JPH0360067B2 - - Google Patents

Description

Detailed Description of the Invention (Field of Application of the Invention) The present invention relates to a so-called "merging zone" in which, for example, a flow-in injection analysis method, a fixed amount of a reagent solution and a sample solution are combined and injected into a flowing eluent. This invention relates to a liquid injection device that facilitates liquid injection into molds.

(Background of the Invention) Liquid chromatography or flow injection analysis, which is generally known as a method for analyzing components in a sample solution, involves injecting a sample solution (hereinafter simply referred to as a sample) into a flow of eluent. Since the pressure inside the system is high, a pressure-resistant liquid injection device is usually used to inject the sample.

FIG. 1 schematically shows a typical liquid injection system in liquid chromatography, and a well-known six-way valve 4 is used as the liquid injection device.

be done.

To give an overview of this liquid injection system, the eluent tank 1
The eluent sent from the pump 2 to the channel 3 normally passes through one channel of the six-way valve 4, which is in communication as shown by the solid line in the figure, to the channel 5, the resin-filled column 6, and then to the detector 7. liquid. On the other hand, the other two passages inside the six-way valve 4 are connected to liquid measuring tubes (generally consisting of tubes mounted on the outside of the valve, and simply referred to as loops, henceforth abbreviated as such).
8 are connected and communicated with each other, and a sample in a sample container 9 is suctioned by a pump 10 to fill the loop. Then, the passage in the six-way valve 4 is switched as shown by the broken line in the figure, and the sample is injected into the flow of the eluent as a "plug flow", thereby increasing the affinity of the resin in the column 6 with each component in the sample. Due to the differences in the chemical composition, predetermined components are separated and analyzed using a detector.

The six-way valve 4 has a pair of stator (fixed body) and rotor (rotating body) that have airtight opposing surfaces, and the stator has a total of 6 small openings at each 60° rotation position, and the rotor is adjacent to It is well known as having three bridging grooves that communicate small openings, and the communication relationship can be switched as shown in the figure by rotating the rotor by 60 degrees. Since the injection mode is simple and can be performed by rotating the rotor, it is now widely used.

Flow-in injection analysis, which is attracting attention along with liquid chromatography, uses a reagent that reacts with specific components in the sample and measures the reaction products with a colorimeter, ion electrode, etc. This can be achieved by replacing the eluent with a reagent solution (hereinafter simply referred to as reagent) in the liquid injection system shown in Figure 1, and by omitting column 6, but in reality it requires a constant flow of expensive reagents. Since this is extremely uneconomical, a method of injecting a fixed amount of sample and reagent into the flow of eluent has been considered.
A method according to Publication No.-87464 has been proposed.

The above-mentioned publication describes a so-called "merging zone type" injection method in which sample S and reagent R are combined in parallel flow between eluent T as shown in FIG. 2A, using two sets of six-way valves. As shown in Figure 2, a "Sandermansch type" injection method in which sample S is sandwiched between reagent R has been disclosed, but the former "merging zone type" injection method allows for good contact between the reagent and the sample. Although it has the advantage of saving reagents, since two sets of six-way valves and two associated pumps are used, it is difficult to completely synchronize the liquid delivery state and the switching timing of the six-way valves, which impairs analytical accuracy. It has been pointed out that there is a problem with the equipment that has unavoidable effects on the equipment.

Furthermore, although the device disclosed in the above publication has the function of simultaneously injecting the sample and reagent into the flow of eluent, it cannot be used as is as a device that injects only the sample into the flow of eluent. It had a limited use.

(Objective of the Invention) As described above, the first object of the present invention is to provide an injection method in which two liquids such as a sample and a reagent are simultaneously injected into the flow of another liquid such as an eluent. It is an object of the present invention to provide a liquid injection device that can accurately perform a "merging zone type" injection that provides a good contact state of liquid with simple operation.

Another object of the present invention is to improve a device that realizes the above-mentioned "merging zone type" liquid injection or a further improved multi-liquid injection with a simple operation, and furthermore, by another operation of the same device, For example, it is an object of the present invention to provide a multifunctional liquid injection device that is capable of injecting only one liquid, such as injecting only a sample in a flow of eluent.

