Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of Complex water body multi-parameter based on microflow control technique and examines equipment fastly, the Complex water body
It includes chip and detection device that multi-parameter examines equipment fastly;Wherein, the chip be rotary chip or straight-line chip, it is described
Chip includes the reaction tank for example reaction;The detection device is used to detect the signal of the sample in the reaction tank.
In the present invention, the Complex water body multi-parameter examines equipment by using microflow control technique fastly, can be by core
Multiple reaction tanks are arranged on piece, so as to be completed in a short time the synchronous detection of a large amount of samples, and can pass through chip
Interior structure design, completes the operation such as sample pretreatment, reaction, and detection process Highgrade integration is easy to operate, and precision is high.
According to the present invention, there is no particular limitation for the structure of the chip, can be rotary chip or straight-line core
Piece can be the various well known shapes such as circle, rectangle.
As the rotary chip, refer to can on chip a little where chip rotation in surface.From
From the point of view of rotation, the rotary chip is preferably circular or regular polygon, more preferably round.It is described rotary
When chip is round, preferably rotated around its center of circle.
A preferred embodiment according to the present invention, as shown in Figure 1, the multiple reaction tank is arranged with the core
The center of piece is on the circumference in the center of circle.Center of the i.e. the multiple reaction tank apart from the chip is equidistant.
Another preferred embodiment according to the present invention, the reaction tank is divided into multiple groups, and every group of reaction tank has
Multiple reaction tanks, every group of multiple reaction tanks are separately positioned on using the center of the chip as one in one group of concentric circles in the center of circle
Circumference on.That is center of every group of the multiple reaction tanks apart from the chip is equidistant.
There is no particular limitation for the rotating manner of the rotary chip, it is preferable that the rotary chip can pass through
It drives either manually or by the driving part in detection device and is rotated in detection device, preferably around the rotary chip
Center rotation.From detection device is simplified, cost is reduced, convenient for from the point of view of portable operation, the rotary chip is excellent
Gating can be manually rotated.And from detection efficiency is improved, it is realized in the short time from the point of view of detecting on a large scale, the rotary core
Piece preferably passes through the driving rotation of the driving part in detection device.
As the straight-line chip, refers to the chip that the reaction tank on chip is arranged in rows, is typically designed to rectangle,
And with reaction tank more than a row.The reaction tank of straight-line chip, generally can be by making straight-line core due to marshalling
Piece is mobile relative to the detection device and is detected, such as the pull straight-line chip in detection device.
In the present invention, the reaction tank on the chip can be 2 or more, preferably 5 or more, more preferably 10-
50.It can also include runner on the chip for the ease of reaction, the runner flows between differential responses pond for sample
It is dynamic.The set-up mode of the runner needs to cooperate chip detection demand to carry out, such as when needing to carry out multistep reaction in the chips,
It can be set to include successively reaction tank-runner-reaction tank-runner-reaction tank structure, to complete in multiple reaction tanks
Different reactions.In order to control the flowing of sample, various promotion mixed structures, micro-valve etc. can also be set in the chips,
Whether for controlling the mixing and flowing of sample.
A preferred embodiment according to the present invention is provided with the mark for determining detection signal on the chip
Note, the label are correspondingly arranged with the reaction tank.
A preferred embodiment according to the present invention, as shown in Figure 1, the chip has multiple reaction tanks, Duo Gesuo
Reaction tank is stated to be arranged in using the center of the chip to be correspondingly arranged with the reaction tank useful on more than one circumference in the center of circle
In the label for determining detection signal.In the use process of chip, by rotary chip, so that the reaction tank in chip is located at inspection
The corresponding inspection positions of device are surveyed, while can determine corresponding detection part.Preferably, it is respectively corresponded with each reaction tank
It is provided with the label for determining detection signal, thus a chip can be completed in a short time a variety of different Testing index
Detection.And detection process is easy to operate, and accuracy is high, and can be suitable for various detection methods.
