JP2000009734A - Analytical equipment and analysis method using the same and reagent vessel and deoxygenation mechanism used for the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the deterioration of a coloring reagent in a liquid chromatograph. SOLUTION: A deoxygenation mechanism 58 is installed on the head of a tube 52 for supplying air to a reagent vessel 50 of a coloring reagent supply part 11. The deoxygenation mechanism 58 is equipped with an oxygen removal agent vessel 55 for holding an oxygen removal agent 54. The air introduced into the reagent vessel 50 through the tube 52 for introduction of oxygen which passes through the oxygen removal agent 54, to thereby remove the oxygen. As the oxygen removal agent 54, an oxygen absorbent, such as reduced iron powder, reduced copper powder, alkali solution of pyrogallol, dithionite aqueous solution or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to quantitative and / or qualitative analysis. About.

[0002]

2. Description of the Related Art A typical example of a liquid chromatograph using a post-column derivatization method is an amino acid analyzer. This is an analyzer generally used for amino acid analysis, in which amino acids are separated using an ion exchange resin or the like, and then derivatized with an analysis reagent (coloring reagent) for detection. Ninhydrin is generally used as a coloring reagent for the detection of amino acids by the post-column derivatization method.

[0003]

The ninhydrin reagent used for detecting amino acids and the like is very easily oxidized,
If it comes into contact with air, it will be quickly deteriorated. Therefore, conventionally, in an amino acid analyzer using ninhydrin, measures have been taken to prevent the coloring reagent from coming into direct contact with air.

As a countermeasure, first, a coloring reagent bottle containing a ninhydrin reagent is sealed with an inert gas (nitrogen gas or helium gas), and the bottle is filled into the coloring reagent bottle so as to fill a void generated by consumption of the reagent. A method of supplying an inert gas may be used. However, this method requires a gas cylinder or a gas supply pipe as an inert gas supply source to the analyzer, and furthermore, it is necessary to provide a gas pipe system inside the analyzer to supply nitrogen to the coloring reagent bottle. However, the device configuration becomes considerably complicated.

[0005] In addition, a method of providing an oily thin layer having a relatively low specific gravity, such as paraffin, at an interface where a ninhydrin solution in a coloring reagent bottle comes into contact with air to isolate oxygen from oxygen has conventionally been adopted. However, in this method, handling of the oily thin layer is extremely troublesome, and this oily thin layer is
It makes it difficult to wash the coloring reagent bottle. Furthermore, when this method is adopted, when the ninhydrin solution is completely consumed, the oily thin layer is sucked and introduced into the analysis system,
Not only does the detection signal become abnormal, but it becomes very difficult to clean the piping of the analysis system.

Accordingly, the present invention provides an analyzer using an easily oxidizable reagent, such as an amino acid analyzer or a catecholamine analyzer, which does not complicate the piping and mechanism and makes it difficult to clean. An object of the present invention is to provide a technique capable of preventing deterioration of a reagent without using it.

[0007]

To achieve the above object, the present invention provides an analyzer having an analysis mechanism for analyzing a sample and a reagent supply mechanism for supplying an analysis reagent to the analysis mechanism. The reagent supply mechanism comprises: (1) a reagent container for holding the reagent, a reagent flow path for connecting the reagent container and the analysis mechanism in a communicable manner, and air from which oxygen has been removed using an oxygen scavenger. A reagent container having a deoxygenation mechanism for supplying the reagent to the container, or (2) a reagent container for holding a reagent, and a reagent flow path for connecting the reagent container and the analysis mechanism in a communicable manner; Is an airtight container made of a flexible material that can be flexibly deformed according to the internal pressure of the container.

According to the present invention, a method of analyzing a sample using a reagent includes: (1) removing oxygen from an air sucked into a reagent container using an oxygen scavenger in advance; (2) An analysis method is provided in which an airtight container made of a flexible material that can be flexibly deformed according to an internal pressure is used as a reagent container for holding a reagent.

Furthermore, the present invention provides a deoxygenating mechanism and a reagent container for use in the above-described analyzer and method.

[0010]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, oxygen is removed from air supplied to a reagent container by a deoxygenating mechanism to avoid deterioration of the reagent due to oxygen.

