JP2008256412A - Sample solid phase load channel device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a system capable of feeding a liquid without contacting a sample liquid to a glass or metal part of a liquid feeder for reducing such a labor work that in measuring an object component in water sample, a sample liquid is fed to a solid phase to be condensed, but high adsorptive agricultural chemical and inorganic material are contained therein, and these materials are adsorbed in a sample liquid feeder to cause the troublesome of precise measuring so that the labor work of separate condensing operation is required for measuring the objective component. <P>SOLUTION: In a channel device feeding a sample liquid to a solid phase with a syringe made of glass or metal and the like through a channel switching part, this sample solid phase load channel device feeds the sample liquid without contacting it to the syringe by setting a sample liquid flowing out part between the syringe and the channel switching part. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an apparatus for feeding and concentrating a sample solution to a solid-phase extraction device when measuring a target component in water.

  When measuring a target component in water, a sample solution is sent to a solid-phase extraction cartridge or the like and concentrated. These target components may also contain highly adsorbent agricultural chemicals and inorganic substances. These adsorptive substances may be adsorbed by the sample liquid delivery device.

  Conventionally, in the analysis of inorganic components, a peristal type non-metal liquid feed pump is usually used for feeding a sample liquid, but there is a problem in accurate liquid feeding. Moreover, the component with high fat solubility might adsorb | suck to piping. Furthermore, a material having low adsorptivity such as Teflon (registered trademark) has a problem that it is too hard to be used for piping or the like.

  In addition, liquid feeding systems using plungers are widely used, but sample liquid is sucked and discharged using a metal, glass, etc. in the syringe, so that the problem of adsorption of agricultural chemicals and inorganic substances can be avoided. I couldn't.

  A conventional liquid delivery system using a plunger system will be described with reference to FIG. The sample liquid container 1 is connected to a solid phase cartridge 4 through a check valve (or switching valve) 3. A syringe 5 made of metal or glass is connected to the check valve 3. In addition, it is possible to appropriately provide a mobile phase liquid feeding path and a cleaning liquid liquid feeding path.

  In this operation, the sample liquid 6 is sucked from the sample liquid container 1 by the suction of the syringe 5, passes through the liquid feeding path 11, and is sucked into the syringe 5 through the check valve 3. For this reason, the sample liquid 6 is filled in the syringe 5 with a necessary amount. Therefore, after the measurement, the liquid is fed to the solid phase cartridge 4 through the check valve 3 by pushing out the plunger.

  Therefore, the sample solution 6 is taken into the syringe 5 and the adsorption of the target component, especially the component that is adsorbed in the syringe 5 is inevitable. For this reason, in an inorganic analysis, it cannot prevent that the blank influence by the elution of the metal ion from glass, etc. appear.

Further, the sample liquid 6 sucked by the syringe 5 through the valve 3 is stored between the sample liquid 6 and the syringe 5, and the sample liquid 6 is introduced into the analysis channel 2 by switching the valve 3. The system (Patent Document 1) that performs this has already been published.
However, in such a conventional example, the switching valve or the like increases the size and complexity of the device, and the cost is unavoidable.

JP 60-142262 A

  Therefore, in any apparatus that currently feeds sample liquids, substances with high adsorptivity and inorganic substances are adsorbed to glass and the liquid feed line, and are therefore excluded from the components to be measured. On the other hand, at present, the adsorption to the liquid feeding line is performed by reducing the degree of adsorption by selecting a material and adding a solvent to the sample liquid.

However, depending on the physical properties, there are many components that are adsorbed on glass and the like, and there is no countermeasure. Therefore, in order to measure the target component, it is necessary to perform a concentration operation separately by manual operation.
Furthermore, accurate liquid feeding using a glass syringe is important for accurate liquid feeding of the sample liquid.

  Therefore, in the present invention, the sample liquid is fed using a syringe of glass, metal or the like that can accurately measure and feed the liquid, and the sample is not brought into contact with the glass or metal part of the liquid feeding system. It is a system that can send liquid, and the system is small, extremely simple, and easy to operate.

  In order to solve the above problems, the present invention proposes the following. First of all, in a flow path device for sending a sample liquid to a solid phase by a syringe made of glass, metal or the like via a flow path switching section, a sample liquid retention section is provided between the syringe and the flow path switching section. A sample solid-phase load channel device is proposed, in which the sample liquid is fed without contacting the syringe.

