JP3554194B2 - Analysis equipment - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to quantitative and / or qualitative analysis, and in particular, an analyzer suitable for liquid chromatographic analysis using a reaction reagent that is easily oxidized.About.
[0002]
[Prior 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) and detected. Ninhydrin is generally used as a coloring reagent for the detection of this amino acid by the post-column derivatization method.
[0003]
[Problems to be solved by the invention]
The ninhydrin reagent used for detection of amino acids and the like is very easily oxidized and quickly deteriorates when exposed to air. 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.
[0004]
Therefore, as a countermeasure, first, the coloring reagent bottle containing the ninhydrin reagent is sealed with an inert gas (nitrogen gas or helium gas), and the bomb is filled with the inert gas from the cylinder so as to fill the void generated by the consumption of the reagent. Is supplied. However, this method requires a gas cylinder or 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]
Also, a method of providing an oily thin layer having a relatively low specific gravity, such as paraffin, at the interface where the ninhydrin solution in the coloring reagent bottle comes into contact with air and isolating it from oxygen has conventionally been adopted. However, in this method, handling of the oily thin layer is extremely troublesome, and the oily thin layer makes it difficult to wash the coloring reagent bottle. Furthermore, when this method is used, when the ninhydrin solution is completely consumed, the oily thin layer is sucked and introduced into the analysis system, and not only the detection signal becomes abnormal, but also the analysis system pipe is washed. It becomes very difficult.
[0006]
Therefore, the present invention provides an analyzer using an easily oxidizable reagent, such as an amino acid analyzer or a catecholamine analyzer, without using a substance that does not complicate the piping and mechanism and makes cleaning difficult. It is another object of the present invention to provide a technique capable of preventing deterioration of a reagent.
[0007]
[Means for Solving the Problems]
In order 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 a reagent for analysis to the analysis mechanism, wherein the reagent supply mechanism includes:
(1) A reagent container for holding a reagent, a reagent flow path that connects the reagent container and the analysis mechanism in a communicable manner, and deoxygenation for supplying air from which oxygen has been removed using an oxygen scavenger to the reagent container. Having a mechanism, or
(2) A reagent container for holding a reagent, and a reagent flow path for connecting the reagent container and the analysis mechanism so as to be able to communicate with each other, and the reagent container is flexibly deformable according to the internal pressure of the container. An airtight container made of a conductive material,
An analyzer is provided.
[0008]
In the present invention, as a method of analyzing a sample using a reagent,
(1) removing oxygen from the air sucked into the reagent container using an oxygen scavenger in advance, or
(2) using an airtight container made of a flexible material that can be deformed flexibly according to the internal pressure, as a reagent container for holding the reagent;
An analysis method is provided.
[0009]
Further, the present invention provides a deoxygenating mechanism and a reagent container for use in the above-described analyzer and analysis method.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the oxygen is removed from the air supplied to the reagent container by the deoxygenating mechanism, thereby avoiding the 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 for introducing the external air into the reagent container via the oxygen-absorbing agent container. And an air flow path. 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. Note that the oxygen scavenger may be held in the oxygen scavenger container in advance.
[0012]
The oxygen scavenger desirably has at least the same oxygen absorption capacity as 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 Co., Ltd. is commercially available. In the case where reduced iron powder is used as the oxygen scavenger, it is preferable that the total volume of the powder be at least 1/10 or more of the capacity of the reagent container, because the effect can usually be maintained for about one month.
[0013]
In the present invention, instead of providing such a deoxygenating mechanism, an airtight container made of a flexible material that can be flexibly deformed according to the internal pressure may be used as the reagent container. With this configuration, when the internal pressure of the container is reduced due to the delivery of the reagent, the container itself is deformed in accordance with the internal pressure, so that the internal pressure of the container and the atmospheric pressure are balanced, without supplying air into the container, The reagent can be supplied without delay. In this case, it is not necessary to replace the volume of the consumed reagent 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 desirably made of a fluorine-containing resin such as polytetrafluoroethylene or a derivative thereof from the viewpoint of chemical resistance. In addition, 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. This is preferable because the needle can be penetrated through the sealing member so that the reagent flow path can be easily communicated with almost no air.
