JPH07311187A - Method and apparatus for injecting sample in liquid chromatography - Google Patents

Abstract

PURPOSE:To provide a method and apparatus for infecting sample in liquid chromatography constituted to inject a sample to be measured through a sample injection pipe into a sample supply piping system in which accuracy is enhanced in the measurement. CONSTITUTION:In the method for sucking a sample solution 30 and injecting the sample solution into a sample supply piping system coupled with a detector using an injector 22, an operation for sucking the air 33, 34 into the injector 22 and an operation for sucking a liquid 51 composed of a substance having no chemical nor physical effect on the sample solution 30 are effected once (or a plurality of times). Subsequently, the sample solution 30 is sucked into the injector 22 and injected, collectively with the air 33, 34 and the liquid 51, into a sample supply piping system 14x.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample injecting method and an injecting apparatus in a liquid chromatography device, and more particularly to injecting a sample to be measured by using a sample injecting pipe and injecting it into a sample supply pipe system connected to a detecting means. The present invention relates to a sample injection method and an injection device in a liquid chromatography device configured as described above.

[0002]

2. Description of the Related Art Generally, a liquid chromatography apparatus is widely used as a chemical analysis means for separating and quantifying chemical substances. In particular, a liquid chromatography apparatus using a semi-micro column having an inner diameter of 1 to 2 mm has an advantage that it can provide highly sensitive, high resolution and highly accurate analysis results.
Active research is being done.

FIG. A is a block diagram showing a schematic configuration of a liquid chromatography apparatus corresponding to a gradient method in which the composition of a solvent flowing in a column is changed with time.

Referring to FIG. A, the liquid chromatography apparatus includes a first pump 11A for feeding a first solvent A,
A second pump 11B for feeding the second solvent B,
The pumps 11A and 11B are controlled by the system controller 12 to supply the developing solvents A and B to the mixer 13.

After the solvents A and B are mixed in the mixer 13 at a desired mixing ratio, the sample to be measured is mixed with this solvent mixture in the sampler 14 (the sample to be measured mixed with the solvent mixture is sampled). Solution). This sample solution is sucked into the sample injection 22 (described later) using the syringe 15,
The sample solution sucked into the sample injection pipe 22 is injected into the column 16 together with the solvent A and / or B.

When passing through the column 16, the chemical substances in the sample solution are separated and supplied to the detector 17 together with the solvent. The detector 17 quantitatively and / or qualitatively analyzes the chemical substances contained in the supplied solvent A and / or B. After analysis in the detector 17, the solvent and chemicals are discarded as waste in the waste sump 18.

Here, FIG. B shows the sample injection tube 22 provided in the sampler 14. The sample injection pipe 22 injects a sample solution 30 (shown by satin in the figure) toward the column 16 when the liquid chromatography device is in the measurement mode, and a washing liquid 31 (washing liquid) when the liquid chromatography device is in the washing mode. Liquid for hatching (shown by hatching in the figure). Incidentally, 32 is a resin pipe for connecting the sample injection pipe 22 to the syringe 15 and the like, and 37 is a contact member for connecting the sample injection pipe 22 and the resin pipe 32 in a liquid-tight manner.

Conventionally, in order to suck the sample solution 23 into the sample injection tube 22, the sample injection tube 22 and the resin pipe 32 are filled with the washing liquid 31 in advance, first the air 33 is sucked, and then the sample solution 30. Is inhaled, and then the air 34 is inhaled again. As described above, the sample solution 30 is added to the sample injection tube 22.
And the air 33, 34 (hereinafter, the air in the sample injection tube 22 is referred to as an air layer), the sample solution 30 in the sample injection tube 22 becomes a pair of air layers 33, 3
It will be sandwiched between 4.

Further, conventionally, in order to inject the inhaled sample solution 30 into the column 16 as described above, the range shown by an arrow L in the drawing is injected into the column 16. That is, the sample solution 30 and the pair of air layers 33, 3
It was configured to inject only 4 toward the column 16.

