CN115096871A - Detection device applied to multichannel SERS micro-fluidic chip - Google Patents
Detection device applied to multichannel SERS micro-fluidic chip Download PDFInfo
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- CN115096871A CN115096871A CN202210862608.XA CN202210862608A CN115096871A CN 115096871 A CN115096871 A CN 115096871A CN 202210862608 A CN202210862608 A CN 202210862608A CN 115096871 A CN115096871 A CN 115096871A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/10—Integrating sample preparation and analysis in single entity, e.g. lab-on-a-chip concept
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2300/00—Additional constructional details
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- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
Abstract
The application provides a detection device applied to a multichannel SERS microfluidic chip, which comprises a microfluidic pipeline and a detection chip; the detection chips comprise a plurality of detection chips, the detection chips are connected to the output pipeline end of the microfluidic pipeline in parallel, and the input pipeline end of the microfluidic pipeline is used for inputting a sample solution to be detected; each detection chip comprises an SERS substrate used for detecting objects to be detected with different properties, and the SERS substrate comprises any one of the following nano porous silver structures: the surface of the nano porous silver structure is modified by a single lipid film, and the surface of the nano porous silver structure is modified by a double lipid film; the SERS substrate adsorbs molecules to be detected in the sample solution to be detected, and a Raman signal of the molecules to be detected adsorbed by the detection chip is detected through the handheld Raman spectrometer. The problem of the waiting of different properties wait to detect the thing and be difficult to detect simultaneously, detection efficiency is low is solved, realize multichannel simultaneous detection, improve detection efficiency.
Description
Technical Field
The application relates to the technical field of detection devices, in particular to a detection device applied to a multichannel SERS micro-fluidic chip.
Background
The Surface Enhanced Raman Scattering (SERS) technology is a novel trace analysis technology, can obtain information of influence of genes, chemical bonds and microenvironment on sample structures from a molecular level, and can obtain fingerprint spectrums of the sample structures in real time, has large information quantity, has the characteristics of high sensitivity, strong specificity, no marking, no damage, real-time detection and the like, cannot be interfered by media such as solution and the like, and is widely applied to the fields of biochemical detection and the like. The micro-fluidic chip is a core technology applied to the field of micro total analysis systems.
At present, the common method of combining the SERS technology with the microfluidic chip has been improved from disposable detection to reusable, such as application No. 201810524022.6, which discloses a reusable high-throughput SERS microfluidic chip and its application, including a reaction chip and a detection chip connected in series by a microfluidic pipeline; the reaction chip is used for mixing and reacting a liquid sample containing heavy metal ions with a DNA enzyme reagent; the detection chip is used for detecting reactants after reaction of the reaction chip. The application of the reusable high-flux SERS microfluidic chip is also provided, and the reusable high-flux SERS microfluidic chip is applied to detecting the content of trace harmful metal ions in a water environment. The designed SERS microfluidic chip can be repeatedly recycled, has simple process, low cost and high efficiency, and can be produced in batches. The method can detect a plurality of data at one time, and has the characteristics of high speed, high efficiency and high throughput detection. Although the multi-channel detection device can be repeatedly used, the problems of low detection efficiency, weak signal intensity and the like due to different hydrophilic and lipophilic characteristics of different objects to be detected cannot be solved, and multiple types of detection can be simultaneously carried out.
Disclosure of Invention
The main purpose of this application is to provide a detection device who is applied to multichannel SERS micro-fluidic chip, aims at solving the problem that the thing that awaits measuring of different properties is difficult to detect simultaneously, detection efficiency hangs down.
