US3862038A - Liquid chromatographic system - Google Patents

Liquid chromatographic system Download PDF

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Publication number
US3862038A
US3862038A US351501A US35150173A US3862038A US 3862038 A US3862038 A US 3862038A US 351501 A US351501 A US 351501A US 35150173 A US35150173 A US 35150173A US 3862038 A US3862038 A US 3862038A
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United States
Prior art keywords
specimen
column
eluent
liquid
tube
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Expired - Lifetime
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US351501A
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English (en)
Inventor
Seiji Takeuchi
Yoshinori Takata
Kazunori Fujita
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Hitachi Ltd
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Hitachi Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/24—Automatic injection systems

Definitions

  • a liquid chromatographic system comprising an eluent supplying device, a column packed with a filling substance, an eluent guide tube having one end communicated with the column and the other end communicated with the supplying device through a specimen injector having a specimen measuring tube to measure a predetermined quantity of specimen sent from a specimen supplying device and to hold the measured specimen therein, and a specimen guide tube having one end inserted directly into the filling substance and the other end connected with the specimen injector.
  • One object of the present invention is to provide a high liquid-chromatographic system in which the specimen can be prevented from diffusing at the specimen introducing part.
  • Another object of the present invention is to provide a liquid-chromatographic system capable of a rapid analysis with high accuracy.
  • a liquidchromatographic system comprising an eluent supplying device, a column packed with a filling substance, an eluent guide tube having one end communicated with the column and the other end connected with the eluent supplying device, and a specimen introducing tube having one end inserted directly into the filling substance packed in the column and the other end connected with a specimen supplying device.
  • FIG. 1 shows the schematic structure of a conventional apparatus for use in liquid chromatography.
  • FIG. 2 shows the schematic structure as a whole of an apparatus for use in a liquid-chromatographic systern embodying the present invention.
  • FIGS. 3A and 3B show the perspective and top views of a specimen injector used in the apparatus shown in FIG. 2.
  • FIG. 4 illustrates the condition of connecting the specimen injector shown in FIG. 3 with a column.
  • FIGS. 5A and 5B are respectively chromatograms obtained by the conventional chromatographic and the chromatographic system according to the present invention.
  • FIG. 6 shows the cross section of the principal part of another example of a column as used in the chromatographic system shown in FIG. 2.
  • FIGS. 7A and 7B show another example of a specimen injector as used in the chromatographic system shown in FIG. 2.
  • FIG. 1 which shows the structure of a conventional chromatographic system there are illustrated a tank 41 containing an eluting developer or eluent, a pump 42 to compress and feed the eluent into a pressure gauge 43 to measure the output pressure of the pump 42, a specimen injector 44 having a change-over valve such as a flow injector, a specimen introducing tube 45, a packing 46, a column filler 47, a stainless steel column 48, a filter 49, a packing 50, a space 51 between the specimen guide tube 45 and the column filler 47 and a guide tube shifter 52 to shift the specimen guide tube 45.
  • a tank 41 containing an eluting developer or eluent
  • a pump 42 to compress and feed the eluent into a pressure gauge 43 to measure the output pressure of the pump 42
  • a specimen injector 44 having a change-over valve such as a flow injector
  • a specimen introducing tube 45 such as a flow injector
  • a packing 46 such as
  • the specimen introducing device as indicated at A in FIG. 1 is used.
  • a specimen is taken into the flow injector 44, then the specimen is introduced through the specimen introducing tube 45 into the column 48, and finally the specimen is therein eluted.
  • the filler 47 packed in the column e.g., organic polymeric adsorbent and ion exchange resin, will be compressed and shrink under the action of the high pressure of about kg/cm at which the specimen is transported through a high-pressure duct and the space 51 is created between the end of the specimen introducing tube 45 and the filler 47 so that the specimen introduced into the column 48 is diffused and diluted.
  • Another conventional method of chromatography has employed a specimen introducing device as designated at B in FIG. 1.
  • the specimen transported through a high pressure duct is introduced through the specimen introducing tube 45 fixed to the shifter 52 into the column 48 and expanded.
  • the column 48 must be made of stainless steel to withstand the high pressure at which the specimen is maintained.
  • Stainless steel is not transparent and it is impossible to externally observe the variation in the space. Therefore, it is necessary to manipulate the guide tube shifter 52 only through inexact finger touch and to bring the specimen introducing tube 45 in contact with the filler 47. It has, however, proved that such an operation can hardly be performed properly.
  • FIG. 2 is the general view of a liquidchromatographic system embodying the present invention.
  • Each of tanks 1 and 2 contains an eluent.
  • Pumps 3 and 4 serve to feed the eluent.
  • the tanks 1 and 2 and the pumps 3 and 4 constitute an elute supplying device.
  • a column 5 is packed with a filler 6.
  • a specimen injector 7 is of loop valve type and has a specimen measuring and holding tube 8 to measure a predetermined quatity of specimen from a specimen supplying device (not shown) and to hold the measured specimen therein.
  • Guide tubes 9, 9' and 9" are communicated at one-ends thereof with the column and at the other ends thereof with the eluent supplying device and serve to introduce the eluent from the device into the column through the specimen injector 7 and an electromagnetic valve 10.