[0010]

[Problems to be Solved by the Invention] However, the sample solution 3
In the configuration in which only 0 and the pair of air layers 33 and 34 are injected toward the column 16, the sample solution 30 adheres to the inner wall of the pipe leading to the column 16 and reaches the column 16 and the detector 17. The amount of the sample solution 30 is reduced by the amount attached to the inner wall of the pipe, which causes a problem that the measurement accuracy is reduced. The problem is that the sample solution 30 is, for example, 2 μl (microliter) when injected.
If it is too small, the measurement accuracy will be affected significantly.

The present invention has been made in view of the above points, and it is an object of the present invention to provide a sample injection method and an injection device in a liquid chromatography apparatus capable of improving the measurement accuracy.

[0012]

[Means for Solving the Problems] The above problems can be solved by taking the following measures.

According to a first aspect of the present invention, there is provided a liquid chromatography apparatus comprising a sample injection pipe for inhaling a sample to be measured from a container storing the sample to be measured and injecting the sample into a sample supply piping system connected to a detecting means. In the sample injection method, first, the operation of inhaling air into the sample injection tube and the operation of inhaling a liquid made of a substance that has no chemical or physical influence on the sample to be measured are repeated once or several times. Then, the sample to be measured is sucked from the container in which the sample to be measured is stored in the sample injection pipe, and then the air, liquid, and sample to be measured sucked into the sample injection pipe are collectively injected into the sample supply piping system. It is characterized by that.

Further, in the sample injection device in the liquid chromatography apparatus according to the second aspect of the present invention, the sample injection device comprises the first container for storing the sample to be measured and a substance which does not exert a chemical influence or a physical influence on the sample to be measured. The second container containing the liquid and the sample or liquid to be measured are sucked from the first or second container, and the sucked sample and liquid to be measured are injected into the sample supply piping system connected to the detection means. Sample injection pipe, sample injection pipe drive means for moving the sample injection pipe between the first container and the second container, and injection into the sample supply pipe system by driving the sample injection pipe drive device. The sample to be measured or liquid is selectively sucked into the sample injection tube so that one or more moving layers separated by an air layer are present on the downstream side of the sample to be measured, and Maintenance It is characterized in that provided with the suction / injection control means for injecting a measured sample and the liquid in the sample supply pipe system.

[0015]

When the sample to be measured is injected into the sample supply pipe system connected to the detecting means by using the sample injection method and the injection device having the above-mentioned structure, the liquid is also injected into the sample supply pipe system together. It When the sample to be measured advances toward the detection means, this liquid follows and follows the sample to be measured, so that even if the sample to be measured adheres to the inner wall of the sample supply pipe,
The liquid advances while picking up (that is, absorbing) the adhered sample to be measured.

Therefore, when the sample to be measured and the liquid have reached the detecting means, there is almost no sample to be measured remaining in the sample supply pipe, and almost all the sample to be measured injected into the sample supply piping system is detected by the detecting means. The measurement accuracy can be improved.

[0017]

Embodiments of the present invention will now be described with reference to the drawings.

FIG. 3 shows a schematic configuration of a liquid chromatography apparatus to which a sample injection method and an injection apparatus according to an embodiment of the present invention are applied. In each of the drawings used for explaining the present invention, the same reference numerals are given to the components corresponding to the conventional components shown in FIGS. 9 and 10.

As shown in FIG. 3, the liquid chromatography apparatus has a sample holder 21 in which a plurality of sample containers 21a (constituting a first container) are formed, and each sample container 2
The sample to be measured is held at 1a. Each sample container 21
a has a capacity of about 200 μl, and the needle-like sample injection tube 22 movably held by the robot 22a is inserted into the sample container 21a at the position P ₁ shown in FIG.

