an example of this, in which files of different types of samples 1 to 3 are combined.

Each file created in this way is stored in the microcomputer built into the control unit by operating the registration key.

Next, when actually performing preparative separation using the file created in this way, turn on the power, select one of the multiple modes displayed on the mode display section 51 by operating the mode selection key, and select the combination file mode. The selection is made while all modes are displayed on the display section 51.

Then, after operating the file key or combination file key of the function key 54 to call up a predetermined file for the mode in question, confirming its contents, and making appropriate corrections and changes as necessary, press the start key of the operation key 53. or by a drive signal from an external device, the fraction collector 14 is started to perform fractionation.

That is, the fraction collector 14 moves the arm 47 and the tube holder 45 to a predetermined position based on the selected file contents, determines the peak of the chromatogram recorded in the recorder 13, and determines the peak of the chromatogram recorded in the recorder 13, and determines the determination or the set time. Condition 5. The target component introduced into the conduit 11 is fractionated into a predetermined test tube 15.

Of these, the arm 47 is normally located on one side of the opening window 37 as shown in FIG. It is stationary directly above.

When moving the arm 47 and tube holder 45 under such circumstances, in the manual mode, operate the corresponding key of the operation key 53 to move the arm 47, etc. one step at a time, while in the case of automatic preparative separation, A control signal is output from the control unit to the first and second pulse motors 22 and 38, and the motor 22
, 38 are driven at a predetermined rotational speed.

When the first pulse motor 22 is driven, its power is transmitted from the drive shaft 23 to the shaft 20 via the coupling 21, and the timing pulley 25 fixed to the shaft 20 rotates, and the timing pulley 25 and the other A timing belt 26 wound around the timing pulley 25 rotates, and a guide block 27 fixed to the belt 26 moves one step at a time in the Y direction along guide rods 32 and 33.

Therefore, the base plate 28 fixed to the guide block 27 and the arm plate 35 integral with the plate 28 move together with the block 27, so that the arm 47 moves. On the other hand, when the second pulse motor 38 is driven, its power is transmitted from the timing pulley 40 on the driving side to the other pulley 41 via the timing belt 42, and as the belt 42 rotates, the The guide block 43 is the guide rod 46°46
Move one step at a time in the X direction along

In this case, when the drain piece 65 is attached to the rack 59 and used, the tube holder 45 is placed directly above the drain groove 66 when the arm 47 moves in the Y direction, and is moved along the groove 66. The dripping liquid from the conduit 11 is allowed to fall into the drain groove 66. On the other hand, when moving in the X direction, it moves one step at a time starting from the drain groove 66 as shown by the arrow in FIG. 10, and drains unnecessary dripped liquid. Drop it on f166.

Therefore, even when the solenoid valve is not used, the unnecessary liquid is reliably drained and the surroundings of the rack 59 can be prevented from being contaminated by scattering. On the other hand, the unnecessary liquid flows down along the drain groove 66 and flows through the drain hole 67 into the drain tube 7o. It is guided and stored in the drain container 69.

Then, the tube holder 45 starts to collect the test tube 1.
When the holder 45 moves directly above the holder 5, the output of control signals from the control unit to the first and second pulse motors 22 and 38 is stopped, and the movement of the holder 45 is stopped. Therefore, at this time, the dripped liquid from the conduit 11 is stored in the test tube 15 directly below, and when the preparative collection time has elapsed, a control signal is sent from the control unit to the pulse motors 22 and 38 again, and the tube holder 45 is moved to the corresponding step. It moves onto the drain groove 66 and waits for the next signal. Also,
For continuous fractionation.

Based on the parameter input of TUB, COLL, and TUB, move to the corresponding test tube 15 position.

When a target component is fractionated into a predetermined test tube 15 in this manner, various fractionation methods can be selected depending on the purpose of analysis. For example, when separating a target component in manual mode, it is possible to perform arbitrary separation by operating keys while viewing the chromatogram recorded on the recorder 13, making it suitable for preliminary experiments etc. .

Furthermore, if peaks recorded in a chromatogram appear stably over time in, for example, a preliminary experiment, fractionation in time mode is suitable. This time mode allows you to select two types of preparative separation methods by setting the set time to a fixed time interval or an arbitrary time interval.
Requires RAIN and COLL inputs.

