WO2008004550A1 - Liquid analyzer - Google Patents

Liquid analyzer Download PDF

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Publication number
WO2008004550A1
WO2008004550A1 PCT/JP2007/063303 JP2007063303W WO2008004550A1 WO 2008004550 A1 WO2008004550 A1 WO 2008004550A1 JP 2007063303 W JP2007063303 W JP 2007063303W WO 2008004550 A1 WO2008004550 A1 WO 2008004550A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid
transported
flow
electrode
capturing means
Prior art date
Application number
PCT/JP2007/063303
Other languages
French (fr)
Japanese (ja)
Inventor
Kunio Harada
Sakuichiro Adachi
Hideo Enoki
Hironobu Yamakawa
Nobuhiro Tsukada
Original Assignee
Hitachi High-Technologies Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi High-Technologies Corporation filed Critical Hitachi High-Technologies Corporation
Priority to JP2008523689A priority Critical patent/JP4651715B2/en
Publication of WO2008004550A1 publication Critical patent/WO2008004550A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502769Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by multiphase flow arrangements
    • B01L3/502784Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by multiphase flow arrangements specially adapted for droplet or plug flow, e.g. digital microfluidics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/42Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/42Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B01F25/4317Profiled elements, e.g. profiled blades, bars, pillars, columns or chevrons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40Static mixers
    • B01F25/42Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B01F25/43197Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor characterised by the mounting of the baffles or obstructions
    • B01F25/431971Mounted on the wall
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30Micromixers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/06Fluid handling related problems
    • B01L2200/0673Handling of plugs of fluid surrounded by immiscible fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00Additional constructional details
    • B01L2300/06Auxiliary integrated devices, integrated components
    • B01L2300/0627Sensor or part of a sensor is integrated
    • B01L2300/0636Integrated biosensor, microarrays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00Additional constructional details
    • B01L2300/08Geometry, shape and general structure
    • B01L2300/0809Geometry, shape and general structure rectangular shaped
    • B01L2300/0816Cards, e.g. flat sample carriers usually with flow in two horizontal directions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00Additional constructional details
    • B01L2300/08Geometry, shape and general structure
    • B01L2300/0861Configuration of multiple channels and/or chambers in a single devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2400/00Moving or stopping fluids
    • B01L2400/04Moving fluids with specific forces or mechanical means
    • B01L2400/0403Moving fluids with specific forces or mechanical means specific forces
    • B01L2400/0415Moving fluids with specific forces or mechanical means specific forces electrical forces, e.g. electrokinetic

Definitions

  • the present invention relates to an analyzer that detects the amount of a component contained in a sample.
  • the present invention relates to analysis techniques with very small samples.
  • a sample and a reagent are conventionally dispensed into a plastic or glass reaction container, and the mixture is mixed to irradiate light into a sample solution to measure the amount of components. It was. However, in recent years, a small amount of sample solution used for analysis has been demanded in order to reduce reagent costs and environmental burden.
  • Patent Document 1 As a method for transporting a very small amount of liquid, there is a technique for controlling the propagation of the liquid by injecting oil segmented with the liquid into the microchannel (for example, Patent Document 1). In addition, there is a technique for preventing mixing of an aqueous solution sample by introducing an immiscible liquid segment, an air segment, and a sample segment into a conduit using a piston or the like (for example, Patent Document 2). Furthermore, there is a technique for introducing a droplet into a hydrophobic liquid and electrostatically inducing the droplet to sort the droplet (for example, Patent Document 3).
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2003-200041
  • Patent Document 2 U.S. Pat.No. 4,259,291
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-37346
  • Patent Document 4 U.S. Pat.No. 4,390,403
  • the object of the present invention is to accurately transport a minute liquid and to accurately capture a sample or the like at a measurement position for analysis.
  • the liquid capturing means is used when the micro liquid is driven by the flow of the transport medium and the micro liquid is stopped at a desired position.
  • the liquid analyzer includes an introduction port for introducing the liquid to be transported, a medium flow generating section that generates a circulation flow for the transport medium for transporting the liquid to be transported, and the transported liquid.
  • a measuring unit that measures the liquid to be transported, and the transport liquid capturing means has a maximum width in a plane substantially perpendicular to the flow direction of the transport medium, and the transport of the flow path. Maximum width in a plane substantially perpendicular to the flow direction of the working medium It is characterized by Richi / J.
  • the liquid analysis method includes a first step of introducing the first transported liquid from the introduction port, and a first process of transporting the first transported liquid in the flow path by the flow of the transport medium.
  • One of the first transported liquid and the second transported liquid and the one captured by the transported liquid capturing means is brought into contact with the other transported liquid.
  • the micro liquid is transported by the flow of the transport medium, it is possible to reliably transport the micro liquid regardless of the difference in liquid properties. Further, when performing analysis and detection while transporting a sample, it is possible to determine the position by capturing a micro liquid such as a sample without stagnation of the flow of the transport medium. Thus, analysis and detection can be performed in parallel while transporting a plurality of micro liquids in parallel.
  • FIG. 1 to 6 are schematic views showing the configuration of the liquid analyzer
  • FIG. 1 is a plan view seen through the second substrate 5
  • FIG. 2 is taken along the line AA in FIG.
  • Fig. 3 is a cross-sectional view from the front side
  • Fig. 3 is a cross-sectional view from the side along B-B in Fig. 1
  • Fig. 4 is a cross-sectional view from the plane side along CC in Fig. 2.
  • FIG. 5 is a three-dimensional view of the whole
  • FIG. 6 is a three-dimensional view of the components shown in FIG.
  • the liquid analyzer in the present embodiment mainly includes the first substrate 1, the outer spacer 2, the inner spacer 3, the stirring mechanism 4, the second substrate 5, and the introduction port from the lower side.
  • Cylinder 6, medium flow generation unit 7, transported liquid recovery unit frame It consists of 8 parts, and after lamination, it is joined so that the liquid to be transported and the transport medium do not leak from the internal space.
  • the stirring mechanism 4 in the present embodiment represents structures (fins) for deforming and bonding the transported liquid side by side.
  • An agitation mechanism such as an ultrasonic agitation mechanism, a screw mechanism, or a mechanism that rotates a member such as a spatula may be used.
  • the medium flow generation unit 7 generates a liquid flow for a transfer medium for transferring a sample or the like. It is a part that has a pump or waterwheel-like member inside that discharges the medium taken in from one end and discharges it from the other end, and circulates in the medium, and the principle for generating the flow is not questioned.
  • the flow rate may be controllable according to the flow load.
  • the first substrate 1 has a transported liquid capturing means 9 for capturing a transported liquid such as a sample and a waste liquid capturing means 10 for capturing a waste liquid.
  • the transported liquid catching means 9 is arranged downstream of the introduction port cylinder (introduction port) 6 in the flow direction of the transport medium when the medium flow generation unit is regarded as the starting point in the flow direction of the transport medium.
  • the first substrate 1 and the second substrate 5 are made of a material that transmits light of a necessary wavelength for liquid transportation described later and detection of the amount of components contained in the sample. Only the portion of the substrate 1 and the second substrate 5 corresponding to the position of the transported liquid capturing means 9 may be a material that transmits light. Further, the transported liquid capturing means 9 is composed of an electrode, an electret region, or a combination of an electret region and an electrode, and is similar to the first substrate 1 and the second substrate 5. A material that transmits light is used. In the first embodiment, an example in which an electrode is used for the transported liquid capturing means 9 will be described. Therefore, the electrode is patterned on all the positions of the transported liquid capturing means 9 on the upper surface of the first substrate 1 shown in FIG.
  • insulating film of about 1 ⁇ m force and about 100 ⁇ m, and the surface of the insulating film is treated with water repellent treatment.
  • insulator material fluorine-based resin, SiO (quartz), SiN, Al 2 O (alumina), HfO are used.
  • Electrode materials include ITO, SnO, ZnO, ZnO + AlO + GaO.
  • Each electrode is arranged independently
  • each electrode is connected like the electrode 11 shown in FIG. 7, and is patterned so as to have the same potential.
  • the surface of the second substrate 5 shown in FIG. The counter electrode 12 is provided on the part of the electrode facing position or on the surface including all of the electrodes, and the surface is covered with an insulating film of about 0 .: L m to 100 m like the electrode, and further the insulating film The surface is treated with water repellency.
  • the counter electrode 12 that does not require the counter electrode 12 is not used, the liquid to be transported can be controlled with a simple configuration using only the electrode on the first substrate.
  • the drawing is simplified for easy folding, and the electrode and the counter electrode 12 are illustrated as being embedded in the first substrate 1 and the second substrate 5, respectively.
  • the configuration of the electrode of this example is patterned so that the electrode has the same potential as described above.
  • substantially only a pair of the electrode and the counter electrode 12 is provided.
  • one substrate is provided with an electrode group that is a plurality of separated electrodes that are turned on and off in synchronization by being supplied with the same potential, and the other substrate is connected to the electrode group.
  • Opposing electrodes are provided, and the electrode group and the opposing electrode form a pair of electrode groups.
  • the flow path 13 is a space 16 having a substantially rectangular cross section in the direction perpendicular to the flow except for the transported liquid recovery part 14 and the inlet 15.
  • a portion of the space 16 in the flow path 13 used for analysis and / or detection of the liquid to be transported is shown as an analysis region 17 in FIG.
  • the width W and height H, which are dimensions of a substantially rectangular cross section in the direction perpendicular to the flow, of the flow path 13 in the analysis region 17 are as shown in FIG.
  • the flow path of the liquid analyzer is filled with a transport medium in advance. (Filling of the transport medium 18 can be performed from the waste liquid port, for example, using the waste liquid port as the transport medium inlet / outlet port.) At that time, in order not to leave bubbles in the flow path 13, The flow path 13 and the medium flow generation section 7 are filled with the transfer medium 18 so that bubbles do not enter the flow path 13 after the flow is generated in the transfer medium 18 by the generation section 7.
  • the transported liquid capture means 9 is closer to the transport medium 18 than the liquid level. It is introduced so that the liquid level of the transport medium 18 in the transported liquid recovery unit 14 which is not located is the top.
  • the gas phase region that is not filled with the transport medium 18 and is in contact with the transport medium 18 may remain. Thereby, when bubbles are mixed at the time of introduction, the bubbles can be removed by letting gas escape to the gas phase region.
  • the transport medium to be used is silicone oil or fluorine-based oil or the like, which is a liquid having a dielectric constant lower than that of the transported liquid and does not react with the transported liquid. Thereafter, the medium flow generator 7 is driven to generate a flow as indicated by an arrow in FIG. The speed of the flow is a force that varies depending on the reaction time and measurement time at the time of analysis.
  • 8A to 8D are enlarged views of the introduction port and a part of the transported liquid capturing means 9 of FIG. 2, and the steps from the introduction of the sample and the reagent to the mixing are arranged in chronological order and are represented by a plurality of diagrams. .
  • the switch (voltage application control means) 19 is turned on, and a voltage is applied between the electrode 11 that is the transported liquid capturing means 9 and the counter electrode 12.
  • the first transported liquid 20 as the sample to be analyzed is introduced into the flow path 13 in the analysis region 17 from the inlet 15 using a pipetter (introducing means) 21 or the like.
  • the introduced first transported liquid 20 is attracted by the force of the force electrode 11 caused by the flow of the transport medium 18 and is captured on the electrode 11 as the transported liquid capturing means 9 as shown in FIG. 8B.
  • the second transported liquid 22, which is a reagent for analyzing the first transported liquid 20, is transferred from the inlet 15 to the analysis region 17 using a pipetter 21 or the like. Introduce into the channel 13.
  • the introduced second transported liquid 22 is caused to flow by the flow of the transport medium 18, but “is attracted by the electrostatic force of the electrode 11 and is captured by the electrode 11 as the transported liquid capturing means 9 as shown in FIG. 8D.