[0014]
The present invention is applicable regardless of whether the supply of the analysis reagent is performed before or after the separation of the sample. That is, the present invention can be applied not only to the above-described post-column derivatization method but also to a pre-column derivatization method.
[0015]
The present invention is particularly suitable for a liquid chromatograph device, an amino acid analyzer using ninhydrin described above, a catecholamine analyzer using diphenylethylenediamine, or an automatic analyzer for blood biochemistry, such as an analyzer using an easily oxidizable reagent. And it is particularly effective for analytical methods.
[0016]
【Example】
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
<Example 1>
A. Device configuration
As shown in FIG. 1, the amino acid analyzer of this embodiment includes a separation system 100, an analysis system 110, and a reagent supply system 120.
[0017]
The separation system 100 includes buffer solution bottles 1 to 4 and a column regenerating solution bottle 5 (each having a capacity of 1 L), a buffer solution pump 7, an ammonia filter column 8, an autosampler 9, and a separation column 10. They are connected by piping in this order. An electromagnetic valve 6 is provided in a pipe between the buffer solution bottles 1 to 4 and the column regenerating solution bottle 5 and the buffer solution pump 7, respectively.
[0018]
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. A pipe is connected between the detector 15 and the separation column 10 of the separation system 100 via a reaction tube 14, and a mixer 13 is provided in a pipe between the separation column 10 and the reaction tube 14. ing. 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.
[0019]
The reagent supply system 120 includes a color reagent supply unit 11 for supplying ninhydrin, a color reagent buffer supply unit 17 for supplying a buffer for ninhydrin, and a color reagent pump 12. The coloring reagent supply section 11 and the coloring reagent buffer supply section 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.
[0020]
When this apparatus is used, the buffer solution bottles 1 to 4 hold the buffer solution, and the column regenerating solution bottle 5 holds the column regenerating solution, from which the buffer solution selected by the solenoid valve series 6 is selected. Alternatively, the regenerating solution is sent to the separation column 10 via the ammonia filter column 8 and the autosampler 9 by the buffer solution pump 7. In the analysis of the sample, the sample to be analyzed is introduced into the mobile phase (buffer solution) in the pipe by the autosampler 9 and separated while moving in the separation column 10 together with the mobile phase.
[0021]
The ninhydrin reagent is held in the coloring reagent supply unit 11 of the reagent supply system 120, and the buffer is held in the coloring reagent buffer supply unit 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 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 detected 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.
[0022]
B. Reagent supply system
(1) Coloring reagent
The ninhydrin reagent and the 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, dissolving by bubbling with nitrogen gas for 5 minutes or more, adding 81 mg of sodium borohydride to the obtained solution, and adding nitrogen for 30 minutes or more. Prepared by bubbling with gas. 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.
[0023]
As described above, since the ninhydrin reagent contains a reducing agent (sodium borohydride in this embodiment) that is oxidized when exposed to oxygen, the ninhydrin reagent is quickly deteriorated by contact with air.
[0024]
(2) Coloring reagent supply section
As shown in FIG. 2, the coloring reagent supply unit 11 used in this embodiment includes a reagent container (coloring reagent bottle: 1 L in capacity) 50 and a deoxygenating mechanism 58. Here, the color reagent supply unit 11 for supplying the ninhydrin reagent will be described. However, the color reagent buffer supply unit 17 for supplying the ninhydrin buffer has the same configuration.
[0025]
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.
[0026]
The reagent delivery tube 51 (inner diameter 2.0 mm, outer diameter 3.0 mm) is a pipe that connects the reagent container 50 and the coloring reagent pump 12 so as to be able to communicate with each other, and the ninhydrin reagent held inside the reagent container 50. This is a liquid sending pipe for sending 56 to the coloring reagent pump 12. 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 submerged in the coloring reagent solution 56 for use.