In the present invention, the label can be the label with specific color or shape, such as can pass through printing
Or the modes such as stickup are formed on the chip, the groove with specific shape, the notch etc. being also possible on chip.It is described
There is no particular limitation for the shape of label, achievees the purpose that identify and distinguish between, such as can be triangle, square, just
Pentagon, star, naturally it is also possible to for number, letter or various irregular shapes.Can only it be arranged on 1 on chip
Label is stated, the label is for determining that the detection signal of chip (can be same detection signal, be also possible in multiple reaction tanks not
With the detection ordering of signal), thus when carrying out different tests with different chips convenient for determining detection mode;It can also on chip
With corresponding one group even each corresponding detection signal of reaction tank setting, to complete the detection of unlike signal in a chip.
In the present invention, as long as differential responses pond can be with after the set-up mode of the multiple reaction tank rotates chip
Positioned at the detection zone of detection device.By the multiple reaction tank being arranged in the center center of circle of the chip
On more than one circumference, so as to complete the detection of multiple reaction tanks on chip with single detection part, reaches batch and examine
The purpose of survey.
According to the present invention, the chip includes substrate and cover plate, and the substrate is fixedly connected (also referred to as with the cover plate
" fixed chip "), alternatively, the substrate and the cover plate can be mutually shifted, thus change in the chip reaction tank and/
Or the connected relation (also referred to as " slidingtype chip ") between runner.It is set in general, being examined fastly in Complex water body multi-parameter of the invention
It is above-mentioned fixed chip used in standby, slidingtype chip also can be used as needed.
As the slidingtype chip, can have reaction tank and/or runner on the substrate, and in the cover plate
It is upper that there is reaction tank and/or runner, by being mutually shifted for the substrate and the cover plate, can make between runner and reaction tank
Connected relation change, such as form two disconnected reaction tanks on substrate, form runner on cover plate, it is mobile before runner
Two reaction tanks cannot be connected to;And being mutually shifted by cover plate and cover plate, runner can be connected to two reaction tanks, so that
Sample and/or preset reagent in two reaction tanks can react to each other, consequently facilitating the progress reacted in control chip.It is described
Can according to need on slidingtype chip and multiple reaction tanks and multiple runners be set, adapt to Complex water body multi-parameter examine fastly in it is various
Complicated, high pass quantitative response demand.Above-mentioned movement can be sliding or rotation etc. in plane.
A preferred embodiment according to the present invention, as shown in the a-d in Fig. 2, the rotatable chip 1 includes base
Piece and cover plate, the reaction tank setting on the substrate, are provided with reagent, the substrate and the cover plate on the cover plate
Relative movement, so that the reaction tank is interconnected or separates with the reagent.A in Fig. 2 shows rotatable chip 1
Substrate, be provided with reaction tank thereon, b shows the cover plate of rotatable chip 1, is provided with reagent thereon.C, d in Fig. 2
Two kinds of rotation status figures of the respectively described rotatable chip 1 show the state that reaction tank is connected to from different reagents.
According to the present invention, it further includes sample introduction component that the Complex water body multi-parameter examines equipment fastly, and the sample introduction component is used for
By sample feeding into the chip.There is no particular limitation for the sample introduction component, can complete above-mentioned sample feeding operation i.e.
Can, existing any sampling device can be used.From the point of view of convenient for operation and portability, it is preferable that described
Sample introduction component is manual injector.
As a kind of manual injector of the invention, as shown in figure 3, the manual injector 1 includes sample cell 12, control
Portion 11 and out sample portion 13, the control unit 11 are connected with the sample cell 12, for entering sample and being maintained at the sample
In product pond 12 or sample is made to release the sample cell 12 through the sample portion 13 out, the sample portion 13 out is located at the sample cell 12
The side opposite with the control unit 11;The injection port 23 of the manual injector 1 and chip 2 is tightly connected.