  • Mix with the first transported liquid 20 that has already been captured, where the pipettor for introducing the sample and the pipetter for introducing the reagent may be the same or different. Note that the order of introduction of the first transported liquid and the second transported liquid may be shifted first.
  • FIG. 9A and 9B are enlarged views of the introduction port and a part of the transported liquid capturing means 9 in FIG. 2, and the processes from mixing of the sample and reagent to analysis are arranged in time series and expressed in multiple diagrams. Speak.
  • the switch 19 is turned off, and the voltage applied between the electrode 1 1-1 as the transported liquid capturing means 9-1 and the counter electrode 12 is released and the electrode is released.
  • a voltage is again applied between the electrode 11-2 which is the transported liquid capturing means 9-2 and the counter electrode 12.
  • the first transported liquid 20 and the second transported liquid 22 are caused to flow by the flow of the transport medium 18, and are stirred by being subjected to physical deformation through the stirring mechanism 4 to become the reaction liquid 23.
  • the first transported liquid 20 and the second transported liquid 22 are attracted by the electrostatic force of the electrode 11-2, and as shown in FIG. 9B, the second transported liquid capturing means 9-2 Captured on some electrode 11-2.
  • a light source 25 and a light receiving unit 26 are arranged corresponding to the second transported liquid capturing means 9-2 and the positions corresponding to the transported liquid capturing means 9 subsequent to the second transported liquid capturing means 9-2.
  • the measurement light 27 is irradiated from the light source 25 through the second substrate 5, the reaction solution 23, and the first substrate 1, and is detected by the light receiving unit 26.
  • the components of the reaction solution 23 are analyzed, and as a result, the amount of the specific component contained in the first transported liquid 20 that is the sample to be analyzed is measured. can do.
  • the reaction results are measured by measuring the reaction proceeding in the reaction solution 23 over time, and finally determining the amount of the components. Then, in order to supply samples and reagents one after another into the liquid analyzer and sequentially analyze the components, switch 19 is repeatedly turned on and off, and reaction solution 23 is moved between the measurement units one after the other to measure. Do. As a result, multiple sample measurements can be performed in parallel, improving the throughput of the apparatus. At that time, when the reaction liquid 23 is present in each of the plurality of transported liquid capturing means 9, the electrode 11 is electrically integrated, so that the switches are turned off all at once, depending on the location of the flow path in the analysis region 17.
  • reaction liquids cannot be separated from the transported liquid capturing means 9 at the same time due to the difference in flow velocity.
  • a voltage is applied to the transported liquid capturing means 9 after the switch is turned off and all the reaction liquids 23 are separated, the timing at which each reaction liquid 23 is separated or each reaction liquid 23 is subjected to the next reaction. Even if the timing of reaching the transport liquid capturing means 9 is different, each reaction liquid can be reliably moved and captured.
  • FIGS. 10A to 10D are enlarged views of the display orientation of FIG. 3 returned to the horizontal direction.
  • the reaction liquid 23 for which the measurement has been completed is released from the capture of the last transported liquid capturing means 9 and is flowed to the position of FIG. 10A by the flow of the transport medium 18.
  • the height of the transported liquid recovery unit 14 is larger than the height H of the flow path 13, so that the first substrate 1 and the second substrate 5 are sandwiched until then.
  • the reaction liquid 23 becomes the waste liquid 28 in principle.
  • the diameter d of the waste liquid 28 that has been crushed into a disk shape and released into a spherical shape is larger than the height H, which is the gap between the first substrate 1 and the second substrate 5, so that the flow path 13 is closed. None enter the space 16 again. If the waste liquid 28 has a specific gravity smaller than that of the transport medium 18, it floats up in the transported liquid recovery unit 14, and is collected by suction with a sipper 29 or the like as shown in FIG. 10C.
  • the waste liquid 28 If the waste liquid 28 has a specific gravity greater than that of the transport medium 18, it will settle in the transported liquid recovery section 14, and is collected by suction with a sipper (collection means) 29 as shown in FIG. 10D.
  • a sipper (collection means) 29 When the waste liquid 28 has a specific gravity greater than that of the transport medium 18 and precipitates, a plurality of waste liquids 28 are collected into a large lump, and the closed space of the flow path 13 that is the gap between the first substrate 1 and the second substrate 5 Since there is a possibility of re-entering 16, it is preferable to provide a sedimentation portion 30 that is a depression region as shown in FIG. 10D.
  • the waste liquid trapping means 10 is for increasing the waste liquid trapping effect based on the same principle as the transported liquid trapping means 9 and is provided at a location on the top surface of the first substrate 1 where the transported liquid recovery unit 14 is located. It is In the case where an electrode is used for the waste liquid capturing means 10, the waste liquid is optically disposed by providing a measuring portion (not shown) similar to the above at a position corresponding to the waste liquid capturing means 10 with light transmission. It is possible to detect the amount.
  • FIG. 11 shows an enlarged part of the analysis region 17 in FIG.
  • the width X of the transported liquid capturing means 9 is smaller than W with respect to the width W of the flow path 13 in the analysis region 17, that is, W> X. Yes.
  • the maximum width of the transported liquid capturing means 9 is smaller than the maximum width of the flow path 13 in a plane substantially perpendicular to the direction of the transport medium flow. This is to prevent the transported liquid from blocking the flow path 13 when the transported liquid is captured by the transported liquid capturing means 9.
  • the liquid to be transported that has entered the flow path 13 in the analysis area 17 is sandwiched between the first substrate 1 and the second substrate 5. It is crushed into a disk with a diameter of D and a height of H.
  • the diameter D of the liquid to be transported is equal to the diameter D of the first liquid to be transported 20 which is a sample to be analyzed and the diameter D of the second liquid to be transported 22 which is a reagent.
  • the diameter D of the reaction liquid 23 after mixing and stirring the first transported liquid 20 and the second transported liquid 22 that are smaller than the width X of the liquid 13 and the width of the flow path 13 It is set to be smaller than W. That is, the maximum width of the reaction solution 23 is smaller than the maximum width of the flow path 13 on a surface substantially perpendicular to the direction of the flow of the transfer medium.
  • the width X of the transported liquid capturing means 9 is larger than the width W of the flow path 13 in the analysis region 17, if the diameter D of the transported liquid is small, the transported liquid stagnates on the spot. However, since the transport medium flows from the side, the transport medium does not stagnate. However, in this case, the transported liquid moves within the width X of the transported liquid capturing means 9, and the position in the width X direction is not fixed. Therefore, the measurement light 27 is not reliably irradiated to the reaction solution 23 at the measurement position, and the analysis accuracy is lowered.
  • the diameter D of the liquid to be transported is smaller than the width X of the liquid transport capturing means 9, the location is not fixed as described above.
  • the diameter D is smaller than the width X of the transported liquid capturing means 9.
  • its diameter D is set to be approximately the same as width X, and the first transported liquid captures the transported liquid. As long as it is on the means 9, the second liquid to be transported can come into contact with the first liquid to be mixed.
  • the transport medium is circulated inside the apparatus, and the liquid to be transported is transported in the circulation flow, thereby mixing with the reagent to be analyzed, stirring, moving to the measuring section, and collecting section. It is possible to automate the movement to a high speed with a simple configuration.
  • Example 2 In this embodiment, an electrode is used for the transported liquid capturing means 9 in the first embodiment, whereas an electret insulator is used for the transported liquid capturing means 9.
  • a part of the insulating film is an electret region.
  • the configuration in the present embodiment is basically the same as that in the first embodiment except for the wiring such as the electrode 11, the counter electrode 12, and the switch 19 for applying a voltage.
  • the liquid to be transported is captured in the region 31 in which only the range of the transported liquid capturing means 9 as shown in FIG.
  • An electret toy is a state in which a high voltage is applied while heating a polymer material so that the magnetic material is magnetized to the north and south poles, or is charged semipermanently by corona discharge (for example, Non-patent document 1). If electretized areas are used, polarization can be maintained as shown in Fig. 12A without a power supply.
  • the medium flow generation unit 7 The flow rate is controlled by the flow rate control unit, and the flow is temporarily generated so that the attractive force in the flow direction of the medium is captured and temporarily stronger than the electrostatic force.
  • the medium flow rate control unit performs control such as speeding up the rotation of the pump.
  • an electrode, a power source for applying a voltage to the electrode, and a control mechanism for the electrode are not required, so that the structure can be simplified and the cost can be reduced.
  • Non-Patent Document 1 Proceedings of the 9th Japan Power Society Energy Technology Symposium
  • the region where one electret is seen as viewed from the counter electrode and the region occupied by one electrode are arranged so as to at least partially overlap.
  • Example 1 the voltage is continuously applied between the electrode 11 and the counter electrode 12 while the transported liquid is captured, but in this example, as shown in FIG.
  • Example 2 the liquid to be transported is captured in the region where the electret is trapped, and a voltage that temporarily cancels electretization is applied between the electrode 11 and the counter electrode 12 as shown in FIG. 13B. Then, the captured transported liquid is released.
  • each reaction solution cannot be separated from each transported liquid capturing means 9 at the same time due to the difference in flow rate depending on the location of the flow path in the analysis region 17. It is possible. However, if the switch is turned off when the switch is turned on and all the reaction liquids 23 are separated, the next transported liquid capturing means 9 is already in a state where it can capture the reaction liquid 23. Even if the timing at which the reaction solution 23 is separated or the timing at which each reaction solution 23 reaches the next transported liquid capturing means 9 is different, each reaction solution can be reliably moved and captured.
  • the droplets are transported by the oil flow, captured by the electret toy region, and opened by voltage application. It is possible to extend the lifetime of the insulating film disposed on the electrode by reducing the time for applying the voltage to the electrode.
  • FIG. 14 shows an example of this.
  • a plurality of inlets and a plurality of analysis regions 17 are respectively arranged in branch paths that are branches.
  • the difference between this example and Example 1 to Example 3 is that it has a plurality of analysis regions 17 used for analyzing the liquid to be transported. That is.
  • the electrode shape is a force that allows a plurality of objects having the shape shown in FIG. 7 to be provided in the number of the analysis regions 17 as shown in FIG.
  • it may be integrated as shown in Fig. 15B, and parallel analysis may be performed almost simultaneously.
  • the shape of the transported liquid capturing means 9 of the electrode 11 can be round or square.
  • the electrode as in Example 3 may be used, as in Example 2 where an electrode may be used, as in Example 2, or an electret-cut area may be used. Or use a combination of the electret area and the combined area.
  • a plurality of analyzes can be performed in parallel in each of the plurality of regions.
  • the width X of the transported liquid capturing means is larger than W with respect to the width W of the flow path in the analysis region, so that the transported liquid is captured by the transported liquid capturing means.
  • the transported liquid does not block the flow path.
  • the transport medium overflows from the flow path and enters another flow path, disturbing the flow of the transport medium not only in one flow path but also in a plurality of flow paths.
  • FIG. 1 is a plan view showing a configuration of a liquid analyzer according to the present invention.
  • FIG. 2 is a cross-sectional view from the front showing the configuration of the liquid analyzer according to the present invention.
  • FIG. 3 is a cross-sectional view from the side showing the configuration of the liquid analyzer according to the present invention.
  • FIG. 4 is a cross-sectional view from the plane side of the liquid analyzer according to the present invention.
  • FIG. 5 is a three-dimensional view of a liquid analyzer according to the present invention.
  • FIG. 6 is a three-dimensional view showing the components shown in FIG. 5 in an exploded manner.
  • FIG. 7 is a diagram showing only electrodes of the liquid analyzer according to the present invention.
  • FIG. 8A is a partially enlarged view of a part of the transported liquid capturing means from the introduction locus in FIG.
  • FIG. 8B is a partially enlarged view of the introduction locus from FIG. 2 to a part of the transported liquid capturing means.