Figure 14 shows an example of fractionation at regular intervals; in this example, No.
, Since 5TART and PK are set for 2 peaks,
ABSO, LEVEL and 5LO are the peak determination methods.
The former is selected from PE LEVEL, and its predetermined value is input as a parameter as LA. therefore,
In this case, each peak exceeding the LA value is collected at equal intervals (1 minute intervals), and the sequence can be started from No. 2 peak.

By setting 5TART and PK in the constant interval separation mode in this way, it is possible to start separation from any peak, substantially correcting changes in retention time, and also to perform uniform separation at equal intervals. This means that the desired component can be reliably and rationally fractionated using a small amount of test tube 15, compared to the conventional method.

On the other hand, FIG. 15 shows an example of fractionation at arbitrary intervals, in this example 5AFE, PK, and 5TART.

Since PK is not set, ABS required for peak determination
It is not necessary to input parameters such as O, LEVEL or 5LOPE LEVEL, and fractionation is performed from the 1st test tube 15 to the 9th test tube 15, and the fractionation time is at least 1 minute for the 1st test tube 15. Maximum 6.5 in 9th test tube 15
It is set to minutes. In addition, the peak width is wide and the test tube 15
If you are concerned about the capacity of the
By inputting the parameter O for N and setting the fractionation time appropriately, fractions can be fractionated continuously like the fifth to seventh test tubes 15.

In addition, if you want to reliably separate only the target component, preparative separation using peak mode is suitable, and the preparative method can be divided into two types: when all peaks that have been identified as peaks are collected, and when any peak is collected. These are divided into ALL and PEAK in advance.
Parameter input is O or 1. In addition, it goes without saying that it is necessary to input the parameters of the peak determination method and its required value.

Figure 16 shows an example in which peak determination is performed with 5 LOPEs and all peaks determined are fractionated. In this example, negative peaks (N[L2, 3) are set, and unnecessary peaks (N(LL and LL) are set. 2 peaks between MAS
K is provided to prevent fractionation, and NO, which has a wide peak width,
For 5 peaks, set PEAK WIDTH,
The separation time is regulated by inputting a parameter for the separation time. By setting MASK and PEAK WIDTH in the all-peak fractionation mode in this way, only the desired peak can be fractionated using the minimum amount of test tubes 15.

On the other hand, in FIG. 17, an arbitrary peak (NIIL2, 4.6) is specified for the peak determined by ABSO, LEVEL, peak division is set for N[L4 peaks, and the desired division interval is set. The fractionation time is input as a parameter, and the divided components are fractionated into separate test tubes 15. For the peaks determined in this way, by assuming an arbitrary peak and performing fractionation, only the substantially necessary components can be rationally fractionated using the minimum amount of test tubes 15.

For such time mode and peak mode, two kinds of safety functions can be set to compensate for changes in retention time. There is a safety peak that stops the subsequent preparative collection, and a start peak that starts the preparative conditions from the time the specified peak is determined, and these peak determinations are performed at ABSO, LEVEL, or 5L.
Either OPELEVEL may be used.

Among these, safety peak specifies one or more peaks in time mode or peak mode,
and the appearance time of the peak is T, MIN and T, MA
Sections are restricted by X, and if the peak does not appear within that time range, the subsequent progression of the sequence is stopped. For example, if the Nil 1 peak for which the safety peak is set as shown in Figure 18 appears outside the specified time range as shown by the broken line, the subsequent preparative collection is stopped, and the N[L1 peak is set as the safety peak. can be set to any peak instead.

However, if you set the safety peak at the first peak that appears as shown in the figure, you will be able to quickly learn about changes in retention time and take appropriate measures, and you will also be able to prevent subsequent preparative separations, where the reliability of preparative separation tends to decrease. stop immediately,
This is more effective than settings for other peaks in that you can quickly switch to another meaningful analysis.

In addition, as mentioned above, the start beak starts the preparative separation conditions from the time when a specific peak is identified as a peak. By setting the preparative separation start conditions, changes in retention time can be substantially compensated for.

In this case, if the start peak is set to the peak that appears first, the analysis will proceed while allowing a large change in retention time, which may prolong the analysis time. For example, as shown in Figure 18, A start peak is set at the Na2 peak, and N[L1
By setting the above-mentioned safety peak at the peak and managing the degree of change in retention time via the Nll peak, it is possible to rationalize the start peak setting.