[0011] The above-described deoxygenating mechanism includes an oxygen-absorbing agent container for holding an oxygen-absorbing agent that removes oxygen from air and an external air introduced into the reagent container via the inside of the oxygen-absorbing agent container. It is desirable to provide an air flow path for performing the operation. The capacity of the oxygen scavenger container is preferably at least 1/10 of the capacity of the reagent container in order to secure a sufficient oxygen absorption amount. It should be noted that the oxygen scavenger container may hold an oxygen scavenger in advance.

It is desirable that the oxygen scavenger has an oxygen absorbing capacity at least equal to the capacity of the reagent container in order to maintain the effect for about one month. Examples of the oxygen scavenger include reduced iron powder, reduced copper powder, an aqueous alkaline solution of pyrogallol, and an aqueous solution of dithionite.
These may be used alone or in combination. Of these, reduced iron powder is preferred from the viewpoint of availability and cost. As an oxygen scavenger composed of reduced iron, for example, "Ageless" manufactured by Mitsubishi Gas Chemical Company, Inc. is commercially available. When reduced iron powder is used as the oxygen scavenger, the total volume of the powder is one of the capacity of the reagent container.
A value of / 10 or more is usually preferable because the effect can be maintained for about one month.

In the present invention, instead of providing such a deoxygenating mechanism, an airtight container made of a flexible material that can be deformed flexibly according to the internal pressure may be used as the reagent container. With this configuration, when the internal pressure of the container decreases with the delivery of the reagent, the container itself is deformed in accordance with the internal pressure, and the internal pressure of the container and the atmospheric pressure are balanced, so that air is not supplied into the container, The reagent can be supplied without delay. In this way, the volume of the consumed reagent does not need to be replaced by any gas, and oxygen does not enter the container, so that the reagent can be prevented from being deteriorated by oxidation. In this case, the inner wall of the reagent container is preferably made of a fluororesin such as polytetrafluoroethylene or a derivative thereof from the viewpoint of chemical resistance. Further, the reagent container is provided with an opening for connecting the reagent supply tube so that the reagent supply tube can be communicated, and a sealing member for sealing the opening, and one end of the reagent supply tube is provided with a hollow needle. By penetrating the needle through the sealing member, the reagent flow path can be easily communicated with little air intrusion, which is preferable.

The present invention is applicable irrespective of whether the supply of the analysis reagent is before or after the separation of the sample.
That is, not only the post-column derivative method described above,
It can also be applied to the precolumn derivatization method.

The present invention is particularly suitable for a liquid chromatograph, and uses a reagent which is easily oxidized, such as an amino acid analyzer using ninhydrin, a catecholamine analyzer using diphenylethylenediamine, or an automatic analyzer for blood biochemistry. The present invention is particularly effective for the analysis apparatus and the analysis method used.

[0016]

Embodiments of the present invention will be described below with reference to the drawings. Example 1 A. Apparatus Configuration As shown in FIG. 1, the amino acid analyzer of the present embodiment includes a separation system 100, an analysis system 110, and a reagent supply system 120.

The separation system 100 includes a buffer solution bottle 1 to 4 and a column regenerating solution bottle 5 (capacity: 1 L each), a buffer solution pump 7
, Ammonia filter column 8, autosampler 9
And a separation column 10, which are connected in this order by piping. Electromagnetic valves 6 are provided in the pipes between the buffer solution bottles 1 to 4 and the column regenerating solution bottle 5 and the buffer solution pump 7, respectively.

The analysis system 110 includes a reaction tube 14 having a heater for heating an internal liquid, a detector 15 for detecting an amino acid colored by a reaction, and a data processing device 16. The detector 15 includes a flow cell 18 and a lamp 19. The detector 15 and the separation system 100
Is connected by a pipe via a reaction tube 14, and a mixer 13 is provided in a pipe between the separation column 10 and the reaction tube 14. The data processing device 16 is an information processing device including a display device, an external storage device, a main storage device, and a central processing unit.

The reagent supply system 120 includes a color reagent supply section 11 for supplying ninhydrin, a color reagent buffer supply section 17 for supplying a ninhydrin buffer, and a color reagent pump 12. The coloring reagent supply unit 11 and the coloring reagent buffer supply unit 17 are connected to the mixer 13 of the analysis system 110 via a coloring reagent pump 12 by piping. The piping between the coloring reagent supply unit 11 and the coloring reagent buffer supply unit 17 and the coloring reagent pump 12 is provided with an electromagnetic valve 6, respectively.