In order to achieve the above object, the present application provides a detection apparatus applied to a multichannel SERS microfluidic chip, including a microfluidic pipeline and a detection chip;
the detection chips comprise a plurality of detection chips, the detection chips are connected to the output pipeline end of the microfluidic pipeline in parallel, and the input pipeline end of the microfluidic pipeline is used for inputting a sample solution to be detected;
each detection chip comprises an SERS substrate used for detecting objects to be detected with different properties, and the SERS substrate comprises any one of the following nano porous silver structures: the surface of the nano porous silver structure is modified by a single lipid film, and the surface of the nano porous silver structure is modified by a double lipid film;
the SERS substrate adsorbs molecules to be detected in the sample solution to be detected, and a Raman signal of the molecules to be detected adsorbed by the detection chip is detected through a handheld Raman spectrometer.
Further, the manufacturing process of the SERS substrate includes:
washing the silver flakes with the purity of 99.9% by using double deionized water, and placing the washed silver flakes into potassium chloride water with preset concentration to perform electrochemical reaction to obtain silver flakes plated with silver chloride;
stirring the solution in which the silver chips plated with the silver chloride are positioned, placing the silver chips plated with the silver chloride into a reducing agent, and reducing the silver chips plated with the silver chloride into nano-porous silver chips in situ through the reducing agent;
and washing the porous silver sheet by using deionized water and ethanol to obtain the nano porous silver structure.
Further, the potassium chloride water was electrochemically reacted by 0.15 v.
Further, the diameter of each pore diameter in the nano-porous silver structure is 60-80 nm.
Furthermore, the detection chips comprise three detection chips, namely a first detection chip, a second detection chip and a third detection chip;
the SERS substrate in the first detection chip adopts a nano porous silver structure with a surface modified by a single lipid film;
the SERS substrate in the second detection chip adopts a nano porous silver structure with the surface modified by double lipid films;
the SERS substrate in the third detection chip adopts the nano-porous silver structure.
Further, a single lipid membrane is deposited on the nano-porous silver structure through a technology of constructing an ordered ultrathin molecular membrane, so that the nano-porous silver structure with the surface modified by the single lipid membrane is obtained.
Further, the step of modifying the surface of the nano-porous silver structure to generate a monolayer lipid membrane comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid membrane;
pressing the lipid membrane at a preset speed until the lipid membrane is subjected to a target surface pressure;
and (3) pulling up the glass slide positioned in the water and the nano porous silver structure positioned on the glass slide at a specified speed until the nano porous silver structure is exposed out of the water surface, thus obtaining the nano porous silver structure with the surface modified by the monolayer lipid film.
Further, the step of modifying the surface of the nano-porous silver structure to generate a monolayer lipid membrane comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid film;
pressing the lipid membrane at a preset speed until the lipid membrane is subjected to a target surface pressure;
pulling up the glass slide positioned in the water and the nano porous silver structure positioned on the glass slide at a designated speed until the nano porous silver structure is exposed out of the water surface;
and inserting the nano-porous silver structure into the water again to realize the nano-porous silver structure with the surface modified by the double lipid films.
Further, the reducing agent is sodium borohydride solution.
Furthermore, the input pipeline end of the microfluidic pipeline is set to be a Y-shaped pipeline, the containing cavity where the sample solution to be detected is located is communicated with the first port of the Y-shaped pipeline, and the second port of the Y-shaped pipeline is communicated with the containing cavity where a cleaning solution for cleaning the microfluidic pipeline is located.
The detection device who is applied to multichannel SERS micro-fluidic chip that provides in this application has following beneficial effect:
through setting up a plurality of detection chips that connect in parallel, and set up the nano-porous structure that is used for detecting the molecule of waiting to detect that corresponds the nature on detecting the chip to solve the waiting of different properties and detect the thing and be difficult to detect simultaneously, detection efficiency hangs down the problem, realize the multichannel and detect simultaneously, improve detection efficiency.
Drawings
Fig. 1 is a schematic structural diagram of a detection apparatus applied to a multichannel SERS microfluidic chip according to an embodiment of the present application.
The implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Referring to fig. 1, in an embodiment of the present application, a detection apparatus applied to a multichannel SERS microfluidic chip is provided, including a microfluidic pipeline 2 and a detection chip 1; the detection chip 1 comprises a plurality of detection chips, the detection chips are connected to the output pipeline end of the micro-fluidic pipeline 2 in parallel, and the input pipeline end of the micro-fluidic pipeline 2 is used for inputting a sample solution 3 to be detected; wherein, each detection chip 1 is including being applied to detecting the SERS basement that different properties detected the thing, and the SERS basement is including any one in following nanometer porous silver structure 5: the surface of the nano porous silver structure 51 is modified by a single lipid film, the surface of the nano porous silver structure 52 is modified by a double lipid film, and the surface of the nano porous silver structure 53 is pure nano porous silver; the SERS substrate adsorbs molecules to be detected in a sample solution to be detected, and a Raman signal of the molecules to be detected adsorbed by the detection chip 1 is detected through the handheld Raman spectrometer.
The application is applied to detect waiting to detect the sample of waiting to detect different properties in waiting to detect liquid, more specifically is through decorating the surface of nanometer porous silver structure 5 to the realization is richened and is realized detecting waiting to detect the sample of different properties, if the sample that waits to detect of different properties includes at least one: hydrophilic pesticides, lipophilic pesticides, charged pesticides; the multi-channel detection of the object to be detected is realized, and the detection efficiency is improved.
In the embodiment, the microfluidic pipeline 2 is used for conveying a sample solution to be detected to an area to be detected, the microfluidic pipeline 2 comprises an input pipeline end and an output pipeline end, wherein the sample solution to be detected enters into the output pipeline end from the input pipeline end, a plurality of detection chips 1 are connected in parallel at the output pipeline end, each detection chip 1 comprises an SERS substrate used for detecting objects to be detected with different properties, SERS refers to a surface enhanced Raman scattering technology and is a novel trace analysis technology, information of influence of genes, chemical bonds and micro environments on a sample structure can be obtained from a molecular level, a fingerprint spectrum of the sample structure can be obtained in real time, the information amount is very large, and the method has the characteristics of high sensitivity, strong specificity, no mark, no damage, real-time detection and the like, and cannot be interfered by media such as solution and the like; in this embodiment, the SERS substrate includes a nanoporous silver structure 5, specifically includes nanoporous silver structures 5 with different surface modifications, such as a nanoporous silver structure 51 with a single lipid film modified surface, a nanoporous silver structure 52 with a double lipid film modified surface, or a nanoporous silver structure 53; amplifying and displaying the nano porous silver structure 5 through an electron microscope to observe whether the pore state distribution of the nano porous silver structure 5 on the SERS substrate is uniform or not, or to observe whether the pore state distribution of the nano porous silver structure 5 modified by adding a lipid film is uniform or not; if the morphology distribution of the nano-porous silver structure 52 with the double-layer lipid film modified surface is uneven in the chip where the nano-porous silver structure 52 with the double-layer lipid film modified surface is observed through a high-magnification scanning electron microscope, the nano-porous silver structure 52 with the double-layer lipid film modified surface is uneven in pore shape, and the nano-porous silver structure is a defective product; when the morphology distribution of the nanoporous silver structure 51 with the monolayer lipid film modified on the surface is uniform in the chip with the nanoporous silver structure 51 with the monolayer lipid film modified on the surface observed by a high-magnification scanning electron microscope, it indicates that the pores of the nanoporous silver structure 51 with the monolayer lipid film modified on the surface are uniform, and the chip is a good product. The SERS base is used for adsorbing the molecules to be detected of waiting to detect sample solution, the Raman signal of the molecules to be detected of the nanoporous silver structure 5 on the detection chip 1 is detected through the hand-held Raman spectrometer, when adsorbing the molecules to be detected of corresponding attribute, then the Raman signal can be amplified to the signal of the sixth power of ten of original Raman signal, set up this nanoporous silver structure 5 in order to realize amplifying the Raman signal to adsorbed chemical molecule, and then look over whether there is the object to be detected of the different nature that needs detected in waiting to detect sample solution.
