CN105102976B - Micro-fluidic chip for chromium in continuous monitoring water and the survey chromium device comprising it - Google Patents

Micro-fluidic chip for chromium in continuous monitoring water and the survey chromium device comprising it Download PDF

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Publication number
CN105102976B
CN105102976B CN201380075382.8A CN201380075382A CN105102976B CN 105102976 B CN105102976 B CN 105102976B CN 201380075382 A CN201380075382 A CN 201380075382A CN 105102976 B CN105102976 B CN 105102976B
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China
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reagent
chromium
substrate
sample
micro
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CN105102976A (en
Inventor
韩宗勋
安宰勋
缮井硲
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Academy Industry Foundation of POSTECH
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Academy Industry Foundation of POSTECH
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Priority to KR1020130037733A priority Critical patent/KR101466301B1/en
Priority to KR10-2013-0037733 priority
Application filed by Academy Industry Foundation of POSTECH filed Critical Academy Industry Foundation of POSTECH
Priority to PCT/KR2013/010244 priority patent/WO2014163271A1/en
Publication of CN105102976A publication Critical patent/CN105102976A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76Chemiluminescence; Bioluminescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18Water
    • 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
    • B01F25/433Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
    • B01F25/4331Mixers with bended, curved, coiled, wounded mixing tubes or comprising elements for bending the flow
    • 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
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18Water
    • G01N33/1813Water specific cations in water, e.g. heavy metals
    • 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
    • B01L3/502715Containers 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 interfacing components, e.g. fluidic, electrical, optical or mechanical interfaces

Abstract

Micro-fluidic chip according to an aspect of the present invention, including:First substrate, it is connected in parallel and sense channel that end side is connected with outlet with the reduction passage and the reagent hybrid channel formed with reduction passage, the reagent hybrid channel for mix reagent and the side end for composite sample and reagent;And second substrate, have towards the sense channel and make the test section of light transmission, the second substrate is combined with the first substrate.

Description

Micro-fluidic chip for chromium in continuous monitoring water and the survey chromium device comprising it
Technical field
The present invention relates to a kind of micro-fluidic chip of chromium concn being present in using chemoluminescence method continuous monitoring in water and Include its survey chromium device.
Background technology
Chromium is primarily used for the material of alloy, pigment, leather, textile industry, catalyst, timber preservative etc., due to tool There is chemical stability to be used as the gilding for preventing metal erosion more.With the increase of above-mentioned industrial production activities, the row of chromium Put the pollution for causing surface water and underground water.
Natural chromium ion exists in the form of a variety of chemical valences, but most stable of chromium (III) and chromium (IV) are only existed in water.Chromium (III) it is to participate in glucose, cholesterol, the essential nutrient of the metabolism such as fat, if lacking chromium (III), body weight will be reduced, also The function that can cause to remove glucose from blood is damaged.Moreover, if chromium (III) contacts skin for a long time, may result in Quick or cancer.But chromium (III) is relatively low to the solubility of water and to biological permeability of the membrane, therefore it is generally acknowledged that toxicity not It is high.Unlike this, chromium (IV) is higher to the solubility and mobility of water, and oxidability and to biological permeability of the membrane compared with Height, harmful effect can be brought to the various internal organs such as kidney, liver, lung, can also cause the inflammation of skin or mucous membrane.
As noted previously, as these respective concentration are entered by the different qualities and toxicity of chromium (III) and chromium (IV) exactly Row analysis is extremely important.Especially, chromium (III) and chromium (IV) are easily converted each other according to environment by redox reaction, therefore Need persistently to be monitored water quality.According to the pollution discharge standard of South Korea, what is be allowed in water resource conservation zone is total Chromium concn is 0.5ppm, and below 2ppm is then limited in other areas, and the concentration of chromium (IV) is in water resource conservation zone 0.1ppm, below 0.5ppm is then limited in other areas.In addition, Environmental Protection Agency USA (Environmental Protection Agency, EPA) provide that chromium (IV) is carcinogen, the total chromium concn being allowed in drinking water is limited in Below 0.1ppm.
For analyzing in water chromium in the prior art, the chromium analysis using chemiluminescence reaction are measure as following [anti- Answer formula 1] shown in the basic conditions and in the presence of chromium (III) catalyst by luminol (luminol, the 5- of hydrogen peroxide oxidation Amino-2,3-dihydro-1,4-phthalazinedione the intensity of the light (425nm)) sent.The light now sent The intensity of line is proportional to the concentration of chromium (III), therefore the intensity by determining light can carry out quantitative analysis to chromium (III).
[reaction equation 1]
For chromium (IV), because not participating in the chemiluminescence reaction of luminol directly, make in acid condition After chromium (IV) is reduced into chromium (III) with reducing agent, total chromium concn is analyzed.Chromium (IV) is reduced into the reaction of chromium (III) As shown in [reaction equation 2].
[reaction equation 2]
The method analyzed by chemoluminescence method chromium (III) and chromium (IV) is as follows:First, by sample and reducing agent Reacted, after the chromium (IV) in sample is reduced into chromium (III), then determine total chromium concn.Meanwhile surveyed without using reducing agent Determine the concentration of chromium (III), then calculate the difference of the concentration of total chromium and chromium (III) and just can obtain the concentration of chromium (IV).Prior art is fitted The micro-fluidic chip for analyzing chromium in water is have developed with described method, but there are the following problems.
Firstth, the luminol oxidation reaction as caused by hydrogen peroxide hastens very fast due to reaction in the basic conditions, is Effectively determine that maximum chemical is luminous, it is necessary to which the chemical illuminating reagent mixing for reducing injection luminol and hydrogen peroxide as far as possible is logical The length in road.Moreover, in order to analyze the concentration of chromium (IV) exactly, the chromium (IV) 100% in sample should be reduced into chromium (III), thus sufficient reaction time is needed.Therefore, it should be designed to that the length for reducing passage is relative and be longer than chemical illuminating reagent The length of hybrid channel.However, in the prior art, the length of chemical illuminating reagent hybrid channel is gone back chromium (IV) with being used for The length of the former reduction passage into chromium (III) is identical, therefore can not detect the concentration of chromium (III) and chromium (IV) exactly, and Detection sensitivity declines.
Secondth, not only produced using the chemiluminescence reaction of luminol in the presence of chromium (III), can also be in other metals Produced in the presence of ion (iron (II), cobalt (II), copper (II), nickel (II) etc.).Prior art is not accounted for these interference The effect of material, therefore can not selectively analyze the concentration of chromium in sample.