When using this apparatus, buffer bottles 1-4
Holds a buffer solution, and a column regenerating solution bottle 5 holds a column regenerating solution, from which a buffer solution or a regenerating solution selected by a solenoid valve series 6 is supplied by a buffer solution pump 7 to an ammonia filter. It is sent to the separation column 10 via the column 8 and the autosampler 9.
In the sample analysis, the sample to be analyzed is introduced into the mobile phase (buffer solution) in the pipe by the autosampler 9,
It is separated while moving in the separation column 10 together with the mobile phase.

A ninhydrin reagent is held in the coloring reagent supply section 11 of the reagent supply system 120, and a buffer is held in the coloring reagent buffer supply section 17. These liquids are sent to a mixer 13 by a coloring reagent pump 12 via a solenoid valve series 6, mixed with a mobile phase containing a sample separated by a separation column 10, and then heated in a reaction tube 14. As a result, the amino acids of the sample contained in the mobile phase react with ninhydrin, which is a coloring reagent, to develop color. Next, the mobile phase is sent to the detector 15. The detector 15 continuously detects the amino acids that have been colored by the ninhydrin reaction, and notifies the data processing device 16 of a signal indicating the detection result. The data processing device 16 outputs the detection data and the chromatogram as shown in FIG. 6 to the display device based on the notified detection result, and stores and stores the data in an external storage device.

B. Reagent Supply System (1) Coloring Reagent The ninhydrin reagent and ninhydrin buffer used in this example were prepared as follows. That is, the ninhydrin reagent was prepared by adding 39 g of ninhydrin to 979 mL of propylene glycol monomethyl ether, and dissolving it by bubbling with nitrogen gas for 5 minutes or more.
81 mg of sodium borohydride was added to the obtained solution, and the solution was prepared by bubbling with nitrogen gas for 30 minutes or more. The buffer for ninhydrin was prepared by adding 204 g of lithium acetate dihydrate, 123 ml of glacial acetic acid, and 401 mL of propylene glycol monoethyl ether to 336 mL of distilled water to make the total volume 1 L, and bubbling with nitrogen gas for 10 minutes or more. did.

As described above, since the ninhydrin reagent contains a reducing agent (sodium borohydride in this embodiment) which is oxidized when exposed to oxygen, the ninhydrin reagent is rapidly deteriorated by contact with air.

(2) Coloring Reagent Supply Section The color reagent supply section 11 used in this embodiment includes a reagent container (coloring reagent bottle: capacity 1 L) 50 and a deoxygenating mechanism 58 as shown in FIG. . Here, the color reagent supply unit 11 for supplying the ninhydrin reagent will be described, but the color reagent buffer supply unit 17 for supplying the ninhydrin buffer has the same configuration.

The opening of the reagent container 50 is sealed by a lid 57 made of silicone rubber, and two polytetrafluoroethylene tubes 51 and 52 are inserted into the lid 57.

Reagent delivery tube 51 (2.0 m inner diameter)
m, an outer diameter of 3.0 mm) is a pipe that connects the reagent container 50 and the color reagent pump 12 so as to be able to communicate with each other, and sends the ninhydrin reagent 56 held inside the reagent container 50 to the color reagent pump 12. Is a liquid sending pipe. It is desirable to use a material such as polytetrafluoroethylene having high chemical resistance for the reagent delivery tube 51. A filter 53 is attached to the tip of the reagent delivery tube 51 inside the reagent container 50. At the time of analysis work, the filter 53 is used by being immersed in the coloring reagent solution 56.

The air introduction tube 52 (with an inner diameter of 0.
5 mm and an outer diameter of 1.6 mm) are open to the atmosphere via a deoxygenation mechanism 58, and the reagent container 50
This is a pipe for eliminating the decompression inside by introducing air from which oxygen has been removed. At the time of the analysis operation, the reagent container 5 out of the both ends of the air introduction tube 52 is
The end inside 0 is placed on the reagent liquid surface so as not to touch the coloring reagent solution 56. A screw is formed at the other end of the air introduction tube 52.