(Summary of the Invention) In accordance with the above object, the present invention provides a "merging zone type" system in which two types of liquids are placed in a steady flow of other liquids.
The liquid injection device is characterized in that the injection operation can be carried out by rotating only one rotor, and the gist of this liquid injection device is that a pair of airtightly opposed A stator and a rotor whose surfaces can be switched to a first and second position by sliding rotation at a certain angle are provided with a plurality of liquids belonging to each of the first, second, and third liquid systems on one opposing surface. The liquid injection device is provided with small openings and a plurality of bridging grooves on the pair of opposing surfaces that are selectively aligned with the small openings and complementary to form liquid passages of each system, the stator and by switching the position of the rotor, (a) the first liquid system is for the eluent and has small openings at the inlet and outlet of the liquid passage, these inlets and outlets are communicated by a bridging groove in the first position, and In the second position it is blocked.

(b) The second liquid system is for the sample liquid, and the third liquid system is for the sample liquid or dilution water, each having two small openings connected to both ends of the liquid measuring tube of each system,
These small openings for each system are in communication with the liquid filling circuit of each system by the bridging groove at the first position, and are in communication with the inlet and outlet of the first liquid system, respectively, at the second position.

According to this liquid injection device, in the first position, the first liquid system forms a steady flow of liquid through the liquid passage whose inlet and outlet are aligned by the bridge groove, while the second liquid system In the third liquid system, a liquid filling circuit is connected to a loop that is a liquid measuring tube, and a certain amount of liquid determined by the length of the loop is filled into the loop.

On the other hand, when the stator and rotor are moved relative to each other and switched to the second position, the bridging groove moves in the liquid passage between the inlet and outlet of the first liquid system and becomes disconnected, while the second liquid system and Communication between both ends of the third liquid system and the liquid filling circuit is cut off, and both ends of the third liquid system are communicated with the inlet and outlet of the first liquid system.

Therefore, the liquid passage formed between the pair of opposing surfaces of the stator and rotor includes each loop along the way: first liquid inlet, second liquid system loop, third liquid system loop, first liquid system outlet. As a result, two types of liquids can be injected into the liquid flow of the first liquid system as a "merging zone type."

It is clear that such a liquid injection device can be used as is in a flow injection analysis method using the first liquid as an eluent, the second liquid as a reagent, and the third liquid as a sample.

The present invention also provides a multifunctional liquid injection device that can be used, for example, to inject only the second liquid into the flow of the first liquid as a “plug flow” from the above-mentioned two-liquid simultaneous injection type device. , it has the feature that it can be changed by adding some configurations. That is, such a multifunctional liquid injection device has the same manner of forming liquid passages at the first position and the second position as in the above-described two-liquid simultaneous injection type device,
Furthermore, the rotor is provided so as to be able to slide and rotate from the first position to a third position opposite to the second position, and in this third position, both ends of the loop of the second liquid system are connected to the first position. The loop of the third liquid system is communicated with the inlet and outlet of the liquid system, but is realized by a configuration in which the loop of the third liquid system is not communicated with the inlet and outlet of the first liquid system.

According to such a configuration, the liquid passages described above are formed at the first position and the second position, and the filling of the liquid into the loop and the simultaneous injection of two liquids of the "merging zone type" are performed. When the first position is further switched from the first position to the third position, the liquid passage formed between the pair of opposing surfaces of the stator and rotor is as follows: first liquid system inlet → third liquid system loop → The path takes the form of the first liquid system outlet, and the second liquid is injected as a "plug flow."

In this case, as mentioned above, if the first liquid is the eluent, the second liquid is the sample, and the third liquid is the reagent, when switching to the second position, the "merging zone type" sample,
It becomes a simultaneous reagent injection mode, and when switching to the third position, it becomes a "plug flow" sample injection mode, which can be used for flow injection or liquid chromatography.