As in one embodiment, the detection chip 1 includes two detection chips 1, two detection chips 1 are connected in parallel at the end of the output pipeline, and one detection chip of the two detection chips 1 is a nano-porous silver structure 51 (i.e. the detection chip is the first detection chip 11) with a surface modified by a single lipid film, and is used for adsorbing and detecting the lipophilic pesticide; the other detection chip 1 is a nano-porous silver structure 52 (namely, the detection chip is a second detection chip 12) with a double-layer lipid membrane modified surface, and is used for adsorbing and detecting the charged pesticide; a sample solution to be detected is shunted to the two detection chips 1 from the output pipeline end, if a Raman signal of a molecule to be detected of the nano porous silver structure 5 positioned on the detection chips 1 is detected by a handheld Raman spectrometer, if the molecule to be detected with the corresponding property is adsorbed, if lipophilic pesticide is adsorbed in the first detection chip 11 in which the nano porous silver structure 51 with the surface modified by the single lipid film is positioned, the Raman signal is amplified to a signal which is six times of ten times of the original Raman signal, which indicates that the nano porous silver structure 51 with the surface modified by the single lipid film is adsorbed to the lipophilic pesticide, namely the lipophilic pesticide exists in the sample solution to be detected; if the raman signal of the molecule to be detected of the nanoporous silver structure 5 on the detection chip 1 is detected by the handheld raman spectrometer, when the molecule to be detected with the corresponding property is adsorbed, if the charged pesticide is adsorbed in the second detection chip 12 where the nanoporous silver structure 52 with the surface modified by the bilayer lipid membrane is located, the raman signal is amplified to a signal which is six times of ten times of the original raman signal, which indicates that the nanoporous silver structure with the surface modified by the bilayer lipid membrane adsorbs the charged pesticide, that is, the charged pesticide exists in the sample solution to be detected. The multi-channel detection device for the molecules to be detected with different properties in the same sample solution to be detected realizes the simultaneous detection of the molecules to be detected with different properties, and improves the detection efficiency. In this embodiment, the magnification of the electron microscope is mainly the form in which the nanoporous structure can be observed, and the specific magnification is not limited herein. In other embodiments, a plurality of parallel detection chips 1 for detecting different properties may also be provided, and the number of channels detected in parallel is not limited here.
In this embodiment, the manufacturing process of the SERS substrate includes:
step 1, washing silver flakes with the purity of 99.9% by using double deionized water, and placing the washed silver flakes into potassium chloride water with a preset concentration to perform an electrochemical reaction to obtain silver flakes plated with silver chloride;
step 2, stirring the solution in which the silver pieces plated with the silver chloride are positioned, placing the silver pieces plated with the silver chloride in a reducing agent, and reducing the silver pieces plated with the silver chloride into nano porous silver pieces in situ through the reducing agent;
and 3, washing the porous silver sheet by using deionized water and ethanol to obtain the nano porous silver structure 53.
In this embodiment, in step 1, a silver sheet with a purity of 99.9% is washed by using di-deionized water (dd-H2O), and the washed silver sheet is placed in a potassium chloride aqueous solution electrolyte with a preset concentration to perform an electrochemical reaction, wherein the concentration of the potassium chloride aqueous solution can be preset to be 1 mol/l of potassium chloride aqueous solution, at this time, the surface of the metal silver sheet is changed from glossy silver color to dark yellow color, and the electrochemical reaction is taken by the user after the metal silver sheet is changed to dark yellow color, so that the silver sheet plated with silver chloride can be obtained; stirring the water solution in which the silver sheet plated with the silver chloride is positioned to enable the silver sheet to be in the dynamically stirred liquid, then placing the silver sheet in a reducing agent, and reducing the silver sheet into a nano porous silver sheet through the original taste of the reducing agent, wherein the silver sheet quickly enters the reducing agent from the dynamically stirred liquid, the reducing agent can adopt a sodium borohydride solution, reducing the silver sheet plated with the silver chloride through the sodium borohydride solution, bubbles appear in the sodium borohydride solution at the moment, judging that the silver sheet plated with the silver chloride is reduced into the nano porous silver sheet when the bubbles in the sodium borohydride solution are eliminated, then washing through deionized water and ethanol to obtain a required nano porous silver structure, in a specific embodiment, washing the reduced nano porous silver sheet with the deionized water firstly, then washing through the ethanol, and respectively carrying out cross washing on the nano porous silver sheet through the deionized water for three times and the ethanol for three times, to obtain the desired nanoporous silver structure 53.