  Secondly, the sample liquid retention portion has a capacity of about 1 to 1.5 times as much as a single suction and / or discharge amount of the sample liquid. Propose.

  Thirdly, the sample is provided with a syringe drive unit that is controlled so that a stop time is set until the decompression / pressurization state in the syringe that occurs during the suction and / or discharge is eliminated. Solid phase load channel device. Propose.

  Fourthly, the present invention proposes a sample solid-phase load channel device characterized in that a pressure gauge for measuring the pressure in the syringe is provided in the syringe and the pressure gauge is connected to a data analysis unit.

  Fifth, the present invention proposes a sample solid-phase load channel device characterized in that a display unit for a corrected liquid feeding amount is provided based on the pressure data sent to the data analysis unit.

  Sixth, a sample solid-phase load channel device is proposed in which a liquid is supplied to the sample solution retention part.

  Seventhly, a sample provided with a position sensor linked to the drive unit of the syringe, and detecting the movement of the liquid level in the sample liquid etc. retention part generated during the suction and / or discharge. A solid-phase load channel device is proposed.

  Eighth, a sample solid phase load channel device is proposed in which the liquid is water or ethylene glycol.

  Ninth, a sample solid-phase load channel device is proposed in which the sample solution is an agrochemical or an inorganic component.

  Tenthly, a sample solid-phase load channel device is proposed in which the pesticide is imidazolinone, oxine copper or diquat.

According to the present invention, since the liquid sample can be fed without contacting the syringe, the plunger system is connected between the syringe and the valve provided in the liquid feed channel. Therefore, it is possible to send liquid accurately without contacting the syringe and the metal ion in the inorganic analysis. The blank effect and adsorption effect due to elution are reduced.
Further, when the sample solution is a pesticide, the imidazolinone pesticide tends to be adsorbed to the metal, and the adsorption thereof is prevented.
Further, the sample liquid retaining portion has a small and simple structure, and the apparatus can be simplified and miniaturized, and the equipment and operation can be greatly simplified.

  According to the present invention, the syringe drive is stopped until the decompression and pressurization state in the syringe is resolved, and after waiting for the decompression state to be resolved, the accurate amount of liquid feeding can be ensured by driving again.

  According to the present invention, the pressure gauge for measuring the pressure in the syringe is provided in the syringe, and the pressure gauge is connected to the data analysis unit, so that the pressure in the syringe can be easily measured, and at the time of liquid feeding The pressure data is sent to the data analysis unit, and a numerical result obtained by correcting the liquid feeding amount with the pressure is obtained, so that the liquid feeding amount is accurately ensured.

  According to the present invention, since the sample liquid etc. staying part is supplied with water, ethylene glycol, etc., when the sample liquid etc. staying part is only air, it is accurate by compressing air. This eliminates the inconvenience of not being able to deliver liquids and can expect accurate liquid delivery.

  According to the present invention, there is provided a position sensor linked to the drive unit of the syringe. Therefore, in the present apparatus provided with the sample liquid retention part, the apparatus performs the suction and discharge of air. The pressure reduction and pressurization state in the syringe can be grasped by the state such as the movement of the liquid level in the syringe and the compression of air.

  According to the present invention, even when the sample solution is an agrochemical or an inorganic component, contact of the sample solution with a glass, a syringe containing metal, or the like is prevented, and the blank effect and the adsorption effect are reduced.

As shown in FIG. 2, in the liquid feeding system using a conventional plunger system, the present invention retains a sample liquid or the like between a check valve (or switching valve) 3 serving as a flow path switching unit and a syringe 5. The feature is that the portion 7 is provided. The sample liquid retention portion for retaining the sample liquid, such as sample liquid, air, liquid, etc., is suitably formed of Teflon (registered trademark), PEEK, polypropylene, etc., which are unlikely to be adsorbed, and appropriately formed as a loop, a straight cylinder, etc. The suction volume is equal to or larger than the suction volume, for example, about 1.5 times. In other configurations, the sample liquid container 1 is connected to the solid phase cartridge 4 as the solid phase via the check valve 3 by the liquid supply path 2, and other mobile phase liquid supply path and cleaning liquid supply path are provided. What can be done is the same as the conventional example described in FIG.
In addition, various types such as a disk-type solid phase can be used as the solid phase.