  • FIG. 2 is a partially enlarged view of the introduction locus of FIG. 2 up to a part of the transported liquid capturing means.
  • the introduction locus in FIG. 2 is also a partially enlarged view of a part of the transported liquid capturing means.
  • FIG. 9 is a partially enlarged view of the introduction locus of FIG. 2 and a part of the transported liquid capturing means.
  • FIG. 9 is a partially enlarged view from the introduction locus of FIG. 2 to a part of the transported liquid capturing means.
  • FIG. 10A is an enlarged view of the display orientation of FIG.
  • FIG. 10B is an enlarged view of the display orientation of FIG.
  • FIG. 10C is an enlarged view of the display orientation of FIG.
  • FIG. 10D is an enlarged view of the display orientation of FIG.
  • FIG. 11 is a partially enlarged view of the analysis region 17 in FIG.
  • [12A] Enlarged view of a cross section using an electretized insulator for the liquid feed capturing means.
  • [12B] An enlarged view of a cross section using an electretized insulator for the liquid feed capturing means.
  • FIG. 13A is an enlarged view of a cross section in which an insulator electretized and an electrode are used in combination for the liquid feed capturing means.
  • FIG. 13B is an enlarged view of a cross section in which an insulator electretized and an electrode are combined in the liquid feeding capturing means.
  • FIG. 14 is a plan view showing the configuration of a liquid analyzer according to the present invention, which is an example having a plurality of analysis regions.
  • [15A] A diagram showing an example of the electrode shape of the liquid analyzer shown in FIG.
  • FIG. 15B A diagram showing an example of the electrode shape of the liquid analyzer shown in FIG.

Abstract

A liquid analyzer in which fine liquid droplets are moved by means of a flow of a transporting medium and the fine liquid droplets are mixed/stirred and are measured through capture in a desired position. Thus, fine liquid droplets which are difficult to transport can be accurately transported, and the sample combined with a reagent can be captured and analyzed in a measuring position.

Description

明 細 書  Specification
液体分析装置  Liquid analyzer
参照による取り込み  Import by reference
[0001] 本出願は、 2006年 7月 5日に出願された日本特許出願第 2006— 185106号の優 先権を主張し、その内容を参照することにより本出願に取り込む。  [0001] This application claims the priority of Japanese Patent Application No. 2006-185106 filed on Jul. 5, 2006, and is incorporated herein by reference.
技術分野  Technical field
[0002] 本発明は、試料中に含まれる成分量を検出する分析装置に関する。特に、微少量 の試料での分析技術に関する。  The present invention relates to an analyzer that detects the amount of a component contained in a sample. In particular, the present invention relates to analysis techniques with very small samples.
背景技術  Background art
[0003] 試料中に含まれる成分量を検出する分析にお!、ては、ハロゲンランプ等からの白 色光を試料溶液に照射し、試料溶液を透過してきた光を回折格子で分光して必要な 波長成分を取り出し、その吸光度を割り出すことで目的の成分量を測定する分光分 析技術が広く用いられている。また光照射系については、白色光を回折格子で分光 した後、試料溶液に照射する手法や、多波長光度計を用いる手法も使用されている 。これらの技術に基づく分析装置においては、従来、プラスチックやガラスの反応容 器内に試料と試薬を分注し、これらを混合して試料溶液とした物に光を照射し、成分 量を測定していた。しかし、近年、試薬コストの削減や、環境への負荷低減のため、 分析に用いる試料溶液の微少量ィ匕が求められて 、る。  [0003] For analysis to detect the amount of components contained in a sample! It is necessary to irradiate the sample solution with white light from a halogen lamp, etc., and to split the light transmitted through the sample solution with a diffraction grating Spectral analysis techniques are widely used in which the wavelength component is taken out and the absorbance is determined to measure the amount of the target component. As for the light irradiation system, a method of irradiating a sample solution after separating white light with a diffraction grating and a method using a multiwavelength photometer are also used. In an analyzer based on these technologies, a sample and a reagent are conventionally dispensed into a plastic or glass reaction container, and the mixture is mixed to irradiate light into a sample solution to measure the amount of components. It was. However, in recent years, a small amount of sample solution used for analysis has been demanded in order to reduce reagent costs and environmental burden.
[0004] 微少量の液体を搬送する方式としては、マイクロチャネル内に液体とセグメントィ匕し たオイルを注入し、液体の伝搬を制御する技術がある(例えば、特許文献 1)。また、 導管に不混和性液体のセグメントと空気のセグメントと試料のセグメントをピストンなど を用いて導入し、水溶液試料の混合を防止する技術がある (例えば、特許文献 2)。 さらに、疎水性液体に液滴を導入し、液滴を静電誘導して液滴を選別などする技術 がある(例えば特許文献 3)。  [0004] As a method for transporting a very small amount of liquid, there is a technique for controlling the propagation of the liquid by injecting oil segmented with the liquid into the microchannel (for example, Patent Document 1). In addition, there is a technique for preventing mixing of an aqueous solution sample by introducing an immiscible liquid segment, an air segment, and a sample segment into a conduit using a piston or the like (for example, Patent Document 2). Furthermore, there is a technique for introducing a droplet into a hydrophobic liquid and electrostatically inducing the droplet to sort the droplet (for example, Patent Document 3).
[0005] 微小量の液体を操作する方式としては、複数の電極間に電圧を印加して生じた電 界にお 、て電界中の物質を分極させ、静電力により電界の集中する方向に移動させ る現象 (Dielectrophoresis)を利用する技術がある(例えば、特許文献 4)。 [0006] 特許文献 1:特開 2003— 200041号公報 [0005] As a method of operating a minute amount of liquid, a substance in an electric field is polarized in an electric field generated by applying a voltage between a plurality of electrodes, and moved in a direction in which the electric field is concentrated by electrostatic force. There is a technology that utilizes the phenomenon (Dielectrophoresis) (for example, Patent Document 4). [0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-200041
特許文献 2 :米国特許 4259291号  Patent Document 2: U.S. Pat.No. 4,259,291
特許文献 3:特開 2005 - 37346号公報  Patent Document 3: Japanese Patent Laid-Open No. 2005-37346
特許文献 4:米国特許 4390403号  Patent Document 4: U.S. Pat.No. 4,390,403
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 従来のプラスチックやガラスの反応容器に試薬や試料を分注する液体分析装置で は、試料溶液を微少量ィ匕すると、液の取り扱いが困難になり、また分注、混合時に発 生しうる気泡等により測定の精度が落ちるおそれがあった。  [0007] In a conventional liquid analyzer that dispenses reagents and samples into a plastic or glass reaction vessel, if a small amount of sample solution is added, it becomes difficult to handle the solution, and also occurs during dispensing and mixing. There was a risk that the measurement accuracy would be reduced by possible bubbles.
[0008] また、マイクロチャネルなどにオイルなどや試料を導入する場合には、マイクロチヤ ネルなどの内部で試料を捕捉すると、当該内部のオイルなどの流れも遮られてしま!/ヽ [0008] In addition, when oil or a sample is introduced into a microchannel or the like, if the sample is captured inside the microchannel or the like, the flow of oil or the like inside the microchannel is also blocked! / ヽ
、試料などの制御が困難となる。さらに、特許文献 2のように試料などの移送にピスト ンなどを用いる場合、ピストンを押して圧力を加えるため予めピストンを引いて導管に 負圧を与えると、その内部に気泡が発生しうるという問題がある。この場合には、正確 な試料溶液の搬送を妨害、試料溶液に光を照射して成分量を測定するときの気泡の 悪影響等の問題が生じうる。 It becomes difficult to control the sample. Furthermore, when using a piston or the like to transfer a sample or the like as in Patent Document 2, if a negative pressure is applied to the conduit by pulling the piston in advance in order to apply pressure by pushing the piston, bubbles may be generated inside it. There is. In this case, the accurate transport of the sample solution may be hindered, and problems such as adverse effects of bubbles may occur when measuring the component amount by irradiating the sample solution with light.
[0009] 本発明では、微小液体を的確に搬送し、かつ試料等を的確に計測位置で捕捉し、 分析をすることを目的として 、る。  The object of the present invention is to accurately transport a minute liquid and to accurately capture a sample or the like at a measurement position for analysis.
課題を解決するための手段  Means for solving the problem
[0010] 上記課題を解決するために、微小液体を搬送用媒体の流れにより駆動し、微小液 体を所望の位置で停止させるときに液体捕捉手段を用いる。 [0010] In order to solve the above problems, the liquid capturing means is used when the micro liquid is driven by the flow of the transport medium and the micro liquid is stopped at a desired position.
[0011] 液体分析装置としては、被搬送液体を導入するための導入口と、前記被搬送液体 を搬送させるための搬送用媒体について、循環の流れを生じさせる媒体流発生部と 、前記被搬送液体と前記搬送用媒体とが流れる流路と、前記流路の少なくとも一部 に設けられ、かつ、前記被搬送液体を捕捉する被搬送液体捕捉手段と、前記被搬送 液体捕捉手段に捕捉された被搬送液体にっ ヽて計測する計測部とを有し、前記被 搬送液体捕捉手段は前記搬送用媒体の流れの方向と実質的に垂直な面での最大 幅が、前記流路の前記搬送用媒体の流れの方向と実質的に垂直な面での最大幅よ りち/ J、さいことを特徴とする。 [0011] The liquid analyzer includes an introduction port for introducing the liquid to be transported, a medium flow generating section that generates a circulation flow for the transport medium for transporting the liquid to be transported, and the transported liquid. A flow path through which the liquid and the transport medium flow, a transported liquid capturing unit that is provided in at least a part of the flow path and captures the transported liquid, and is captured by the transported liquid capturing unit. A measuring unit that measures the liquid to be transported, and the transport liquid capturing means has a maximum width in a plane substantially perpendicular to the flow direction of the transport medium, and the transport of the flow path. Maximum width in a plane substantially perpendicular to the flow direction of the working medium It is characterized by Richi / J.
[0012] 液体分析方法としては、導入口より第 1の被搬送液体を導入する第 1の工程と、搬 送媒体の循環による流れで前記第 1の被搬送液体を流路内で搬送する第 2の工程と 、前記第 1の工程の後に前記導入口より第 2の被搬送液体を導入する第 3の工程と、 前記第 3の工程の後に前記搬送媒体の前記流れによって前記第 2の被搬送液体を 流路内で搬送する第 4の工程と、搬送された前記第 1の被搬送液体もしくは搬送され た前記第 2の被搬送液体の 、ずれかを第 1捕捉手段で捕捉する第 5の工程と、前記 第 1の被搬送液体もしくは前記第 2の被搬送液体の 、ずれかの一方であって前記被 搬送液体捕捉手段が捕捉したものと、前記 、ずれかの他方とを接触させて混合液体 とする第 6の工程と、前記混合液体を前記第 1捕捉手段もしくは第 2被搬送液体捕捉 手段で捕捉して計測する第 7の工程とを有することを特徴とする。  [0012] The liquid analysis method includes a first step of introducing the first transported liquid from the introduction port, and a first process of transporting the first transported liquid in the flow path by the flow of the transport medium. A second step of introducing a second liquid to be transported from the introduction port after the first step, and a second target by the flow of the transport medium after the third step. A fourth step of transporting the transport liquid in the flow path and a fifth step of capturing by the first capturing means whether the first transported liquid transported or the transported second transported liquid is shifted. One of the first transported liquid and the second transported liquid and the one captured by the transported liquid capturing means is brought into contact with the other transported liquid. A sixth step of converting the mixed liquid into the first capturing means or the second transported liquid. And having a seventh step of measuring captures in 捉 means.