  • a specimen introducing tube 11 has its one end inserted into the filler 6 in the column through an electromagnetic valve 12 and the other end coupled through the specimen injector 7 to the specimen supplying device not shown in the figure.
  • a detector 13' detects the specimen out of the column 5 and is coupled to a recorder 13.
  • a motor 14 drives the loop valve type specimen injector 7 and motors l5 and 16 actuate the electromagnetic valves and 12.
  • a switching circuit 17 controls the switching operation of the motors l4, l5 and 16.
  • a synchronous circuit 18 serves to synchronously actuate these motors 14, and 16.
  • the eluent is fed by means of the pump 3 into the guide tube 9 and further fed into the column 5 via the loop valve type specimen injector 7 and the electromagnetic valve 10.
  • the pump 4 is kept stopped.
  • a predetermined quantity of the specimen is held in the measuring and holding tube 8 during the normal condition and the specimen is directly injected out of the specimen introducing tube 11 into the column filler 6.
  • the operation of the associated mechanisms is as follows. Namely, the switching circuit 17 is actuated to actuate the synchronous circuit 18, which then drives the motors 14, 15 and 16. Accordingly, the electromagnetic valve 10 is closed, to stop the pump and simultaneously the electromagnetic valve 12 is opened to start the pump 4.
  • the specimen in the tube 8 is pushed by the eluent and introduced into the column through the electromagnetic valve 12 and the specimen introducing tube 11. Then, the specimen is eluted and developed in the column 5 and the thus processed specimen is poured out of the bottom of the column 5, detected by the detector 13' and recorded on the recorder 13.
  • the switching circuit 17, which performs such an operation as described above when operated along with the synchronous circuit 18, can actuate separately the specimen injector 7 and the electromagnetic valve 10 and 12 through appropriate selection of the switch so that it is also possible to introduce the specimen and/or the eluent into the column 5 at the top of and through the side wall of the column 5 and to simultaneously perform the introduction of the specimen and the eluent.
  • FIGS. 3A and 3B respectively represent the perspective and top views of such a specimen injector as indicated at numeral 7 in FIG. 2.
  • the loop valve 7 comprises upper and lower members 19 and 20 slidably connected with each other and the lower member 20 is rotated on the sliding surface 21 relative to the upper member 19.
  • Two narrow, concentric circular grooves are cut in the sliding surface, the outer groove consisting of a groove 22 indicated by dotted line and a groove 23 indicated by solid line constructed independent of each other and each of the grooves 22 and 23 subtending an angle of 60 with respect to the center and the inner groove being continuously cut to always maintain the communicating condition, as seen in FIG. 3B.
  • the upper member 19 of the loop valve 5 is maintained stationary and connected with a plurality of pipes coupled to distributing systems.
  • the pipes 25 and 26 are respectively the entrance and the exit for the specimen.
  • the upper and the lower members 19 and 20 of the loop valve 7 are communicated with each other through the groove 22 so that the eluent is fed by the pump 3 into the guide tube 9.
  • the eluent is then sent into the column 5 through the inner groove 24 and the guide tube 9.
  • the switching circuit 17 is actuated, the loop valve 7 is rotated and the groove of the sliding surface 21 communicates with the groove 23.
  • the pump 3 is stopped, the electromagnetic valve 10 is closed, the pump 4 is in turn started, and the eluent is introduced into the tube 9" to push out a predetermined quantity of specimen held in the measuring tube 8 so that the specimen may be introduced through the guide tube 11 into the column 5.
  • the chromatogram may be obtained with the chromatographic system being in the stage described above, but there is another way of obtaining the chromatogram, in which the switching circuit 17 is actuated again to restore the system in the normal condition so that the eluent is poured into the column at the top thereof after the specimen has been injected. It is also possible to simultaneously introduce the specimen and the eluent into the column 5 respectively through the tube 11 and the tube 9 by separately actuating the electromagnetic valve 10 and the pump 3.
  • FIG. 3B is the top view of the loop valve 7 described above, especially of the connecting part thereof. From the figure, it will be seen that the inner groove 24 is always maintained in a communicating condition and the other groove communicates with the groove 22 and the groove 23 by the rotation of the lower member 20 of the loop valve by towards right and left.
  • FIG. 4 illustrates a concrete way of connecting the column 5 and the loop valve 7 shown in FIG. 3.
  • the same reference numerals and characters are applied to equivalent parts or elements.
  • a column envelope 29 has an inlet and outlet ports 30 and 31 through which water having a constant temperature is taken in and out to circulate around the column 5.
  • Packings 32 are used with the column caps 28 to facilitate the hermetical sealing.
  • Filters 33 serve to prevent the filler from flowing out of the column.
  • the specimen introducing tube 11 penetrates the side wall of the column 5 and is inserted into the column filler 6. The position of the penetration of the tube 11 through the wall is located below that level of the top of the filler which is assumed when the filler 6 contracts due to the high pressure liquid flowing into the column 5.
  • the pump 3 In the normal state, the pump 3 is operated and the eluent is passed through the inner grove 24 of the loop valve 7. The eluent is then fed into the column 5 through the guide tube 9 and the valve 10 and after reaching the state in equilibrium with the filler 6 finally fed to the detector 13' to be recorded. This recorded data becomes the base line of the chromatogram obtained thereafter.
  • the specimen measuring tube 8 measures a constant quantity of specimen by the suction through the specimen outlet port 26 since the specimen inlet port 25 is connected with the specimen supplying device not shown in the figure.
  • the loop valve 7 When the loop valve 7 is rotated through an angel of 60, the pump 3 is stopped. Then, the valve 10 is opened and simultaneously the pump 2 is operated and the valve 12 is opened.