The principle of generating the nano-porous silver structure 53 is to respectively oxidize pure silver with smooth and flat surface into silver chloride through electrochemical reaction, and generate the nano-porous silver structure through original taste reduction induction by a reducing agent.
In this embodiment, the reducing agent is a substance that loses electrons or deviates electrons in the redox reaction. The reducing agent itself has reducing properties and is oxidized, and the product is called an oxidation product. The reduction and the oxidation reaction are carried out simultaneously, that is, the reducing agent is oxidized to form an oxide by itself at the same time as the oxidation reaction with the reduced material. The reactant containing a certain substance whose valence is increased is a reducing agent.
In this example, potassium chloride water was electrochemically reacted by 0.15 volts. The solution of the potassium chloride water is subjected to electrochemical reaction by adopting 0.15V voltage, so that the required nano-porous material with uniform pore size can be obtained, and the pore size is 60-80nm, thereby facilitating the observation through an electron microscope in the subsequent process.
In this embodiment, the diameter of each pore size in the nanoporous silver structure 53 is 60-80 nm. The pore diameter of 60-80nm is adopted, so that each pore diameter in the nano porous silver structure 53 is within the size range, the precise control of the nano porous silver structure 53 is realized, and the subsequent surface modification and the observation of an electron microscope are facilitated.
In this embodiment, the detecting chip 1 includes three detecting chips, which are respectively a first detecting chip 11, a second detecting chip 12 and a third detecting chip 13; the SERS substrate in the first detection chip 11 adopts a nano porous silver structure 51 with a surface modified by a single lipid film; the SERS substrate in the second detection chip adopts a nano porous silver structure 52 with a surface modified by double lipid films; the SERS substrate in the third detection chip adopts a silver sheet nano-porous silver structure 53.
In this embodiment, three detection chips 1 for detecting different molecules to be detected in a sample solution to be detected are provided, which are a first detection chip 11, a second detection chip 12 and a third detection chip 13, wherein the SERS substrate of the first detection chip 11 employs a nano-porous silver structure 51 with a single-layer lipid film modified surface for adsorbing lipophilic pesticide in the molecules to be detected, a raman signal of the molecules to be detected of the nano-porous silver structure 51 with a single-layer lipid film modified surface on the first detection chip 11 is detected by a handheld raman spectrometer, and when the molecules to be detected with corresponding properties are adsorbed, if the lipophilic pesticide is adsorbed in the first detection chip 5 where the nano-porous silver structure 51 with a single-layer lipid film modified surface is located, the raman signal is amplified to a signal which is a sixth power of ten times of the original raman signal, indicating that the nano-porous silver structure 51 with the surface modified by the monolayer lipid film is adsorbed to the lipophilic pesticide, and indicating that the lipophilic pesticide exists in the sample solution to be detected; if the raman signal of the molecule to be detected of the nano-porous silver structure 51 with the surface modified by the single lipid film on the first detection chip 11 is detected by the handheld raman spectrometer, no amplification signal is found in the raman signal, that is, the raman signal is not detected or is very weak, it indicates that the nano-porous silver structure 51 with the surface modified by the single lipid film does not adsorb the lipophilic pesticide, that is, the lipophilic pesticide does not exist in the sample solution to be detected or the concentration of the lipophilic pesticide is low enough to be calculated. The SERS substrate of the second detection chip 12 adopts a nano-porous silver structure 52 with a surface modified by double lipid films, and is used for adsorbing whether charged pesticides exist in molecules to be