CN119319004A - Microfluidic chip - Google Patents

Microfluidic chip Download PDF

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Publication number
CN119319004A
CN119319004A CN202411759500.3A CN202411759500A CN119319004A CN 119319004 A CN119319004 A CN 119319004A CN 202411759500 A CN202411759500 A CN 202411759500A CN 119319004 A CN119319004 A CN 119319004A
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module
micro
thiourea
reduction
temperature
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CN119319004B (en
Inventor
鲁罗平
冉运蒸
田相鹏
方芳
刘卓
严宗镣
钟建伟
沈宇军
廖红华
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Hubei University for Nationalities
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Hubei University for Nationalities
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Hematology (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)

Abstract

本发明公开了一种微流控芯片,包括:进样模块通过外部电路驱动注射泵将待混合样品在注入量可控的情况下注入到微储液混合模块中;微储液混合模块用于消解后含有硒的样品、硫脲、盐酸流体、载气以及载流体的充分微混合后进入硫脲在线预还原模块;硫脲在线预还原模块采用加热反应和制冷还原反应生成硒化氢气体进入微气液分离芯片;半导体制冷模块设置在硫脲在线预还原模块的下方,用于对半导体制冷片温度进行实时控制,实现加热反应和制冷还原反应;收集模块用于收集得到的硒化氢气体。通过微储液混合模块对样品进行混匀,再通过硫脲在线预还原模块的反应区进行加热反应和制冷还原反应生成硒化氢气体,缩短硒元素的合成还原时间。

The invention discloses a microfluidic chip, comprising: a sample injection module drives a syringe pump through an external circuit to inject a sample to be mixed into a micro-liquid storage mixing module under the condition that the injection amount can be controlled; the micro-liquid storage mixing module is used for fully micro-mixing the sample containing selenium after digestion, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid, and then enters the thiourea online pre-reduction module; the thiourea online pre-reduction module uses heating reaction and refrigeration reduction reaction to generate hydrogen selenide gas to enter the micro gas-liquid separation chip; a semiconductor refrigeration module is arranged below the thiourea online pre-reduction module, and is used to control the temperature of the semiconductor refrigeration chip in real time to realize heating reaction and refrigeration reduction reaction; a collection module is used to collect the obtained hydrogen selenide gas. The sample is mixed by the micro-liquid storage mixing module, and then the reaction area of the thiourea online pre-reduction module is heated and refrigerated to generate hydrogen selenide gas, thereby shortening the synthesis reduction time of the selenium element.

Description

Microfluidic chip
Technical Field
The invention relates to the technical field of microfluidic chips, in particular to a microfluidic chip containing a micro-liquid storage mixing module and a thiourea online pre-reduction module.
Background
Micro-fluidic chip technology (Microfluidics) based on micro-electromechanical systems (MEMS) is a technology of integrating basic operation units such as sample preparation, reaction, separation, detection and the like in biological, chemical and medical analysis processes onto a micron-scale chip, and can automatically complete the whole analysis process, and micromixing is a core technology in the micro-fluidic chip technology (Microfluidics) and has become a key technology for measuring and synthesizing microelements, and the reaction synthesis of fluids is accurately controlled in a micron-to-nanometer-scale space through a microchannel, a microcolumn barrier and the like, so that the high-efficiency and accurate measurement of the content of microelements is realized.
In recent years, on-line combination technology research on microfluidic chips mainly includes that efficient micromixing is performed on a micromixing device to realize subsequent reaction detection. The rapid determination method for trace elements (such as selenium element) mainly comprises an electrochemical method, an electronic activation method, a fluorescence photometry method, an inductively coupled plasma mass spectrometry method, an atomic spectrometry method and the like. If a glass beaker is used as a container for rapid determination of selenium element, after the digested selenium-containing sample, HCL and thiourea are added into the first glass beaker, a semiconductor electronic refrigerator at the bottom of the beaker is used for mixing reaction, the mixed reaction sample is transferred into a second beaker, ar and KBH4 are added, and then an ultrasonic mixer is used for pre-reduction to generate hydrogen selenide gas. And (3) allowing the hydrogen selenide gas after the micro-mixing to enter a gas-liquid separator to realize the determination of selenium element. The selenium element measuring method has the problems that the measured value is seriously interfered, the operation is complicated and the cost is high, because two glass beakers are needed for experiments when the mixed reaction reduction is carried out, the semiconductor electronic refrigerator and the ultrasonic mixer are used for assistance, the cost is increased, the operation difficulty is increased, the sample after the mixed reaction needs an assistance container for transferring, the interference exists in the transferring process, the accuracy of the measured value is interfered, and the transferring difficulty is increased due to the shape of the sample.
Based on the problems presented above, microfluidic technology is based. The research of the online combination technology on the micro-hybrid chip is developed deeply, and the method has very important significance for realizing the application of the high-efficiency trace element measurement in the fields of biology, chemical analysis and the like. One key factor in realizing micro-fluidic chip-atomic fluorescence online combined integrated rapid detection of trace elements (such as selenium) is how to effectively realize sample micro-mixing and micro-reaction, which directly relates to whether the subsequent trace elements can be detected with high efficiency. If the sample is not thoroughly mixed, the subsequent reaction is insufficient and the required sample cannot be obtained or the obtained sample is insufficient, and the reduction reaction cannot be carried out to generate hydrogen selenide gas.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a micro-fluidic chip, which solves the technical problems in the prior art.