The sample injection tube 22 has a thin tube shape as shown in an enlarged view in FIGS. 1 and 2, and its material is selected from stainless steel which is resistant to corrosion. The syringe 15 is connected to the sample injection pipe 22 through a resin pipe 32 made of diflon, Teflon or the like and a joint 15a. The syringe 15 is configured to be driven by a syringe drive device 39, and the sample solution 30 is sucked into the sample injection tube 22 from the selected sample container 21a by driving the syringe 15.

As described above, when the syringe drive device 39 is driven with the sample injection tube 22 inserted in the sample container 21a, the sample solution 30 loaded in the sample container 21a is transferred to the sample injection tube 22. Although inhaled, the sample injection tube 22 is separated from the sample container 21a, and the air is driven by driving the syringe driving device 39.
Can be inhaled into.

Further, a liquid port 38 (constituting a second container) filled with a liquid (which will be described in detail later) that follows the sample solution 30 is provided near the sample holding portion 21. Has been done. Then, insert the sample injection tube 22 into the liquid port 38 after having moved the sample injection tube 22 to the position shown in the drawing P ₃ by driving the robot 22a, and drives the syringe drive device 39 in this inserted state As a result, the liquid can be sucked into the sample injection tube 22.

On the other hand, the sample storage loop 14 ₇ cooperating with the six-way valve 14 is provided with an injection part 14 x for receiving the tip of the sample injection tube 22. The sample solution 30 and the liquid 5 collected in the sample injection pipe 22 by the sample injection method described later.
1 (shown in FIG. 1) is injected into this injection portion 14x.
As a specific injection method, first, the robot 22a moves the sample injection tube 22 to a position P ₂ corresponding to the injection section 14x, and then the sample injection tube 22 is inserted into the injection section 14x.
By operating the syringe drive device 39 again in this state, the sample solution 30 and the liquid 51 collected in the sample injection tube 22 are injected into the injection part 14x.

In the liquid chromatography device according to the present embodiment, the second hexagonal valve 23 is connected to the sample outlet of the detector 17, and is separated by the column 16 and further detected by the detector 17 and then discharged. Separate the sample into the waste liquid reservoir 18
And the sample injection tube 22 can be selectively supplied.

In the state shown in FIG. 3, the sample to be separated discharged from the detector 17 is the waste liquid reservoir 18 as shown by the arrow.
Sent to. On the other hand, when the sample to be separated is fed to the sample injection pipe 22, the sample is the joint 1 provided in the syringe 15.
5a through the flow path 15b formed in the sample injection tube 22
Is supplied to. The flow channel 15b is formed in a T-shape so that both the sample supplied from the syringe 15 and the sample supplied from the hexagonal valve 23 can be sent to the sample injection tube 22.

Further, in the liquid chromatography apparatus according to this embodiment, the container 24 holding the washing liquid for washing the column 16 and the piping system (sample supply piping system) cooperating with the column 16 is provided.
The cleaning liquid is supplied from the container 24 to the hexagonal valve 23 via the pump 25. In the state shown in FIG. 3, the cleaning liquid is sent to the sample injection pipe 22 through the joint 15a and cleaned. When cleaning the sample injection tube 22,
Robot 22a moves to different waste liquid recovery position of the position P ₁ to P ₃ of the sample injection tube 22 (not shown).

The sample holding unit 21, the robot 22a, the syringe driving device 39, etc. are the controller 50.
(Constituting inhalation / infusion control means),
The drive is controlled by the controller 50. The controller 50 is composed of, for example, a microcomputer, and drives the above-mentioned devices 21, 22a, 39 according to a preset program. The operation of injecting the sample solution 30 and the liquid 51 into the sample injection tube 22, which is the main part of the present invention, is also performed according to the sample injection program stored in this microcomputer.