Note that this start beak can be applied not only to the time mode but also to the beak mode.

On the other hand, when different kinds of samples are to be fractionated continuously, or when the same sample is to be fractionated in both time mode and peak mode, fractionation in combination file mode is preferable. Prepare appropriate files for each of the three types of samples as shown,
By combining these files, the above-mentioned sample analysis can be performed continuously and rationally.

(Effects of the Invention) As described above, the fraction collector of the present invention inputs a file specifying a peak determination level and a predetermined peak on a chromatogram that exceeds the level into the control unit, and based on the above file specifies the specified peak. Since it is now possible to fractionate, any peak above a predetermined level can be specified and fractionated, which has the effect of allowing rational analysis to be carried out using the minimum amount of component collection containers.

Furthermore, the fraction collector of the present invention inputs into the control unit a file specifying a peak determination level and a specific peak on the chromatogram exceeding the level as preparative start conditions, and performs fractionation from the specified peak based on the file. Since it is possible to perform preparative separation, it is possible to compensate for changes in retention time and perform reliable and stable preparative separation.

Furthermore, the fraction collector of the present invention combines two or more files specifying a peak determination level and a predetermined peak on a chromatogram exceeding the level, or a combination of two or more files specifying a fractionation time interval, or A combination file consisting of multiple files combining one or more of these files can be input into the control unit and preparative separation can be performed based on the file, so files can be easily created based on existing files. At the same time, since fractionation can be performed continuously in the same or different modes, there is a favorable effect for continuous fractionation of different types of samples.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram showing an example of an analysis system to which the present invention is applied, and Fig. 2 is a perspective view showing the external appearance of a fraction collector to which the present invention is applied, showing the condition when the drain piece is not in use. Figure 3 is a vertical cross-sectional front view of Figure 2;
The figure is a longitudinal cross-sectional side view of Figure 2, with additional notes showing how the drain piece is used, Figure 5 is an explanatory diagram showing an example of parameter input used in the present invention, and Figures 6 (a) and (b) ) is an explanatory diagram showing two peak determination methods adopted in the present invention, Fig. 7 is an explanatory diagram showing an example of setting the safety peak adopted in the present invention, and Fig. 8 is an explanatory diagram showing an example of setting the start peak adopted in the present invention. FIG. 9 is an explanatory diagram showing an example of peak division adopted in the present invention. FIG. 10 is a plan view showing how the rack and drain piece used in the present invention are installed. 12 is a sectional view taken along line AA' in FIG. 10, and FIG. 13 is a sectional view taken along line BB' in FIG. 10. , 1st
Figure 4 is an explanatory diagram showing an example of fractionation at fixed time intervals, Figure 15 is an explanatory diagram showing an example of fractionation at arbitrary time intervals, Figure 16 is an explanatory diagram showing an example of fractionation of all peaks, and Figure 17 is an explanatory diagram showing an example of fractionation at arbitrary time intervals. The figure is an explanatory diagram showing an example of fractionation using an arbitrary peak, and Figure 18 is an explanatory diagram showing an example of fractionation using safety peak and start peak settings.
FIG. 19 is an explanatory diagram showing an example of fractionation in the combination file mode. 14... Fraction Collector Patent Applicant Gascro Industries Co., Ltd. Agent Patent Attorney Chiaki Takeshi Figure 5 Figure 74 Figure 15 Figure 76 Figure 77 0 10 20 30 40mtn

Claims (3)

[Claims] (1) A fraction collector characterized in that a file specifying a peak determination level and a predetermined peak on a chromatogram exceeding the level is input into a control unit, and the specified peak can be fractionated based on the file. . (2) Input a file specifying the peak determination level and a specific peak on the chromatogram that exceeds the level as the preparative start condition into the control unit, and confirm that the preparative collection is enabled from the specified peak based on the above file. Features a fraction collector. (3) Combine two or more files specifying the peak judgment level and a predetermined peak on the chromatogram that exceeds the level, or combine two or more files specifying the separation time interval.
A fraction collector characterized in that a combination file consisting of a plurality of files consisting of a combination of the above or a combination of one or more of these files is input to a control unit, and fractionation can be executed based on the file.