The invention provides a microfluidic chip, which comprises a sample injection module, a micro liquid storage mixing module, a thiourea online pre-reduction module, a semiconductor refrigeration module and a collection module,
The sample injection module drives the injection pump through an external circuit to inject the sample to be mixed into the micro-liquid storage mixing module under the condition of controllable injection quantity;
the micro-liquid storage mixing module is used for fully micro-mixing the digested selenium-containing sample, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid and then entering the thiourea online pre-reduction module;
The thiourea online pre-reduction module adopts heating reaction and refrigeration reduction reaction to generate hydrogen selenide gas which enters a micro gas-liquid separation chip;
The semiconductor refrigeration module is arranged below the thiourea online pre-reduction module and is used for controlling the temperature of the semiconductor refrigeration sheet in real time to realize heating reaction and refrigeration reduction reaction;
the collecting module is used for collecting the obtained hydrogen selenide gas.
Optionally, the sample injection module comprises a syringe pump, a sample injection tube, an electric liquid valve and a first electric air valve;
the injection pump is used for injecting the digested selenium-containing sample, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the sample injection tube;
the sample injection pipe is used for inputting the digested selenium-containing sample, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the micro liquid storage mixing module;
the electric liquid valve is used for controlling the injection amount of the digested selenium-containing sample, thiourea and hydrochloric acid fluid flowing into the micro liquid storage mixing module;
the first electric air valve is used for controlling the injection amount of carrier gas to be reacted, which is input into the micro-liquid storage mixing module;
One end of the sample feeding pipe is connected with the micro liquid storage mixing module, the other end of the sample feeding pipe is connected with the injection pump, and the electric liquid valve and the first electric air valve are respectively arranged on the sample feeding pipe.
Optionally, the micro liquid storage mixing module is sequentially provided with a glass substrate layer, a PDMS bottom layer and a micro liquid storage mixing layer from bottom to top, wherein the micro liquid storage mixing layer comprises an inverted triangle mixing cavity layer and an S-shaped mixing channel layer which are communicated with each other;
The inverted triangle mixing cavity layer is used for primarily micro-mixing the digested selenium-containing sample, thiourea and hydrochloric acid fluid;
The S-shaped mixing channel layer is used for fully micro-mixing the digested selenium-containing sample, thiourea and hydrochloric acid fluid after preliminary micro-mixing.
Optionally, the inverted triangle mixing chamber layer comprises a plurality of circular inlets, an inverted triangle mixing chamber, and a first array of obstacles;
The circular inlet is connected with the inverted triangle mixing cavity through the flow guide pipe, the first barrier array is located in the inverted triangle mixing cavity, the first barriers are 6 elliptic barriers, the arrangement mode is inverted triangle array emission, the number of the elliptic barriers is 3, 2 and 1 from the upper part to the lower part in sequence, the size of each elliptic barrier is the same, and the distance between each elliptic barrier is the same.
Optionally, a second barrier is arranged below the S-shaped channel of the S-shaped mixed channel layer, the second barrier is 21 square barriers, the sizes of the square barriers are different, the arrangement mode of the square barriers is that the square barriers are transversely arranged, three rows of square barriers are arranged in total, 7 square barriers are arranged in each row, the space between the first row and the third row of square barriers is increased from left to right in sequence, and the space between the second row of square barriers is increased from right to left in sequence.
Optionally, the thiourea online pre-reduction module comprises a glass substrate layer, a PDMS bottom layer and a pre-reduction unit layer which are sequentially arranged from top to bottom, wherein the pre-reduction unit layer comprises an S-shaped heating reaction zone layer and an S-shaped reduction refrigeration zone layer which are communicated with each other;
The S-shaped heating reaction zone layer is used for fully micro-mixing the digested sample containing selenium, thiourea and hydrochloric acid fluid and then carrying out heating reaction with CH 4N2 S to generate selenium;
The S-type reduction refrigeration zone layer is used for carrying out refrigeration reduction reaction on selenium and KBH 4 to obtain hydrogen selenide.
Optionally, the semiconductor refrigeration module comprises a control unit, a detection circuit and a semiconductor refrigeration piece;
The control unit is used for generating control signals for controlling the temperature of the semiconductor refrigerating sheet, and the control signals comprise heating signals and refrigerating signals;
The detection circuit is used for collecting the temperature of the semiconductor refrigerating sheet in real time;
the semiconductor refrigerating sheet provides corresponding temperatures for the thiourea on-line pre-reduction module to perform heating reaction and refrigeration reduction reaction according to the control signal of the control unit.
Optionally, when the control signal is a heating signal, one end of the semiconductor refrigeration piece is a refrigeration end, the other end of the semiconductor refrigeration piece is a heat dissipation end, the heat dissipation end is arranged below the S-shaped heating reaction zone layer, and when the control signal is a refrigeration signal, one end of the semiconductor refrigeration piece is refrigeration, the other end of the semiconductor refrigeration piece is a refrigeration end, and one of the refrigeration ends is arranged below the S-shaped reduction refrigeration zone layer.