On the other hand, FIG. 4 shows the six-way valve 2 in the apparatus of FIG.
3 shows a rotated state. In the state shown in the figure,
The sample to be separated discharged from the detector 17 passes through the hexagonal valve 23 along the arrow and is sent to the needle 22 via the flow path 15b in the joint 15a. Further, the cleaning liquid from the container 24 is blocked by the hexagonal valve 23. As a result, the robot 22a moves the sample injection tube 22 to a position on the sample holder 21 corresponding to an appropriate sample container 21a, so that the sample to be separated discharged from the detector 17 is transferred to the predetermined sample container 2
It becomes possible to collect in 1a.

Especially when a semi-micro column having an inner diameter of 1.0 to 2.0 mm is used as the column 16 for liquid chromatograph, the total flow rate of the solvent is as small as 50 to 200 μl / min. The increase in the volume of the separated sample does not pose a problem, and the sample to be separated can be sufficiently collected in the sample container 21a having a volume of several hundred μl.

3 (A) and 3 (B) are diagrams for explaining switching of the flow path of the sample to be separated discharged from the detector 17 by the hexagonal valve 23.

[0031] Referring to FIG. 3 (A), the hexagonal valve 23 has a rotatable valve element 23R, the valve body 23R straight tubular through channel 23 _{1-23 6,} connecting flow connecting these Road 23a ~
23c is formed. Here, the connection flow path 23a connects the straight tubular through-flow paths 23 ₁ and 23 ₆ and
b connects the straight tubular through-flow passages 23 ₂ and 23 _3, and further, the connecting flow passage 23c connects the straight tubular through-flow passages 23 ₅ and 23 ₆ .

In the state shown in FIG. 3A, the straight tubular through-flow channel 23 ₁ is connected to the sample injection tube 2 via the syringe joint 15a.
The straight tubular through-flow passage 23 matching the port I connected to
₂ matches the port D connected to the outlet of the detector 17,
The straight tubular through passage 23 ₃ is aligned with the port W connected to the waste liquid reservoir 18. On the other hand, the straight tubular through passage 23 ₆ is aligned with the port C connected to the container 24 holding the cleaning liquid, and the straight tubular through passages 23 ₅ and 23 ₆ are not connected to any port.

In the above configuration, in the state of FIG. 3A, the sample to be separated discharged from the detector 17 is discarded from the port D through the connecting flow path 23b and the port W to the waste liquid reservoir 18. Further, the cleaning liquid from the container 24 is supplied to the sample injection pipe 22 through the connection flow path 23a.

When the valve body 23R is rotated in the arrow direction,
It is shown in FIG. In the state shown in the figure, the port
I is a straight tubular through flow path 23₂, 23b and 23₃Through
Connected to the detector 17, and the port C has a straight tubular through flow.
Road 23₁, 23a and 23 ₆Connected to. Accuse
The straight tubular through-flow passage 23₆Is not connected to any port
Therefore, the cleaning liquid supplied from the container 24 flows through the straight pipe.
Road 23₆Blocked at. In addition, in the waste liquid reservoir 18
In the state of FIG. 3 (B), the connected port W is the connection flow path 2
Straight tubular through flow path 23 through 3c_FiveConnected to the
Tubular through channel 23 _FiveThere was no port connected to
Therefore, the sample is not discharged to the waste liquid reservoir 18.

FIG. 6 is a detailed view of the robot 22a described above. As shown in the figure, the robot 22a includes a base 40.
And an arm 44. The base 40 is supported by the horizontal shafts 41a and 41b, and is configured to be movable in the arrow X direction in the drawing. The arm 44 is supported by vertical shafts 45a and 45b planted in the base 40, and is configured to be movable in the arrow Z direction in the figure.

A horizontal movement motor 42, which is a stepping motor, is attached to a chassis (not shown), and the horizontal movement motor 42 and the base 40 are connected by a timing belt 43. Therefore, when the horizontal movement motor 42 is driven, the base 40 moves in the arrow X direction.

On the other hand, a lifting motor 46 composed of a stepping motor is attached to the base 40, and the lifting motor 46 and the arm 44 are connected by a timing belt 47. Therefore, when the lifting motor 46 is driven, the arm 44 moves up and down in the arrow Z direction.