3rd, because the pH value of sample changes during being mixed with the distilled water injected during analysis chromium (III), deposit The mixed crystallization of chromium (III) and metal ion can be generated in the live sample of other metal ions, and then chromium may occur (III) the also coprecipitation phenomena of coprecipitation.In the event of coprecipitation phenomena, in the sample that will result in injection micro-fluidic chip Chromium (III) concentration reduce, and then cause analytical error, the precipitation can also cause micro-fluidic chip to be blocked.
4th, in order to analyze chromium (III) and chromium (IV), it is necessary to two calibration curves (calibration curve, total chromium and The calibration curve of chromium (III)).
5th, enter detector because micro-fluidic chip makes light around with transparent glass substrate, therefore detect spirit Sensitivity declines, and also resulting in device and using becomes difficult.
The content of the invention
Technical problem
The present invention provides one kind to by chromium in chemoluminescence method continuous monitoring water, connect without carrying out separation process Chromium (III) and chromium (IV) are detected with high efficiency, high sensitivity under continuous flow regime, and can be made not interfering with material Into influence in the case of to chromium carry out selective enumeration method micro-fluidic chip and include its survey chromium device.
Technical scheme
Micro-fluidic chip according to an aspect of the present invention, first substrate, formed with for composite sample and reagent Reduction passage, the reagent hybrid channel for mix reagent and a side end mix logical with the reduction passage and the reagent Road is connected in parallel and sense channel that end side is connected with outlet;And second substrate, have logical towards the detection Road and the test section for making light transmission, the second substrate are combined with the first substrate.
The reduction passage can be longer than the reagent hybrid channel, the first substrate and second substrate can by with Can the material of color of extinction formed, or be dyed to can extinction color.
Can be formed with for injecting the sample injection port of sample and reduction for injecting reducing agent on the first substrate Agent inlet, the sample injection port are connected using specimen access as mediator with reduction passage, and the reducing agent inlet is with also Former agent passage is that mediator is connected with reduction passage, and can be formed with for the first reagent of injection on the first substrate One reagent inlet and the second reagent inlet for injecting the second reagent, the first reagent inlet pass through the first reagent Passage is connected with reagent hybrid channel, and the second reagent inlet is connected by the second reagent passage with reagent hybrid channel.
The sense channel can overlap and a side end and end side interactive connection, and the sense channel is therefrom Centre more more reduce to both sides side, and it is described reduction passage and the reagent hybrid channel can overlap and a side end and End side interconnects.
Survey chromium device according to another aspect of the present invention, including:Micro-fluidic chip, including first substrate and the second base Plate, wherein first substrate formed with for the reduction passage of composite sample and reagent, the reagent hybrid channel for mix reagent, And one side end with it is described reduction passage and the reagent hybrid channel be connected in parallel and what end side was connected with outlet Sense channel, and second substrate has towards the sense channel and makes the test section of light transmission, the second substrate and institute State first substrate combination;Detector, it is configured to towards the test section;And supply department, for being supplied to the micro-fluidic chip Answer sample and reagent.
The reduction passage can be longer than the reagent hybrid channel, the first substrate and second substrate can by with Can the material of color of extinction formed, or be dyed to can extinction color.
Reducing agent that can be formed with the sample injection port for injecting sample, for injecting reducing agent on the first substrate Inlet, the first reagent inlet for injecting the first reagent and the second reagent inlet for injecting the second reagent.
The supply department can supply sample to the sample injection port, and potassium sulfite is supplied to the reducing agent inlet, The luminol of the cushioning liquid of alkalescence condition is dissolved in the first reagent inlet supply, to the second reagent inlet Supply is dissolved in the hydrogen peroxide of the cushioning liquid of alkalescence condition.
The supply department can by bromide ion together with first reagent and second reagent supplied to described micro-fluidic Chip, the supply department can be by ethylenediamine tetra-acetic acid (EDTA;Ethylenediaminetetraacetic acid) with described the One reagent and second reagent are supplied to the micro-fluidic chip together.
The sense channel can overlap and a side end and end side interactive connection, and the sense channel is therefrom Centre more more reduces to both sides side.
Advantageous effects
In the present invention, reduction passage is made in micro-fluidic chip so that the chromium (IV) in sample can be reduced into chromium (III), so as to analyzing chromium (III) and chromium (IV) exactly.
Moreover, pass through the asymmetrical reduction for designing the reagent hybrid channel and injection sample that make injection chemical illuminating reagent Passage has different length, uses and reduces the caused chemiluminescent loss in reagent hybrid channel as far as possible, so as to low Detectable limit and high sensitivity detect to chromium.
Moreover, being contained in the complexing agent of chemical illuminating reagent in sense channel and sample meets and removed present in sample The metal ion of interference effect can be produced, so as to carry out selective enumeration method to chromium under continuous flow regime.
Moreover, analysis chromium (III) when by reducing agent inlet inject sample, therefore will not occur chromium (III) precipitation or Coprecipitation phenomena with disturbing metal, so as to carry out the analysis of chromium concn exactly.
In addition, the slope of the calibration curve of the total chromium of 2 times of the slope of the calibration curve of chromium (III), therefore only with the school of total chromium Directrix curve is with regard to that can analyze the concentration of chromium (III) and chromium (IV), so as to shorten analysis time.
The micro-fluidic chip of the present embodiment is made of light absorbent, and detector is entered to prevent the light of surrounding, so as to To obtain the chemiluminescence signal of highly sensitive stabilization, scene is readily applied to.
Brief description of the drawings
Fig. 1 is the top view for the micro-fluidic chip upper plate for showing one embodiment of the invention.
Fig. 2 is the top view for the micro-fluidic chip lower plate for showing one embodiment of the invention.
Fig. 3 is the structure chart for the survey chromium device for showing one embodiment of the invention.
Fig. 4 a show to be based on to whether there is 0.1M bromide ions and the chemiluminescence signal of chromium (IV) concentration in chemical illuminating reagent.
Fig. 4 b show the calibration curve based on the chromium (IV) that 0.1M bromide ions are whether there is in chemical illuminating reagent.
Fig. 5 shows the chemiluminescence based on chromium (IV) concentration obtained by black micro-fluidic chip and transparent micro-flow control chip Signal.