発明の効果  The invention's effect
[0013] 本発明によれば、微小液体を搬送用媒体の流れにより搬送するため、微小液体の 液性の違いに関らずに確実な搬送が可能となる。また、試料を搬送しながら分析及 び検出をするのに際し、搬送用媒体の流れを停滞させることなく試料などの微小液 体を捕捉して位置を定めることができる。これにより、複数の微小液体を並列して搬 送させながら、分析と検出とを並行することができる。  [0013] According to the present invention, since the micro liquid is transported by the flow of the transport medium, it is possible to reliably transport the micro liquid regardless of the difference in liquid properties. Further, when performing analysis and detection while transporting a sample, it is possible to determine the position by capturing a micro liquid such as a sample without stagnation of the flow of the transport medium. Thus, analysis and detection can be performed in parallel while transporting a plurality of micro liquids in parallel.
本発明の他の目的、特徴及び利点は添付図面に関する以下の本発明の実施例の 記載から明らかになるであろう。  Other objects, features and advantages of the present invention will become apparent from the following description of embodiments of the present invention with reference to the accompanying drawings.
実施例 1  Example 1
[0014] 図 1から図 6は液体分析装置の構成を示す略図であり、図 1は第 2の基板 5を透過し て見た平面図で、図 2は図 1の A— A部に沿った正面側からの断面図で、図 3は図 1 の B— B部に沿った側面側からの断面図で、図 4は図 2の C C部に沿った平面側か らの断面図で表している。また、図 5は全体を立体図で表しており、図 6は図 5に示す 構成部品を分解して表した立体図である。  1 to 6 are schematic views showing the configuration of the liquid analyzer, FIG. 1 is a plan view seen through the second substrate 5, and FIG. 2 is taken along the line AA in FIG. Fig. 3 is a cross-sectional view from the front side, Fig. 3 is a cross-sectional view from the side along B-B in Fig. 1, and Fig. 4 is a cross-sectional view from the plane side along CC in Fig. 2. ing. FIG. 5 is a three-dimensional view of the whole, and FIG. 6 is a three-dimensional view of the components shown in FIG.
[0015] 図 6により、本実施例での液体分析装置の構成を説明する。本実施例での液体分 析装置は主に、図 6において下側から、第 1の基板 1、外側スぺーサ 2、内側スぺー サ 3、攪拌機構 4、第 2の基板 5、導入口筒 6、媒体流発生部 7、被搬送液体回収部枠 8の部品から構成され、積層後、内部の空間から被搬送液体や搬送用媒体が漏れな いように接合されている。本実施例での攪拌機構 4は、搬送される液体を変形、結合 などさせるための構造物 (フィン)を並べて表している。超音波攪拌の機構、スクリュー 機構やへら等の部材を回転させる機構などの攪拌機構でもかまわない。また、媒体 流発生部 7は、試料などを搬送させるための搬送用媒体について、液流を発生させ るものである。一方端部から取り込んだ媒体を他方端部から吐き出し、媒体に循環す る流れを発生させるポンプや水車状の部材を内部に持つ部品であり、流れを発生さ せる原理は問わない。流れの負荷に応じて流量を制御可能としてもよい。第 1の基板 1には、試料などの搬送される液体を捕捉する被搬送液体捕捉手段 9と廃液を捕捉 する廃液捕捉手段 10を持つ。被搬送液体捕捉手段 9は、搬送用媒体の流れ方向に おいて媒体流発生部を起点とみるときに、導入口筒(導入口) 6より搬送用媒体の流 れ方向での下流に配置される。 With reference to FIG. 6, the configuration of the liquid analyzer in the present embodiment will be described. In FIG. 6, the liquid analyzer in the present embodiment mainly includes the first substrate 1, the outer spacer 2, the inner spacer 3, the stirring mechanism 4, the second substrate 5, and the introduction port from the lower side. Cylinder 6, medium flow generation unit 7, transported liquid recovery unit frame It consists of 8 parts, and after lamination, it is joined so that the liquid to be transported and the transport medium do not leak from the internal space. The stirring mechanism 4 in the present embodiment represents structures (fins) for deforming and bonding the transported liquid side by side. An agitation mechanism such as an ultrasonic agitation mechanism, a screw mechanism, or a mechanism that rotates a member such as a spatula may be used. The medium flow generation unit 7 generates a liquid flow for a transfer medium for transferring a sample or the like. It is a part that has a pump or waterwheel-like member inside that discharges the medium taken in from one end and discharges it from the other end, and circulates in the medium, and the principle for generating the flow is not questioned. The flow rate may be controllable according to the flow load. The first substrate 1 has a transported liquid capturing means 9 for capturing a transported liquid such as a sample and a waste liquid capturing means 10 for capturing a waste liquid. The transported liquid catching means 9 is arranged downstream of the introduction port cylinder (introduction port) 6 in the flow direction of the transport medium when the medium flow generation unit is regarded as the starting point in the flow direction of the transport medium. The
第 1の基板 1と第 2の基板 5は、後述する液体搬送、及び、試料中に含まれる成分 量検出のために、必要な波長の光を透過する材料を用いているが、第 1の基板 1と第 2の基板 5の、被搬送液体捕捉手段 9の位置に対応する部分のみが光を透過する材 料になっていても良い。また、被搬送液体捕捉手段 9は、電極、エレクトレツトイ匕され た領域、もしくはエレクトレット化された領域と電極の組合せにより構成されており、第 1の基板 1と第 2の基板 5と同様に光を透過する材料を用いている。本実施例 1では、 被搬送液体捕捉手段 9に電極を用いた例で説明する。そのため、図 2に示す第 1の 基板 1の上面に第 1の基板 1の被搬送液体捕捉手段 9として、被搬送液体捕捉手段9 の位置すべてに電極がパターンユングされており、その表面を 0. 1 μ m力ら 100 μ m 程度の絶縁膜で覆い、さらに絶縁膜の表面を撥水処理している。絶縁物の材料とし ては、フッ素系などの榭脂、 SiO (石英)、 SiN、 Al O (アルミナ)、 HfOを利用する The first substrate 1 and the second substrate 5 are made of a material that transmits light of a necessary wavelength for liquid transportation described later and detection of the amount of components contained in the sample. Only the portion of the substrate 1 and the second substrate 5 corresponding to the position of the transported liquid capturing means 9 may be a material that transmits light. Further, the transported liquid capturing means 9 is composed of an electrode, an electret region, or a combination of an electret region and an electrode, and is similar to the first substrate 1 and the second substrate 5. A material that transmits light is used. In the first embodiment, an example in which an electrode is used for the transported liquid capturing means 9 will be described. Therefore, the electrode is patterned on all the positions of the transported liquid capturing means 9 on the upper surface of the first substrate 1 shown in FIG. It is covered with an insulating film of about 1 μm force and about 100 μm, and the surface of the insulating film is treated with water repellent treatment. As the insulator material, fluorine-based resin, SiO (quartz), SiN, Al 2 O (alumina), HfO are used.
2 2 3 2 ことができる。また、電極の材料としては、 ITO、 SnO、 ZnO、 ZnO+Al O +Ga O  2 2 3 2 can Electrode materials include ITO, SnO, ZnO, ZnO + AlO + GaO.
2 2 3 2 2 2 3 2
(AZOもしくは GZO)を利用することができる。各電極は、それぞれ単独に配置され(AZO or GZO) can be used. Each electrode is arranged independently
3 Three
、外部で配線されていてもかまわないが、本実施例では、それぞれの電極は図 7に示 す電極 11のように接続され、同一電位になるようにパターンユングされている。また、 電極の対抗電極として、図 2に示す第 2の基板 5の第 1の基板と対向する面の、当該 電極の対向位置の部分、もしくは複数の当該電極の全てを含む面に対向電極 12が 設けられ、電極同様にその表面を 0.: L mから 100 m程度の絶縁膜で覆い、さら に絶縁膜の表面を撥水処理している。ここで、対向電極 12を設けなくともよぐ対向 電極 12を不使用の場合には、第 1の基板上の電極のみの簡単な構成で被搬送液体 の制御ができる。一方、使用の場合には、電極による搬送液体の制御の精度を高め ることができる。本実施例では、わカゝりやすくするために図を簡略ィ匕し、電極と対向電 極 12がそれぞれ第 1の基板 1と第 2の基板 5に埋め込まれたように図示している。 However, in this embodiment, each electrode is connected like the electrode 11 shown in FIG. 7, and is patterned so as to have the same potential. In addition, as a counter electrode of the electrode, the surface of the second substrate 5 shown in FIG. The counter electrode 12 is provided on the part of the electrode facing position or on the surface including all of the electrodes, and the surface is covered with an insulating film of about 0 .: L m to 100 m like the electrode, and further the insulating film The surface is treated with water repellency. Here, when the counter electrode 12 that does not require the counter electrode 12 is not used, the liquid to be transported can be controlled with a simple configuration using only the electrode on the first substrate. On the other hand, in the case of use, it is possible to improve the accuracy of controlling the liquid transported by the electrodes. In this embodiment, the drawing is simplified for easy folding, and the electrode and the counter electrode 12 are illustrated as being embedded in the first substrate 1 and the second substrate 5, respectively.
[0017] 本実施例の電極の構成は、電極が前述のように同一電位になるようにパターンニン グされている。ここで、実質上電極と対向電極 12の一対のみとしている。すなわち、 一方の基板には分離された複数の電極であって同電位が供給されることによって同 期してスィッチのオン'オフ動作される電極群が設けられ、他方の基板には当該電極 群と対向する電極が設けられ、電極群と対向する電極とがー対の電極群をなして 、 る。 [0017] The configuration of the electrode of this example is patterned so that the electrode has the same potential as described above. Here, substantially only a pair of the electrode and the counter electrode 12 is provided. In other words, one substrate is provided with an electrode group that is a plurality of separated electrodes that are turned on and off in synchronization by being supplied with the same potential, and the other substrate is connected to the electrode group. Opposing electrodes are provided, and the electrode group and the opposing electrode form a pair of electrode groups.
[0018] 各部品を積層し接合して組み立てられた液体分析装置内部には、主に第 1の基板 1、外側スぺーサ 2、内側スぺーサ 3、第 2の基板 5、被搬送液体回収部枠 8により図 4 に矢印で示すような流れを可能にする流路 13が形成される。流路 13は、被搬送液 体回収部 14と導入口 15の部分以外は、流れに垂直な方向の断面が実質的に長方 形の空間 16になっている。流路 13の空間 16の内、被搬送液体の分析かつ、もしくは 検出に使用される部分を図 4に分析領域 17として示す。分析領域 17内の流路 13の 、流れに垂直な方向の実質的に長方形をした断面の寸法である幅 Wと高さ Hは、そ れぞれ図 3に示す通りである。  [0018] Inside the liquid analyzer assembled by laminating and joining the components, there are mainly a first substrate 1, an outer spacer 2, an inner spacer 3, a second substrate 5, and a liquid to be transported. A flow path 13 that enables a flow as indicated by an arrow in FIG. The flow path 13 is a space 16 having a substantially rectangular cross section in the direction perpendicular to the flow except for the transported liquid recovery part 14 and the inlet 15. A portion of the space 16 in the flow path 13 used for analysis and / or detection of the liquid to be transported is shown as an analysis region 17 in FIG. The width W and height H, which are dimensions of a substantially rectangular cross section in the direction perpendicular to the flow, of the flow path 13 in the analysis region 17 are as shown in FIG.
[0019] 次に、本実施例による液体分析装置の使用方法を説明する。 Next, a method for using the liquid analyzer according to the present embodiment will be described.