Further, the present invention can be applied to multi-liquid injection of three or more liquids when the rotor and stator are of the three-position switching type. Therefore, this three-position switching type liquid injection device has a stator (or rotor) having a plurality of small openings for each system belonging to n (n is an integer of 3 or more) liquid systems; One of them (the first liquid system) has small inlet and outlet openings that are communicated at the first position and blocked at the second and third positions rotated forward or backward from the first position. In particular, the other (n-1) liquid systems are characterized by having a set of small openings that connect both ends of each loop to the liquid filling system, the inlet and the outlet, and The number of openings is given by 2+4・(n-1) (where n is an integer of 3 or more and represents the number of liquid systems), and the circumferential positions of these small openings are
It can be designed on the basis that it is located on a radial line divided by an angle equal to 360° divided by 6+4·(n-1).

Further, the entire liquid feeding system may be at normal pressure, pressurized, or reduced pressure.

(Embodiments of the invention and their effects) The present invention will be described below based on embodiments shown in the drawings. The embodiments shown in Figs. 3 to 8 have two modes: a mode in which the sample (second liquid) and a reagent (third liquid) are simultaneously injected into the flow of the eluent (first liquid), and a mode in which only the sample is injected. This example shows a multifunctional injection device used for sample analysis in which the mode can be selected by rotating the rotor in the forward or reverse direction. Needless to say, it becomes a dedicated liquid injection device that only performs two-liquid simultaneous injection mode.
In applications where the method is used only for flow injection analysis, it may be useful to eliminate the possibility of erroneous operation.

FIG. 3 is a sectional view showing the outline of the structure of the liquid injection device of this example. In the figure, 21 is a disc-shaped stator, and at its periphery there is a circular rotor case 22 having a U-shaped cross section. The tips of the ring flange are engaged, and the stator 21 and rotor case 22 are connected by bolts 2.
3, it is firmly bound.

In the hollow area surrounded by the stator 21 and the rotor case 22, there is a rotor 24 that is in air (liquid) tight contact with the inner surface of the stator 21 under a predetermined pressure condition, and a drive disk that rotates the rotor 24. 2
5, and the rotor 24 via this driving disk 25.
A spring 26 that applies a pressing force to the stator 21 is housed therein, and a rotary drive shaft 27 extends from the back surface of the drive disk 25 to the outside of the rotor case 22 . Reference numeral 28 denotes an operating handle that projects from the extending end of the rotary drive shaft 27 in the radial direction.

A plurality of small openings a to j are formed in the hollow inner surface of the stator 21, as shown in FIG. are connected and communicated. The small openings a to j are arranged such that a and f are located on one diameter line of the stator, and four small openings b to e and g to j are arranged symmetrically on both sides in the relationship shown in the figure. It's summery. Further, the small opening a has a cross groove extending in the radial direction and in a direction perpendicular thereto.
a' and a'' are arranged in succession, and grooves f' and f'' which extend slightly in the radial direction and the circumferential direction are arranged in series in the small opening f.

Further, as shown in FIGS. 5A and 5B, on the surface of the rotor 24 facing the stator 21, at the radial positions where the small openings a to j face, there is a circumferential spacing between adjacent small openings on the stator side. A plurality of bridging grooves B to G that selectively connect the portions, and a bridging groove A extending in the diametrical direction that bridgingly communicates the grooves a'' and f'' that are connected to the small openings a and f are formed. There is. These bridging grooves A and B to G are formed by providing recesses on the surface of the rotor in this example, but this is because only both ends of the grooves are opened on the rotor surface, and the grooves are bored inside in the middle. It may be something that has been done. Also, for convenience, the grooves are emphasized and drawn thick in the drawings, but in reality, fine line-like grooves are sufficient.

The stator 21 and rotor 24 having the above configuration are connected to each other through small openings a to j and grooves a′, a″, f′,
f'' and bridging grooves A to G on the rotor side face each other in airtight contact as shown in FIG. , the position can be changed to the states shown in Figs. 6 to 8. These figures show that liquid passages for eluent T, sample S, and sample R are formed by alignment of the small opening and the groove. This is a schematic representation of the current state.