Optionally, the control unit comprises an infrared processing controller, a temperature intelligent controller, a temperature data acquisition controller, a PWM controller and a temperature control circuit, and the detection circuit comprises a temperature acquisition circuit, an ADC circuit and an infrared receiving circuit;
the infrared receiving circuit is used for receiving the infrared signals sent by the infrared remote controller, identifying and converting the infrared signals into electric signals, and transmitting the electric signals to the infrared processing controller;
The infrared processing controller is used for identifying the electric signals to obtain corresponding temperature parameters set by remote control and sending the temperature parameters to the temperature intelligent controller;
The temperature acquisition circuit is used for transmitting the temperature signal of the semiconductor refrigerating sheet to the ADC circuit for analog-to-digital conversion to obtain a digital signal, and transmitting the digital signal to the temperature data acquisition controller;
The temperature data acquisition controller processes the digital signals to obtain current temperature data of the semiconductor refrigerating sheet and forwards the current temperature data to the temperature intelligent controller;
The temperature intelligent controller performs intelligent temperature control analysis according to the received temperature data and the temperature parameters to obtain a temperature control signal, and sends the temperature control signal to the PWM controller;
The PWM controller generates PWM waveforms according to the temperature control signals and sends the PWM waveforms to the temperature control circuit;
the temperature control circuit controls the power-on time of the semiconductor refrigerating sheet according to the PWM waveform;
The semiconductor refrigeration piece is used for providing corresponding temperatures for the thiourea on-line pre-reduction module to perform heating reaction and refrigeration reduction reaction under the control of the temperature control circuit.
Optionally, the collecting module comprises a discharging pipe and a second electric air valve, one end of the discharging pipe is connected with an outlet of the thiourea online pre-reduction module, the other end of the discharging pipe is connected with the micro gas-liquid separation chip, the second electric air valve is arranged on the discharging pipe,
The discharging pipe is used for inputting hydrogen selenide generated by reduction into the micro gas-liquid separation chip;
The second electric air valve is used for controlling the injection amount of the hydrogen selenide gas into the micro-liquid storage mixing module.
The invention has the beneficial effects that:
According to the microfluidic chip provided by the embodiment of the invention, the sample injection module is used for injecting and pressurizing reaction liquid and carrier gas, the reaction liquid is uniformly mixed in the mixing channel after entering the micro-liquid storage mixing module, the mixed liquid enters the reaction zone of the thiourea on-line pre-reduction module after being pressurized, efficient heat transfer is realized under the heating effect of the semiconductor refrigeration module, the synthesis reaction is completed in the reaction channel, the mixed liquid enters the reduction refrigeration zone after the reaction is finished, efficient pre-reduction is realized under the refrigeration effect of the semiconductor refrigeration module, and the determined selenium element is obtained after the reduction is finished and is discharged through the discharging pipe. According to the technical scheme provided by the embodiment of the invention, the inverted triangle mixing cavity with the built-in barrier is connected with the mixing channel with the built-in barrier and the pre-reduction channel with the S-shaped structure, so that the efficient mixing of the reaction liquid and the current carrying can be realized, the uniformity of the system is ensured, the heat transfer and refrigeration effects are improved by utilizing the semiconductor heating and the semiconductor refrigeration, and the synthesis reduction time of the selenium element is shortened.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. Like elements or portions are generally identified by like reference numerals throughout the several figures. In the drawings, elements or portions thereof are not necessarily drawn to scale.
Fig. 1 shows a block diagram of a microfluidic chip according to an embodiment of the present invention;
fig. 2 shows a schematic structural diagram of a microfluidic chip according to an embodiment of the present invention;
FIG. 3 shows a schematic diagram of the sample injection module;
FIG. 4 shows a schematic structural diagram of a micro-reservoir mixing module;
FIG. 5 shows simulated concentration clouds of mixing by a micro-reservoir mixing module;
FIG. 6 shows a schematic structural diagram of a thiourea on-line prereduction module;
Fig. 7 shows a schematic structural diagram of the semiconductor refrigeration module.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
As used in this specification and the appended claims, the term "if" may be interpreted as "when..once" or "in response to a determination" or "in response to detection" depending on the context. Similarly, the phrase "if a determination" or "if a [ described condition or event ] is detected" may be interpreted in the context of meaning "upon determination" or "in response to determination" or "upon detection of a [ described condition or event ]" or "in response to detection of a [ described condition or event ]".
As shown in fig. 1, a schematic structural diagram of a microfluidic chip is shown, which comprises a sample injection module, a micro-liquid storage mixing module, a Thiourea (TU) online pre-reduction module, a semiconductor refrigeration module and a collection module, wherein the sample injection module drives an injection pump to inject a sample to be mixed into the micro-liquid storage mixing unit through an external circuit under the condition that the injection amount is controllable, the micro-liquid storage mixing module is used for fully micro-mixing a sample containing selenium after digestion, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid, and then the sample enters the thiourea online pre-reduction module, the thiourea online pre-reduction module adopts a heating reaction and a refrigeration reduction reaction to generate hydrogen selenide gas to enter a micro-gas-liquid separation chip, the semiconductor refrigeration module is arranged below the thiourea online pre-reduction module and is used for controlling the temperature of a semiconductor refrigeration chip in real time, so as to realize the heating reaction and the refrigeration reduction reaction, and the collection module is used for collecting the obtained hydrogen selenide gas.