detected; if the raman signal of the molecule to be detected of the nanoporous silver structure 52 with the surface modified by the bilayer lipid membrane on the second detection chip 12 is detected by the handheld raman spectrometer, when the molecule to be detected with the corresponding property is adsorbed, if the charged pesticide is adsorbed in the second detection chip 12 with the nanoporous silver structure 52 with the surface modified by the bilayer lipid membrane, the raman signal is amplified to a signal which is six times of ten times of the original raman signal, which indicates that the nanoporous silver structure 52 with the surface modified by the bilayer lipid membrane adsorbs the charged pesticide, and indicates that the charged pesticide exists in the sample solution to be detected; if the raman signal of the molecule to be detected of the nanoporous silver structure 52 with the surface modified by the bilayer lipid film on the second detection chip 12 is detected by the handheld raman spectrometer, no amplification signal is found in the raman signal, that is, the raman signal is not detected or is very weak, it indicates that the nanoporous silver structure 52 with the surface modified by the bilayer lipid film does not adsorb the charged pesticide, that is, the charged pesticide does not exist in the sample solution to be detected or the concentration of the charged pesticide is not enough to calculate. The SERS substrate in the third detection chip 13 adopts a nano-porous silver structure 53 for adsorbing the hydrophilic pesticide in the molecule to be detected, the nano-porous silver structure 53 adopts an original nano-porous silver structure 53 without modifying the surface, if a raman signal of the molecule to be detected of the nano-porous silver structure 53 on the third detection chip 13 is detected by a handheld raman spectrometer, when the molecule to be detected with the corresponding property is adsorbed, if the hydrophilic pesticide is adsorbed in the third detection chip 13 where the nano-porous silver structure 53 is located, the raman signal is amplified to a signal which is six times the original raman signal, which indicates that the nano-porous silver structure 53 adsorbs the hydrophilic pesticide, that is, the hydrophilic pesticide exists in the sample solution to be detected; if the raman signal of the molecule to be detected of the nanoporous silver structure 53 on the third detection chip 13 is detected by the handheld raman spectrometer, and the raman signal is not found to have any amplification signal, that is, the raman signal is not detected or is very weak, it indicates that the nanoporous silver structure 53 does not adsorb the hydrophilic pesticide, that is, the sample solution to be detected does not have the hydrophilic pesticide or the concentration of the hydrophilic pesticide is low enough to be calculated. Through setting up multiple passageway, be applied to the detection chip 1 of different SRS bases to detect the molecule of waiting to detect in waiting to detect sample solution of different properties, improve detection efficiency.
In this example, a monolayer lipid film was deposited on the nanoporous silver structure 5 by a technique of constructing an ordered ultrathin molecular film (Langmuir-Blodgett) to obtain a nanoporous silver structure 51 with a monolayer lipid film modification occurring on the surface. More specifically, a monolayer lipid film was deposited on the nanoporous silver sheet by the langmuir-blodgett method, and the surface pressure of the monolayer lipid film was measured by a williams paper-to-pressure sensor to obtain a desired monolayer lipid film.
In this embodiment, the step of surface modification of the nanoporous silver structure to generate monolayer lipid membrane modification comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid film;
extruding the lipid membrane at a preset speed until the lipid membrane bears the target surface pressure;
and (3) pulling up the glass slide positioned in the water and the nano porous silver structure positioned on the glass slide at a specified speed until the nano porous silver structure is exposed out of the water surface, thus obtaining the nano porous silver structure 51 with the surface modified by the monolayer lipid film.