In this example, the above-mentioned small openings a to j have the following relationships with external attachment devices and the like. a is an eluent outlet, which is connected so as to be able to selectively communicate with a flow injection system and a liquid chromatography analysis line. f is the eluent inlet, pump P
It is connected to an eluent tank (not shown) via. b and e are connected to both ends of the sample loop 30. Also, j and g at symmetrical positions are the reagent loop 31
connected to both ends of the C and d constitute two points in the sample filling circuit, one of which c is connected to the sample container 32, and the other d is connected to a suction pump (not shown). Similarly, i and h located at symmetrical positions are connected with i to the reagent container 33 and h to a suction pump (not shown).

FIG. 6 shows a state in which the stator and rotor are aligned in one position (neutral position), which is the liquid filling mode, and this becomes the reference position of the liquid injection device. In this state, small openings a and f
The bridging groove A on the rotor side is the groove a'' on the stator side,
f'', a liquid passage of f→f''→A→a''→a is formed, and the eluent is in a steady flow by pump P.

In addition, the small openings b, c, d, and e of the sample system are formed by bridging grooves C and D from c→C→b→loop 30→e→D→
A liquid passage d is formed, and the loop 30 is filled with the sample from the sample container 32.

Similarly, the reagent system liquid path i→G→j→loop 31
→g→F→h, the reagent is filled into the loop 31.

In FIG. 7A, the rotor 24 is slidably rotated relative to the stator 21 in the counterclockwise direction in the figure (hereinafter, counterclockwise rotation in the figure is referred to as forward rotation, and clockwise rotation is referred to as reverse rotation), and the rotor 24 is moved to the second position ( This figure shows a state in which the liquid passage is changed to the forward rotation position (normal rotation position), and the liquid passage is changed as follows by this rotation. That is, the bridging groove A is out of alignment with the grooves a'' and f'' on the stator side, and direct communication with the eluent is therefore cut off.

Further, as the bridging grooves B, C, and D rotate, the communication relationship between the small openings b to e of the sample system is changed as follows. That is, B is a groove a' on the stator side and a small opening b, C is a small opening c and d, and D is a small opening e and a groove f' on the stator side. Therefore, this liquid path becomes f→f'→D→e→loop 30→b→B→a'→a between the inlet and outlet of the eluent, and the sample is injected into the flow of the eluent. It turns out.

In addition, the alignment of the small openings g to j of the other reagent system and the bridging grooves E, F, and G on the rotor side was changed, and the liquid passage was formed from f→f′→ between the eluent inlet and outlet.
E→g→loop 31→j→G→a′→a, and the reagent is injected into the eluent flow.

As a result, in the injection mode at the second position, the eluent is divided into two at the inlet f,
One goes through loop 30 and the other goes through loop 31
, and are merged at the outlet f, and these liquid passage changes occur in a complete cycle and the merging is caused by a single eluent flow, making it possible to achieve extremely accurate "merging zone type" two-liquid simultaneous processing. Injection will be accomplished.

Moreover, in this injection mode in this example, if the filling amount of the left and right loops 30 and 31 in the figure is set slightly larger for the latter reagent side, the seventh
Injection format as shown in Figure B, that is, sample S
The sample is injected in a state where it is surrounded by the reagent R, and the effect is obtained that the reaction between the sample and the reagent can be carried out favorably as a whole.

FIG. 8A shows a state in which the rotor 24 is slidably rotated (reversely rotated) in the clockwise direction in the figure relative to the stator 21, and these are switched to the third position (reversely rotated position). , Due to this rotation, the liquid passage is changed in a manner similar to that shown in FIG. 7 above.

That is, the communication of the eluent immediately through the bridging groove A is cut off, and the sample system changes from f→f'→E→e→
A liquid passage of loop 30→b→C→a′→a is formed to communicate the inlet f and outlet a of the eluent system.

However, in the reagent system, the small opening j at one end of the loop 31 is not bridged, and the liquid passage of this system is blocked at j of f→f'→F→g→loop 31→j. Does not cause liquid flow. this is,
This occurs because no bridging groove is provided between bridging grooves A and G in the rotor shown in FIG. 5A.

As a result, in the injection mode at the third position, only the sample in the loop 30 is injected into the eluent, and the sample S is injected into the eluent as a "plug flow" as shown in FIG. injection is realized.