Fig. 6 is to appearing in the chemiluminescence of the 500ppb chromium (III) of sense channel with cooling type CCD (Cooled CCD) The photo that camera is observed.
Fig. 7 shows chemiluminescence signal, and these chemiluminescence signals are to be longer than reagent hybrid channel in reduction passage Micro-fluidic chip (micro-fluidic chip A) and reduction passage and the length identical micro-fluidic chip of reagent hybrid channel are (micro-fluidic Chip B), the standard specimen different with the ratio of chromium (IV) with chromium (III) in the total chromium of 1000ppb determines.
Fig. 8 a are shown based on chromium (III) and the chemiluminescence signal of chromium (IV) concentration obtained from injection reducing agent.
Fig. 8 b show the calibration curve of chromium (III) and chromium (IV) obtained from injecting reducing agent.
Fig. 9 a show the chemiluminescence signal based on total chromium and chromium (III) concentration.
Fig. 9 b show the calibration curve of total chromium and chromium (III).
Figure 10 shows be based on being mixed with the sample of chromium (III) and iron (II) whetheing there is EDTA and whetheing there is the chromium of reducing agent (III) chemiluminescence signal.
Figure 11 shows to be mixed with the chemistry hair of chromium (III) obtained from injection distilled water in the sample of chromium (III) and iron (II) Optical signal.
Embodiment
Below, embodiments of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art in the invention are easy Implement the present invention.The present invention can be implemented in a variety of different ways, however it is not limited to following embodiments.
Fig. 1 is the top view for the micro-fluidic chip upper plate for showing one embodiment of the invention, and Fig. 2 is to show that the present invention one is implemented The top view of the micro-fluidic chip lower plate of example.
The micro-fluidic chip 30 of the present embodiment includes upper plate (first substrate) 10 and lower plate (second substrate) 20.Upper plate 10 is Square plate shape, formed with sample injection port 11, reducing agent inlet 12, the first reagent inlet 13 and the second reagent on upper plate 10 Inlet 14.Moreover, formed with the linking part 31 for being combined with sample ascending pipe 52, reducing agent injection on sample injection port 11 Formed with the linking part 32 for being combined with reducing agent ascending pipe 53 on mouth 12.
Formed with the linking part 34 for being combined with reagent ascending pipe 54, the injection of the second reagent on first reagent inlet 13 Formed with the linking part 35 for being combined with reagent ascending pipe 55 on mouth 14.
In addition, formed with specimen access 11a, reducer channel 12a, the first reagent passage 13a, the second reagent on upper plate 10 Passage 14a, reduction passage 15, reagent hybrid channel 16 and sense channel 17.Sample injection port 11 is connected with specimen access 11a, Reducing agent inlet 12 is connected with reducer channel 12a.Sample containing chromium is injected by sample injection port 11, passes through reducing agent Inlet 12 is injected for reducing the reducing agents such as the potassium sulfite of chromium (IV).
Specimen access 11a and reducer channel 12a is connected with reduction passage 15, sample and reducing agent in passage 15 is reduced It is mixed, is reduced agent comprising chromium (IV) in the sample and is reduced into chromium (III).Reduction passage 15 overlaps and a side end Interconnected with end side.One side end of reduction passage 15 is connected with specimen access 11a and reducer channel 12a, and End side is connected with sense channel 17.
First reagent inlet 13 is connected with the first reagent passage 13a, the second reagent inlet 14 and the second reagent passage 14a connections.The luminol, bromide ion and EDTA for being dissolved in alkalescence condition cushioning liquid can be injected by the first reagent inlet 13, Can by the second reagent inlet 14 inject be dissolved in for dissolve the luminol alkalescence condition cushioning liquid in peroxidating Hydrogen, bromide ion and EDTA.
First reagent passage 13a and the second reagent passage 14a are connected with reagent hybrid channel 16, in reagent hybrid channel 16 Middle luminol and hydrogen peroxide are mixed.Reagent hybrid channel 16 overlaps and a side end interacts company with end side Connect.One side end of reagent hybrid channel 16 is connected with the first reagent passage 13a and the second reagent passage 14a, and another side Portion is connected with sense channel 17.
One side end of sense channel 17 is connected with reduction passage 15 and reagent hybrid channel 16, and shape in end side Into there is outlet 18, to discharge reagent and sample for reaction.Formed with linking part 33 on outlet 18, so as to discharge Pipe combines.
Sense channel 17 overlaps and a side end interconnects with end side.The length of overlapping sense channel 17 Degree more more reduces from center to both sides side, and the center configuration of sense channel 17 is into the center alignment with circle detection portion 21.
One side end of sense channel 17 is connected in parallel with reduction passage 15 and reagent hybrid channel 16, therefore logical in detection The sample and reagent to be met in road is mixed, and so as to eliminate the interference effect in sample, while produces chemiluminescence reaction.
The length of reduction passage 15 is 2 times to 6 times of the length of reagent hybrid channel 16.Thus, chromium (IV) can be logical through reducing Road 15 is reduced agent and is reduced into chromium (III).The length for being additionally, since reagent hybrid channel 16 forms shorter so that in reagent The chemiluminescent loss occurred in hybrid channel 16 be reduced to it is minimum, so as to low detectable limit and high sensitivity to chromium Detected.
Linking part 31,32,33,34,35 is formed by polymer or pipe (tubing) etc., and with hole so as to pipe or Pipeline combines with being readily able to handling.
Upper plate 10 can be formed by the polymer with light absorptive, particularly can by black dimethyl silicone polymer (PDMS, Polydimethylsiloxane) formed.But upper plate 10 can be formed by the material of a variety of colors with light absorptive, Huo Zheke It is dyed to the color with light absorptive.
In addition, the 17 corresponding bottom of sense channel in lower plate 20 with upper plate 10 is formed with test section 21.Lower plate 20 by The PDMS of black is formed, and test section 21 is filled with transparent PDMS so that the light as caused by chemiluminescence reaction passes through.Test section 21 can be formed by way of injecting transparent PDMS after black PDMS formation holes.But when lower plate 20 is colored, only detect Portion will not be colored and be formed as transparent.
As described above, when upper plate 10 and lower plate 20 are formed as with light absorptive, the light injected from outside is absorbed by, from And the chemiluminescence signal that can be stablized, and detectable limit and sensitivity can be improved.
Below, the manufacture method of upper plate 10 and lower plate 20 is illustrated.The spin coating photoresist on ready silicon wafer Afterwards, place and irradiate ultraviolet in the state of photomask, then cured and development and form positive needle drawing case.