It is desirable that the reagent container (including the buffer solution container for reagent) 50 be disposed at a position higher than the reagent suction pump 12. By doing so, the pressure is increased by its own weight, which is particularly effective for feeding a highly viscous reaction reagent buffer. Preferably, the reagent container 50
Is, as shown in FIG.
cm or more. With such a configuration, the same effect as that of applying a pressure of 0.05 atm or more can be obtained with a normal reagent (buffer solution and ninhydrin solution).

(3) Deoxidizing Mechanism The deoxidizing mechanism 58 includes an oxygen scavenger container 55 for holding the oxygen scavenger 54. In this embodiment, the air introduced into the reagent container 50 via the oxygen introduction tube 52 is:
Oxygen is removed by passing through the oxygen scavenger 54. Therefore, according to the present embodiment, the reagent container 50
The internal color reagent (and the color reagent buffer held in the color reagent buffer supply mechanism 17 having the same configuration) can be prevented from coming into contact with oxygen, and the reagent can be prevented from deteriorating. .

The oxygen scavenger 54 is not particularly limited as long as it has a sufficient oxygen removing ability. For example, an oxygen absorbing agent such as an alkali solution of pyrogallol, an aqueous solution of dithionite, or heated reduced copper is used. Agents can be used. In this embodiment, an iron powder made of reduced iron having a large specific surface area (for example, “Ageless” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
(Trade name)) 100 mL was used. Reduced iron powder is suitable for the present invention because of its remarkably high oxygen adsorption ability.

In the present embodiment, a deoxygenator 58 in which a bag-containing oxygen absorber 54 is sealed in an oxygen absorber container 55 is used. The bag of the oxygen scavenger 54 is made of a material having high air permeability such as a nonwoven fabric. The oxygen scavenger container 55 is provided with a projection 59 having an opening at one end. The protrusion 59 is formed with a screw thread so as to be screwable with a screw provided at the end of the air introduction tube. The opening of the projection 59 is sealed with a cap (not shown) when not in use. At the time of use, the cap is removed, the opening is opened, the screw of the air introduction tube 52 is screwed into the screw of the projection 59, and the hole 60 is opened at the other end of the container 55 to form an air suction port. The hole 60 is desirably opened so that the air flow path becomes as long as possible. The air inlet 60
As long as a sufficient amount of air can be inhaled, it is desirable that the diameter be as small as possible so that the air can pass through the oxygen scavenger 54 without fail. In this embodiment, the diameter is about 1 to 2 mm. Thus, the deoxidizing mechanism 58 of the present embodiment has a structure in which the sucked air does not directly reach the opening of the projection 59 without passing through the oxygen scavenger.

In this embodiment, the oxygen-absorbing agent 54 is sealed in advance in the oxygen-absorbing agent container 55, but the opening and closing of the oxygen-absorbing agent which can be opened and closed by fasteners or the like is performed. 55, an oxygen scavenger may be added at the time of use.

A container 55 having a lid which can be sealed by screwing
3 is shown in FIG. The container 55 shown here has a body 55b and a lid 55a having screws 30 that can be screwed together.
And an air suction tube 5 at the bottom of the main body 55b.
The screw 31 that can be screwed with the screw of the screw member 52a provided at the tip of the second member is formed. The lid 55a is provided with a through hole 32 for taking in air.

When the container 55 is used, as shown in FIG. 3, the screw member 52a of the air suction tube 52 is fastened to the screw 31 at the bottom of the main body 55b, and an oxygen absorber 54 containing a non-woven bag inside. Is used with the cover 55b fastened in a state in which is inserted. With such a container 55, an effect similar to that of the deoxidizing mechanism 58 of the present embodiment can be obtained.

C. Effects of the present embodiment In this embodiment, an amino acid mixture solution (protein hydrolyzate) containing a certain amount (2.0 nm) of aspartic acid is used as a sample, and aspartic acid is separated and detected by a conventional method. Based on the peak area of the signal intensity of aspartic acid, the presence or absence of deterioration of the coloring reagent was examined. The separation column 10 has "2622SC" manufactured by Hitachi, Ltd.
(Inner diameter 4.6 mm, length 60 mm) and 8 for the ammonia filter column, "2650" manufactured by Hitachi, Ltd.
L "(inner diameter 4.6 mm, length 40 mm), and" PH-KIT "manufactured by Mitsubishi Chemical Corporation as a buffer solution.
The reaction tube 14 has an inner diameter of 4.6 mm and a length of 40 mm.
mm and the reaction temperature was 135 ° C.

