JPS63253247A - Sampling device - Google Patents

Abstract

PURPOSE:To execute sampling with good reproducibility by providing two systems of flow passages for a solvent and sample to a rotary measuring plate and bringing the solvent into contact with the inlet of a capillary tube before injecting the sample into the capillary tube. CONSTITUTION:The capillary tube 1 for a electrokinetic chromatography or electrophoresis is connected to a sampling means 10 constituted by holding the rotary measuring plate 10c in place between a pair of valve seats 10a and 10b. An arc-shaped groove 10n is formed in the hole 10g of the seat 10a of the means 10 on the surface in contact with the plate 10c and an arc-shaped groove 10p is formed in the holes 10, 10j of the plate 10c on the surface in contact with the seat 10a. An arc-shaped groove 10q is formed in the hole 10m of the seat 10b on the surface in contact with the plate 10c. The sample is first supplied from a syringe 9 and the solvent is supplied from a solvent supplying means 8. The sample taken into the part of a length (d) is force-fed into the tube 1 by the solvent.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to electrokinetic chromatography or electrokinetic chromatography.
The present invention relates to a sample collection device suitable for an analytical device.

<Prior Art> FIG. 4 is a block diagram showing the principle of electrokinetic chromatography. Reference numeral 1 denotes a capillary tube constituting the column, for example, a fused silica capillary tube is used. 2.3 is a container containing a mixed solution (solvent) of a buffer solution and ionic micelles, and both ends of the capillary tube 1 are inserted into these containers. For micelles, for example, Dodecyl! 1l
Ionic micelles formed by dissolving ltl sodium (SDS) in a buffer solution are used. E is a power source, the positive side of which is connected to the electrode 4 immersed in the container 2, and the negative side connected to the electrode 5 immersed in the container 3, to apply a voltage to both ends of the key pillar tube 1. A detector 6 such as an ultraviolet spectrophotometer is provided on the negative side of the capillary tube 1 near the electrode 5 . 7 is a sample bottle containing a sample.

With this configuration, sample collection is performed by transferring the capillary tube 1 from the container 2 to the sample bottle 7, keeping the liquid level in the sample bottle 7 higher than the liquid level in the container 2, and using the head H.

Two phases, micelles and liquid solution, flow in capillary 1, and when i% lightning voltage is applied, vi
The 1i liquid flows in the six directions of arrows due to electroosmotic flow. On the other hand, dissolved 5DS (micelle) is an anion, and by electrophoresis! ! The solution tries to move toward the positive electrode in the opposite direction to the flow of the solution, but as mentioned above! Since the moving speed of the 1illi solution is 1 m (1! gas permeation flow), it eventually reaches the container 3 later than the buffer solution.

When a sample SM is introduced into such a capillary tube 1, sample components that are not dissolved in the micelles at all move to the negative electrode 5 together with the buffer solution on the electroosmotic flow. On the other hand, sample components that completely dissolve in the micelles migrate at the same rate as the micelles? h L, , reaches the container 3 side the latest. Also, intermediate sample components that dissolve to some extent in the micelles migrate at moderate speeds. As a result, the sample components moving in the capillary tube 1 have a retention time corresponding to the difference in solubilization rate, and the separated sample components are detected by the detector 6 installed at the outlet side of the capillary tube 1. Then, a chromatogram corresponding to the solubilization rate of the sample components can be obtained.

By the way, in order to perform analysis with good reproducibility using such an analyzer, it is necessary to always inject a certain amount of sample into the capillary tube 1 from the sample bottle 7.
In the conventional apparatus shown in the figure, in order to obtain the desired head pressure, the work of lifting the sample bottle 7 and the work of transferring the capillary tube 1 from the container 2 to the sample bottle 7 are performed manually. sample was difficult to inject.

<Problems to be solved by the invention> The technical problem to be solved by the present invention is the analysis of the electrokinetic chromatography, etc. mentioned above! ! The objective is to enable sample collection with good reproducibility at different locations.