In this example, the step of modifying the surface of the nanoporous silver structure with a monolayer lipid film is as follows: firstly, a Hamilton micro-injector is adopted to drop the lipid solution on the water surface, the amount of the lipid solution dropped on the water surface can be selected according to actual needs, such as the height of 1 mm of the lipid solution paved on the water surface, and can also be adjusted according to the actual needs, after the lipid solution is evaporated for a preset time to form a lipid film, for example, in a specific embodiment, the lipid solution is evaporated for 15 minutes to form a required lipid film, and the lipid film is extruded at a constant speed of 5 mm per minute, so that the lipid film bears the target surface pressure. The nano-porous silver sheet is attached to the glass slide and clamped to the clamp, and the clamp is used for fixing the nano-porous silver sheet on the glass slide. And then, pulling the glass slide upwards at a constant rate of 0.1 millimeter per minute until the silver sheet is completely exposed out of the water surface to realize monolayer lipid membrane modification, wherein the surface pressure of the nano-porous silver sheet on the glass slide is kept unchanged in the process of carrying out the monolayer lipid modification. In other embodiments, the slide in water and the nanoporous silver structure on the slide can be pulled up at other specified speeds until the nanoporous silver structure is exposed to the water. In this example, the illustrated water represents deionized water.
In this embodiment, the step of surface modification of the nanoporous silver structure to generate monolayer lipid membrane modification comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid film;
extruding the lipid membrane at a preset speed until the lipid membrane bears a target surface pressure;
pulling the glass slide in the water and the nano porous silver structure on the glass slide upwards at a specified speed until the nano porous silver structure is exposed out of the water surface;
the nanoporous silver structure is re-inserted into water to realize the nanoporous silver structure 52 with the double lipid membrane modified surface.
In this example, the step of modifying the surface of the nanoporous silver structure with a monolayer lipid film is as follows: firstly, a Hamilton micro-injector is adopted to drop the lipid solution on the water surface, the amount of the lipid solution dropped on the water surface can be selected according to actual needs, such as the height of 1 mm of the lipid solution paved on the water surface, and can also be adjusted according to the actual needs, after the lipid solution is evaporated for a preset time to form a lipid film, for example, in a specific embodiment, the lipid solution is evaporated for 15 minutes to form a required lipid film, and the lipid film is extruded at a constant speed of 5 mm per minute, so that the lipid film bears the target surface pressure. The nano-porous silver sheet is attached to the glass slide and clamped to the clamp, and the clamp is used for fixing the nano-porous silver sheet on the glass slide. And then, pulling the glass slide upwards at a constant rate of 0.1 millimeter per minute until the silver sheet is completely exposed out of the water surface to realize monolayer lipid membrane modification, wherein the surface pressure of the nano-porous silver sheet on the glass slide is kept unchanged in the process of carrying out the monolayer lipid modification. In other embodiments, the slide in the water and the nanoporous silver structure on the slide can be pulled up at other specified speeds until the nanoporous silver structure is exposed to the water. And then the nano porous silver structure is inserted into water again, a lipid film is arranged on the water surface by adopting the mode, and the glass slide is pulled upwards at a constant speed of 0.1 millimeter per minute until the silver sheet is completely exposed out of the water surface to carry out double-layer lipid film modification so as to realize the nano porous silver structure with the surface subjected to double-layer lipid film modification, namely the nano porous silver structure 52 with double-layer surface modification. In this example, the illustrated water represents deionized water.
The double-layer surface modification of the nano-porous silver structure is based on single-layer surface modification, and single-layer surface modification is performed again to obtain the double-layer surface modified nano-porous silver structure 52.
In this example, the reducing agent is sodium borohydride solution. The sodium borohydride solution can be prepared by 0.1M, and the silver sheet plated with silver chloride can be effectively reduced into the nano-porous silver sheet by 0.1 mol of the sodium borohydride solution.
In this embodiment, the input pipeline end of the microfluidic pipeline 2 is set to be a Y-shaped pipeline, the chamber 3 in which the sample solution to be detected is located is communicated with the first port of the Y-shaped pipeline, and the second port of the Y-shaped pipeline is communicated with the chamber 4 in which the cleaning solution for cleaning the microfluidic pipeline 2 is located.