  Next, the operation will be described. When the syringe 5 is sucked by a drive unit of the syringe 5 (using a vacuum pump or the like, not shown), for example, a syringe pump, the sample solution is removed from the sample solution container 1 via the sample solution retention portion 7 and the check valve 3. 6 is aspirated and sucked into the sample liquid retention portion 7. Therefore, the sample solution 6 does not enter or come into contact with the syringe 5. For this reason, the SS (floating solid substance) component mixed in the sample liquid 6 does not enter, the problem of deterioration of the plunger seal is solved, and the life is longer than that of the conventional plunger liquid feeding system. Derived from long-term use.

In order to measure the pressure in the syringe 5, a pressure gauge 10 is provided in the syringe 5. As the pressure gauge, various small types such as a vacuum gauge, an elastic pressure gauge, and an electric resistance pressure gauge are used. The data measured by this pressure gauge is transmitted to a data analysis unit such as a separately installed PC, and used as a sample for liquid feeding control.
In addition, it is recommended that an appropriate liquid feeding amount is calculated by the PC by the liquid feeding control calculated and displayed on the PC display unit.

The position sensor is a sensor that measures the positional relationship between the air and the liquid in the sample liquid retention part 7, and is provided at an appropriate location in the sample liquid retention part 7, taking a liquid level sensor using infrared rays as an example. The surface of the sample 6 and / or liquid 8 filled in the sample liquid retaining portion 7 by a sensor for detecting contact or a pressure sensor when the sample liquid 6 and / or the liquid 8 is applied to one end. It is configured to sense the movement or sense the positions of the upper and lower ends of the air and control the syringe 5 drive unit.
Depending on the viscosity of the sample liquid 6, control for determining the operation stop time of the syringe drive unit based on the measurement result of the position sensor may be considered.

  In the system of the first embodiment, in order to flow the sample liquid 6 at a high flow rate, if the sample liquid retaining portion 7 has a small inner diameter, the inside is decompressed and the suction speed cannot be increased. Therefore, in the case of liquid feeding by the liquid feeding program, it is necessary to correct the program or use a sample liquid etc. having a large inner diameter 7 to reduce the internal resistance. When the inner diameter is large, the sample solution may be mixed into the syringe 5 depending on the mounting method. Therefore, when the diameter of the sample liquid retention portion 7 is increased, the lower end portion of the sample liquid retention portion 7 and the upper end of the syringe 5 are connected when the sample liquid retention portion 7 and the syringe 5 are connected as shown in FIG. It is good to make the structure which connects.

Moreover, it can also be made the structure which connects the lower end of the syringe 5 installed upwards and the lower end of the syringe 5 installed upwards in exactly the same way (FIG. 4).
As described above, when the inner diameter of the sample liquid retaining portion 7 is increased, a mounting structure for taking the sample liquid from the lower side of the pipe of the sample liquid retaining portion 7 is effective.

  In the plunger-type liquid feeding system shown in FIG. 2, when a highly viscous sample is fed, the inside of the syringe 5 is depressurized by the plunger suction, so that accurate liquid feeding is difficult. In such a case, when the suction or discharge of the syringe 5 is completed, the operation of the syringe drive unit is temporarily stopped for several seconds, so that accurate liquid feeding can be performed by the subsequent suction and discharge.

  In consideration of the viscosity of the sample liquid 6, this temporary stop is stopped for about 2 to 20 seconds for a desired amount, a time that can be sucked and discharged, and a time that bubbles (air space) in the sample liquid 6 are not mixed. good.

According to the embodiment of the system shown in FIG. 2, the liquid feeding error is displayed in the table shown in FIG. 5 by an experiment showing the relationship between the actual liquid feeding amount and the space due to the difference in the liquid feeding speed in 100 ml liquid feeding. According to this, it is shown that the error increases as the liquid feeding speed increases.
However, when the space Vol (the air space 9 between the liquid 8 (water, ethylene glycol, etc.) supplied to the sample liquid retention portion 7 and the sample liquid 6) is not large (˜1 or 1.5 ml), Even if the liquid speed is somewhat high, the error is not so large. If the error is about 10%, it can be seen that liquid can be sent in the space Vol: 1 ml in the case of 60 ml / min, and in the space Vol: 1.5 ml in the case of 40 ml / min.