  • the eluent fed from the tank 2 to the pump 4 is caused to flow through the tube 9" and the groove 23 in the sliding surface 21 so as to push out the measured specimen in the tube 8.
  • the specimen pushed out by the eluent is fed into the column 5 through the specimen introducing tube 11 and the valve 12.
  • the specimen in the column 5 is eluted and developed, decomposed into individual constituents and the separated components are detected by the detector 13 to be converted into the corresponding electrical signals which is recorded on the recorder 13.
  • FIGS. 5A and 5B show the examples of the chromatograms obtained by the chromatographic-system according to the conventional method and the method of the present invention, respectively.
  • the same chemicals are commonly used in the conventional chromatographic system and the chromatographic system of the present invention.
  • Aminex A-4 positive ion exchange resin is used for filler; Alkaline earth metals such as Mg, Ca, Sr and Ba for the specimen; and a buffer solution of ammonium acetate for the eluent.
  • the peaks b, c and d correspond to Mg, Ca, Sr and Ba, respectively.
  • the specimen introducing tube penetrates the side wall of the column and inserted directly into the tiller, the specimen is pushed into the column by the eluent, and another guide tube to introduce the eluent is provided at the top of the column.
  • the specimen introducing tube is so provided as to penetrate the side wall of the column while the eluent guide tube is communicated with the column through the top of the column. It is also possible to send both the tubes through the top of the column into the column and especially to construct the tubes in coaxial structure at the top of the column, in which the inner tube and the outer tube serve respectively at the specimen introducing tube and the eluent guide tube.
  • FIG. 6 shows such an example of a coaxial double tube. The explanation of the respective parts in FIG. 6 is not given here since they are similar to those cap 28 with the column 5 and the specimen introducing tube 11 is passed through the guide tube 9 and inserted directly into the filler 6.
  • the specimen and the eluent are both introduced into the column through the column cap 28 provided at the top of the column and the rapid analyis of the specimen can be carried out through an operation similar to that described above. Further, It is also possible to send both the tubes separately or in double structure into the column through the side wall, the bottom column cap or the side wall near the bottom of the column.
  • the length Ls between the end of the specimen introducing tube 11 and the end of the column should be chosen to be 10% of the total length of the column. This length is slightly larger than that of the space defined between the end of the column and the top level of the contracted filler which, of all the usable fillers selected, has the largest contraction coefficient.
  • FIGS. 7A and 7B show two alternative change-over states of the valve of a specimen injector as another embodiment of the present invention.
  • FIG. 7A which shows the normal state
  • the eluent is directly introduced into the column 5 and in the meanwhile a predetermined quantity of specimen is measured by and held in the measuring tube 8.
  • FIG. 5A is changed over th the other one shown in FIG. 58 by rotating the valve through an angle of 60
  • the specimen held in the measuring tube 8 is pushed out by the eluent and introduced directly into the column 5.
  • one of the tubes 9 and 11 can be eliminated. Namely, a single tube, which is directly inserted into the filler 6 of the column 5 through the top, the side wall or the bottom of the column 5, can serve as both the specimen introducing tube 11 and the eluent guide tube 9.
  • the specimen introducing tube is inserted directly into the tiller contained in the column so that the dilution and diffusion of the specimen introduced into the column due to the contraction of the filler owing to the high pressure liquid flowing into the column can be prevented. Therefore, a better chromatogram can be obtained from the specimen and the rapid analysis becomes possible.
  • a liquid-chromatographic system comprising a column packed with a filler, a specimen supplying means for supplying a specimen to be separated, an eluent supplying means for supplying an eluent, said cluent eluting and developing said specimen within said column, a flow path change-over means connected with said specimen supplying device and said eluent supplying device for selectively supplying said speeimen and said eluent to said column, an eluent guide tube having a first end communicated with said column and a second end connected with said flow path change-over means, a specimen introducing tube having a first open end penetrating into said filler in said column and a second end connected with said flow path change-over means, and a detecting means for detecting the eluted and developed specimen from said column.
  • a liquid-chromatographic system as claimed in claim 1, wherein said flow path change-over means includes an upper and lower member in slidable contact, said lower member being rotatable with respect to said upper member at a surface of slidable contact.
  • a liquid-chromatographic system comprising a column packed with a filler, a specimen supplying device for supplying a specimen, and eluent supplying device for compressing and supplying an eluent, a flow path change-over means connected with said specimen supplying device and said eluent supplying device, said flow path change-over means including a specimen measuring tube for measuring a predetermined quantity of specimen, a conduit having a first open end penetrating into said filler in said column and a second end connected with said flow path change-over means, a means for holding said specimen supplied from said specimen supplying device in said specimen measuring tube and for introducing said specimen held in said specimen measuring tube into said column through said conduit by action of eluent supplied from said eluent supplying device, and a detector for detecting the spec imen from said column, whereby, by a selective change-over operation of said flow path change-over means and through said specimen measuring tube, said specimen supplying device and said conduit are selectively communicated with and disconnected from