As can be seen from fig. 2, the sample injection areas 1-5 of the micro-liquid storage mixing module are respectively connected with injection pumps in the sample injection module, the sample injection area 1 is an inlet of a sample containing Se (VI) after digestion, the sample injection area is an inlet of Thiourea (TU), the sample injection area 3 is an inlet of HCL fluid, the sample injection area 4 is an inlet of carrier fluid 1, the sample injection area 5 is a standby carrier fluid inlet, the sample injection area 6 is an inlet of Ar carrier gas, the sample injection area 6 is connected with a carrier gas bottle in the sample injection module, the inverted triangle mixing cavity layer 7 of the micro-liquid storage mixing module is connected with the S-shaped mixing channel layer 8, the S-shaped mixing channel layer is connected with the Thiourea (TU) on-line pre-reduction module heating reaction area 9, the Thiourea (TU) on-line pre-reduction module heating reaction area 9 is connected with the Thiourea (TU) on-line pre-reduction module reducing refrigeration area 10, a semiconductor heating sheet 11 is arranged in the heating reaction area 9, a semiconductor cooling sheet 12 is arranged in the Thiourea (TU) on-line pre-reduction module reducing refrigeration area 10 is connected with a discharge port 13.
As shown in fig. 3, the sample injection module comprises an injection pump, a sample injection tube, an electric liquid valve and a first electric air valve, wherein the injection pump is used for injecting the digested sample containing selenium, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the sample injection tube. The sample feeding tube is used for inputting the digested selenium-containing sample, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the micro liquid storage mixing module. The electrokinetic liquid valve is used for controlling the injection amount of the digested selenium-containing sample, thiourea and hydrochloric acid fluid flowing into the micro liquid storage mixing module. The first electric air valve is used for controlling the injection amount of carrier gas to be reacted, which is input into the micro-liquid storage mixing module. One end of the sample feeding pipe is connected with the micro liquid storage mixing module, the other end of the sample feeding pipe is connected with the injection pump, and the electric liquid valve and the first electric air valve are respectively arranged on the sample feeding pipe. The injection module drives the injection pump through an external circuit to simultaneously inject the digested sample containing Se (VI), TU, HCL, ar carrier gas and carrier fluid, and simultaneously opens an electric liquid valve and an electric air valve on the sample inlet pipe, so that the sample enters the micro liquid storage mixing module under the condition of controlled quantity, and the injection of the sample is realized.
As shown in fig. 4, the micro-liquid storage mixing module is sequentially provided with a glass substrate layer, a PDMS (polydimethylsiloxane) bottom layer and a micro-liquid storage mixing layer from bottom to top, wherein the micro-liquid storage mixing layer comprises an inverted triangle mixing cavity layer and an S-shaped mixing channel layer which are communicated, the inverted triangle mixing cavity layer is used for primarily micro-mixing a sample containing selenium after digestion, thiourea and hydrochloric acid fluid, and the S-shaped mixing channel layer is used for fully micro-mixing the sample containing selenium after digestion, thiourea and hydrochloric acid fluid after primary micro-mixing. As shown in fig. 5, a simulated concentration cloud of the micro-reservoir mixing module for mixing is shown.
Wherein, the mixed chamber layer of reverse triangle includes a plurality of circular inlets, the mixed cavity of reverse triangle and first barrier array, in this embodiment, adopts 5 circular inlets, and circular inlet is connected with the mixed cavity of reverse triangle through the honeycomb duct, and first barrier array is located the mixed cavity of reverse triangle, and first barrier is 6 oval barrier, and the arrangement is reverse triangle array and discharges, from last down arranging 3, 2, 1 oval barrier of number in proper order, and the size of every oval barrier is the same, and the interval between every oval barrier is the same. The height of the inverted triangle mixing chamber is 2000um, the size of the elliptical obstacles in the inverted triangle mixing chamber is short axis length=300 um, long axis length=400 um, and the spacing between the elliptical obstacles is 800um.
The S-shaped channel of S-shaped mixed channel layer below sets up the second barrier, and the second barrier is 21 square barriers, and the size of every square barrier is all different, the arrangement of square barrier is horizontal emission, arranges three rows altogether, and 7 square barriers are arranged to every row, and the interval between square barrier of first row and third row increases in proper order from left to right, and the interval between square barrier of second row increases in proper order from right to left. The width of the channel containing square barriers below the S-shaped mixing channel is 1400um, the channel without barriers above is 1000um, the square barriers of the S-shaped rotary mixing channel are different in size and length from 10um to 60um, the width is 1400um, the distance between the square barriers is 40um, 50um, 60um, 70um, 80um, 90um and 100um from left to right in sequence in a first row and a third row, and the distance between the square barriers is 40um, 50um, 60um, 70um, 80um, 90um and 100um in sequence from right to left in a second row.