[0020] 最初に、分析のための準備を行う。液体分析装置の流路内には、予め搬送媒体を 満たしておく。(なお、搬送媒体 18の充填は、例えば廃液ポートを搬送媒体導入出 口として使用し、廃液ポートから行うことができる。)その時、流路 13内に気泡が残ら ないように、また、媒体流発生部 7により搬送媒体 18に流れが発生した後に流路 13 内に気泡が入り込まないように、流路 13内及び媒体流発生部 7内を搬送媒体 18で 満たした上で、流路 13における搬送媒体 18の液面よりも被搬送液体捕捉手段 9の 位置しない領域である被搬送液体回収部 14における搬送媒体 18の液面が上になる ように導入する。また、被搬送液体捕捉手段 9の位置しない領域である被搬送液体 回収部 14では、搬送媒体 18で満たさず、搬送媒体 18と接する気相領域が残るよう にしてもよい。これにより、導入時に気泡が混入した場合に、気体を当該気相領域へ 逃がして気泡を除去することができる。使用する搬送媒体は、シリコーンオイルゃフッ 素系オイル等で、被搬送液体と反応しない、前記被搬送液体よりも低誘電率の液体 である。その後、媒体流発生部 7を駆動し、図 4に矢印で示すような流れを発生する。 流れの速さは分析時の反応時間や計測時間により変化する力 おおよそ 0. lmm/ Secから 50mmZSecの緩やかな流れである。 [0020] First, prepare for analysis. The flow path of the liquid analyzer is filled with a transport medium in advance. (Filling of the transport medium 18 can be performed from the waste liquid port, for example, using the waste liquid port as the transport medium inlet / outlet port.) At that time, in order not to leave bubbles in the flow path 13, The flow path 13 and the medium flow generation section 7 are filled with the transfer medium 18 so that bubbles do not enter the flow path 13 after the flow is generated in the transfer medium 18 by the generation section 7. The transported liquid capture means 9 is closer to the transport medium 18 than the liquid level. It is introduced so that the liquid level of the transport medium 18 in the transported liquid recovery unit 14 which is not located is the top. Further, in the transported liquid recovery unit 14 where the transported liquid capturing means 9 is not located, the gas phase region that is not filled with the transport medium 18 and is in contact with the transport medium 18 may remain. Thereby, when bubbles are mixed at the time of introduction, the bubbles can be removed by letting gas escape to the gas phase region. The transport medium to be used is silicone oil or fluorine-based oil or the like, which is a liquid having a dielectric constant lower than that of the transported liquid and does not react with the transported liquid. Thereafter, the medium flow generator 7 is driven to generate a flow as indicated by an arrow in FIG. The speed of the flow is a force that varies depending on the reaction time and measurement time at the time of analysis.
[0021] 続いて、実際の分析手順の試料と試薬の導入カゝら混合までを説明する。図 8Aから 図 8Dは図 2の導入口と被搬送液体捕捉手段 9の一部までを拡大した図であり、試料 と試薬の導入から混合までを時系列に並べて複数の図で表して 、る。  [0021] Subsequently, the process up to mixing of the sample and the reagent in the actual analysis procedure will be described. 8A to 8D are enlarged views of the introduction port and a part of the transported liquid capturing means 9 of FIG. 2, and the steps from the introduction of the sample and the reagent to the mixing are arranged in chronological order and are represented by a plurality of diagrams. .
[0022] まず、図 8Aのようにスィッチ (電圧印加制御手段) 19をオンにし、被搬送液体捕捉 手段 9である電極 11と対向電極 12の間に電圧を印加しておく。次に、分析する試料 である第 1の被搬送液体 20を、ピぺッタ (導入手段) 21等を用いて導入口 15から分 析領域 17の流路 13内に導入する。導入された第 1の被搬送液体 20は搬送媒体 18 の流れにより流される力 電極 11の静電力によって引力を受け、図 8Bのように被搬 送液体捕捉手段 9たる電極 11の上で捕捉される。続いて図 8Cのように、第 1の被搬 送液体 20を分析するための試薬である第 2の被搬送液体 22を、ピぺッタ 21等を用 いて導入口 15から分析領域 17の流路 13内に導入する。導入された第 2の被搬送液 体 22は搬送媒体 18の流れにより流されるが、「電極 11の静電力によって引力を受け 、図 8Dのように被搬送液体捕捉手段 9たる電極 11で捕捉され、既に捕捉されていた 第 1の被搬送液体 20と混合する。ここで、試料を導入するピぺッタと試薬を導入する ピぺッタは同一のもの、異なるもののいずれであってもよい。なお、第 1の被搬送液体 と第 2の被搬送液体との導入の順番は、 、ずれが先であっても良 、。  First, as shown in FIG. 8A, the switch (voltage application control means) 19 is turned on, and a voltage is applied between the electrode 11 that is the transported liquid capturing means 9 and the counter electrode 12. Next, the first transported liquid 20 as the sample to be analyzed is introduced into the flow path 13 in the analysis region 17 from the inlet 15 using a pipetter (introducing means) 21 or the like. The introduced first transported liquid 20 is attracted by the force of the force electrode 11 caused by the flow of the transport medium 18 and is captured on the electrode 11 as the transported liquid capturing means 9 as shown in FIG. 8B. The Subsequently, as shown in FIG. 8C, the second transported liquid 22, which is a reagent for analyzing the first transported liquid 20, is transferred from the inlet 15 to the analysis region 17 using a pipetter 21 or the like. Introduce into the channel 13. The introduced second transported liquid 22 is caused to flow by the flow of the transport medium 18, but “is attracted by the electrostatic force of the electrode 11 and is captured by the electrode 11 as the transported liquid capturing means 9 as shown in FIG. 8D. Mix with the first transported liquid 20 that has already been captured, where the pipettor for introducing the sample and the pipetter for introducing the reagent may be the same or different. Note that the order of introduction of the first transported liquid and the second transported liquid may be shifted first.
[0023] 次に、実際の分析手順の試料と試薬の混合カゝら分析までを説明する。図 9A,図 9 Bは図 2の導入口と被搬送液体捕捉手段 9の一部までを拡大した図であり、試料と試 薬の混合から分析までを時系列に並べて複数の図で表して ヽる。 [0024] まず、図 9Aのようにスィッチ 19をオフにし、被搬送液体捕捉手段 9— 1である電極 1 1—1と対向電極 12の間に印加されていた電圧をー且解除し、電極 11— 1上から第 1の被搬送液体 20と第 2の被搬送液体 22への引力を解除し、これらの液体が電極か ら離れた後で、図 9Bのように再度スィッチ 19をオンにし、被搬送液体捕捉手段 9— 2 である電極 11— 2と対向電極 12の間に再度電圧を印加する。第 1の被搬送液体 20 と第 2の被搬送液体 22は、搬送媒体 18の流れにより流され、攪拌機構 4を通過して 物理的な変形を受けるなどによって攪拌され、反応液 23となる。そして、第 1の被搬 送液体 20と第 2の被搬送液体 22は、電極 11— 2の静電力によって引力を受け、図 9 Bのように 2番目の被搬送液体捕捉手段 9 - 2である電極 11 - 2上に捕捉される。 2 番目の被搬送液体捕捉手段 9— 2以降の被搬送液体捕捉手段 9に対応する位置に は、図 9Bに示すように計測部 24として光源 25と受光部 26が対応して配置されてお り、光源 25から第 2の基板 5、反応液 23、及び第 1の基板 1を通して計測光 27が照射 され、受光部 26で検出される。受光部 26で検出した計測光 27を分析することにより 、反応液 23の成分を分析し、その結果で、分析する試料である第 1の被搬送液体 20 に含まれる特定の成分の量を測定することができる。 [0023] Next, the analysis up to the mixing of the sample and the reagent in the actual analysis procedure will be described. 9A and 9B are enlarged views of the introduction port and a part of the transported liquid capturing means 9 in FIG. 2, and the processes from mixing of the sample and reagent to analysis are arranged in time series and expressed in multiple diagrams. Speak. First, as shown in FIG. 9A, the switch 19 is turned off, and the voltage applied between the electrode 1 1-1 as the transported liquid capturing means 9-1 and the counter electrode 12 is released and the electrode is released. 11—1 Release the attractive force from the top to the first transported liquid 20 and the second transported liquid 22, and after these liquids have left the electrodes, switch 19 is turned on again as shown in FIG. 9B. Then, a voltage is again applied between the electrode 11-2 which is the transported liquid capturing means 9-2 and the counter electrode 12. The first transported liquid 20 and the second transported liquid 22 are caused to flow by the flow of the transport medium 18, and are stirred by being subjected to physical deformation through the stirring mechanism 4 to become the reaction liquid 23. Then, the first transported liquid 20 and the second transported liquid 22 are attracted by the electrostatic force of the electrode 11-2, and as shown in FIG. 9B, the second transported liquid capturing means 9-2 Captured on some electrode 11-2. As shown in FIG. 9B, a light source 25 and a light receiving unit 26 are arranged corresponding to the second transported liquid capturing means 9-2 and the positions corresponding to the transported liquid capturing means 9 subsequent to the second transported liquid capturing means 9-2. Accordingly, the measurement light 27 is irradiated from the light source 25 through the second substrate 5, the reaction solution 23, and the first substrate 1, and is detected by the light receiving unit 26. By analyzing the measurement light 27 detected by the light receiver 26, the components of the reaction solution 23 are analyzed, and as a result, the amount of the specific component contained in the first transported liquid 20 that is the sample to be analyzed is measured. can do.
[0025] 反応結果の測定として、多くの場合、反応液 23内部で進む反応の様子を経時的に 測定し、最終的にその成分量を求める。そして、液体分析装置内に次々と試料と試 薬を供給し、順にその成分を分析するために、スィッチ 19のオン、オフを繰り返して 反応液 23を次々と計測部間を移動させ、計測を行う。これにより、複数の試料計測を 並行して進め、装置のスループットを向上することができる。その際、複数の被搬送 液体捕捉手段 9各々に反応液 23が存在する場合、電極 11は電気的に一体であるた め一斉にスィッチがオフになる力 分析領域 17内の流路の場所によっては流速の違 いなどにより、それぞれの反応液がそれぞれの被搬送液体捕捉手段 9から同時に離 れないことが考えられる。しかし、スィッチがオフになり全ての反応液 23が離れた後で 被搬送液体捕捉手段 9に電圧が印加されれば、各反応液 23が離れるタイミング、も しくは各反応液 23が次の被搬送液体捕捉手段 9に到達するタイミングが違って ヽて も、各々の反応液を確実に移動、捕捉することが可能である。  [0025] In many cases, the reaction results are measured by measuring the reaction proceeding in the reaction solution 23 over time, and finally determining the amount of the components. Then, in order to supply samples and reagents one after another into the liquid analyzer and sequentially analyze the components, switch 19 is repeatedly turned on and off, and reaction solution 23 is moved between the measurement units one after the other to measure. Do. As a result, multiple sample measurements can be performed in parallel, improving the throughput of the apparatus. At that time, when the reaction liquid 23 is present in each of the plurality of transported liquid capturing means 9, the electrode 11 is electrically integrated, so that the switches are turned off all at once, depending on the location of the flow path in the analysis region 17. It is conceivable that the reaction liquids cannot be separated from the transported liquid capturing means 9 at the same time due to the difference in flow velocity. However, if a voltage is applied to the transported liquid capturing means 9 after the switch is turned off and all the reaction liquids 23 are separated, the timing at which each reaction liquid 23 is separated or each reaction liquid 23 is subjected to the next reaction. Even if the timing of reaching the transport liquid capturing means 9 is different, each reaction liquid can be reliably moved and captured.