Means for Solving the Problems The present invention has a configuration including a pair of fixed valve seats, a metering plate sandwiched between the valve seats and rotating around a rotating shaft, and rotating the metering plate in a fixed sequence. a means for supplying a sample, and a means for supplying a solvent at a constant head pressure; A capillary tube for sample analysis is connected to the one valve seat, and before the sample is injected into the capillary tube, the sample is passed from the one valve seat through the metering plate. In a state where the solvent is discharged from the other valve seat, the solvent introduced from the one valve seat is brought into contact with the inlet of the capillary tube and discharged while cleaning this part, and the sample is injected into the capillary tube. One of the holes filled with the sample in the measuring plate is connected to the capillary tube, and the other end of this hole is brought into contact with the solvent, and the sample is injected into the capillary tube by the liquid pressure of the solvent. I did it like that.

Function> The above technical means works as follows. That is, in the state before the sample is injected, the sample is injected from the one valve seat using a syringe or the like, and after filling the measuring hole provided in the measuring plate, the remaining sample is poured into the other valve seat. is discharged from. At this time, the inlet portion of the capillary tube is washed with the solvent.

When the sample is injected into the capillary tube, the metering plate rotates, the metering hole is connected between the capillary tube and the solvent path, and the sample taken into the metering hole is injected into the solvent. It is hydraulically pumped into the capillary tube.

The sample injected into the capillary tube is determined by the content of the metering hole, the time that the metering hole is connected to the xebillary tube, and the head pressure of the solvent, and by keeping these constant, it is determined by the amount necessary for analysis. It is possible to inject extremely small samples with good reproducibility (injection).In addition, since the connection part of the capillary tube is cleaned with the solvent mentioned above, the capillary tube will not be blocked by dust, etc., and it will be easy to use during analysis. Gas generated by electrolysis does not enter the capillary tube, and measurement interruptions due to gas inflow do not occur.

・<Example> The present invention will be described in detail below with reference to the drawings. FIG. 1 is a block diagram showing an embodiment of the present invention.

In the figure, the same elements as those in FIG. 4 are given the same reference numerals, and explanations thereof will be omitted. Reference numeral 8 denotes a solvent supply means for supplying a solvent at a constant head pressure. Two pipes 8a and 8b included in this are connected in the middle, and the solvent stored in a tank 8d is sent from the bottom of the pipe 8a by a pump 8c. It will be done. The solvent that overflowed in the tube 8a is refluxed back to the tank 8d via 1I8b.

Reference numeral 9 is a syringe for supplying a sample, and reference numeral 10 is a sample collection means for injecting a constant, very small amount of sample into the xevilar tree 71.

11 is a switch that applies a high voltage power source E to both ends of the main 11 pillar reach tube 1, and is operated by a control signal from a sequencer to be described later.

Reference numeral 12 denotes a sequencer that provides control signals to the sample collection means 10, the switch 11, and the signal processing section 13 according to a predetermined sequence. Note that 14 is an ammeter and 15 is a recorder. 1
6 is a constant temperature bath.

The sample collection means 10 will be explained in detail with reference to the exploded perspective view of FIG. , 10a, 10b are disc-shaped valve seats;
10c is a disk-shaped measuring plate made of ceramics, for example, which is sandwiched between these valve seats. There is a hole 10d in the valve seat 10a.
, 10e, 10t, 109 are provided, and the measuring plate 10
C has holes 10h and 10L.

10J is provided, and a hole 10 of 10m is provided in the valve seat 10b.
There are 10 turtles.

Shafts are inserted through the holes 10a, 10h, and 10k.

An arc-shaped groove 101 formed on the surface in contact with the metering plate 10c is connected to the hole 109 of the valve seat 10a, and the groove 101 is connected to the hole 109 of the valve seat 10a.
An arc-shaped groove 10p formed on a surface in contact with the valve seat 10a is connected to the hole 10J, and a hole 10W of the valve seat 10b is connected to the hole 10J.
L is connected to an arcuate groove 10g formed in contact with the measuring plate 10c.

Among these, the hole 10s is a solvent injection hole, the hole 10m is a solvent discharge hole, and the hole 10i is a sample injection hole.

The capillary tube 1 is connected to the hole 10f of the valve seat 10a, and the hole 10e is used as a sample discharge hole.

FIG. 3 is an explanatory diagram for explaining the operation of the sample collection means configured as described above, in which figure (a) shows the state before the sample is injected into the capillary tube 1, and figure (b) shows the state before sample injection. Indicates the state at the time. In the state before sample injection, holes 10e and 1
0t, 10* are in a straight line, holes 10s, 10J, 1
0 strategy is groove 10TL.