The sample injection tube 22 is fixed to the arm 44 by a stopper 49. Further, the base 40 is provided with a guide member 48 extending downward from the arm 44 for protecting the sample injection tube 22 particularly near the tip end portion.

The robot 22a constructed as described above moves the sample injection tube 22 in the X and Z directions in the figure by driving and controlling the motors 42 and 46 by the controller 50. Sample injection tube 2
2 is selectively inserted into and removed from the injection part 14x, the sample container 21a provided in the sample holding part 21, and the liquid port 38. Along with the movement operation of the sample injection tube 22, a syringe drive device 39
The sample solution 30, the solution 51 and the air are sucked into the sample injection tube 22 by operating the
0, liquid 51 and air are injected into the injection part 14x, and the sample to be separated is loaded into the sample container 21a.

That is, in the liquid chromatography apparatus according to this embodiment, the robot 22a and the syringe drive device 39 are used.
By the operation of, the sample solution 30, the liquid 51, and the air can be selectively injected into the sample injection tube 22.

Next, the sample injection tube 2 which is the main part of the present invention.
A method of injecting the sample solution 30 into the inside 2 will be described.

As described above, the injection of the sample solution 30 into the sample injection tube 22 is executed according to the sample injection program executed by the controller 50. FIG. 7 shows a sample injection program executed by the controller 50, and FIG. 1 shows that the sample solution 30 (shown as satin in the figure), the air layers 33 and 34, and the transfer liquid layer 51 are inhaled according to the sample injection program. The sample injection pipe 22 in a state is shown.

When the sample injection program shown in FIG. 7 is started, the controller 50 first performs a cleaning process in the system in step 10 (step is abbreviated as S in the figure). This cleaning process is performed by flowing the cleaning liquid loaded in the container 24 into the piping system as described above.

When the cleaning process is performed in step 10,
In the subsequent step 12, the controller 50 drives the robot 22a so that the sample injection tube 22 is not inserted in any of the injection part 14x, the sample container 21a, and the liquid port 38, that is, the tip opening of the sample injection tube 22 is in the air. The sample injection tube 22 is moved to a position where the sample injection tube 22 is opened. Then, in a state in which the tip opening of the sample injection tube 22 is opened in the air, the controller 50 causes the syringe driving device 3 to operate.
For example, 200nl (nano
Liter) of air is sucked into the sample injection pipe 22 (the air injected in step 12 is referred to as an air layer 33).

In step 12, the air layer 33 becomes the sample injection tube 2
After being formed inside 2, the controller 50 drives the robot 22a to insert the sample injection tube 22 into the liquid port 38 in step 14. Then, the controller 50 operates the syringe drive device 39 in a state where the sample injection pipe 22 is inserted into the liquid port 38, so that, for example, 200 nl of the liquid 51 is injected into the sample injection pipe 2.
Inhale into 2.

Further, when the liquid 51 is sucked into the sample injection tube 22 in step 14, the controller 50 then performs the same operation as described in step 12 in step 16, for example, 200 nl of air is injected into the sample injection tube 22. 22 (inject air injected in step 12 into air layer 34)
And).

In step 16, the air layer 34 becomes the sample injection tube 2
After being formed inside 2, the controller 50 then drives the robot 22a to insert the sample injection tube 22 into a predetermined sample container 21a in step 18. And
When the sample injection tube 22 is inserted into the sample container 21a, the controller 50 operates the syringe drive device 39 to inhale the sample solution 30 into the sample injection tube 22 by a preset amount.

In step 18, the sample solution 30
Is inhaled into the sample injection tube 22, then step 2
At 0, the controller 50 performs the same operation as described in step 12, and sucks, for example, 200 nl of air into the sample injection tube 22 (the air injected in step 12 is the air layer 35).