  The liquid used in this experiment is tap water, and similar data are obtained with purified water. In addition, the sample liquid retention portion 7 has an inner diameter of 2 mm.

According to the embodiment of the system shown in FIG. 2, an error of liquid feeding by an experiment showing the relationship between the actual liquid feeding amount and the liquid feeding speed due to the difference in the liquid feeding speed in 100 ml liquid feeding is displayed in the table of FIG. The liquid feeding error increases as the space Vol increases.
However, when the liquid feeding speed is not so high (˜40 ml / min), the error is not so large even if the space Vol is somewhat large. If the error is about 10%, the liquid can be fed at 40 ml / min when the space Vol is 2 ml, and 60 ml / min when the space Vol is 1 ml.

  The liquid used in this experiment is tap water. Similar results were obtained with purified water. Further, the inner diameter of the sample liquid retaining portion 7 was 2 mm.

  A system for filling the sample liquid retention part 7 with a liquid will be described. This is provided in the case where the sample liquid retaining portion 7 is only air, and when accurate liquid feeding cannot be performed due to air compression or the like. As this liquid, water or ethylene glycol is used.

  In advance, a liquid 8 such as water or ethylene glycol is filled in the sample liquid retention portion 7 in advance. Then, a suction operation is performed by driving the syringe 5. The operation at that time is shown in FIG. In the sample liquid retention part 7, the liquid 8 and the sample liquid 6 in the sample liquid retention part such as water and ethylene glycol are sucked through the space 9. Accordingly, the suction of the sample liquid 6 into the syringe 5 is prevented.

Conventional plunger feed system diagram Plunger type liquid feeding system of the present invention Other embodiment of the plunger system of the present invention Liquid delivery system diagram Other embodiment of the plunger system of the present invention Liquid delivery system diagram Example table of liquid feeding error according to the present invention Example table of liquid feeding error according to the present invention Operation explanation diagram of the embodiment of the present invention

Explanation of symbols

1 Sample container 2 Liquid feed path 3 Check valve / switching valve 4 Solid phase (cartridge)
5 Syringe 6 Sample liquid 7 Sample liquid retention area (pre-volume)
8 Sample liquid and other liquid in the reservoir (ethylene glycol, etc.)
9 Space 10 Pressure gauge

Claims (10)

  In the flow path device for feeding the sample liquid to the solid phase by a syringe made of glass, metal or the like via the flow path switching section, by providing a retention section for the sample liquid between the syringe and the flow path switching section, A sample solid-phase load channel device for feeding a sample solution without contacting the syringe.   2. The sample solid-phase load channel device according to claim 1, wherein the sample solution retention portion has a capacity of about 1 to 1.5 times a single suction and / or discharge amount of the sample solution. .   The sample according to claim 1, further comprising a syringe drive unit that is controlled so that a stop time is set until the decompression / pressurization state in the syringe that occurs during the suction and / or discharge is eliminated. Solid phase load channel device.   2. The sample solid-phase load channel device according to claim 1, wherein a pressure gauge for measuring the pressure in the syringe is provided in the syringe, and the pressure gauge is connected to a data analysis unit.   5. The sample solid-phase load channel device according to claim 4, further comprising a display unit for correcting a liquid feeding amount based on pressure data sent to the data analysis unit.   2. The sample solid phase load channel device according to claim 1, wherein a liquid is supplied to the sample solution retention part.   2. The sample fixing device according to claim 1, wherein a position sensor linked to the drive unit of the syringe is provided to sense the movement of the liquid level in the sample liquid retention portion that occurs during the suction and / or discharge. Phase load channel device.   The sample solid phase load channel device according to claim 6, wherein the liquid is water or ethylene glycol.   The sample solid-phase load channel device according to claim 1, wherein the sample solution contains an agrochemical or an inorganic component.   The sample solid-phase load channel device according to claim 9, wherein the pesticide is imidazolinone, oxine copper, or diquat.

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