The manual injector 1 can cooperate with the chip 2, realize sample introduction and control sample in the chip 2
Flow process purpose, the manual injector 1 can be used for sampling, thus the dress that the very big operation simplified needs
It sets, is highly convenient for the use of sampling device under various application scenarios.Flow process of the above-mentioned control sample in chip 2, simultaneously
Including the process for pushing sample to move forward or back, so as to so that the function of chip is more diversified, such as sample can be made anti-
Again by some reaction tank to accelerate the mixing of sample, or after first being mixed with the sample in some chamber, then with it is other
The sample of reaction tank mixes.
As needed, the injection port 23 can protrude from the outside of chip, also can be set in the inside of chip, preferably
The injection port 23 is provided with screw thread, to be screwed on sample portion 13 out.
According to the present invention, the manual injector 1 can be according to different hand samplings from the connection relationship of the chip 2
Device is selected.
A preferred embodiment according to the present invention takes for the ease of the completion of manual injector 1 is used alone
Sample process, sample portion 13 and the injection port 23 of chip 2 out of the manual injector 1 are removably tightly connected.It, can be with when sampling
The manual injector 1 is removed, enter sample by the operation control unit 11 and is maintained in the sample cell 12, then
By going out after sample portion 13 connect with the injection port 23 of chip 2 for manual injector 1, operate the control unit 11 will sample described in out
Release the injection port that the sample cell 12 enters the chip 11 in sample portion 13.
It can be to be screwed on or connected by elastic sealing element as the above-mentioned concrete mode being removably tightly connected
It connects, the bottom in the preferably described sample portion 13 out has helicitic texture or flexible seal member, is preferably screwed on.The helicitic texture can
Think internal thread structure or external thread structure;The flexible seal member can be rubber stopper.
Another preferred embodiment according to the present invention, in order to be further simplified device, the manual injector 1
Sample portion 13 is fixedly connected with the injection port 23 of the chip 2 out.It is highly preferred that the sample cell 12 of the manual injector 1, out sample
The injection port 23 of portion 13 and the chip 2 is formed as one, in use, sample can directly be added in sample cell 12, then will
The control unit 11 is coupled with sample cell 12, by operation control portion 11, controls the flow process of sample in the chips.
A further preferred embodiment according to the present invention, the control unit 11 control the inner cavity of sample cell 12
The range of (i.e. the chamber for sample storage of sample cell 12 and the formation of control unit 11) volume change is according in the chip 2
Portion's structure is selected.As long as the sample of specified amount is packed into sample cell as a result, so that it may which accurate control sample is in chip 2
Each runner, the mobility status in reaction tank, facilitate the control that sample flow in experimentation is repeated several times, improve experiment
Repeatability.
In accordance with the present invention it is preferred that the control unit 11 and the sample cell 12 are detachably connected.By by the control
Portion 11 processed and the sample cell 12 are detachably connected, the two can be separated, convenient for adding sample in sample cell.
According to the present invention, there is no particular limitation for the shape of the sample cell 12 and the control unit 11, and the two can phase
Mutually cooperation, realization enter sample and are maintained in the sample cell 12 or sample is made to go out sample portion 13 described in release the sample
Product pond 12.Specifically, the sample cell 12 and the control unit 11 are preferably all cylindricality.The control unit 11 and the sample
Also there is no particular limitation for the connection type in product pond 12, such as can be connected and sealed, be screwed on by seal member etc., from
From the aspect of operating the control unit 11, the preferably described control unit 11 is screwed on the sample cell 12.
A preferred embodiment according to the present invention, the process that the control unit 11 controls sample flow pass through described
The cavity volume of sample cell 12 caused by relative motion between control unit 11 and the sample cell 12, which changes, to be completed.
Preferably, the sample cell 12 and control unit 11 can be set to tube-in-tube structure.Wherein, the control unit 11 can be with
As outer cylinder or inner cylinder.It is highly preferred that the inside of the sample cell 12 is arranged in the control unit 11.Specifically, the sample
Product pond 12 can be the outer cylinder of upper opening, and the control unit 11 can be the inner cylinder of sealed bottom.Preferably, the control unit
11 may be set to be telescopic piston.By setting piston for control unit 11, can be relatively moved in sample cell 12.It is logical
Crossing makes control unit 11 and sample cell 12 cooperate, and control unit 11 relatively moves inside sample cell 12, makes the interior of sample cell 12
Chamber size changes, and control sample enters or outflow sample cell 12.