[0027]
In addition, the air introduction tube 52 (inner diameter 0.5 mm, outer diameter 1.6 mm) is open to the atmosphere via a deoxygenation mechanism 58 to prevent the inside of the reagent container 50 from being depressurized as the reagent is consumed. This is a pipe for eliminating the problem by introducing air from which oxygen has been removed. At the time of the analysis operation, the end in the reagent container 50 of the both ends of the air introduction tube 52 is arranged 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.
[0028]
It is desirable that the reagent container (including the buffer solution container for the reagent) 50 be disposed at a position higher than the reagent suction pump 12. By doing so, pressure is applied by its own weight, which is particularly effective for feeding a highly viscous reaction reagent buffer. Preferably, the reagent container 50 is higher than the reagent suction pump 12 by 50 cm or more as shown in FIG. In this way, the same effect can be obtained with a normal reagent (buffer solution and ninhydrin solution) as when the pressure is increased to 0.05 atm or more.
[0029]
(3) Deoxygenation mechanism
The oxygen scavenging 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 passes through the oxygen scavenger 54 to remove oxygen. Therefore, according to the present embodiment, it is possible to prevent the coloring reagent inside the reagent container 50 (and the coloring reagent buffer held in the coloring reagent buffer supply mechanism 17 having the same configuration) from coming into contact with oxygen. And deterioration of the reagent can be prevented.
[0030]
The oxygen scavenger 54 is not particularly limited as long as it has a sufficient oxygen removing ability. For example, an oxygen absorbent such as an alkali solution of pyrogallol, an aqueous solution of dithionite, and heated reduced copper is used. be able to. In this example, 100 mL of iron powder made of reduced iron having a large specific surface area (for example, “Ageless” (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used. Reduced iron powder is suitable for the present invention because of its remarkably high oxygen adsorption ability.
[0031]
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 protrusion 59 having an opening at one end. The protrusion 59 has a thread formed so as to be screwable with a screw provided at an 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 to the screw of the projection 59, and the hole 60 is opened at the other end of the container 55 to serve as an air suction port. The hole 60 is desirably opened so that the air flow path is as long as possible. In addition, as long as a sufficient amount of air can be sucked, the air suction port 60 is desirably small so that the air can surely pass through the oxygen scavenger 54. In the present embodiment, the diameter is 1 to 2 mm. About. 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.
[0032]
In this embodiment, the oxygen-absorbing agent container 55 is used in which the oxygen-absorbing agent 54 is sealed in advance. However, the oxygen-absorbing agent container 55 is provided with an opening and closing port for the oxygen-absorbing agent that can be opened and closed by a fastener or the like. Alternatively, an oxygen scavenger may be added at the time of use.
[0033]
FIG. 3 shows an example of a container 55 having a lid that can be sealed by screwing. The container 55 shown here is composed of a main body 55b having a screw 30 that can be screwed together and a lid 55a. The bottom of the main body 55b is screwed with a screw of a screw member 52a provided at the tip of the air suction tube 52. A possible screw 31 is formed. The lid 55a is provided with a through hole 32 for taking in air.
[0034]
At the time of use, as shown in FIG. 3, the container 55 has the screw member 52a of the air suction tube 52 fastened to the screw 31 at the bottom of the main body 55b, and the oxygen-absorbing agent 54 in a non-woven bag is put inside. The lid 55b is fastened and used in this state. With such a container 55, an effect similar to that of the deoxidizing mechanism 58 of the present embodiment can be obtained.
[0035]
C. Effects of this embodiment
In this example, a mixed solution (protein hydrolyzate) containing a fixed amount (2.0 nm) of aspartic acid was used as a sample, and aspartic acid was separated and detected by a conventional method, and the detected signal of aspartic acid was used. Based on the peak area of the intensity, 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 the ammonia filter column 8 has "2650L" (manufactured by Hitachi, Ltd.) (inner diameter 4.6 mm). , 40 mm in length), and “PH-KIT” manufactured by Mitsubishi Chemical Corporation as a buffer solution. The reaction tube 14 used had an inner diameter of 4.6 mm and a length of 40 mm, and the reaction temperature was 135 ° C.