In addition, in the above description, the lengths of bridge grooves B to G, the arrangement of small openings a to j, and the grooves on the stator side, especially
It goes without saying that the lengths a' and f', as well as the rotational angles at which the rotor is switched from the first position to the second and third positions, are set to suit the respective operations described above. .

According to this embodiment described above, by rotating the rotor by selecting forward or reverse from the first position, which is the liquid filling mode, the stator and rotor are rotated to the second position or the third position. By simply switching the combination relationship), it is possible to inject only the sample into the eluent, or to simultaneously inject the sample and reagent in a ``merging zone type'' system, although the operation is extremely simple. First, it has an excellent function of being able to select two modes of injection, and the structure of the device itself is only a single valve mechanism, so its usefulness is extremely great.

(Modifications and Applications of the Invention and Their Effects) The present invention is not limited to the embodiments described above, and various embodiments can be considered. For example, as already stated, as shown in FIGS. If the liquid injection device shown in FIG. 8 is only capable of switching the position between FIG. 6 and FIG. 7A, and the position switching to FIG. This is a "merging zone type" dedicated device for simultaneous injection of two liquids, and in this case, there is another bridge between the bridge grooves A and G of the rotor shown in Figure 4A. It is possible to use a rotor with symmetrical bridging grooves as a whole without any problem.

Furthermore, the grooves formed on the stator and rotor are actually fine linear grooves, and the rotor, which is usually made of polyimide, Teflon, etc., is pressed against the stator with a sufficiently large pressing force. Therefore, it is possible and easy to draw various grooves geometrically as long as there is no hindrance to liquid flow. Various groove shapes and small opening arrangements can be considered for a device that can be used in the mode of simultaneous injection of two liquids, or a multifunctional device that can be used in conjunction with the mode of injecting only one liquid.

Figures 9A and 9B show a stator (Figure A) and a rotor (Figure B) as examples of such deformation.
Also, Figure 10 shows the filling mode at the neutral position (Figure A),
The two-liquid simultaneous injection mode in the forward rotation position (Figure B) and the one-liquid injection mode in the reverse rotation position (Figure C) are shown, respectively.

In addition, the above figures 3 to 8 and 9
The embodiments shown in Figures and Figure 10 are for the case where n = 3 small openings formed in the stator (or rotor), but this is also possible when n = 4, 5 or more. , and in Figure 11 I to H, n=
4, FIG. 12 A to D show the case where n=5.

Fig. 11 A shows the stator, B shows the rotor, and when these are combined, the liquid passage is switched between the neutral position, the normal rotation position where the rotor is rotated counterclockwise, and the opposite rotation position becomes as follows. Note that h is the inlet of the first liquid system, and a is the outlet.

(Neutral position) First liquid system (): h→h'→A→a'→a Other liquid systems (,,): Fill each loop (forward rotation position: rotate the rotor 20 degrees counterclockwise in the figure) rotate) Therefore, if the loops of each liquid are the same length (L〓=L〓=L〓), the mode of liquid injection will be as shown in Fig. 11C, and if L〓=〓+L〓, then 1st
Figure 1 becomes d.

(Reverse rotation position) Therefore, the mode of liquid injection is as shown in FIG. 11(e).

Note that injecting the liquid at the forward rotation position in this case is effective for diluting the liquid or analyzing a sample that requires a two-step reaction.

Figure 12 also shows the same relationship for n=5 liquids,
, is shown below. However, the inlet of the first liquid system is j, and the outlet is a.

(Neutral position) 1st liquid system (): j → j' → A → a' → a Other liquid systems (,,,): Fill each loop (forward rotation position: rotate the rotor counterclockwise in the figure 16 ° rotation) (Reverse rotation position) The manner of liquid injection in the cases shown in FIGS. 12A and 12B is as shown in FIG. 12C in the forward rotation position and as shown in FIG. 12D in the reverse rotation position.

The liquid injection device of the present invention is applied to sample analysis such as flow injection analysis.
For example, it can be used to appropriately supply necessary reagents in a reaction system that performs a reaction using transmitted reagents.