The embedded channel height of the micro liquid storage mixing module is 300um, the blocking effect is realized through the built-in elliptical barrier with the height of 300um, so that effective mixing of samples is realized, HSeO 4 and HCL are realized, when the samples pass through the inverted triangle mixing cavity, the flow paths of the fluids can be changed due to the blocking of the elliptical barrier, the fluid which is originally parallel or laminar flow is split front and back of the barrier, the different fluids can be mixed on smaller space scale due to the splitting effect, after the fluid bypasses the barrier, the fluids are converged again, due to the difference of flow speed and flow direction, the fluids can generate shearing force and vortex flow in the converging area, the vortex can greatly increase the contact area between the fluids, the original laminar flow structure can be broken, so that collision and preliminary mixing can be realized in a shorter time, after the samples after the preliminary micro mixing flow into the S-shaped mixing channel, the different spaces between the square barriers with the height of 300um can form capillary effect, the different fluids can be absorbed spontaneously after passing through the barrier space, the different fluids can generate different flow paths through the viscous force and the liquid surface tension, the selenium can be fully mixed, and the micro-mixed samples can be fully contacted with the selenium 2SeO4.
As shown in fig. 6, the thiourea online pre-reduction module comprises a glass substrate layer, a PDMS bottom layer and a pre-reduction unit layer which are sequentially arranged from top to bottom, wherein the pre-reduction unit layer comprises an S-type heating reaction zone layer and an S-type reduction cooling zone layer which are communicated with each other, the S-type heating reaction zone layer is used for fully micro-mixing a digested sample containing selenium, thiourea and hydrochloric acid fluid and then carrying out a heating reaction with CH 4N2 S to generate selenium, and the S-type reduction cooling zone layer is used for carrying out a refrigeration reduction reaction on the selenium and KBH 4 to obtain hydrogen selenide.
The Thiourea (TU) on-line pre-reduction module is heated and cooled through a semiconductor to realize the reaction and reduction of selenium, H 2SeO4 containing selenium flows into an S-shaped heating reaction zone, at the moment, H 2SeO4 and CH 4N2 S react under the condition that a semiconductor piece is heated to generate hexavalent Se, and after hexavalent Se flows into an S-shaped reduction cooling zone, hexavalent Se reacts with KBH 4 to generate H 2 Se containing tetravalent selenium under the condition of cooling.
As shown in fig. 7, the semiconductor refrigeration module comprises a control unit, a detection circuit and a semiconductor refrigeration sheet, wherein the control unit is used for generating control signals for controlling the temperature of the semiconductor refrigeration sheet, the control signals comprise heating signals and refrigeration signals, the detection circuit is used for collecting the temperature of the semiconductor refrigeration sheet in real time, and the semiconductor refrigeration sheet provides corresponding temperatures for the thiourea on-line pre-reduction module to perform heating reaction and refrigeration reduction reaction according to the control signals of the control unit.
The semiconductor refrigeration module realizes the visualization and intelligent heating and refrigeration of the Thiourea (TU) on-line prereduction module through the control unit and the detection circuit, thereby realizing the conversion from high-valence selenium element to low-valence selenium element. The semiconductor refrigerating sheet is formed by two different types of semiconductor materials and then connected with direct current to heat and refrigerate. The two semiconductor materials for semiconductor heating and cooling are P-type and N-type semiconductor chips, the P-type semiconductor surface is a heating surface (pink surface in fig. 6), and the N-type semiconductor surface is a cooling surface (blue surface in fig. 6).
The control unit comprises an infrared processing controller, a temperature intelligent controller, a temperature data acquisition controller, a PWM controller and a temperature control circuit. The temperature data acquisition controller is used for acquiring temperature data at a high speed. The PWM controller is used for generating PWM waveforms according to instructions given by the temperature intelligent controller, and sending the PWM waveforms to the temperature control circuit, and the temperature control circuit controls the power-on time of the semiconductor refrigerating sheet according to the PWM waveforms so as to realize quick and accurate temperature control of the thiourea in the online pre-reduction module.
The detection circuit comprises a temperature acquisition circuit, an ADC circuit and an infrared receiving circuit, wherein the temperature acquisition circuit is used for realizing temperature data amplification and filtering and detecting the temperature in the thiourea online pre-reduction module in real time. The ADC circuit is used for realizing conversion from an analog signal to a digital signal, the infrared receiving circuit is used for receiving an infrared signal sent by the infrared remote controller, identifying and converting the infrared signal into an electric signal, transmitting the electric signal to the infrared processing controller, the infrared processing controller is used for identifying the electric signal to obtain a corresponding temperature parameter set by remote control and sending the temperature parameter to the temperature intelligent controller, the temperature collecting circuit is used for a temperature signal of the semiconductor refrigerating sheet, and transmitting the temperature signal to the ADC circuit to be subjected to analog-digital conversion to obtain a digital signal, and transmitting the digital signal to the temperature data collecting controller.
The temperature data acquisition controller processes the digital signals to obtain current temperature data of the semiconductor refrigeration piece and forwards the current temperature data to the temperature intelligent controller, the temperature intelligent controller is used for rapidly and accurately controlling temperature, the temperature intelligent controller performs intelligent temperature control analysis according to the received temperature data and the temperature parameters to obtain temperature control signals, the temperature control signals are sent to the PWM controller, the PWM controller generates PWM waveforms according to the temperature control signals and sends the PWM waveforms to the temperature control circuit, the temperature control circuit controls the power-on time of the semiconductor refrigeration piece according to the PWM waveforms, and the semiconductor refrigeration piece is used for providing corresponding temperatures for the thiourea on-line pre-reduction module to perform heating reaction and refrigeration reduction reaction under the control of the temperature control circuit.