By performing the processing of steps 10 to 20 described above, the air layer 33, the liquid 51, the air layer 34, the sample solution 30, and the sample solution 30 are introduced into the sample injection pipe 22 from the upper portion thereof as shown in FIG. The air layers 35 are sequentially arranged. Further, the washing liquid 31 remaining when the process of step 10 is performed is present above the air layer 33.

In the following step 22, the controller 50
Drives the robot 22a to insert the sample injection tube 22 into the injection part 14x. The controller 50 operates the syringe drive device 39 while the sample injection tube 22 is inserted into the injection part 14x,
The sample solution 30 sucked in the sample injection tube 22 is filled with the sample solution 1
Inject 4x. At the time of this injection processing, the range shown by the arrow L1 in FIG. 1 is configured to be injected into the injection portion 14x.

That is, in the injection process of step 22, the air layer 33, the liquid 51, the air layer 34, the sample solution 30, the air layer 3
5 is injected into the injection part 14x. And the injection part 14x
The sample solution 30 injected from the column is supplied to the column 16 and the detector 17 through the six-way valve 14 and a predetermined analysis process is performed.

By the way, when the sample solution 30 is injected into the injection part 14x according to the above-described sample injection program, the liquid 51 is also injected into the injection part 14x according to the sample solution 30. In this liquid 51, the sample solution 30 is the detector 17
Since the sample solution 30 follows the sample solution 30 as it travels toward, the liquid 51 adheres to the inside of the pipe even if the sample solution 30 adheres to the inner wall of the pipe from the injection part 14x to the detector 17. The process proceeds while picking up (i.e., absorbing) the sample solution 30 thus prepared.

Therefore, when the sample solution 30 and the liquid 51 reach the detector 17, there is almost no sample solution 30 remaining in the pipe, and almost all the sample solution 30 injected into the injection part 14x is detected. It can be introduced into the container 17. As described above, by adopting the sample injection method according to the present embodiment, substantially the entire amount of the sample solution 30 sucked into the sample injection tube 22 can be used for the analysis in the detector 17, thus improving the analysis accuracy. Can be achieved. According to the experiment by the present inventor, when the injection amount of the sample solution 30 was 2 μl (microliter), RSD (relative standard deviation) of 0.2% could be realized in the peak area.

On the other hand, the material of the liquid 51 is the sample solution 3
It is determined by the material of No. 0 and the material of the washing liquid. Further, generally, when the material of the sample solution 30 is estimated, the material of the washing liquid is determined correspondingly. Therefore, the material of the liquid 51 can be determined according to the material of the washing liquid. FIG. 8 shows the liquid 51
The material of indicates a combination example of the materials of the washing liquid. still,
The combination of the material of the liquid 51 and the washing liquid is not limited to the example shown in the figure, and various combinations can be considered according to the material of the sample solution 30 and the like. Further, as shown in the figure, it is also possible to use the same material for the liquid 51 and the washing liquid.

FIG. 2 shows a modification of the sample injection method. The sample injection method shown in FIG.
By performing the processes of 2 to 16 once more before carrying out Step 18, it is possible to further form the liquid 52 and the air layer 36 in the sample injection tube 22 with respect to the configuration shown in FIG. It is a feature.

With the configuration shown in FIG.
After absorbing the sample solution 30 adhering to the inside of the pipe, the liquid 52 proceeds while absorbing the sample solution 30 adhering to the inside of the pipe, so that the sample solution 30 adhering to the inside of the pipe can be absorbed more reliably. It is possible to further improve the analysis accuracy. As described above, the number of liquids and air layers sucked into the sample injection tube 22 may be single or plural, and as the number increases, the analysis accuracy can be improved.