FIG. 4 shows the measurement results obtained immediately after the replacement of the coloring reagent bottles (that is, immediately after the ninhydrin reagent and the ninhydrin buffer solution were respectively supplied to the two reagent containers 50 immediately after opening). When replacing the coloring reagent,
At the same time, the oxygen scavenger 54 was also replaced with a new one. In FIG. 4, the component names of each peak are indicated using the following abbreviations. As
p: aspartic acid, Thr: threonine, Ser: serine, Glu: glutamic acid, Gly: glycine, Al
a: alanine, Cys: cysteine, Val: valine,
Met: methionine, Ile: isoleucine, Leu:
Leucine, Tyr: tyrosine, Phe: phenylalanine, Lys: lysine, NH3: ammonia, His: histidine, Trp: tryptophan, Arg: arginine.

Next, the same sample was obtained under the same measurement conditions.
FIG. 5 shows the results obtained by measuring the peak area of aspartic acid at 15 days and 33 days after the reagent exchange, respectively, as a relative value with the value immediately after the reagent exchange being 100%. For comparison, the results when the deoxygenating mechanism 58 was not provided and the tip of the air introduction tube 52 was opened to the atmosphere were also obtained.
It is shown in accordance with FIG. As can be seen from the graph of FIG. 5, when the deoxidizing mechanism 58 was used, the deterioration of the reagent was much less than when the chamber was opened to the atmosphere, and a stable measurement result was obtained. That is, in the present embodiment, the color-forming reagent replacement 2
Up to a week later, the peak area was constant, there was almost no change in the activity of the reagent, and an area value of 90% or more was secured even about one month after the replacement of the coloring reagent. From this, it was found that according to this example, there was no practical problem even if the coloring reagent was used continuously for one month.

The oxygen absorption amount of the oxygen scavenger 54 used in this example was 1000 mL. The coloring reagent bottle 50 used in the present embodiment is sealed in advance with nitrogen gas before use. However, when the coloring reagent is replaced together with the reagent bottle 50 when opening or inserting the tubes 51 and 52, a slight amount of air is used. Penetrates the bottle. In this embodiment, the oxygen in the air that has entered here is also absorbed by the oxygen scavenger 54 of the oxygen scavenging mechanism 58. Therefore, the oxygen absorption amount required for the oxygen scavenger 54 to be used is determined by the volume of air (1 in this embodiment) that is sucked when the reagent in the coloring reagent bottle 50 is consumed and emptied.
In addition to L), it is desirable to calculate including the amount of oxygen entering at the time of replacement and the contact time with oxygen in the atmosphere.
Usually, an oxygen scavenger having an oxygen absorption amount of about the bottle volume of the coloring reagent bottle 50 (that is, about 5 times the amount of oxygen sucked into the bottle) can be used for about one month.

When replacing the coloring reagent and / or oxygen scavenger, the reagent container 55 previously filled with nitrogen is kept in a state where the deoxygenating mechanism 58 is attached in order to minimize oxygen entering the reagent container. Each, reagent supply unit 1
It is desirable to replace the entirety.

<Second Embodiment> In the first embodiment, the deoxygenating mechanism 58 and the coloring reagent container 50 are connected by using the air suction tube 52. However, the present invention is not limited to such a configuration. Instead, for example, as shown in this embodiment, the deoxygenating mechanism 58 may be directly mounted on the coloring reagent container 50 (and the coloring reagent buffer solution container). Next, the configuration of the deoxidizing mechanism 58 of the present embodiment will be described. The configuration of the amino acid analyzer of this example other than that shown here is as follows:
This is similar to the first embodiment. Although only the coloring reagent supply unit 11 will be described here,
The coloring reagent supply section 11 and the coloring reagent buffer supply section 17 have the same configuration.