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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US351501A 1972-04-17 1973-04-16 Liquid chromatographic system Expired - Lifetime US3862038A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116046A (en) * 1977-08-05 1978-09-26 Hoffmann-La Roche Inc. Liquid chromatography system
US4158630A (en) * 1978-02-24 1979-06-19 Stearns Stanley D Chromatographic multi-sample valving apparatus
US4310420A (en) * 1979-03-14 1982-01-12 Japan Spectroscopic Co., Ltd. Mobile phase supplying method in the liquid chromatography and apparatus therefor
US4444066A (en) * 1981-06-29 1984-04-24 Beckman Instruments, Inc. High pressure sample injector valve
US4840730A (en) * 1986-07-25 1989-06-20 Sepragen Corporation Chromatography system using horizontal flow columns
US5169522A (en) * 1990-09-25 1992-12-08 Ht Chemicals, Inc. Column slurry packing compressor
US20140091746A1 (en) * 2011-06-27 2014-04-03 Kabushiki Kaisha Toshiba Electromagnetic pump compensation power supply apparatus and electromagnetic pump system

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5518166U (ko) * 1978-07-25 1980-02-05
JPS55160848A (en) * 1979-06-01 1980-12-15 Kiriyama Seisakusho:Kk Liquid chromatography column

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446057A (en) * 1966-10-14 1969-05-27 Varian Associates Method and apparatus for chromatography
US3510271A (en) * 1963-04-11 1970-05-05 Pharmacia Fine Chem Inc Chromatographic separation employing a gel bed

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3510271A (en) * 1963-04-11 1970-05-05 Pharmacia Fine Chem Inc Chromatographic separation employing a gel bed
US3446057A (en) * 1966-10-14 1969-05-27 Varian Associates Method and apparatus for chromatography

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116046A (en) * 1977-08-05 1978-09-26 Hoffmann-La Roche Inc. Liquid chromatography system
US4158630A (en) * 1978-02-24 1979-06-19 Stearns Stanley D Chromatographic multi-sample valving apparatus
US4310420A (en) * 1979-03-14 1982-01-12 Japan Spectroscopic Co., Ltd. Mobile phase supplying method in the liquid chromatography and apparatus therefor
US4444066A (en) * 1981-06-29 1984-04-24 Beckman Instruments, Inc. High pressure sample injector valve
US4840730A (en) * 1986-07-25 1989-06-20 Sepragen Corporation Chromatography system using horizontal flow columns
US5169522A (en) * 1990-09-25 1992-12-08 Ht Chemicals, Inc. Column slurry packing compressor
US20140091746A1 (en) * 2011-06-27 2014-04-03 Kabushiki Kaisha Toshiba Electromagnetic pump compensation power supply apparatus and electromagnetic pump system
US9397544B2 (en) * 2011-06-27 2016-07-19 Kabushiki Kaisha Toshiba Electromagnetic pump compensation power supply apparatus and electromagnetic pump system

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