(Effects of the Invention) As described above, the liquid injection device according to the present invention has a simple structure as a “merging zone type” for simultaneous injection of two or multiple liquids.
The operation is extremely easy, and the injection can be performed accurately.Furthermore, in a device that allows the injection mode to be selected in two ways, different injection modes can be selected as appropriate with one device. The fact that it can be adopted is even more important, and its usefulness is extremely great.

It goes without saying that if the reagent is replaced with water or the like, the sample can be injected and delivered while being diluted.

[Brief explanation of drawings]

Figure 1 is a diagram showing an example of a liquid injection device using a known six-way valve, Figure 2 A and B are diagrams each showing a mode of two-liquid injection, and Figure 3 is a diagram showing an example of an embodiment of the present invention. A schematic diagram of the liquid injection device, FIG. 4A is a front view of the stator, FIG.
Figure 5 A is a front view of the rotor, and Figure 5 A is a front view of the rotor.
6 to 8 are diagrams showing the state of liquid passage formation accompanying the switching of the positions of the stator and rotor in the embodiment shown in FIG. 3, and FIG. A front view showing the stator and rotor of another example of
Figure 10 A, B, and C are diagrams showing the state of liquid passage formation accompanying the position switching of the stator and rotor shown in Figure 8. 1st
An explanatory diagram of the case where the four liquids are injected into the flow of the first liquid. FIGS. DESCRIPTION OF SYMBOLS 1... Eluent tank, 2... Pump, 3, 5... Channel, 4... Hexagonal valve, 6... Column, 7... Detector, 8... Loop, 9... Sample container, 10... …
Pump, 21... Stator, 22... Rotor case, 23... Bolt, 24... Rotor, 25...
Rotation drive disk, 26...Spring, 27...Rotation drive shaft, 28...Operation handle, 29...Pipe, 30
... Sample loop, 31 ... Reagent loop, 32 ...
Sample container, 33... Reagent container, S... Sample, R...
...Reagent, T...Eluent.

Claims (1)

[Scope of Claims] 1. A stator and a rotor, each of which has a pair of airtight opposing surfaces that can be switched to a first and a second position by sliding rotation at a certain angle;
A plurality of small openings belonging to each of the second and third liquid systems are provided, and a plurality of bridging grooves that are selectively aligned with these small openings and complementary to the liquid passages of each system are provided in the pair of said small openings. A liquid injection device provided on opposing surfaces, characterized in that by switching the positions of the stator and rotor, the communication relationship of the liquid passages in each system can be changed to the following A and B. The one-component system is for the eluent and has small openings at the inlet and outlet of the liquid passage, which are communicated by a bridging groove in a first position and blocked in a second position. The second liquid system is for the sample liquid, and the third liquid system is for the reagent liquid or dilution water, each having two small openings connected to both ends of the liquid measuring tube of each system,
These small openings for each system are communicated with the liquid filling circuit of each system by the bridging groove at the first position, and communicated with the inlet and outlet of the first liquid system at the second position, respectively. 2 A stator and a rotor whose pair of airtight opposing surfaces slide and rotate at a fixed angle to be able to switch from the first position to the second and third positions in the forward and reverse rotation directions, A plurality of n (n is an integer of 3 or more) small openings belonging to each liquid system are provided on the opposing surface, and are selectively aligned with these small openings to complementarily form liquid passages for each system. The liquid injection device is provided with a plurality of bridging grooves on the pair of opposing surfaces, and the communication relationship of the liquid passages in each system is changed to the following A and B by switching the positions of the stator and rotor. Characteristic liquid injection device A The first liquid system, which is one of the n liquid systems, is for eluent and has small openings as an inlet and an outlet of a liquid passage. They are communicated by a bridging groove at the first position, and are blocked at the second and third positions. Of the (n-1) other liquid systems other than the first liquid system, one is for the sample liquid. and the other is for reagent solution or dilution water, and has two small openings connected to both ends of the liquid measuring tube of each system, and these two small openings of each system are connected to the first one. At the position, the bridge groove communicates with each liquid filling circuit, at the second position, the inlet and outlet of the first liquid system are connected, and at the third position, only some of the other liquid systems are connected. It communicates with the inlet and outlet of the first liquid system. 3. The liquid injection device according to claim 2, wherein n is 3.