After silicon wafer upper black PDMS formed with positive needle drawing case is cured, upper plate 10 can just be obtained from chip separation To the black PDMS upper plates formed with cloudy needle drawing case.Lower plate 20 also manufactures using with the identical method of upper plate 10.
For upper plate 10 and lower plate 20, after its bound fraction is surface-treated by arc discharge, with the inspection of upper plate 10 The center and the mode of the center alignment of the test section 21 of lower plate 20 for surveying passage 17 are combined.
Sample and reducing agent are moved to sense channel 17 through reducing passage 15, and reagent is moved to inspection through reagent hybrid channel 16 Passage 17 is surveyed, so as to cause chemiluminescence reaction.Sample and reagent movement after sense channel 17 causes chemiluminescence reaction To outlet 18.
Fig. 3 is the structure chart for the survey chromium device for showing one embodiment of the invention.
Knowable to reference picture 3, the survey chromium device of the present embodiment, including be inserted in the housing 41 to form profile and configure and examining Detector 42, micro-fluidic chip 30 and the supply department 51 that sample and reagent are supplied to micro-fluidic chip 30 of the lower section of survey portion 21. Housing 41 is formed as slightly in the boxed-section shape of cuboid.Housing 41 is formed by the metal for dying black to absorb light, miniflow Control chip 30 is fixedly arranged on above housing 41.Thus, extraneous light is blocked to enter detector 42, so it is only anti-through chemiluminescence Light caused by answering passes through test section 21 and injects detector 42.
In addition, sample ascending pipe 52 is equipped with the linking part 31 of sample injection port 11, located at reducing agent inlet Reducing agent ascending pipe 53 is equipped with 12 linking part 32.Set moreover, being connect on the linking part 34 of the first reagent inlet 13 There is the first reagent ascending pipe 54, the second reagent ascending pipe 55 is equipped with the linking part 35 of the first reagent inlet 14.
Supply department 51 is provided with peristaltic pump, and supply department 51 supplies sample to sample ascending pipe 52, and to reducing agent ascending pipe 53 supply potassium sulfites.Moreover, supply department 51 supplies luminol to the first reagent ascending pipe 54, and to the second reagent ascending pipe 55 Supply hydrogen peroxide.
51 reagent without interruption of supply department and sample, arranged by outlet 18 after the sample and reagent reacting supplied Go out.Thus, the survey chromium device of the present embodiment can continuous monitoring chromium.
Bromide ion is fed to micro-fluidic chip 30 by supply department 51 together with reagent, and thus chemiluminescence intensity increase, enters And the sensitivity for surveying chromium device is improved, lower detectable limit can be had by surveying chromium device.Moreover, supply department 51 is by EDTA and reagent Supply together.EDTA reacts with metal ion and forms complex compound in the basic conditions, thus removes and participates in Rumi contained by sample Other metal ions of the chemiluminescence reaction of promise, so as to avoid the measure of chromium concn inaccurate.
Detector 42 accesses power supply 61.Caused signal in detector 42 is processed moreover, connecing and setting on detector 42 Signal after processing is sent to connected computer 63 by the digital multimeter 62 of processing, digital multimeter 62.
[experimental example 1]
In experimental example 1, the micro-fluidic chip using the present embodiment and the survey chromium device comprising it are determined based on chromium The chemiluminescence intensity of concentration.Chemical illuminating reagent is used to from sample detect chromium (III), its in the basic conditions with chromium (III) Carry out reaction and cause chemiluminescence.Chemical illuminating reagent is made up of luminol and hydrogen peroxide, and chemiluminescent intensity is according to Shandong The concentration of minot and hydrogen peroxide can change.
Cushioning liquid preparation method for chemoluminescence method is as follows:By 30.09g boric acid (H3BO3), 10.2g bromination The EDTA ((HOOCCH of potassium (KBr), 2.92g2)2HNCH2CH2NH(CH2COOH)2) be dissolved in distilled water, recycle 5M hydrogen PH value is tuned into 10.9 by potassium oxide (KOH) solution, and final volume is turned into 1L.The preparation method of chemical illuminating reagent is as follows: 0.02g luminol is dissolved in cushioning liquid and adjusted after pH value reaches 10.9, final volume is turned into 100mL.Oxidant Preparation method it is as follows:0.868mL hydrogen peroxide is dissolved in the cushioning liquid and adjusted after pH value reaches 10.9, is made most Final volume turns into 100mL.For make chromium (IV) be reduced into chromium (III) reducing agent its preparation method it is as follows:By 0.1104g's Potassium sulfite (K2SO3) be dissolved in distilled water and adjust after pH value reaches 2.5, final volume is turned into 100mL.Chromium (III) and chromium (IV) standard specimen its preparation method is as follows:Respectively by chromic nitrate nonahydrate (Cr (NO3)3·9H2) and potassium chromate O (K2CrO4) be dissolved in the solution that distilled water prepares 1000ppm after, by dilute with 5ppb, 50ppb, 125ppb, 250ppb, 500ppb, 1000ppb concentration are prepared respectively.
Chemical illuminating reagent is that luminol is injected by the first reagent inlet 13, and hydrogen peroxide is noted by the second reagent Entrance 14 injects.Sample is injected respectively by sample injection port 11, reducing agent by reducing agent inlet 12.Inject each molten The flow velocity of the peristaltic pump used during liquid is 7.5 μ L/min.
Fig. 4 a show to be based on to whether there is 0.1M bromide ions and the chemiluminescence signal of chromium (IV) concentration in chemical illuminating reagent, Fig. 4 b show the calibration curve based on the chromium (IV) that 0.1M bromide ions are whether there is in chemical illuminating reagent.
The standard specimen used in this experimental example is 5ppb, 50ppb, 125ppb, 250ppb, 500ppb, 1000ppb chromium (IV), inject reducing agent and tried using the chemical illuminating reagent of addition 0.1M bromide ions with the chemiluminescence for being not added with bromide ion Agent, chemiluminescence signal of the METHOD FOR CONTINUOUS DETERMINATION based on each concentration.Bromide ion can attack metal ion under alkalescence condition, hydrogen peroxide And the complex that luminol reacts and generated.Thus, it can generate and more cause chemiluminescent excitation state O-phthalic amine (3- Aminophthalate) so that chemiluminescence intensity increase.As shown in fig. 4 a, using the chemiluminescence of addition 0.1M bromide ions During reagent, with using be not added with bromide ion chemical illuminating reagent when compared with, chemiluminescence intensity greatly increases.