The collection module comprises a discharging pipe and a second electric air valve, one end of the discharging pipe is connected with a discharging hole of the thiourea online pre-reduction module, the other end of the discharging pipe is connected with the micro gas-liquid separation chip, the second electric air valve is arranged on the discharging pipe, the discharging pipe is used for inputting hydrogen selenide generated by reduction into the micro gas-liquid separation chip, and the second electric air valve is used for controlling the injection amount of the hydrogen selenide gas into the micro liquid storage mixing module.
H 2 Se enters a micro gas-liquid separation chip of the micro plasma atomic emission spectrum on-line combined integrated system through the gas outlet pipe and the electric gas valve so as to realize rapid determination of trace elements by an on-line combined technology.
Aiming at the defects that the prior art adopts electrochemical method, electronic activation method and other methods for measuring the selenium content, the micro-fluidic technology with weak interference, simple operation, low cost and controllable process is considered to measure the selenium content. According to the microfluidic chip provided by the embodiment of the invention, the sample injection module is used for injecting and pressurizing reaction liquid and carrier gas, the reaction liquid is uniformly mixed in the mixing channel after entering the micro-liquid storage mixing module, the mixed liquid enters the reaction zone of the thiourea on-line pre-reduction module after being pressurized, efficient heat transfer is realized under the heating effect of the semiconductor refrigeration module, the synthesis reaction is completed in the reaction channel, the mixed liquid enters the reduction refrigeration zone after the reaction is finished, efficient pre-reduction is realized under the refrigeration effect of the semiconductor refrigeration module, and the determined selenium element is obtained after the reduction is finished and is discharged through the discharging pipe. According to the technical scheme provided by the embodiment of the invention, the inverted triangle mixing cavity with the built-in barrier is connected with the mixing channel with the built-in barrier and the pre-reduction channel with the S-shaped structure, so that the efficient mixing of the reaction liquid and the current carrying can be realized, the uniformity of the system is ensured, the heat transfer and refrigeration effects are improved by utilizing the semiconductor heating and the semiconductor refrigeration, and the synthesis reduction time of the selenium element is shortened.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit the technical solution of the present invention, and although the detailed description of the present invention is given with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention, and all the modifications or substitutions are included in the scope of the claims and the specification of the present invention.

Claims (10)

1.一种微流控芯片,其特征在于,包括:进样模块、微储液混合模块、硫脲在线预还原模块、半导体制冷模块和收集模块,1. A microfluidic chip, characterized in that it comprises: a sampling module, a micro liquid storage and mixing module, a thiourea online pre-reduction module, a semiconductor refrigeration module and a collection module, 所述进样模块通过外部电路驱动注射泵将待混合样品在注入量可控的情况下注入到微储液混合模块中;The injection module drives the injection pump through an external circuit to inject the sample to be mixed into the micro-liquid storage mixing module with a controllable injection amount; 所述微储液混合模块用于消解后含有硒的样品、硫脲、盐酸流体、载气以及载流体的充分微混合后进入硫脲在线预还原模块;The micro-liquid storage and mixing module is used for fully micro-mixing the sample containing selenium after digestion, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid, and then entering the thiourea online pre-reduction module; 所述硫脲在线预还原模块采用加热反应和制冷还原反应生成硒化氢气体进入微气液分离芯片;The thiourea online pre-reduction module uses heating reaction and cooling reduction reaction to generate hydrogen selenide gas which enters the micro gas-liquid separation chip; 所述半导体制冷模块设置在硫脲在线预还原模块的下方,用于对半导体制冷片温度进行实时控制,实现加热反应和制冷还原反应;The semiconductor refrigeration module is arranged below the thiourea online pre-reduction module, and is used to control the temperature of the semiconductor refrigeration sheet in real time to realize the heating reaction and the refrigeration reduction reaction; 所述收集模块用于收集得到的硒化氢气体。The collecting module is used to collect the obtained hydrogen selenide gas. 2.