In order to complete control unit 11 and sample cell 12 and be tightly connected, preferably set in the lateral wall bottom of the control unit 11
It is equipped with sealing ring, the sealing ring is for sealing gap between the control unit 11 and the sample cell 12.
Another preferred embodiment according to the present invention, the process that the control unit 11 controls sample flow pass through institute
The deformation process for stating control unit 11 itself is completed.The control unit 11 have can deformation part, and can deformation part by this
Deformation changes the volume of 12 inner cavity of sample cell.It is described can deformation part shape and set-up mode there is no particular limitation,
Preferably, the control unit 11 can deformations be divided into the scalable side wall of alterable height.It is specifically as follows folding side wall,
For example formed as longitudinal section be continuous N font tubular or middle part can deformation part connection up and down two can not deformations
Point structure (wherein, can deformation part can be made of flexible material, by can deformation part deformation change up and down two not
Can deformation part mutual alignment relation, such as by horizontal connection structure variation be mutual insert structure) etc..The control unit 11
Side wall as can deformations timesharing, preferably deformation occurs at top, and when use can apply pressure or pulling force at the top of this,
Manipulate the Sidewall Height variation of the control unit 11.
As above-mentioned control unit 11 can deformation part material, preferably flexible material, more preferably flexible macromolecule
Polymer is specifically as follows one of polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polytetrafluoroethylene (PTFE) or a variety of, wherein being preferably
Polyethylene and/or polypropylene.
The material of the manual injector 1, it is however preferred to have translucency and chemically inert material.For the ease of observe into
Sample process, the preferably described sample cell 12 are transparent or semitransparent sample cell.As the material of the sample cell 12, preferably high score
Sub- polymer is specifically as follows polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene (PTFE), polycarbonate, poly- methyl
One of methyl acrylate, ABS plastic, phenolic resin, epoxy resin, glass and quartz are a variety of, wherein preferably poly- second
One of alkene, polypropylene, polystyrene and polyvinyl chloride are a variety of.In addition, the control unit 11 is except can be in addition to deformation part
Part and it is described go out sample portion 13 it is also preferred that using above-mentioned material.
If Fig. 3 shows, it includes manual injector 1 and chip 2 that Complex water body multi-parameter of the invention examines equipment fastly.G shows in Fig. 3
The structure of chip 2 is gone out, the chip 2 is round dispersion shape multiple flow passages chip, including 1 injection port 23 and 6 and injection port
23 22,6 runners 21 of the reaction tank being equally spaced are respectively communicated with each reaction tank 22 and injection port 23;It is only shown in a-d in Fig. 3
The injection port 23 of chip 2 illustrates only the one group of runner 21 and reaction tank 22 of chip 2 in e-f;The manual injector 1 wraps
It includes the sample cell 12 of the tubular of polyethylene, the control unit 11 of cupuliform and sample portion 13, the control unit 11 is arranged in the sample out
The inside in product pond 12, and be removably tightly connected with the sample cell 12, for entering sample and being maintained at the sample
In pond 12 or sample is made to release the sample cell 12, and the lateral wall bottom setting of the control 11 through the sample portion 13 out
There is the sealing ring of rubber system, sample portion 13 is located at the bottom of the sample cell 12 out;The manual injector 1 and the chip 2
The injection port 23 is formed as one.Fluid sample is added in sample cell 12 first when sample introduction, control unit 11 is placed in sample
In pond 12, the sealing ring is contacted with the inner sidewall of sample cell 12, pushes control unit 11 until touching interface bottom.Sample exists
In the lower runner 21 for entering chip 2 of pressure effect, sample flow rate is gradually reduced in flow process, in a period of time (such as 10-
Liquid fills up first reaction tank after 60s), enters liquid release reaction tank 22 since 23 end pressure of injection port at this time is less than
The pressure in gap between two layers of chip, sample will not continue to overflow, and all reaction tanks are filled out after a period of time (such as 10-60s)
Full, sample stops flowing.