In fig. 4b, the calibration curve for adding the chemical illuminating reagent of 0.1M bromide ions is y=0.00100x+0.00289 (R2=0.9999) calibration curve for, being not added with the chemical illuminating reagent of bromide ion is y=0.000182x+0.000212 (R2 =0.9999).Wherein, y represents chemiluminescence intensity, and x represents concentration, R2Represent linear coefficient.This calibration curve is to use The standard specimen prepared by material to be analyzed, since low concentration according to concentration sequential determination chemiluminescence intensity after, will be based on The relation of the chemiluminescence intensity of material concentration to be analyzed is represented with line.
When as shown in Figure 4 b, using the chemical illuminating reagent of addition 0.1M bromide ions, with using the change for being not added with bromide ion Compared when learning luminescence reagent, about 5.5 times of the slope increase of calibration curve.
Moreover, during addition 0.1M bromide ions, detectable limit 0.32ppb, detectable limit during with being not added with bromide ion 1.3ppb is compared, and has about low 4 times of detectable limit.Therefore, can by adding 0.1M bromide ions in chemical illuminating reagent Chromium is detected with higher sensitivity and low detectable limit.
[experimental example 2]
In this experimental example 2, by upper plate 10 and lower plate 20 with black PDMS making and the miniflow made of transparent PDMS Control chip to be applied to survey chromium device, and determine the chemiluminescence intensity of total chromium.This experimental example is carried out in darkroom.
Fig. 5 shows the chemiluminescence based on chromium (IV) concentration obtained by black micro-fluidic chip and transparent micro-flow control chip Signal.
As shown in figure 5, with the micro-fluidic chip that transparent PDMS makes because extraneous light enters detector, background signal The intensity of (background signal) and the noise of signal greatly increase, by chromium (IV) standard specimen (5ppb, 50ppb, 125ppb, 250ppb, 500ppb, 1000ppb) obtained chemiluminescence signal is also because in the light and chemiluminescence reaction of surrounding The scattering of caused light and cause jitter and noise is big.
Moreover, as background signal intensity greatly increases, the chemiluminescence signal of below 50ppb chromium (III) can not be with this Bottom signal difference.The chemiluminescence signal obtained as described previously for the micro-fluidic chip by being made using transparent PDMS, with The intensity of background signal and the increase of noise, detectable limit uprise, and the concentration range of detectable chromium reduces.
The micro-fluidic chip made using black PDMS is reviewed, due to having blocked extraneous light to enter detector, background letter Number intensity and noise reduce, chemiluminescence signal is highly stable.Chromium device is surveyed by using the miniflow made by black PDMS Control chip has effectively blocked extraneous light, so as to be detected with higher sensitivity and low detectable limit to chromium, also The concentration range of detectable chromium can be expanded.
[experimental example 3]
In this experimental example 3,500ppb chromium (III) is injected by sample injection port, and with cooling type CCD (Cooled CCD) camera observes chemiluminescence.Fig. 6 is cooled down to appearing in the chemiluminescence of the 500ppb chromium (III) of sense channel The photo that type CCD (Cooled CCD) camera is observed.Chemiluminescence occurs most in the center section of sense channel 17 To be strong, and the chemiluminescence intensity of start-up portion and tail portion is weaker than center section relatively.This result shows, micro-fluidic The design of chip and the condition of reagent are optimized, enabling measure, which chemically lights, to be occurred to disappearance by chemiluminescence reaction Caused most of light, so as to carry out highly sensitive chromium detection.
[experimental example 4]
In this experimental example 4, in order to confirm that chromium (IV) is reduced into the percent reduction of chromium (III), preparing total chromium concn is all 1000ppb and chromium (III) different with the ratio of chromium (IV) respectively 3:7、5:5、7:3 standard specimen, the standard specimen is distinguished Micro-fluidic chip A and micro-fluidic chip B are implanted sequentially, and determines chemiluminescence signal.
Fig. 7 shows chemiluminescence signal, and these chemiluminescence signals are to be longer than reagent hybrid channel length in reduction passage Micro-fluidic chip A (reduction passage 15:100cm, reagent hybrid channel 16:20 ㎝) and reduction passage and reagent hybrid channel Length identical micro-fluidic chip B (reduction passages 15:20 ㎝, reagent hybrid channel 16:20 ㎝), with chromium in the total chromium of 1000ppb (III) standard specimen different with the ratio of chromium (IV) determines.
For micro-fluidic chip A, the chromium (IV) included in sample is reduced into chromium (III), although the chromium (III) in sample Composition with chromium (IV) shows identical chemiluminescence intensity than different.
For micro-fluidic chip B, the chromium (IV) that is included in sample only some be reduced into chromium (III), therefore with not The sample of congruent ratio shows different chemiluminescence intensities respectively.
As described above, according to the present invention, can because the length for reducing passage 15 is longer than the length of reagent hybrid channel 16 To determine the concentration of chromium (IV) exactly.
[experimental example 5]
In this experimental example 5, in order to confirm whether the big chromium of concentration range (IV) 100% is reduced into chromium (III), by 5ppb, 50ppb, 125ppb, 250ppb, 500ppb, 1000ppb chromium (III) and chromium (IV) standard specimen are implanted sequentially sample note respectively Entrance 11, reducing agent inlet 12 is injected reductant into, and determine chemiluminescence signal.
Fig. 8 a show to inject the chemiluminescence signal based on chromium (III) and chromium (IV) concentration, Fig. 8 b obtained from reducing agent and shown The calibration curve of chromium (III) and chromium (IV) obtained from going out to inject reducing agent.
As shown in Figure 8 a, the chromium (III) of each concentration and chromium (IV) show almost identical chemiluminescence intensity.
In figure 8b, the calibration curve of chromium (III) is y=0.00100x-0.00115 (R2=0.9999), the school of chromium (IV) Directrix curve is y=0.00100x+0.00127 (R2=0.9999).Wherein, y represents chemiluminescence intensity, and x represents concentration, R2Table Timberline property coefficient.
Its slope is identical with the calibration curve of chromium (IV) for chromium (III), and y intercept has very small difference, therefore will be respective Calibration curve be shown in result on a figure, two calibration curves are overlapping as shown in Figure 8 b.