As shown in FIG. 6, the deoxidizing mechanism 58 of this embodiment has a lid for the opening 65 of the coloring reagent container 61. That is, a screw is formed in the opening of the coloring reagent container 61, and a screw that can be screwed with the screw is provided in the oxygen scavenger container 62.
Reference numeral 2 covers the coloring reagent container 61 opening 65.

As shown in FIG. 6, the oxygen absorber container 62
It has a cylindrical shape having a concave portion on one bottom surface, and an oxygen scavenger 54 contained in a non-woven bag is sealed inside. On the inner wall of the concave portion, a screw that can be screwed with a screw provided in the opening 65 of the coloring reagent preparation base 61 is formed. In addition, a through hole 63 for taking in air is provided on a surface other than the concave portion of the bottom surface in which the concave portion is formed.
That is, the screw of the coloring reagent container 61 and the oxygen absorber container 62
When the screw is fastened, the color reagent container 61 opening 65
Is provided with a through hole 64 for supplying air to the coloring reagent container 61. Further, the oxygen scavenger container 62 is provided with a through hole (not shown) into which the reagent delivery tube 51 is inserted.

In this embodiment, as in the first embodiment,
Deterioration of the coloring reagent can be avoided. The use of the deoxidizing mechanism 58 is preferable because it is not necessary to provide a pipe between the reagent container 61 and the deoxidizing mechanism 58, and the apparatus configuration can be simplified.

<Embodiment 3> Although reduced iron was used as the oxygen scavenger 54 in each of the above embodiments, reduced copper was used in this embodiment. When adsorbing oxygen using reduced copper, it is desirable to heat. Therefore, the deoxidizing mechanism 70 of the present embodiment
Includes a constant temperature device 72 as shown in FIG. At the time of use, the reduced copper powder 71 placed in the cylindrical container 73 is mounted on the thermostat 72 so that the copper powder 71 is constantly heated. Tubes 75 and 7 are provided at both ends of the oxygen absorber container 73, respectively.
6 is attached, and one tube 76 is opened to the atmosphere to serve as an air intake. The other tube 75 is connected via a distributor 74 to the tube 52 for introducing the air into the color reagent container 50 and the buffer solution container for the color reagent. Air intake tube 76
After the oxygen introduced by the reduced copper powder 71 in the container 73 heated by the constant temperature device 72 removes oxygen from the air, the reagent container and the reagent are passed through the air delivery tube 75 and the distributor 74. Supplied to the buffer solution container.
Thus, also in the present embodiment, oxygen is removed from the air supplied to each reagent container and the reagent buffer solution container. Therefore, also in the present embodiment, the first and second embodiments are used.
Similarly to the above, the deterioration of the reagent can be avoided.

In this embodiment, the oxygen scavenger can be reused by removing the used copper oxide together with the container 73 from the thermostat 72 and performing a regeneration treatment to return the reduced copper to the reduced copper.

The configuration of the amino acid analyzer of this embodiment is the same as that of the first embodiment except for the configuration shown here. Here, only the coloring reagent supply unit 11 will be described, but also in this embodiment, the coloring reagent supply unit 11 and the coloring reagent buffer supply unit 17 have the same configuration.

<Embodiment 4> In each of the above embodiments, the means for introducing outside air into the container and the means for removing oxygen from the introduced outside air were provided. Is used as the coloring reagent container and the coloring reagent buffer solution container, the reagent can be supplied without introducing outside air into the reagent container. Next, the color reagent supply unit 11 in the present embodiment will be described. The configuration of the amino acid analyzer of this embodiment other than that shown here is the same as that of the first embodiment. Here, only the coloring reagent supply unit 11 will be described, but also in this embodiment, the coloring reagent supply unit 11 and the coloring reagent buffer supply unit 17 have the same configuration.

As shown in FIG. 8, the coloring reagent supply section 11 of the present embodiment comprises a highly flexible bag-shaped container 80 (10 cm × 20 cm) in which a coloring reagent is sealed. It is desirable that the coloring reagent container 80 of the present embodiment has high flexibility and chemical resistance. For example, a polyester bag whose inner wall is coated with polytetrafluoroethylene can be used.