A preferred embodiment according to the present invention, as shown in figure 4, the sample introduction component can also include pretreatment
Portion 14, the pretreatment portion 14 is for pre-processing sample.It is described go out sample portion 13 be located at the pretreatment portion 14 with control
The opposite side in portion 11 processed is forced out described again after the processing for making sample pass through pretreatment portion by the movement of the control unit 11
Manual injector.
According to the present invention, for a variety of pretreatment operations for cooperating sample to need, the pretreatment portion 14 preferably includes 1
Above preprocessing module (14a, 14b, 14c), preferably 2 or more, more preferably 2-5, further preferably 2-3.
As the pretreatment operation carried out in each preprocessing module, can be selected according to the sample of institute's sample introduction.Tool
Body, the preprocessing module in filtering module, enrichment module, separation module, pH adjustment module and the reaction module one
Kind is a variety of.As filtering module, wherein fiber, porous solid, accumulation medium etc. can be set, such as polypropylene is fine
One of dimension, glass fibre, active carbon, gravel are a variety of, wherein preferably polypropylene fibre, glass fibre;As enrichment
Module, wherein aluminium oxide, silica, targeting vector can be set;As reaction module, wherein may include the reaction needed
Object, such as the mercuric sulfate with chloride progress precipitation reaction.For example, when carrying out the pretreatment of phosphate from sewage measurement sample,
The preprocessing module includes filtering module, pH adjustment module and pre-reaction module;Carry out polycyclic aromatic hydrocarbon measurement sample in water
When pretreatment, the preprocessing module includes filtering module and enrichment module.
According to the present invention, by the way that the pretreatment portion 14 and the sample cell 12 is detachably connected, it can be convenient and set
Different preprocessing modules is set, so that manual injector be made to meet the needs of different sample pretreatments and sample introduction.As detachable
The mode of ground connection, the sample cell 12 can pass through plug division, screw thread, buckle or the detachably connected pretreatment of groove
Portion 14.
In order to improve the leakproofness of sample cell 12 and pretreatment portion 14, such as can be in sample cell 12 and pretreatment portion 14
Sealing performance between interconnecting piece can according to need between further setting sealing accessory, such as gasket
Piece etc. guarantees that carry out process is gone on smoothly to improve the leakproofness of sample injector.
As shown in figure 4, the manual injector used includes control unit 11, sample cell 12, pretreatment portion 14 and sample portion 13 out,
Control unit 11, sample cell 12 and pretreatment portion 14 are cylindrical, transparent glass material.The pretreatment portion 14 is filter module
Block.The filtering module is internally provided with polypropylene fibre filter disc;Sample inlet is arranged in its top, on the side wall of the sample inlet
It is provided with internal screw thread.Sample export is set in the bottom of sample cell 12, external screw thread is provided on the side wall of the sample export, it will
The sample inlet of pretreatment portion 14 and the sample export of sample cell 12 are screwed on, and keep pretreatment portion 14 removably close with sample cell 12
Envelope connection.The sample export of pretreatment portion 14 is as sample portion 13 is gone out, and sample portion 13 is located at the middle part of 14 bottom of pretreatment portion out,
The external screw thread for being screwed on micro-total analysis chip is provided on side wall.Control unit 11 can form sample with sealed sample pond 12
Chamber makes the mobile volume that can change sample cavity of control unit 11 by pushing manually, and makes the sample in sample cavity by pre- place
Reason portion 14 is simultaneously extruded by going out sample portion 13.Before starting sample introduction, control unit 11 is opened, sample is injected into sample injector, closes control
The injection port of the sample injector and chip is screwed on by portion 11, and control unit 11 is then pushed to make the smaller volume of sample cavity, and sample passes through
Enter chip after the filter disc filtering of pretreatment portion 14.Observation enters the water sample of chip, has no grainless impurity.