It was found from Fig. 8 result, micro-fluidic chip and can be by concentration range (5 comprising its chemiluminescence detecting ~1000ppb) big chromium (IV) 100% is reduced into chromium (III), therefore can detect the dense of chromium (III) and chromium (IV) exactly Degree, does not have analytical error.
[experimental example 6]
This experimental example 6 determine respectively by 5ppb, 50ppb, 125ppb, 250ppb, 500ppb, 1000ppb total chromium and The chemiluminescence signal based on concentration that chromium (III) standard specimen obtains.
Fig. 9 a show the chemiluminescence signal based on total chromium and chromium (III) concentration, and Fig. 9 b show the calibration of total chromium and chromium (III) Curve.
For the sample of same concentrations, the chemiluminescence intensity of chromium (III) is 2 times of total chromium chemiluminescence intensity.Such as Fig. 8 a Shown, when injecting reducing agent, the chromium (III) and chromium (IV) of same concentrations have almost like chemiluminescence intensity.However, In this experimental example 6, when analyzing chromium (III), when injecting sample by sample injection port 11 and reducing agent inlet 12, and analyzing total chromium, Sample is only injected by sample injection port 11, and reducing agent is injected by reducing agent inlet 12, therefore the concentration of sample is diluted as 1/2, so the chemiluminescence intensity of the chromium (III) of same concentrations is 2 times of the chemiluminescence intensity of total chromium.
Fig. 9 b be by the chemiluminescence signal based on concentration shown in Fig. 9 a respectively for total chromium and chromium (III) in triplicate and Obtain calibration curve, it is known that reappearance is very high, thus relative standard deviation is very small.In figure 9b, the calibration of chromium (III) is bent Line is y=0.00200x+0.00112 (R2=0.9999), the calibration curve of total chromium is y=0.00100x+0.00289 (R2= 0.9999).Wherein, y represents chemiluminescence intensity, and x represents concentration, R2Represent linear coefficient.
It can be seen from this experimental example 6, the slope of chromium (III) calibration curve is 2 times of the slope of total chromium calibration curve.Utilize This relation, pass through total chromium and chromium (III) present in the live sample of total chromium calibration curve analysis, the result of the concentration of chromium (IV) It is similar (table 2) come the result calculated with by two calibration curves (calibration curve of total chromium and chromium (III)).As described above, this hair Bright survey chromium device only can analyze total chromium and chromium (III), chromium (IV) exactly by total chromium calibration curve, can greatly reduce point Analyse the time.
The respective detectable limit of total chromium and chromium (III) obtained from this experimental example 6 is 0.32ppb, 0.13ppb.Moreover, line Property section be that 5ppb~1000ppb include legal restriction concentration, therefore the pretreatment such as dilution or concentration without progress sample can To carry out chromium detection.
[experimental example 7]
Reacted for luminol chemiluminescence, in addition to chromium (III), other metal ion (cobalt (II), iron (II), copper (II), nickel (II) etc.) reaction is also assisted in, metal ion relies heavily on pH including chromium to the solubility and mobility of water Value.For example, the reason such as acid rain can cause the acidifying of water, the pH value of water is down to 4.0~4.5 causes the concentration of metal ion to increase Add, influence to become more serious caused by disturbing metal ion.The purpose of this experimental example 7 is to confirm, the acidifying of water causes pH During value changes, if selective inspection can also be carried out to chromium in the case of interference effect caused by other no metal ions Survey.
The effect for caused by interference metal ion, is eliminated using EDTA cans.EDTA in the basic conditions with metal Ionic reaction and form complex compound, the metal ion for forming complex compound cannot participate in chemiluminescence.On the contrary, chromium (III) and EDTA are anti- At once complex compound is formed at relatively slow speeds compared with other metal ions, therefore be applicable to the selectivity to chromium in sample Analysis.
Figure 10 shows be based on being mixed with the sample of chromium (III) and iron (II) whetheing there is EDTA and whetheing there is the chromium of reducing agent (III) chemiluminescence signal, in Fig. 10, (a) are believed by being only dissolved with the chemiluminescence of the Specimen Determination of 500ppb chromium (III) Number, as the benchmark of the chemiluminescence intensity of other samples, the chemiluminescence intensity of (a) is set as 100%.
In Fig. 10, (b) is not add EDTA's to being used dissolved with the sample of 500ppb chromium (III) and 5ppm iron (II) The chemiluminescence intensity that luminol, hydrogen peroxide are analyzed, show 117% chemiluminescence intensity.Chemiluminescence intensity Increase by 17% is caused because disturbing material i.e. 5ppm iron (II).
In Fig. 10, (c) is that injection and the buffering of (b) identical sample and injection dissolved with luminol, hydrogen peroxide are molten The chemiluminescence signal that the reagent that 10mM EDTA is formed is measured is dissolved in liquid respectively, is shown and (a) identical 100% Chemiluminescence intensity.It was found from the result, disturbed using 10mM EDTA cans caused by there is no 5ppm iron (II) Selective enumeration method is carried out to chromium (III) in the case of effect.
In Fig. 10, (d) is being gone back under the same conditions by the inlet injection in two sample injection ports with (c) Chemiluminescence signal obtained from former agent, show the chemiluminescence intensity equivalent to 50%.50% chemiluminescence intensity is Because the injection of reducing agent causes the concentration of sample to be diluted as 1/2.It was found from the result, using 10mM EDTA when, i.e., The reducing agent for making injection pH value be 2.5 will not also have an impact to chemiluminescence signal.
It was found from Figure 10 result, when the concentration that acidifying causes interference with metal ion uprises, without being separated Process can also carry out selective enumeration method using EDTA to chromium (III) and chromium (IV).
[experimental example 8]
This experimental example 8, will be molten in order to inject whether distilled water produces sediment and carry out when confirmation analysis chromium (III) Solution has the solution ph of 500ppb chromium (III) and 5ppm iron (II) to be tuned into 4.5 to get out sample, by sample injection port 11 and reduction Agent inlet 12 injects the sample, confirms chemiluminescence signal now, and injected and be dissolved with by sample injection port 11 The solution of 500ppb chromium (III) and iron (II) and distilled water is injected by reducing agent inlet 12, confirm chemiluminescence letter now Number.
Prior art is filled with distilled water in chromium (III) in detecting sample by an inlet in two inlets (pH 5.8~6.2).For described situation, due to the sample during the reduction sample of passage 20 and distilled water are mixed PH value changes, and may result in the precipitation of chromium (III).