[0036]
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 the color reagent was replaced, 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. Asp: aspartic acid, Thr: threonine, Ser: serine, Glu: glutamic acid, Gly: glycine, Ala: 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.
[0037]
Next, the same sample was measured under the same measurement conditions, 15 days and 33 days after the reagent replacement, respectively, and the result of measuring the peak area of aspartic acid as a relative value with the value immediately after the reagent replacement as 100%. As shown in FIG. For comparison, the results when the deoxygenating mechanism 58 is not provided and the end of the air introduction tube 52 is opened to the atmosphere are also shown in 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 this example, the peak area was constant until two weeks after the replacement of the coloring reagent, and there was almost no change in the activity of the reagent. Even when about one month had passed since the replacement of the coloring reagent, the area value was 90% or more. Secured. 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.
[0038]
In addition, 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 at the time of use. However, when the coloring reagent is replaced together with the reagent bottle 50 when opening or when the tubes 51 and 52 are inserted, a slight amount of air is generated. 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 scavenger 58. Therefore, the amount of oxygen absorption required for the oxygen scavenger 54 used is not limited to the volume of air (1 L in the present embodiment) sucked when the reagent in the coloring reagent bottle 50 is consumed and emptied, and also the amount of oxygen absorbed during replacement. It is desirable to calculate including the amount of oxygen to be performed 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.
[0039]
When replacing the coloring reagent and / or oxygen scavenger, in order to reduce oxygen entering the reagent container as much as possible, the reagent container 55 pre-filled with nitrogen and the It is desirable to replace the entire supply unit 11.
[0040]
<Example 2>
In the above-described first embodiment, the deoxygenating mechanism 58 and the coloring reagent container 50 are connected using the air suction tube 52. However, the present invention is not limited to such a configuration. As described above, the deoxygenating mechanism 58 may be directly attached to 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. Note that 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.
[0041]
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 removing agent container 62, and when these are fastened, the oxygen removing agent container 62 becomes the color reagent container. 61 covers the opening 65.
[0042]
As shown in FIG. 6, the oxygen scavenger container 62 has a cylindrical shape having a concave portion on one bottom surface, and an oxygen scavenger 54 contained in a nonwoven fabric bag is sealed therein. On the inner wall of the recess, a coloring reagentcontainer61ofA screw that can be screwed with the screw provided in the opening 65 is formed. In addition, a through hole 63 for air intake is provided on a surface other than the concave portion of the bottom surface in which the concave portion is formed, and the bottom surface of the concave portion, that is, the screw of the coloring reagent container 61 and the screw of the oxygen scavenger container 62 are provided. Is fixed, a through hole 64 for supplying air to the coloring reagent container 61 is provided on the surface that covers the coloring reagent container 61 opening 65. The oxygen scavenger container 62 is provided with a through hole (not shown) for fitting the reagent delivery tube 51.
[0043]
Also in the present embodiment, similarly to the first embodiment, it is possible to avoid the deterioration of the coloring reagent. It is preferable to use the deoxidizing mechanism 58 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.
[0044]
<Example 3>
In each of the above embodiments, reduced iron was used as the oxygen scavenger 54, but in this embodiment, reduced copper was used. 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 76 are attached to both ends of the oxygen scavenger container 73, respectively, 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 color reagent container 50 and the tube 52 for introducing air into the color reagent buffer solution container. The air introduced from the air intake tube 76 is subjected to oxygen removal by the reduced copper powder 71 in the container 73 heated by the constant temperature device 72, and then passes through the air delivery tube 75 and the distributor 74. The solution is supplied to each reagent container and reagent buffer solution container. Thus, also in the present embodiment, oxygen is removed from the air supplied to each reagent container and the buffer solution container for reagent. Therefore, also in this embodiment, similarly to the first and second embodiments, the deterioration of the reagent can be avoided.