[0026] 続いて、計測が終了した反応液 23の回収方法について図 10Aから図 10Dを用い て説明する。図 10A,図 10Bは、図 3の表示向きを水平に戻して拡大した図である。 計測が終了した反応液 23は、最後の被搬送液体捕捉手段 9の捕捉から解放され、 搬送媒体 18の流れにより図 10Aの位置に流されてくる。被搬送液体回収部 14まで 更に流されると、被搬送液体回収部 14の少なくとも高さについて流路 13の高さ Hより も大きいことから、それまで第 1の基板 1と第 2の基板 5挟まれて円盤状につぶされて いた状態から解放され、反応液 23自身の表面張力により、図 10Bに示すような球状 へ変形する。これにより、反応液 23は原則として廃液 28となる。円盤状につぶされて いた状態力も解放され球状になった廃液 28の直径 dは、第 1の基板 1と第 2の基板 5 の隙間である高さ Hよりも大きいため、流路 13の閉じた空間 16内に再度入り込むこと はな 、。廃液 28が搬送媒体 18よりも比重が小さければ被搬送液体回収部 14で浮き 上がるので、図 10Cに示すようにシッパー 29等で吸引して回収する。廃液 28が搬送 媒体 18よりも比重が大きければ被搬送液体回収部 14で沈殿するので、図 10Dに示 すようにシッパー(回収手段) 29等で吸引して回収する。廃液 28が搬送媒体 18よりも 比重が大きくて沈殿する場合は、廃液 28が複数集まって大きな塊になり、第 1の基板 1と第 2の基板 5の隙間である流路 13の閉じた空間 16内に再度入り込む可能性があ るため、図 10Dに示すような窪み領域である沈殿部 30を設けるのが良い。廃液捕捉 手段 10は、被搬送液体捕捉手段 9と同様の原理に基づき廃液の捕捉効果を上げる ためのものであり、第 1の基板 1の上面の被搬送液体回収部 14に位置する場所に設 けられている。廃液捕捉手段 10に電極を用いている場合、光透過性を持たせてかつ 廃液捕捉手段 10に対応する位置に上記と同様の計測部(図示せず)を設置すること により、光学的に廃液量を検出することが可能である。 [0026] Subsequently, a method for recovering the reaction solution 23 whose measurement has been completed will be described with reference to FIGS. 10A to 10D. I will explain. 10A and 10B are enlarged views of the display orientation of FIG. 3 returned to the horizontal direction. The reaction liquid 23 for which the measurement has been completed is released from the capture of the last transported liquid capturing means 9 and is flowed to the position of FIG. 10A by the flow of the transport medium 18. When the liquid is further flowed up to the transported liquid recovery unit 14, at least the height of the transported liquid recovery unit 14 is larger than the height H of the flow path 13, so that the first substrate 1 and the second substrate 5 are sandwiched until then. Then, it is released from the state of being crushed into a disk shape and deformed into a spherical shape as shown in FIG. 10B by the surface tension of the reaction solution 23 itself. As a result, the reaction liquid 23 becomes the waste liquid 28 in principle. The diameter d of the waste liquid 28 that has been crushed into a disk shape and released into a spherical shape is larger than the height H, which is the gap between the first substrate 1 and the second substrate 5, so that the flow path 13 is closed. Never enter the space 16 again. If the waste liquid 28 has a specific gravity smaller than that of the transport medium 18, it floats up in the transported liquid recovery unit 14, and is collected by suction with a sipper 29 or the like as shown in FIG. 10C. If the waste liquid 28 has a specific gravity greater than that of the transport medium 18, it will settle in the transported liquid recovery section 14, and is collected by suction with a sipper (collection means) 29 as shown in FIG. 10D. When the waste liquid 28 has a specific gravity greater than that of the transport medium 18 and precipitates, a plurality of waste liquids 28 are collected into a large lump, and the closed space of the flow path 13 that is the gap between the first substrate 1 and the second substrate 5 Since there is a possibility of re-entering 16, it is preferable to provide a sedimentation portion 30 that is a depression region as shown in FIG. 10D. The waste liquid trapping means 10 is for increasing the waste liquid trapping effect based on the same principle as the transported liquid trapping means 9 and is provided at a location on the top surface of the first substrate 1 where the transported liquid recovery unit 14 is located. It is In the case where an electrode is used for the waste liquid capturing means 10, the waste liquid is optically disposed by providing a measuring portion (not shown) similar to the above at a position corresponding to the waste liquid capturing means 10 with light transmission. It is possible to detect the amount.
図 11に、図 4の分析領域 17の一部を拡大して示す。本実施例では、分析領域 17 内の流路 13の前記幅 Wに対し、被搬送液体捕捉手段 9の幅 Xは Wよりも小さい、す なわち W>Xの関係になるように設定している。これにより、搬送用媒体の流れの方 向と実質的に垂直な面において、被搬送液体捕捉手段 9の最大幅が流路 13の最大 幅よりも小さくなる。これにより、被搬送液体捕捉手段 9により被搬送液体を捕捉した 際、被搬送液体が流路 13を塞がないようにするためである。本実施例では、分析領 域 17内の流路 13内に入った被搬送液体は、第 1の基板 1と第 2の基板 5に挟まれて つぶされ、直径 D、高さ Hの円盤状になる。そのとき被搬送液体の直径 Dは、分析す る試料である第 1の被搬送液体 20の直径 Dと、試薬である第 2の被搬送液体 22の直 径 Dは、被搬送液体捕捉手段 9の幅 Xより小さぐ第 1の被搬送液体 20と第 2の被搬 送液体 22が混合、攪拌した後の反応液 23の直径 Dとは同程度になるように、かつ流 路 13の幅 Wよりも小さくなるように設定している。すなわち、搬送用媒体の流れの方 向と実質的に垂直な面において、反応液 23の最大幅が流路 13の最大幅よりも小さく なる。そのため、被搬送液体捕捉手段 9により被搬送液体を捕捉し、被搬送液体がそ の場で停滞してもその脇力も搬送用媒体が流れるため搬送用媒体が滞ることがない 。これにより、搬送用媒体を循環させている場合であっても、搬送用媒体が滞って流 れが乱れる事態を回避できる。さら〖こ、複数の被搬送液体が分析領域 17に位置する ときに一の被搬送液体が被搬送液体捕捉手段で捕捉されていることによって他の被 搬送液体の搬送や捕捉等に影響が及ぶことを回避することができる。 FIG. 11 shows an enlarged part of the analysis region 17 in FIG. In this embodiment, the width X of the transported liquid capturing means 9 is smaller than W with respect to the width W of the flow path 13 in the analysis region 17, that is, W> X. Yes. As a result, the maximum width of the transported liquid capturing means 9 is smaller than the maximum width of the flow path 13 in a plane substantially perpendicular to the direction of the transport medium flow. This is to prevent the transported liquid from blocking the flow path 13 when the transported liquid is captured by the transported liquid capturing means 9. In this embodiment, the liquid to be transported that has entered the flow path 13 in the analysis area 17 is sandwiched between the first substrate 1 and the second substrate 5. It is crushed into a disk with a diameter of D and a height of H. At this time, the diameter D of the liquid to be transported is equal to the diameter D of the first liquid to be transported 20 which is a sample to be analyzed and the diameter D of the second liquid to be transported 22 which is a reagent. The diameter D of the reaction liquid 23 after mixing and stirring the first transported liquid 20 and the second transported liquid 22 that are smaller than the width X of the liquid 13 and the width of the flow path 13 It is set to be smaller than W. That is, the maximum width of the reaction solution 23 is smaller than the maximum width of the flow path 13 on a surface substantially perpendicular to the direction of the flow of the transfer medium. For this reason, even if the transported liquid is captured by the transported liquid capturing means 9 and the transported liquid stagnates on the spot, the transporting medium flows by the side force, so that the transporting medium does not stagnate. Thereby, even when the transport medium is circulated, it is possible to avoid a situation in which the transport medium is stagnated and the flow is disturbed. Furthermore, when a plurality of liquids to be transported are located in the analysis region 17, the fact that one liquid to be transported is captured by the transported liquid capturing means affects the transport or capture of other transported liquids. You can avoid that.
[0028] 分析領域 17内の流路 13の前記幅 Wに対して被搬送液体捕捉手段 9の幅 Xが大き くとも、被搬送液体の直径 Dが小さければ被搬送液体がその場で停滞してもその脇 から搬送用媒体が流れるため搬送用媒体が滞ることはない。しかし、この場合、被搬 送液体捕捉手段 9の幅 X内で被搬送液体が移動し、幅 X方向の位置が定まらな ヽ。 そのため、計測位置で計測光 27が反応液 23に確実に照射されず、分析精度を落と すことになる。 [0028] Even though the width X of the transported liquid capturing means 9 is larger than the width W of the flow path 13 in the analysis region 17, if the diameter D of the transported liquid is small, the transported liquid stagnates on the spot. However, since the transport medium flows from the side, the transport medium does not stagnate. However, in this case, the transported liquid moves within the width X of the transported liquid capturing means 9, and the position in the width X direction is not fixed. Therefore, the measurement light 27 is not reliably irradiated to the reaction solution 23 at the measurement position, and the analysis accuracy is lowered.
[0029] 被搬送液体の直径 Dが被搬送液体捕捉手段 9の幅 Xより小さ 、場合、前述のように 場所が定まらないことになるが、本実施例では、通常第 1の被搬送液体の直径 Dは 被搬送液体捕捉手段 9の幅 Xより小さい。しかし、第 2の被搬送液体と混合し、反応 液 23となったときにその直径 Dが幅 Xと同程度になるように設定してあり、第 1の被搬 送液体が被搬送液体捕捉手段 9上にさえあれば、第 2の被搬送液体が第 1の被搬送 液体と接触して混合できる。  [0029] When the diameter D of the liquid to be transported is smaller than the width X of the liquid transport capturing means 9, the location is not fixed as described above. The diameter D is smaller than the width X of the transported liquid capturing means 9. However, when it is mixed with the second transported liquid and becomes reaction liquid 23, its diameter D is set to be approximately the same as width X, and the first transported liquid captures the transported liquid. As long as it is on the means 9, the second liquid to be transported can come into contact with the first liquid to be mixed.
[0030] 以上のように装置内部で搬送媒体を循環させ、循環の流れで被搬送液体を搬送す ること〖こよって、分析対象の試薬との混合、攪拌、計測部への移動、回収部への移動 を簡単な構成で高速に自動化することができる。  [0030] As described above, the transport medium is circulated inside the apparatus, and the liquid to be transported is transported in the circulation flow, thereby mixing with the reagent to be analyzed, stirring, moving to the measuring section, and collecting section. It is possible to automate the movement to a high speed with a simple configuration.
実施例 2 [0031] 本実施例では、実施例 1での被搬送液体捕捉手段 9に電極を用いていたのに対し 、被搬送液体捕捉手段 9にエレクトレット化された絶縁物を用いた例を説明する。ここ では、絶縁膜の一部がエレクトレツトイ匕された領域となって 、る。 Example 2 In this embodiment, an electrode is used for the transported liquid capturing means 9 in the first embodiment, whereas an electret insulator is used for the transported liquid capturing means 9. Here, a part of the insulating film is an electret region.