Figure 11, which shows to be mixed with the sample of chromium (III) and iron (II), to be injected distilled water and obtains the chemiluminescence of chromium (III) Signal.In fig. 11, (a) is to change 500ppb chromium (III) as obtained from injecting sample injection port 11 and reducing agent inlet 12 Luminous signal is learned, its chemiluminescence intensity is set as 100%.In fig. 11, (b) is by the 500ppb chromium dissolved with pH 4.5 (III) and 5ppm iron (II) sample chemiluminescence as obtained from being injected separately into sample injection port 11 and reducing agent inlet 12 Signal, show that chemiluminescence intensity ratio (a) is high by 17% in Figure 11.In fig. 11, only (d) be by reagent add EDTA and Obtained chemiluminescence signal.Therefore, chemiluminescence intensity increase by 17% is done caused by 5ppm iron (II) in Figure 11 (b) Disturb effect and caused.
In fig. 11, (c) be by sample of the sample injection port injection dissolved with 500ppb chromium (III) and 5ppm iron (II) and The chemiluminescence signal as obtained from reducing agent inlet injects distilled water.If sample not because of the injection of distilled water and by Any influence, then because the concentration of sample is diluted as 1/2,58.5% chemiluminescence intensity should be shown.However, in Figure 11 In, (c) shows 17.3% chemiluminescence intensity.This shows after the sample of pH 4.5 in reducing passage mixes with distilled water PH value uprises, and then produces the deposited phenomenon or the coprecipitation phenomena of iron and chromium of chromium (III), causes chemiluminescence intensity to reduce 41.2%.In fig. 11, (d) is by injecting sample and distilled water with (c) identical method and injecting the examination dissolved with EDTA Chemiluminescence signal obtained from agent, represent to be removed by EDTA with the iron (II) of dissolved state residual in sample, cause 5.4% Chemiluminescence intensity is reduced.It was found from the result, when detecting chromium (III) by chemoluminescence method, if injection distilled water will Generation analytical error, interference effect caused by also can not eliminating other metal ions even if injection EDTA in this case.
[experimental example 9]
In this experimental example 9, using the reagent and addition 10mM EDTA reagent for being not added with EDTA, to participating in luminol The iron (II) of chemiluminescence reaction, cobalt (II), copper (II), nickel (II) and it is mixed with pH 4.5 sample of chromium and has carried out chemistry Luminous detection.
It is dissolved with 500ppb's or 5ppm respectively for the chromium (III) dissolved with 500ppb and the interference metal ion Sample, pH value is tuned into 4.5 using nitric acid.Now, the volume of the salpeter solution for adjusting pH value is the 1/ of volume of sample Less than 1000, the change in concentration of chromium and interference metal in sample can be ignored.Moreover, for total chromium (bag dissolved with 500ppb The chromium (IV) of chromium (III) and 250ppb containing 250ppb) and the examination dissolved with 500ppb or 5ppm respectively of interference metal ion Sample, pH value is tuned into 4.5 using nitric acid.
Chemical illuminating reagent is by the cushioning liquid that adds 10mM EDTA and the cushioning liquid for being not added with EDTA points Not Jia Ru luminol and hydrogen peroxide prepare.
[table 1]
[table 1] shows the chemiluminescence intensity of each sample, be for the chromium (III) dissolved with 500ppb and interference metal from The sample of son, is set as 100% by the chemiluminescence intensity of 500ppb chromium (III) sample, for dissolved with the total chromium of 500ppb and dry The sample of metal ion is disturbed, the chemiluminescence intensity of 500ppb total chromium sample is set as 100%, and inject and be not added with EDTA Chemical illuminating reagent and addition 10mM EDTA chemical illuminating reagent when, for the chemiluminescence intensity of each sample.Chemistry Value on the right side of luminous intensity in bracket is to determine relative standard deviation obtained from chemiluminescence intensity three times for each sample.
When injection is not added with EDTA reagent, because the chemiluminescence for disturbing metal ion to measure present in sample is strong Degree is more than 100%.However, when using addition 10mM EDTA chemical illuminating reagent, metal ion is disturbed in sense channel Removed by EDTA, thus chemiluminescence intensity and 500ppb chromium (III), 500ppb total chromium standard specimen are identical, for interference The concentration of metal ion is the sample of 10 times (5ppm) of chromium concn, can also be in the case where not interfering with effect to 500ppb Chromium (III) and total chromium carry out selective analysis.
[experimental example 10]
This experimental example 10 is carried out to confirm the performance of the detection means of the present embodiment, is analyzed and is collected in factory Sample in total chromium and chromium (III), the concentration of chromium (IV).The sample injection filtered through the filter with 0.45 μm of pore is micro- Fluidic chip, and determine chromium concn.
Table 2 be by total chromium in sample and chromium (III), chromium (IV) concentration analysis result with by atomic absorption and The form that the result of light absorption method analysis is contrasted, atomic absorption can only analyze total chromium concn, and detectable limit is 20ppb.Moreover, light absorption method using UV-visible spectrophotometric determination by chromium (IV) and 1,5- diphenylcarbazides (1, Trap of the red complex under 540nm wavelength of reaction generation 5-diphenylcarbazide) is simultaneously analyzed, It is the high analysis method of selectivity in chromium (IV) analysis due to interference effect caused by other no materials.
To the chromium in the sample according to this experimental example 10, entered using the micro-fluidic chip of the present embodiment by chemoluminescence method The result of row analysis, the concentration of the total chromium included in sample 1, sample 2, sample 3 are respectively 137ppb, 112ppb, 128ppb, class The result analyzed by atomic absorption is similar to, the result of each sample analysis three times is obtained than atomic absorption more Low relative standard deviation.
[table 2]
For the concentration for the chromium (III) analyzed by chemoluminescence method, sample 1, sample 2, sample 3 be respectively 27ppb, 20ppb, 28ppb, similar to the chromium subtracted from the total chromium concn analyzed by atomic absorption by light absorption method analysis (IV) concentration and counted chromium (III) concentration.For the concentration of chromium (IV), using total chromium and the calculated value of chromium (III) concentration with leading to Chromium (IV) concentration for crossing light absorption method analysis is similar.As described above, using the survey chromium device analysis of the present embodiment, can survey exactly Fixed total chromium and chromium (III), the concentration of chromium (IV).