[0045]
In this embodiment, the oxygen scavenger can be reused by taking out the used copper oxide together with the container 73 from the thermostat 72, performing a regeneration process, and returning it to reduced copper.
[0046]
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.
[0047]
<Example 4>
In each of the above embodiments, the means for introducing outside air into the container and the means for removing oxygen from the outside air to be introduced are provided.In this embodiment, the container made of a highly flexible material is a coloring reagent container and By using it as a buffer for a coloring reagent, a reagent can be supplied without introducing outside air into the reagent container. Next, the coloring reagent supply unit 11 in the present embodiment will be described. Note that 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.
[0048]
As shown in FIG. 8, the coloring reagent supply section 11 of the present embodiment includes 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 this embodiment has high flexibility and chemical resistance. For example, a polyester bag whose inner wall is coated with polytetrafluoroethylene can be used.
[0049]
The opening of the coloring reagent container 80 of this embodiment is sealed with a silicone rubber seal 81, while the distal end of the reagent delivery tube 82 of this embodiment is a hollow needle 83. When using the coloring reagent container 80 of this embodiment, this hollow needle 83 is used to pierce and penetrate the seal 81 of the container 80. However, similarly to the above-described embodiments, the hollow needle 83 may be fastened with a screw. Good. Note that the amino acid analyzer of this embodiment is not provided with the deoxygenation mechanism 58 and the air introduction tube 52.
[0050]
In the coloring reagent container 80 of this embodiment, only the pipe 82 to the coloring 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, 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]
【The invention's effect】
Advantageous Effects of Invention According to the present invention, it is possible to prevent deterioration of easily oxidizable color reagent used in a liquid chromatograph apparatus without complicating piping and mechanisms, and without using substances that make cleaning difficult. Can be.
[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, 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 ... A through-hole for air intake, 50 ... Coloring reagent container, 51 ... Tube for reagent delivery, 52 ... Tube for air introduction, 52a ... Screw member for fastening a tube for air suction, 53 ... Filter, 54 ... Oxygen absorber, 55 ... Oxygen absorber container, 55a ... Oxygen absorber container lid, 55b ... Oxygen absorber container main body, 56 ... Coloring reagent solution (ninhydrin reagent), 57 ... Reagent container lid, 58 ... Deoxygenation mechanism, 59 ... Air introduction Tube fastening protrusion, 60: air intake, 61: color reagent container, 62: oxygen absorber, 63: air intake through hole, 64: air supply through hole, 65: color reagent container opening, 70 ... Deoxygenation mechanism, 71 ... Reduced copper powder, 72 ... Constant temperature device, 73 ... Oxygen remover container, 74 ... Distributor, 75 ... Air delivery tube, 76 ... Air intake tube, 80 ... Coloring reagent container, 81 ... Seal: 82: reagent delivery tube; 83: hollow needle; 100: separation system; 110: analysis system; 120: reagent supply system.

Claims (2)

In an analyzer having an analysis mechanism for analyzing a sample and a reagent supply mechanism for supplying a reagent for analysis to the analysis mechanism,
The reagent supply mechanism includes:
A reagent container for holding the reagent,
A reagent flow path that connects the reagent container and the analysis mechanism so that they can communicate with each other,
A reagent suction pump that sucks a reagent from the reagent container and supplies the reagent to the reagent channel;
Having a deoxygenation mechanism for supplying external air to the reagent container,
The reagent container is arranged at a position higher than the reagent suction pump,
And the above-mentioned deoxygenation mechanism has an oxygen scavenger container for holding reduced copper, a constant temperature device for heating the oxygen scavenger container, and an air flow path for introducing external air into the oxygen scavenger container. analysis device according to claim Rukoto equipped with. The reagent container is
The analyzer according to claim 1 , wherein the analyzer is arranged at a position higher than the pump by 50 cm or more.

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