The coloring reagent container 80 of this embodiment has an opening sealed with a silicone rubber seal 81, while the distal end of a reagent delivery tube 82 of this embodiment is a hollow needle 83. I have. When using the coloring reagent container 80 of the present embodiment, the hollow needle 83 is attached to the seal 8 of the container 80.
1 is pierced and used to penetrate, but it may be fastened by screws as in the above-described embodiments. Note that the amino acid analyzer of the present embodiment is not provided with the deoxygenation mechanism 58 and the air introduction tube 52.

In the color reagent container 80 of this embodiment, only the pipe 82 to the color reagent pump 12 is connected and is not open to the atmosphere. Therefore, when the reagent is aspirated, the container itself shrinks and deforms to compress the volume reduced by the aspiration. This ensures that no gas enters the container and the reagent does not come into contact with oxygen. Therefore, according to the present embodiment, the deterioration of the reagent can be avoided.
According to the present embodiment, it is not necessary to provide the deoxidizing mechanism 58, so that the configuration of the apparatus can be simplified, which is preferable.

[0051]

According to the present invention, a chromogenic reagent which can be easily oxidized and used in a liquid chromatograph apparatus can be used without complicating piping and mechanisms, and without using substances which make cleaning difficult. Deterioration can be prevented.

[Brief description of the drawings]

FIG. 1 is a system configuration diagram of an amino acid analyzer.

FIG. 2 is a schematic diagram illustrating a configuration example of a coloring reagent supply unit according to the first embodiment.

FIG. 3 is a cross-sectional view illustrating a configuration example of a deoxygenating mechanism.

FIG. 4 is a chromatogram showing an example of a detection result.

FIG. 5 is a graph showing transition of a peak area with time.

FIG. 6 is a cross-sectional view illustrating a configuration of a deoxygenating mechanism according to a second embodiment.

FIG. 7 is a schematic diagram illustrating a configuration of a deoxygenating mechanism according to a third embodiment.

FIG. 8 is a schematic diagram illustrating a configuration of a coloring reagent supply unit according to a fourth embodiment.

[Explanation of symbols]

1-4 buffer buffer bottle, 5 column regeneration liquid bottle, 6 solenoid valve, 7 buffer buffer pump, 8 ammonia filter column, 9 autosampler, 10 separation column, 11 color reagent supply unit, 12 ... color reagent pump, 13 ... mixer,
14: reaction tube, 15: visible detector, 16: data processing device, 17: color reagent buffer supply unit, 18: flow cell,
19: lamp, 30, 31, screw, 32: air intake through hole, 50: color reagent container, 51: reagent delivery tube, 52: air introduction tube, 52a: air suction tube fastening screw member, 53 ... Filter, 54 ... Oxygen remover, 55 ... Oxygen remover container, 55a ... Oxygen remover container lid,
55b: oxygen absorber container main body, 56: coloring reagent solution (ninhydrin reagent), 57: lid of the reagent container, 58: deoxidizing mechanism, 59: projection for fastening an air introduction tube, 60: air intake, 61 ... Coloring reagent container, 62: Oxygen removing container, 63: Air intake through hole, 64: Air supply through hole, 65: Coloring reagent container opening, 70: Deoxygenation mechanism,
71: reduced copper powder, 72: constant temperature device, 73: oxygen absorber container, 74: distributor, 75: air delivery tube, 76:
Air intake tube, 80 ... color reagent container, 81 ...
Seal, 82: tube for delivering reagent, 83: hollow needle, 1
00: separation system, 110: analysis system, 120: reagent supply system.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G01N 33/68 G01N 35/06 A (72) Inventor Yoshio Fujii 882-Momo, Oaza-shi, Hitachinaka-shi, Ibaraki Pref. (72) Inventor Hiroshi Satake, 882-Chair, Oji-shi, Hitachinaka-shi, Ibaraki, Japan Incorporated Hitachi-Measurement Instruments Division (72) Inventor Seiji Mori 882-City, Oaza, Ichigo, Hitachinaka-shi, Ibaraki F-term in Hitachi Measuring Instruments Division (Reference) 2G042 BD12 BD13 CB03 DA08 EA02 FA11 FB02 GA01 HA01 HA06 HA10 2G045 BB03 DA18 DA35 FA11 FB06 FB11 GC12 HA10 JA08 JA09 2G054 AA02 BB02 BB10 BB13 CA37 JA04 2G058 BA08 BB02 BB09 CE01 CE02 CE03 FA07 GA06 GA14 GD06