如权利要求1所述的微流控芯片,其特征在于,所述进样模块包括注射泵、进样管、电动液阀和第一电动气阀;2. The microfluidic chip according to claim 1, characterized in that the injection module comprises a syringe pump, an injection tube, an electric liquid valve and a first electric gas valve; 所述注射泵用于将消解后含有硒的样品、硫脲、盐酸流体、载气以及载流体注射到进样管;The injection pump is used to inject the digested selenium-containing sample, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the injection tube; 所述进样管用于将消解后含有硒的样品、硫脲、盐酸流体、载气以及载流体输入到微储液混合模块;The sample injection tube is used to input the sample containing selenium after digestion, thiourea, hydrochloric acid fluid, carrier gas and carrier fluid into the micro liquid storage mixing module; 所述电动液阀用于控制消解后含有硒的样品、硫脲、盐酸流体流入到微储液混合模块的注入量;The electric liquid valve is used to control the injection amount of the sample containing selenium after digestion, thiourea, and hydrochloric acid fluid flowing into the micro liquid storage mixing module; 所述第一电动气阀用于控制待反应载气输入到微储液混合模块的注入量;The first electric gas valve is used to control the injection amount of the carrier gas to be reacted into the micro liquid storage mixing module; 所述进样管的一端与微储液混合模块连接,所述进样管的另一端连接注射泵,所述电动液阀和第一电动气阀分别安装在进样管上。One end of the injection tube is connected to the micro liquid storage mixing module, the other end of the injection tube is connected to the injection pump, and the electric liquid valve and the first electric gas valve are respectively installed on the injection tube. 3.如权利要求1所述的微流控芯片,其特征在于,所述微储液混合模块从下到上依次设置有玻璃基底层、PDMS底层和微储液混合层,所述微储液混合层包括相连通的倒三角混合腔层和S形混合通道层;3. The microfluidic chip according to claim 1, characterized in that the micro-liquid storage mixing module is provided with a glass base layer, a PDMS bottom layer and a micro-liquid storage mixing layer in sequence from bottom to top, and the micro-liquid storage mixing layer includes an inverted triangle mixing cavity layer and an S-shaped mixing channel layer connected to each other; 所述倒三角混合腔层用于对消解后含有硒的样品、硫脲、盐酸流体的初步微混合;The inverted triangle mixing chamber layer is used for preliminary micro-mixing of the sample containing selenium after digestion, thiourea and hydrochloric acid fluid; 所述S形混合通道层用于对消解后含有硒的样品、硫脲、盐酸流体初步微混合后的充分微混合。The S-shaped mixing channel layer is used for fully micro-mixing the sample containing selenium after digestion, thiourea and hydrochloric acid fluid after preliminary micro-mixing. 4.如权利要求3所述的微流控芯片,其特征在于,所述倒三角混合腔层包括多个圆形入口、倒三角混合腔体和第一障碍物阵列;4. The microfluidic chip according to claim 3, characterized in that the inverted triangle mixing chamber layer comprises a plurality of circular inlets, an inverted triangle mixing chamber and a first obstacle array; 所述圆形入口通过导流管与倒三角混合腔体连接,所述第一障碍物阵列位于倒三角混合腔体内,所述第一障碍物为6个椭圆形障碍物,排列方式为倒三角阵列排放,从上倒下依次排放个数为3、2、1个椭圆形障碍物,每个椭圆形障碍物的尺寸相同,每个椭圆形障碍物之间的间距相同。The circular inlet is connected to the inverted triangular mixing chamber through a guide tube. The first obstacle array is located in the inverted triangular mixing chamber. The first obstacles are 6 elliptical obstacles, which are arranged in an inverted triangular array. From top to bottom, the numbers of elliptical obstacles are 3, 2, and 1. The size of each elliptical obstacle is the same, and the spacing between each elliptical obstacle is the same. 5.如权利要求4所述的微流控芯片,其特征在于,所述S形混合通道层的S形通道下方设置第二障碍物,所述第二障碍物为21个方形障碍物,每个方形障碍物的尺寸都不相同,所述方形障碍物的排列方式为横向排放,一共排放三排,每一排排放7个方形障碍物,第一排和第三排方形障碍物之间的间距从左到右依次增加,第二排方形障碍物之间的间距从右到左依次增加。5. The microfluidic chip as described in claim 4 is characterized in that a second obstacle is arranged under the S-shaped channel of the S-shaped mixing channel layer, the second obstacle is 21 square obstacles, the size of each square obstacle is different, the square obstacles are arranged in a horizontal arrangement, a total of three rows, each row has 7 square obstacles, the spacing between the first row and the third row of square obstacles increases from left to right, and the spacing between the second row of square obstacles increases from right to left. 6.如权利要求3所述的微流控芯片,其特征在于,所述硫脲在线预还原模块包括从上到下依次设置的玻璃基底层、PDMS底层和预还原单元层,所述预还原单元层包括相连通的S型加热反应区层和S型还原制冷区层;6. The microfluidic chip according to claim 3, characterized in that the thiourea online pre-reduction module comprises a glass substrate layer, a PDMS bottom layer and a pre-reduction unit layer arranged in sequence from top to bottom, and the pre-reduction unit layer comprises an S-shaped heating reaction zone layer and an S-shaped reduction refrigeration zone layer connected to each other; 所述S型加热反应区层将消解后含有硒的样品、硫脲和盐酸流体充分微混合后与CH4N2S进行加热反应生成硒;The S-shaped heating reaction zone layer fully micro-mixes the sample containing selenium after digestion, thiourea and hydrochloric acid fluid, and then heats and reacts with CH 4 N 2 S to generate selenium; 所述S型还原制冷区层用于将硒与KBH4进行制冷还原反应得到硒化氢。The S-type reduction refrigeration zone layer is used to perform a refrigeration reduction reaction on selenium and KBH4 to obtain hydrogen selenide. 7.