They are connected as shown in Figure (a) via 10p and 10i.

In this state, the solvent from the solvent supply means 8 flows into the capillary tube 1, and the sample given from the syringe 9 is discharged from the sample collection means 10.

When the weighing plate 10c is switched to the state shown in Figure (b), the weighing plate 1
0c hole 10. is connected to the capillary tube 1 through the hole 10f, and the sample taken into the hole 10 of length d is forced into the capillary duplex 1 by the flowing solvent as shown.

Note that the switching of the measuring plate 10c is performed at a constant timing by a motor or the like (not shown) based on a control signal from the sequencer 12. Capillary tube 1 has a metering hole 10. A part of the sample taken in is injected,
This stirrup is determined in relation to the time at which the metering hole 10t is connected to the capillary tube 1 and the head pressure of the solvent [-1.

Thereafter, the measuring plate 10c is returned to the state shown in Figure (a), the switch 11 is closed, the high voltage power source E is connected to both ends of the capillary tube 1, and a chromatograph is taken.

After obtaining the desired chromatography, turn off the switch 11,
It becomes the initial state.

Note that the sample injected into the capillary tube 1 is a minute amount (1.~10 rl>), and in the embodiment of the present invention, a part of the sample taken into the measuring hole 10t is dispensed and the minute amount is injected into the capillary tube 1. However, the measuring plate 10c is made thinner and the hole diameter of the measuring hole 10t is made smaller so that a very small amount of sample necessary for analysis can be obtained from which measuring hole part. In this case, all types of samples taken into the measuring hole 10t are injected into the capillary tube 1 as samples.

According to the present invention, the sample injected into the capillary tube is determined by the time during which the measurement hole is connected to the capillary tube and the head pressure of the solvent, and by keeping these constant. The small amount of sample required for analysis can be injected with good reproducibility. In addition, since the connecting portion of the capillary tube is cleaned with the solvent, the capillary tube will not be clogged with dirt or the like, and gas generated by electrolysis during analysis will not enter the capillary duplex. Therefore, there is no interruption in t1 measurement due to gas inflow.

In the above description of the present invention, the case where the sample collection device is used in an electrokinetic chromatograph was explained, but the sample collection device of the present invention is not limited to this, and can be used in a capillary electrophoresis analyzer, a constant velocity electrophoresis analyzer, etc. It can be used as a migration analyzer or a liquid chroma 1-graph sample injection device.

[Brief explanation of the drawing]

Figure 1 does not show the first embodiment of the device of the present invention;
The figure is an exploded perspective view showing the main parts of the device according to the embodiment of the present invention shown in FIG. 1, FIG. 3 is an explanatory diagram for explaining the operation of the device according to the embodiment of the present invention, and FIG. FIG. 5 is an explanatory diagram of the operation of the conventional device shown in FIG. 4. 1... Capillary tube, 3... Solvent container, 6
Detector, 8 Solvent supply means, 9 Syringe, 10 Sample collection means, 10a, 10b Valve seat, 10c Measuring plate, 11 Switch, 12・
...Sequencer, E...High voltage power supply; 1st cause 1? Figure 2 Figure 3 (a) (b) Figure 4 Figure 50 Δ

Claims (1)

[Claims] a pair of fixed valve seats, a metering plate sandwiched between the valve seats and rotating about a rotating shaft, means for rotating the metering plate in a constant sequence, means for supplying a sample, and a metering plate sandwiched between the valve seats and rotating around a rotating shaft; A capillary for sample analysis is provided at the one valve seat, and two channels are provided for flowing the solvent and the sample from the one valve seat through the metering plate to the other valve seat. Before the tube is connected and the sample is injected into the capillary tube, the sample is discharged from the one valve seat through the metering plate and the other valve seat, and introduced from the one valve seat. The solvent is brought into contact with the inlet of the capillary tube and discharged while cleaning this part, and when a sample is injected into the capillary tube, one of the holes filled with the sample in the measuring plate is connected to the capillary tube. A sample collecting device characterized in that the other end of the hole is brought into contact with the solvent, and the sample is injected into the capillary tube by the hydraulic pressure of the solvent.