[0032] 本実施例での構成は、電極 11、対向電極 12及び電圧を印加するためのスィッチ 1 9等の配線を除いて、基本的に実施例 1と同じである。被搬送液体を捕捉するのは、 図 12Aに示すような被搬送液体捕捉手段 9の範囲のみエレクトレツトイ匕した領域 31で ある。エレクトレツトイ匕とは、磁性材料が N極と S極に磁化するように、高分子材料を加 熱しながら高電圧を印加するか、コロナ放電等で半永久的に帯電させた状態である( 例えば、非特許文献 1)。エレクトレット化した領域を使用すれば、電源が無くとも図 1 2Aのように分極を保った状態が実現できる。このエレクトレツトイ匕した領域 31に第 1の 被搬送液体 20、第 2の被搬送液体 22もしくは反応液 23が搬送媒体の流れによって 流れてくると、図 12Bのように静電力で捕捉される。捕捉された第 1の被搬送液体 20 、第 2の被搬送液体 22もしくは反応液 23を解放し、次の被搬送液体捕捉手段 9に移 動するには、媒体流発生部 7に格納する媒体流量制御部によって流量を制御し、媒 体の流れ方向の引力が捕捉して 、る静電力よりも一時的に強くなるように速 、流れを 一時的に発生させれば良い。ここで、媒体流量制御部は、ポンプの回転を速めるな どの制御を行う。このような速い流れは一時的であるため、複数の反応液が各々違う タイミングで被搬送液体捕捉手段9を離れたとしても、次の被搬送液体捕捉手段9は 、既に第 1の被搬送液体 20、第 2の被搬送液体 22もしくは反応液 23を捕捉できる状 態になっているので、各第 1の被搬送液体 20、第 2の被搬送液体 22もしくは反応液 23が離れるタイミング、もしくは各第 1の被搬送液体 20、第 2の被搬送液体 22もしく は反応液 23が次の被搬送液体捕捉手段 9に到達するタイミングが違って 、ても、各 々の反応液を確実に移動、捕捉することが可能である。 The configuration in the present embodiment is basically the same as that in the first embodiment except for the wiring such as the electrode 11, the counter electrode 12, and the switch 19 for applying a voltage. The liquid to be transported is captured in the region 31 in which only the range of the transported liquid capturing means 9 as shown in FIG. An electret toy is a state in which a high voltage is applied while heating a polymer material so that the magnetic material is magnetized to the north and south poles, or is charged semipermanently by corona discharge (for example, Non-patent document 1). If electretized areas are used, polarization can be maintained as shown in Fig. 12A without a power supply. When the first transported liquid 20, the second transported liquid 22 or the reaction liquid 23 flows in the electretized region 31 due to the flow of the transport medium, it is captured by electrostatic force as shown in FIG. 12B. . In order to release the captured first transported liquid 20, second transported liquid 22 or reaction liquid 23 and move to the next transported liquid capturing means 9, the medium stored in the medium flow generation unit 7 The flow rate is controlled by the flow rate control unit, and the flow is temporarily generated so that the attractive force in the flow direction of the medium is captured and temporarily stronger than the electrostatic force. Here, the medium flow rate control unit performs control such as speeding up the rotation of the pump. Since such a fast flow is temporary, even if the plurality of reaction liquids leave the transported liquid capturing means 9 at different timings, the next transported liquid capturing means 9 has already been in the first transported liquid. 20, since the second transported liquid 22 or the reaction liquid 23 can be captured, the timing at which the first transported liquid 20, the second transported liquid 22 or the reaction liquid 23 is separated, or Even if the timing of the first transported liquid 20, the second transported liquid 22 or the reaction liquid 23 reaching the next transported liquid capture means 9 is different, each reaction liquid is reliably moved. It is possible to capture.
[0033] その他の攪拌、計測、廃液回収等に関しては実施例 1と同様である。  [0033] Other stirring, measurement, waste liquid recovery, and the like are the same as in Example 1.
[0034] 本実施例の構成によれば、電極や電極へ電圧を印加する電源、及びその制御の 機構が不要になるため、構造を簡単にしコスト低減ィ匕が可能となる。  [0034] According to the configuration of the present embodiment, an electrode, a power source for applying a voltage to the electrode, and a control mechanism for the electrode are not required, so that the structure can be simplified and the cost can be reduced.
[0035] 非特許文献 1 :日本機械学会 第 9回動力'エネルギー技術シンポジウム講演論文集  [0035] Non-Patent Document 1: Proceedings of the 9th Japan Power Society Energy Technology Symposium
No. 04- 2 実施例 3 No. 04- 2 Example 3
[0036] 本実施例では、被搬送液体捕捉手段 9にエレクトレット化された絶縁膜と電極を組 合せて用いた例を説明する。  In the present embodiment, an example will be described in which the transported liquid capturing means 9 is combined with an electret insulating film and an electrode.
[0037] 本実施例では、対向電極からみて 1のエレクトレツトイ匕した領域と 1の電極の占める 領域とが、少なくとも一部で重なるように配置される。実施例 1との違いは、実施例 1で は被搬送液体を捕捉している間、電極 11と対向電極 12間に電圧を印加し続けるが 、本実施例では、図 13Aに示すように、実施例 2と同様にエレクトレツトイ匕した領域で 被搬送液体を捕捉し、図 13Bに示すように、電極 11と対向電極 12間に、一時的にェ レクトレット化を打ち消す電圧を印加することで、捕捉した被搬送液体を解放する。  [0037] In the present embodiment, the region where one electret is seen as viewed from the counter electrode and the region occupied by one electrode are arranged so as to at least partially overlap. The difference from Example 1 is that in Example 1, the voltage is continuously applied between the electrode 11 and the counter electrode 12 while the transported liquid is captured, but in this example, as shown in FIG. In the same manner as in Example 2, the liquid to be transported is captured in the region where the electret is trapped, and a voltage that temporarily cancels electretization is applied between the electrode 11 and the counter electrode 12 as shown in FIG. 13B. Then, the captured transported liquid is released.
[0038] 複数の被搬送液体捕捉手段 9各々に反応液 23が存在する場合、各電極 11は電 気的に一体であるため、各電極 11と対向電極 12間には一斉に電圧が印加されるが 、実施例 1及び実施例 2と同様に、分析領域 17内の流路の場所によっては流速の違 いなどにより、それぞれの反応液がそれぞれの被搬送液体捕捉手段 9から同時に離 れないことが考えられる。しかし、スィッチがオンになり全ての反応液 23が離れた時 点でスィッチがオフになれば、次の被搬送液体捕捉手段 9は、既に反応液 23を捕捉 できる状態になっているので、各反応液 23が離れるタイミング、もしくは各反応液 23 が次の被搬送液体捕捉手段 9に到達するタイミングが違っていても、各々の反応液 を確実に移動、捕捉することが可能である。  [0038] When the reaction liquid 23 is present in each of the plurality of transported liquid capturing means 9, the electrodes 11 are electrically integrated, so that a voltage is applied simultaneously between the electrodes 11 and the counter electrode 12. However, as in Example 1 and Example 2, each reaction solution cannot be separated from each transported liquid capturing means 9 at the same time due to the difference in flow rate depending on the location of the flow path in the analysis region 17. It is possible. However, if the switch is turned off when the switch is turned on and all the reaction liquids 23 are separated, the next transported liquid capturing means 9 is already in a state where it can capture the reaction liquid 23. Even if the timing at which the reaction solution 23 is separated or the timing at which each reaction solution 23 reaches the next transported liquid capturing means 9 is different, each reaction solution can be reliably moved and captured.
[0039] その他の攪拌、計測、廃液回収等に関しては実施例 1と同様である。  [0039] Other stirring, measurement, waste liquid recovery, and the like are the same as in Example 1.
[0040] 本実施例の構成によれば、液滴をオイル流により搬送し、エレクトレツトイ匕領域によ り捕捉し、かつ電圧印加により開放するため、液滴をより正確に制御するとともに、電 極へ電圧を印加する時間を低減化して電極上に配置する絶縁膜の寿命をより長くす ることがでさる。  [0040] According to the configuration of the present embodiment, the droplets are transported by the oil flow, captured by the electret toy region, and opened by voltage application. It is possible to extend the lifetime of the insulating film disposed on the electrode by reducing the time for applying the voltage to the electrode.
実施例 4  Example 4
[0041] 本実施例では、上記実施例 1から実施例 3における方式において、分析領域 17が 複数ある例を説明する。図 14にその実施例を示す。ここで、複数の導入口と複数の 分析領域 17とが分岐された流路である分岐路に各々配置される。本実施例と、実施 例 1から実施例 3との違いは、被搬送液体の分析に使用される分析領域 17を複数持 つていることである。被搬送液体捕捉手段 9に電極 11を用いる場合、電極形状は、図 7の形状の物を図 15Aのように分析領域 17の本数だけ複数設け、分析用途に合わ せ使い分けられるようにする力、もしくは図 15Bのような一体型にし、並行した分析を ほぼ同時に行うようにしても良い。また、電極 11の被搬送液体捕捉手段 9部の形状 は、丸でも四角でも可能である。なお、被搬送液体捕捉手段としては、実施例 1のよう に電極を用いてもよぐ実施例 2のようにエレクトレツトイ匕された領域を用いてもよぐ実 施例 3のように電極とエレクトレツトイ匕された領域との組合せの構成を用いてもょ 、。 In this embodiment, an example will be described in which there are a plurality of analysis regions 17 in the systems in Embodiments 1 to 3. Figure 14 shows an example of this. Here, a plurality of inlets and a plurality of analysis regions 17 are respectively arranged in branch paths that are branches. The difference between this example and Example 1 to Example 3 is that it has a plurality of analysis regions 17 used for analyzing the liquid to be transported. That is. When the electrode 11 is used for the transported liquid capturing means 9, the electrode shape is a force that allows a plurality of objects having the shape shown in FIG. 7 to be provided in the number of the analysis regions 17 as shown in FIG. Alternatively, it may be integrated as shown in Fig. 15B, and parallel analysis may be performed almost simultaneously. Further, the shape of the transported liquid capturing means 9 of the electrode 11 can be round or square. In addition, as the transported liquid capturing means, the electrode as in Example 3 may be used, as in Example 2 where an electrode may be used, as in Example 2, or an electret-cut area may be used. Or use a combination of the electret area and the combined area.
[0042] 分析領域が複数ある場合には、複数領域の各々にお!、て複数の分析を並行して 進めることができる。このときに、実施例 1と同様に、分析領域内の流路の幅 Wに対し 、被搬送液体捕捉手段の幅 Xは Wよりも大きくするため、被搬送液体捕捉手段により 被搬送液体を捕捉した際、被搬送液体が流路を塞ぐことがない。被搬送液体が流路 を塞ぐと、その流路から搬送媒体が溢れ出して他の流路へ入り込み、 1の流路のみで なく複数の流路での搬送媒体の流れを乱すこととなる。本実施例の構成ではこのよう な事態を回避し、複数の流路による複数分析の並行処理を確実に達成することがで きる。 [0042] When there are a plurality of analysis regions, a plurality of analyzes can be performed in parallel in each of the plurality of regions. At this time, as in Example 1, the width X of the transported liquid capturing means is larger than W with respect to the width W of the flow path in the analysis region, so that the transported liquid is captured by the transported liquid capturing means. In this case, the transported liquid does not block the flow path. When the transported liquid blocks the flow path, the transport medium overflows from the flow path and enters another flow path, disturbing the flow of the transport medium not only in one flow path but also in a plurality of flow paths. With the configuration of this embodiment, such a situation can be avoided, and parallel processing of multiple analyzes using multiple flow paths can be reliably achieved.
上記記載は実施例についてなされたが、本発明はそれに限らず、本発明の精神と 添付の請求の範囲の範囲内で種々の変更および修正をすることができることは当業 者に明らかである。  While the above description has been made with reference to embodiments, it will be apparent to those skilled in the art that the present invention is not limited thereto and that various changes and modifications can be made within the spirit of the invention and the scope of the appended claims.
図面の簡単な説明  Brief Description of Drawings
[0043] [図 1]本発明による液体分析装置の構成を示す平面図。 FIG. 1 is a plan view showing a configuration of a liquid analyzer according to the present invention.
[図 2]本発明による液体分析装置の構成を示す正面側からの断面図。  FIG. 2 is a cross-sectional view from the front showing the configuration of the liquid analyzer according to the present invention.
[図 3]本発明による液体分析装置の構成を示す側面側からの断面図。  FIG. 3 is a cross-sectional view from the side showing the configuration of the liquid analyzer according to the present invention.
[図 4]本発明による液体分析装置の平面側からの断面図。  FIG. 4 is a cross-sectional view from the plane side of the liquid analyzer according to the present invention.
[図 5]本発明による液体分析装置の立体図。  FIG. 5 is a three-dimensional view of a liquid analyzer according to the present invention.