如权利要求6所述的微流控芯片,其特征在于,所述半导体制冷模块包括控制单元、检测电路和半导体制冷片;7. The microfluidic chip according to claim 6, characterized in that the semiconductor refrigeration module comprises a control unit, a detection circuit and a semiconductor refrigeration sheet; 所述控制单元用于产生控制半导体制冷片温度的控制信号,所述控制信号包括加热信号和制冷信号;The control unit is used to generate a control signal for controlling the temperature of the semiconductor refrigeration chip, and the control signal includes a heating signal and a cooling signal; 所述检测电路用于实时采集半导体制冷片的温度;The detection circuit is used to collect the temperature of the semiconductor refrigeration chip in real time; 所述半导体制冷片根据控制单元的控制信号为硫脲在线预还原模块进行加热反应和制冷还原反应提供相应的温度。The semiconductor refrigeration plate provides corresponding temperature for the thiourea online pre-reduction module to perform heating reaction and cooling reduction reaction according to the control signal of the control unit. 8.如权利要求7所述的微流控芯片,其特征在于,在控制信号为加热信号时,所述半导体制冷片一端为制冷端,另一端为散热端,将散热端设置在S型加热反应区层下方,在控制信号为制冷信号时,所述半导体制冷片一端为制冷,另一端为制冷端,将其中一个制冷端设置在S型还原制冷区层下方。8. The microfluidic chip as described in claim 7 is characterized in that, when the control signal is a heating signal, one end of the semiconductor refrigeration plate is a cooling end, and the other end is a heat dissipation end, and the heat dissipation end is arranged below the S-shaped heating reaction zone layer; when the control signal is a cooling signal, one end of the semiconductor refrigeration plate is a cooling end, and the other end is a cooling end, and one of the cooling ends is arranged below the S-shaped reduction cooling zone layer. 9.如权利要求8所述的微流控芯片,其特征在于,所述控制单元包括红外处理控制器、温度智能控制器、温度数据采集控制器、PWM控制器和温度控制电路,所述检测电路包括温度采集电路、ADC电路和红外接收电路;9. The microfluidic chip according to claim 8, characterized in that the control unit includes an infrared processing controller, a temperature intelligent controller, a temperature data acquisition controller, a PWM controller and a temperature control circuit, and the detection circuit includes a temperature acquisition circuit, an ADC circuit and an infrared receiving circuit; 所述红外接收电路用于接收红外遥控器发送的红外信号,并将红外信号识别转换为电信号,将电信号传输到红外处理控制器;The infrared receiving circuit is used to receive the infrared signal sent by the infrared remote controller, identify and convert the infrared signal into an electrical signal, and transmit the electrical signal to the infrared processing controller; 所述红外处理控制器用于对电信号进行识别得到相应的遥控设置的温度参数,并将温度参数发送给温度智能控制器;The infrared processing controller is used to identify the electrical signal to obtain the corresponding temperature parameters set by the remote control, and send the temperature parameters to the temperature intelligent controller; 所述温度采集电路用于半导体制冷片的温度信号,并将温度信号传输到ADC电路进行模数转换得到数字信号,将数字信号传输到温度数据采集控制器;The temperature acquisition circuit is used for the temperature signal of the semiconductor refrigeration chip, and transmits the temperature signal to the ADC circuit for analog-to-digital conversion to obtain a digital signal, and transmits the digital signal to the temperature data acquisition controller; 所述温度数据采集控制器将数字信号进行处理得到半导体制冷片当前的温度数据,并转发给温度智能控制器;The temperature data acquisition controller processes the digital signal to obtain the current temperature data of the semiconductor refrigeration chip and forwards it to the temperature intelligent controller; 温度智能控制器根据接收温度数据和温度参数进行智能控温分析得到控温信号,将控温信号发送给PWM控制器;The temperature intelligent controller performs intelligent temperature control analysis based on the received temperature data and temperature parameters to obtain a temperature control signal, and sends the temperature control signal to the PWM controller; 所述PWM控制器根据控温信号生成PWM波形,并将PWM波形发送给温度控制电路;The PWM controller generates a PWM waveform according to the temperature control signal, and sends the PWM waveform to the temperature control circuit; 所述温度控制电路根据PWM波形对半导体制冷片加电时间进行控制;The temperature control circuit controls the power-on time of the semiconductor refrigeration chip according to the PWM waveform; 所述半导体制冷片用于在温度控制电路的控制下为硫脲在线预还原模块进行加热反应和制冷还原反应提供对应的温度。The semiconductor refrigeration sheet is used to provide corresponding temperature for the thiourea online pre-reduction module to perform heating reaction and cooling reduction reaction under the control of the temperature control circuit. 10.如权利要求1所述的微流控芯片,其特征在于,所述收集模块包括出料管和第二电动气阀,所述出料管的一端与硫脲在线预还原模块的出口连接,出料管的另一端与微气液分离芯片连接,所述第二电动气阀安装在出料管上,10. The microfluidic chip according to claim 1, characterized in that the collection module comprises a discharge pipe and a second electric valve, one end of the discharge pipe is connected to the outlet of the thiourea online pre-reduction module, the other end of the discharge pipe is connected to the micro gas-liquid separation chip, and the second electric valve is installed on the discharge pipe. 所述出料管用于将还原生成的硒化氢输入到微气液分离芯片;The discharge pipe is used to input the hydrogen selenide generated by reduction into the micro gas-liquid separation chip; 所述第二电动气阀用于控制硒化氢气体注入到微储液混合模块中的注入量。The second electric gas valve is used to control the injection amount of hydrogen selenide gas into the micro liquid storage mixing module.
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