Presently preferred embodiments of the present invention is described above, but the invention is not limited in the above, in claims It can be implemented with the range of specification and its accompanying drawing in a manner of various modifications, unquestionable these belong to protection scope of the present invention Within.

Claims (11)

1. a kind of micro-fluidic chip, including:
First substrate, formed with for the reduction passage of composite sample and reagent, the reagent hybrid channel for mix reagent and One side end is connected in parallel and inspection that end side is connected with outlet with the reduction passage and the reagent hybrid channel Passage is surveyed, it is that the reagent mixing is logical that the reduction passage, which is longer than the reagent hybrid channel and the length of the reduction passage, 2 times to 6 times of the length in road;And
Second substrate, have towards the sense channel and make the test section of light transmission, the second substrate and described first Substrate combines,
Wherein, the first substrate and second substrate by with can the material of color of extinction formed, or be dyed to can extinction Color.
2. micro-fluidic chip according to claim 1, wherein,
Injected on the first substrate formed with the sample injection port and the reducing agent for injecting reducing agent for injecting sample Mouthful, the sample injection port is connected using specimen access as mediator with reduction passage, and the reducing agent inlet is led to reducing agent Road is that mediator is connected with reduction passage.
3. micro-fluidic chip according to claim 2, wherein,
Formed with for injecting the first reagent inlet of the first reagent and for injecting the second reagent on the first substrate Second reagent inlet, the first reagent inlet are connected by the first reagent passage with reagent hybrid channel, and described second Reagent inlet is connected by the second reagent passage with reagent hybrid channel.
4. micro-fluidic chip according to claim 1, wherein,
The sense channel overlap and a side end and end side interactive connection, the sense channel from center more to Both sides side more reduces.
5. micro-fluidic chip according to claim 1, wherein,
The reduction passage and the reagent hybrid channel overlap and a side end and end side interactive connection.
6. one kind surveys chromium device, including:
Micro-fluidic chip, including first substrate and second substrate, wherein first substrate are formed with for composite sample and reagent Reduction passage, the reagent hybrid channel for mix reagent and a side end mix logical with the reduction passage and the reagent Road is connected in parallel and sense channel that end side is connected with outlet, and it is logical that the reduction passage is longer than the reagent mixing The length of road and the reduction passage is 2 times to 6 times of the length of the reagent hybrid channel, and second substrate has towards institute The test section stated sense channel and pass through light, the second substrate are combined with the first substrate;
Detector, it is configured to towards the test section;And
Supply department, for supplying sample and reagent to the micro-fluidic chip,
Wherein, the first substrate and second substrate by with can the material of color of extinction formed, or be dyed to can extinction Color.
7. survey chromium device according to claim 6, wherein,
Injected on the first substrate formed with the sample injection port for injecting sample, for injecting the reducing agent of reducing agent Mouth, the first reagent inlet for injecting the first reagent and the second reagent inlet for injecting the second reagent.
8. survey chromium device according to claim 7, wherein,
The supply department supplies sample to the sample injection port, potassium sulfite is supplied to the reducing agent inlet, to described The supply of first reagent inlet is dissolved in the luminol of the cushioning liquid of alkalescence condition, is supplied to the second reagent inlet molten Solution is in the hydrogen peroxide of the cushioning liquid of alkalescence condition.
9. survey chromium device according to claim 8, wherein,
Bromide ion is supplied to the micro-fluidic chip by the supply department together with first reagent and second reagent.
10. survey chromium device according to claim 8, wherein,
The supply department by ethylenediamine tetra-acetic acid together with first reagent and second reagent supplied to described micro-fluidic Chip.
11. survey chromium device according to claim 6, wherein,
The sense channel overlap and a side end and end side interactive connection, the sense channel from center more to Both sides side more reduces.
CN201380075382.8A 2013-04-05 2013-11-12 Micro-fluidic chip for chromium in continuous monitoring water and the survey chromium device comprising it Expired - Fee Related CN105102976B (en)

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CN105527233A (en) * 2015-12-10 2016-04-27 中国计量学院 Determination device of hexavalent chromium in water sample based on microfluidic reaction system and determination method thereof
CN105562131B (en) * 2015-12-18 2017-10-31 苏州汶颢芯片科技有限公司 Micro-fluidic chip, detecting system and the detection method detected for total phosphorus
US20190195806A1 (en) * 2016-06-23 2019-06-27 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Method and device for chemiluminescence-based analysis
KR101921861B1 (en) * 2017-04-28 2019-02-20 포항공과대학교 산학협력단 Method for detecting chromium using chemiluminescene
CN110124760B (en) * 2019-05-15 2021-12-21 无锡壹闪生物科技有限公司 Micro-flow postposition quantitative device and micro-flow control chip
KR102200445B1 (en) * 2019-07-02 2021-01-11 비엘프로세스(주) Chemiluminescence Detection Method and Apparatus for Determination of Chrome Ions using Kalman filter

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006126011A (en) * 2004-10-28 2006-05-18 Ishikawa Seisakusho Ltd Microchip for specimen sample
CN102527306A (en) * 2010-12-28 2012-07-04 中国科学院化学研究所 Array type continuously-flowing microfluidic chip device and manufacture method and application thereof
CN102784674A (en) * 2012-08-13 2012-11-21 苏州汶颢芯片科技有限公司 Centrifugal micro-fluidic chip for detecting chromium ion form in water body and preparation method of centrifugal micro-fluidic chip

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006126011A (en) * 2004-10-28 2006-05-18 Ishikawa Seisakusho Ltd Microchip for specimen sample
CN102527306A (en) * 2010-12-28 2012-07-04 中国科学院化学研究所 Array type continuously-flowing microfluidic chip device and manufacture method and application thereof
CN102784674A (en) * 2012-08-13 2012-11-21 苏州汶颢芯片科技有限公司 Centrifugal micro-fluidic chip for detecting chromium ion form in water body and preparation method of centrifugal micro-fluidic chip

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Microchip-based simultaneous on-line monitoring of Cr(III) and Cr(VI) using highly efficient chemiluminescence detection;Dong Jin Kim,et al.;《Micro Total Analysis Systems 2001》;20011025;第525-526页、摘要以及Fig.1 *
On-line monitoring of chromium(Ⅲ)using a fast micromachined mixer/reactor and chemiluminescence detection;Yi Xu,et al.;《Analyst》;20000314;第125卷;第679-680页、Fig.5 *

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