According to the present invention, the detection device includes more than one detection part.The detection part is used for detection chip
The signal of upper sample.
In the present invention, there is no particular limitation for the detection part, can be used for the various detection parts of chip detection,
Such as the detection part can be chromaticity sensing section, absorbance detection component, fluorescence signal detection part, Raman signal inspection
Survey one of component and infrared spectroscopy detection part or a variety of.It is wherein preferably absorbance detection component and fluorescence detection component
One of or it is a variety of.
A preferred embodiment according to the present invention, as shown in figure 5, the detection part is by light source 31, branch light
Fibre 32 and spectroscopy equipment 33 are constituted.The light source 31 is used for generating the light for carrying out testing required wavelength, the branch optical fiber 32
In detecting optical signalling in multiple reaction tanks simultaneously, the spectroscopy equipment 33 is for collecting the optical signal after reaction tank.When
When being provided with the more than two reaction tanks not waited with the centre distance of the chip on chip, the branch optical fiber 32 can will be used
It is divided into multichannel in the incident light of detection, to realize the detection for the reaction tank not waited with the centre distance of the chip.
According to the present invention, in order to realize data processing, data transmission the effects of, the water quality many reference amounts detection device also wraps
Including can also include the mechanical part for driving chip rotation, signal acquisition component, data processor, data output component, number
According to one of transmission part or a variety of.It further include number as a kind of preferred embodiment of water quality many reference amounts detection device
According to processing component, data output component, data transfer component.As the data processor, such as can be including control
Device, arithmetic unit and central processing unit of register etc.;It may include having the function of images outputting as the data output component
Display screen, touch screen, voice output etc.;As the data transfer component, initial data can be uploaded to remote service
Device is remotely handled, then result is returned directly to designated terminal, can also by data processor generate treated
Information remote transmitting to cloud carries out information collection.
According to the present invention, in order to cooperate the markd chip of tool, the detection of many kinds of parameters is realized, the Complex water body multi-parameter
There is identification component and more than one test section fastly, the identification part is used to detect to be used to determine on the chip in inspection equipment
The label of signal is detected, the test section is used to determine that the detection label of signal to be corresponding on the chip.In chip
In rotary course, the identification part identifies the label that each reaction tank setting is corresponded on the chip, then determines respectively each anti-
The detection mode for answering pond to need to use, to realize the detection respectively to unlike signal object.
Second aspect of the present invention provides a kind of fast detecting method of Complex water body multi-parameter, utilizes the Complex water body of aforementioned present invention
Multi-parameter is examined equipment fastly and is detected, and by sample feeding into the chip, and is detected by the detection device.
In order to which the detection of multi-parameter is rapidly completed, in the present invention it is possible to by rotating the chip or making the core
Piece is mobile relative to the detection device, completes the sample detection in the different reaction tanks.For rotary chip, Ke Yitong
It crosses rotary chip and completes detection;For straight-line chip, can complete to detect by pull chip.
A preferred embodiment according to the present invention, by being arranged on the chip for determining detection signal
Label, determines the detection part that detection device uses.By with the use of having a markd chip, method of the invention can be
Short time handles the detection process of multiple types sample signal, to improve detection speed.
The index that method of the invention can detecte includes COD, total nitrogen, sulfide, total phosphorus etc., specifically be can be used corresponding
Reagent sample is handled after detect., can be preset in the chips by reagent for the reaction for needing to be added reagent, thus
Detection accuracy is improved, and easily facilitates operation.
Method of the invention can according to the needs chip suitably selected to use, detection part, sampling device etc. of detection,
To be attained by good detection effect for various samples, pretreatment appropriate can also be set as needed, reacted
Journey more quickly and easily completes detection.It is especially suitable for being detected for water sample.
The present invention will be described in detail by way of examples below.In following embodiment, specific detection agents difference
The commercially available product for being WAK for the Japanese physical and chemical company trade mark vertical altogether, sample COD, total nitrogen, sulfide, the mixing of total phosphorus titer are molten
Liquid.