[0057]

As described above, according to the present invention, when the sample to be measured is injected into the sample supply pipe system connected to the detecting means, the liquid is also injected into the sample supply pipe system, so that the liquid is When the sample to be measured advances toward the detecting means, it follows and follows the sample to be measured and advances while picking up (absorbing) the sample to be measured attached to the inner wall of the sample supply pipe,
There is almost no sample to be measured remaining in the sample supply pipe when the sample to be measured and the liquid have reached the detecting means, and almost all sample to be injected into the sample supply piping system can be introduced into the detecting means. This has the advantage that the measurement accuracy can be improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a state where a sample solution is sucked into an injector by a sample injection method and an injection device according to an embodiment of the present invention.

FIG. 2 is a diagram showing a state where the sample solution is sucked into the injector by the sample injection method and the injection device according to the embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a liquid chromatography apparatus to which a sample injection method and an injection apparatus according to an embodiment of the present invention are applied.

FIG. 4 is a diagram illustrating the operation of the liquid chromatography device of FIG.

5 (A) and 5 (B) are diagrams showing the configuration and operation of a flow path control means used for collecting the sample to be separated in the apparatus of FIG.

FIG. 6 is an enlarged view showing a configuration near an injector provided in the apparatus of FIG.

FIG. 7 is a flowchart showing the operation of the injection device.

FIG. 8 is a diagram showing an example of a combination of washing liquid and liquid.

FIG. 9 is a diagram showing an outline of a conventional liquid chromatography device.

FIG. 10 is a view showing a state where a sample solution is sucked into an injector by a conventional sample injection method.

[Explanation of symbols]

11, 25 Pump 14 First six-way valve 14 ₇ Sample storage loop 14x Sample injection port 15 Syringe 15a Joint 15b Flow path 16 Column 17 Detector 18 Waste liquid reservoir 21 Sample holding mechanism 21a, 21a 'Sample container 22 Injector 22a Robot 23 Second six-way valve 24 Washing liquid container 30 Sample solution 31 Washing liquid 33 to 36 Air layer 38 Washing port 39 Syringe drive device 40 Base 42 Horizontal movement motor 44 Arm 46 Lifting motor 48 Guide member 50 Controller 51, 52 Liquid

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Riko Suzuki, 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Stock company Shiseido Research Institute (72) Inventor Yu Otsu 1050, Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Stock company Shiseido Research Center (72) Inventor Michihiro Yamaguchi 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Research Institute Co., Ltd. (72) Inventor Hisao Tsuruta 8-47, Fukakusa-Nishiura-cho, Fushimi-ku, Kyoto Prefecture Kyoto Medical equipment Within the corporation

Claims (2)

[Claims] 1. A sample injection method in a liquid chromatography apparatus comprising a sample injection pipe for inhaling the sample to be measured from a container storing the sample to be measured and injecting the sample into a sample supply piping system connected to a detecting means. Therefore, first, the operation of inhaling air into the sample injection tube and the operation of inhaling a liquid made of a substance that has no chemical or physical influence on the sample to be measured are repeated once or a plurality of times. Then, the sample to be measured is sucked from the container in which the sample to be measured is stored in the sample injection tube, and then the air, the liquid, and the sample to be measured sucked into the sample injection tube are collectively collected. A method for injecting a sample in a liquid chromatography apparatus, which comprises injecting into a sample supply piping system. 2. A first container containing a sample to be measured, a second container containing a liquid made of a substance that does not chemically or physically affect the sample to be measured, and the first or first container. A sample injection pipe for inhaling the sample to be measured or the liquid from the second container and for injecting the inhaled sample to be measured and the liquid into a sample supply pipe system connected to a detection means; A sample injection tube driving means for moving between the first container and the second container, and a driving process of the sample injection tube driving means, so that the measured object is measured in the injection direction into the sample supply pipe system. While selectively inhaling the sample to be measured or the liquid into the sample injection tube so that one or more moving layers separated by an air layer are present on the downstream side of the sample, the inhalation state is maintained. While injecting the sample to be measured and the liquid into the sample supply piping system, That the suction / injection control means and sample injector in a liquid chromatography apparatus characterized by comprising a.