[図 6]図 5に示す構成部品を分解して表した立体図。  FIG. 6 is a three-dimensional view showing the components shown in FIG. 5 in an exploded manner.
[図 7]本発明による液体分析装置の電極のみを表した図。  FIG. 7 is a diagram showing only electrodes of the liquid analyzer according to the present invention.
[図 8A]図 2の導入ロカゝら被搬送液体捕捉手段の一部までを部分拡大した図。  FIG. 8A is a partially enlarged view of a part of the transported liquid capturing means from the introduction locus in FIG.
[図 8B]図 2の導入ロカゝら被搬送液体捕捉手段の一部までを部分拡大した図。 圆 8C]図 2の導入ロカも被搬送液体捕捉手段の一部までを部分拡大した図。 圆 8D]図 2の導入ロカも被搬送液体捕捉手段の一部までを部分拡大した図。 圆 9A]図 2の導入ロカゝら被搬送液体捕捉手段の一部までを部分拡大した図。 圆 9B]図 2の導入ロカゝら被搬送液体捕捉手段の一部までを部分拡大した図。 FIG. 8B is a partially enlarged view of the introduction locus from FIG. 2 to a part of the transported liquid capturing means. [8C] FIG. 2 is a partially enlarged view of the introduction locus of FIG. 2 up to a part of the transported liquid capturing means.圆 8D] The introduction locus in FIG. 2 is also a partially enlarged view of a part of the transported liquid capturing means. [9A] FIG. 9 is a partially enlarged view of the introduction locus of FIG. 2 and a part of the transported liquid capturing means. [9B] FIG. 9 is a partially enlarged view from the introduction locus of FIG. 2 to a part of the transported liquid capturing means.
[図 10A]図 3の表示向きを水平に戻して拡大した図。 FIG. 10A is an enlarged view of the display orientation of FIG.
[図 10B]図 3の表示向きを水平に戻して拡大した図。 FIG. 10B is an enlarged view of the display orientation of FIG.
[図 10C]図 3の表示向きを水平に戻して拡大した図。 FIG. 10C is an enlarged view of the display orientation of FIG.
[図 10D]図 3の表示向きを水平に戻して拡大した図。 FIG. 10D is an enlarged view of the display orientation of FIG.
[図 11]図 4の分析領域 17の部分拡大図。 FIG. 11 is a partially enlarged view of the analysis region 17 in FIG.
圆 12A]送液体捕捉手段にエレクトレット化された絶縁物を用いた断面の拡大図。 圆 12B]送液体捕捉手段にエレクトレット化された絶縁物を用いた断面の拡大図。 [12A] Enlarged view of a cross section using an electretized insulator for the liquid feed capturing means. [12B] An enlarged view of a cross section using an electretized insulator for the liquid feed capturing means.
[図 13A]送液体捕捉手段にエレクトレツトイ匕された絶縁物と電極を組み合わせて用い た断面の拡大図。 FIG. 13A is an enlarged view of a cross section in which an insulator electretized and an electrode are used in combination for the liquid feed capturing means.
[図 13B]送液体捕捉手段にエレクトレツトイ匕された絶縁物と電極を組み合わせて用い た断面の拡大図。  FIG. 13B is an enlarged view of a cross section in which an insulator electretized and an electrode are combined in the liquid feeding capturing means.
[図 14]本発明による液体分析装置の構成を示す平面図で、分析領域が複数ある一 例。  FIG. 14 is a plan view showing the configuration of a liquid analyzer according to the present invention, which is an example having a plurality of analysis regions.
圆 15A]図 14による液体分析装置の電極形状の一例を現す図。 [15A] A diagram showing an example of the electrode shape of the liquid analyzer shown in FIG.
圆 15B]図 14による液体分析装置の電極形状の一例を現す図。 [15B] A diagram showing an example of the electrode shape of the liquid analyzer shown in FIG.

Claims

請求の範囲 The scope of the claims
[1] 被搬送液体を導入するための導入口と、  [1] an inlet for introducing the liquid to be transported;
前記被搬送液体を搬送させるための搬送用媒体にっ ヽて、循環の流れを生じさせ る媒体流発生部と、  A medium flow generating section for generating a circulation flow over a conveying medium for conveying the liquid to be conveyed;
前記被搬送液体と前記搬送用媒体とが流れる流路と、  A flow path through which the transported liquid and the transport medium flow,
前記流路の少なくとも一部に設けられ、かつ、前記被搬送液体を捕捉する被搬送 液体捕捉手段と、  A transported liquid capturing means provided in at least a part of the flow path and capturing the transported liquid;
前記被搬送液体捕捉手段に捕捉された被搬送液体について計測する計測部と、 を有し、前記被搬送液体捕捉手段は前記搬送用媒体の流れの方向と実質的に垂直 な面での最大幅が、前記流路の前記搬送用媒体の流れの方向と実質的に垂直な面 での最大幅よりも小さくした液体分析装置。  A measuring unit that measures the liquid to be transported captured by the transported liquid capturing means, and the transported liquid capturing means has a maximum width in a plane substantially perpendicular to the direction of flow of the transport medium. However, the liquid analyzer is smaller than the maximum width in a plane substantially perpendicular to the flow direction of the transport medium in the flow path.
[2] 前記被搬送液体捕捉手段は、前記搬送用媒体の流れ方向にお!、て前記媒体流 発生部を起点とみるときに、前記導入口より前記搬送用媒体の流れ方向での下流に 配置された請求項 1記載の液体分析装置。  [2] The transported liquid capturing means is arranged in a downstream direction of the transport medium in the flow direction of the transport medium when the transport direction of the transport medium is taken as the starting point of the medium flow generation unit. 2. The liquid analyzer according to claim 1, which is arranged.
[3] 前記被搬送液体捕捉手段は、電極であり、前記電極への印加電圧を制御する電 圧印加制御手段をさらに有する請求項 1記載の液体分析装置。 [3] The liquid analyzer according to claim 1, wherein the transported liquid capturing means is an electrode, and further includes a voltage application control means for controlling a voltage applied to the electrode.
[4] 前記電極は複数の第 1電極である請求項 3記載の液体分析装置。 4. The liquid analyzer according to claim 3, wherein the electrodes are a plurality of first electrodes.
[5] 前記電極は複数の第 1電極と前記第 1電極に対向して設置される第 2電極である請 求項 3記載の液体分析装置。 [5] The liquid analyzer according to claim 3, wherein the electrodes are a plurality of first electrodes and a second electrode installed to face the first electrodes.
[6] 前記被搬送液体捕捉手段は、エレクトレット化領域である請求項 1記載の液体分析 装置。 6. The liquid analyzer according to claim 1, wherein the transported liquid capturing means is an electretized region.
[7] 前記被搬送液体捕捉手段は、少なくとも 1つの第 1電極と前記第 1電極と対向する 第 2電極と前記第 2電極からみて前記第 1電極の占める領域と少なくとも一部で重な る領域に配置されるエレクトレットィヒ領域であり、前記第 1電極及び前記第 2電極への 印加電圧を制御する電圧印加制御手段をさらに有する請求項 1記載の液体分析装 置。  [7] The transported liquid capturing means overlaps at least partly with at least one first electrode, a second electrode facing the first electrode, and a region occupied by the first electrode as viewed from the second electrode. 2. The liquid analyzing apparatus according to claim 1, further comprising voltage application control means for controlling an applied voltage to the first electrode and the second electrode, which is an electret region disposed in the region.
[8] 前記搬送媒体は前記搬送液体よりも誘電率の低!、液体である請求項 1記載の液体 分析装置。 8. The liquid analyzer according to claim 1, wherein the transport medium is a liquid having a lower dielectric constant than the transport liquid.
[9] 前記被搬送液体を回収し、かつ前記流路よりも高さの大き!ヽ被搬送液体回収部を さらに有する請求項 1記載の液体分析装置。 9. The liquid analyzer according to claim 1, further comprising a transported liquid recovery unit that recovers the transported liquid and has a height higher than the flow path.
[10] 前記被搬送液体回収部は、窪み領域を具備する請求項 9記載の液体分析装置。 10. The liquid analyzer according to claim 9, wherein the transported liquid recovery unit includes a recessed area.
[11] 前記流路は、少なくとも 1つの前記導入部と少なくとも 1つの前記被搬送液体捕捉 手段とを各々備えた複数の分岐路を有する請求項 1記載の液体分析装置。 11. The liquid analyzer according to claim 1, wherein the flow path has a plurality of branch paths each including at least one introduction section and at least one transported liquid capturing unit.
[12] 導入口より第 1の被搬送液体を導入する第 1の工程と、 [12] a first step of introducing the first transported liquid from the inlet;
搬送媒体の循環による流れで前記第 1の被搬送液体を流路内で搬送する第 2のェ 程と、  A second step of transporting the first liquid to be transported in the flow path by the flow of the transport medium;
前記第 1の工程の後に前記導入口より第 2の被搬送液体を導入する第 3の工程と、 前記第 3の工程の後に前記搬送媒体の前記流れによって前記第 2の被搬送液体 を流路内で搬送する第 4の工程と、  A third step of introducing a second liquid to be transported from the inlet after the first step; and a flow path through the second liquid to be transported by the flow of the transport medium after the third step. A fourth step of transporting within,
搬送された前記第 1の被搬送液体もしくは搬送された前記第 2の被搬送液体のい ずれ力を第 1捕捉手段で捕捉する第 5の工程と、  A fifth step of capturing by the first capturing means any force of the transported first transported liquid or transported second transported liquid;
前記第 1の被搬送液体もしくは前記第 2の被搬送液体の 、ずれかの一方であって 前記被搬送液体捕捉手段が捕捉したものと、前記!ヽずれかの他方とを接触させて混 合液体とする第 6の工程と、  One of the first transported liquid and the second transported liquid, which is misaligned and captured by the transported liquid capturing means, and the other of the misalignment are brought into contact with each other and mixed. A sixth step of liquid,
前記混合液体を前記第 1捕捉手段もしくは第 2被搬送液体捕捉手段で捕捉して計 測する第 7の工程と、  A seventh step of capturing and measuring the mixed liquid by the first capturing means or the second transported liquid capturing means;
を有する液体分析方法。  A liquid analysis method comprising:
[13] 前記混合液体の前記搬送用媒体の流れの方向と実質的に垂直な面での最大幅が 、前記流路の前記搬送用媒体の流れの方向と実質的に垂直な面での最大幅よりも 小さい請求項 12記載の液体分析方法。 [13] The maximum width of the mixed liquid in a plane substantially perpendicular to the direction of flow of the transport medium is the maximum width of the channel in the plane substantially perpendicular to the direction of flow of the transport medium. The liquid analysis method according to claim 12, wherein the liquid analysis method is smaller than a large amount.
[14] 前記第 7の工程では、複数の前記第 2の捕捉手段により経時的な計測を行う請求 項 12記載の液体分析方法。 14. The liquid analysis method according to claim 12, wherein in the seventh step, measurement with time is performed by a plurality of the second capturing means.
[15] 前記第 1の被搬送液体と前記第 2の被搬送液体とは、 V、ずれかが試料であり他方 が試薬である請求項 12記載の液体分析方法。 15. The liquid analysis method according to claim 12, wherein the first transport liquid and the second transport liquid are V, the deviation is a sample, and the other is a reagent.
[16] 前記混合液体を分析用領域から回収用領域へ搬送して回収する第 8の工程をさら に有し、前記混合液体は前記分析用領域から前記回収用領域へ搬送される際に変 形する請求項 14に記載の液体分析方法。 [16] The method further includes an eighth step of transporting and recovering the mixed liquid from the analysis region to the recovery region, and the mixed liquid is changed when transported from the analysis region to the recovery region. 15. The liquid analysis method according to claim 14, wherein the liquid analysis method is formed.
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