Claims (20)

[Claims] 1. An analyzer having an analysis mechanism for analyzing a sample and a reagent supply mechanism for supplying an analysis reagent to the analysis mechanism, wherein the reagent supply mechanism includes a reagent for holding the reagent. A container, a reagent flow path that connects the reagent container and the analysis mechanism in a communicable manner, and a deoxygenation mechanism for supplying air from which oxygen has been removed using an oxygen scavenger to the reagent container. Characteristic analyzer. 2. The oxygen scavenger according to claim 1, wherein the oxygen scavenger includes an oxygen scavenger container for holding an oxygen scavenger for removing oxygen from the air, and external air to the reagent container via the oxygen scavenger container. The analyzer according to claim 1, further comprising an air flow path for introducing the air. 3. The analyzer according to claim 2, wherein the capacity of the oxygen scavenger container is at least 1/10 of the capacity of the reagent container. 4. The analyzer according to claim 2, wherein the oxygen scavenger is held in the oxygen scavenger container in advance. 5. The analyzer according to claim 4, wherein the oxygen scavenger has an oxygen absorption capacity at least equal to the capacity of the reagent container. 6. The oxygen scavenger comprises reduced iron powder, reduced copper powder, an alkaline aqueous solution of pyrogallol,
5. The analyzer according to claim 4, wherein the analyzer is at least one of an aqueous solution of dithionite. 7. The analyzer according to claim 6, wherein the oxygen scavenger is reduced iron powder, and the total volume is at least 1/10 of the capacity of the reagent container. 8. An analyzer having an analysis mechanism for analyzing a sample and a reagent supply mechanism for supplying an analysis reagent to the analysis mechanism, wherein the reagent supply mechanism includes a reagent for holding the reagent. A container, and a reagent flow path that connects the reagent container and the analysis mechanism in a communicable manner. The reagent container is an airtight container made of a flexible material that can be flexibly deformed in accordance with the internal pressure of the container. An analyzer characterized by the following. 9. The analyzer according to claim 1, wherein the inner wall of the reagent container is made of a fluorine-containing resin. 10. The reagent supply mechanism further comprises a pump for sending a reagent from the reagent container to the analysis mechanism via the reagent flow path, wherein the reagent container is at a position higher than the pump. The analyzer according to claim 1, wherein the analyzer is arranged. 11. The analyzer according to claim 10, wherein the reagent container is arranged at a position higher than the pump by 50 cm or more. 12. The analyzer according to claim 1, wherein the analyzer is a liquid chromatograph. 13. The analyzer according to claim 12, wherein the analyzer is an amino acid analyzer, and the reagent contains ninhydrin. 14. The analyzer according to claim 12, wherein the analyzer is a catecholamine analyzer, and the reagent includes diphenylethylenediamine. 15. A method for analyzing a sample using a reagent, characterized in that oxygen is previously removed from the air sucked into the reagent container using an oxygen scavenger. 16. A method for analyzing a sample using a reagent, characterized in that an airtight container made of a flexible material that can be flexibly deformed according to an internal pressure is used as a reagent container for holding the reagent. Analysis method. 17. The reagent container includes an opening for connecting a reagent supply tube so that the reagent supply tube can be communicated, and a sealing member for sealing the opening. The reagent supply tube has one end. Is a hollow needle, and the reagent channel is communicably connected by penetrating the needle through the sealing member.
6. The analysis method according to 6. 18. A container for a reagent used for analyzing a sample, which is an airtight container made of a flexible material that can be flexibly deformed according to an internal pressure, and an opening for connecting a reagent supply tube so as to be able to communicate therewith. And a sealing member for sealing the opening. 19. An analyzer for analyzing a sample using a reagent, comprising: a mechanism for removing oxygen from air supplied to a container of the reagent, wherein the mechanism holds an oxygen scavenger for removing oxygen from the air. And an air flow path for introducing external air into the reagent container through the oxygen absorber container. Oxygen mechanism. 20. The oxygen scavenger according to claim 19, wherein the oxygen scavenger container holds the oxygen scavenger in advance.
The analyzer as described.