In this embodiment, the input pipeline end of the micro-fluidic pipeline 2 is set to be a Y-shaped pipeline, the first port of the Y-shaped pipeline is communicated with the containing cavity 3 where the sample solution to be detected is located, the second port of the Y-shaped pipeline is communicated with the containing cavity 4 where the cleaning solution is located, a flow direction valve is arranged at the intersection of the Y-shaped pipeline and is used for communicating the output pipeline end of the micro-fluidic pipeline 2 with the sample solution to be detected, or the output pipeline end of the micro-fluidic pipeline 2 is communicated with the cleaning solution, so that the micro-fluidic pipeline can be effectively cleaned, and the reuse is realized.
In summary, for the detection apparatus applied to the multichannel SERS microfluidic chip provided in the embodiment of the present application, by setting a plurality of detection chips 1 connected in parallel, and setting the nanoporous silver structure 5 for detecting the molecules to be detected with corresponding properties on the detection chip 1, the problems that the substances to be detected with different properties are difficult to detect simultaneously and the detection efficiency is low are solved, the multichannel simultaneous detection is realized, and the detection efficiency is improved.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, apparatus, article, or method that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, apparatus, article, or method. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, apparatus, article or method that comprises the element.
The above description is only for the preferred embodiment of the present application and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings of the present application, or which are directly or indirectly applied to other related technical fields, are intended to be included within the scope of the present application.
Claims (10)
1. The detection device applied to the multi-channel SERS microfluidic chip is characterized by comprising a microfluidic pipeline and a detection chip;
the detection chips comprise a plurality of detection chips, the detection chips are connected to the output pipeline end of the microfluidic pipeline in parallel, and the input pipeline end of the microfluidic pipeline is used for inputting a sample solution to be detected;
each detection chip comprises an SERS substrate used for detecting objects to be detected with different properties, and the SERS substrate comprises any one of the following nano porous silver structures: the surface of the nano porous silver structure is modified by a monolayer lipid film, and the surface of the nano porous silver structure is modified by a double-layer lipid film;
the SERS substrate adsorbs molecules to be detected in the sample solution to be detected, and a Raman signal of the molecules to be detected adsorbed by the detection chip is detected through a handheld Raman spectrometer.
2. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 1, wherein the manufacturing process of the SERS substrate comprises:
washing the silver flakes with the purity of 99.9% by using double deionized water, and placing the washed silver flakes into potassium chloride water with preset concentration to perform electrochemical reaction to obtain silver flakes plated with silver chloride;
stirring the solution in which the silver pieces plated with the silver chloride are positioned, placing the silver pieces plated with the silver chloride into a reducing agent, and reducing the silver pieces plated with the silver chloride into nano-porous silver pieces in situ through the reducing agent;
and washing the porous silver sheet by using deionized water and ethanol to obtain the nano porous silver structure.
3. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 2, wherein the electrochemical reaction is performed on potassium chloride water by 0.15V.
4. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 3, wherein the diameter of each pore in the nano-porous silver structure is 60-80 nm.
5. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 1, wherein the detecting chips comprise three detecting chips, namely a first detecting chip, a second detecting chip and a third detecting chip;
the SERS substrate in the first detection chip adopts a nano porous silver structure with a surface modified by a single lipid film;
the SERS substrate in the second detection chip adopts a nano porous silver structure with the surface modified by double lipid films;
the SERS substrate in the third detection chip adopts the nano-porous silver structure.
6. The detection device applied to the multichannel SERS microfluidic chip as recited in any one of claims 1 to 5, wherein a single lipid film is deposited on the nanoporous silver structure by a technology of constructing an ordered ultrathin molecular film, so as to obtain the nanoporous silver structure with the surface modified by the single lipid film.
7. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 6, wherein the step of modifying the surface of the nanoporous silver structure by a single lipid film comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid film;
pressing the lipid membrane at a preset speed until the lipid membrane is subjected to a target surface pressure;
and (3) pulling up the glass slide positioned in the water and the nano porous silver structure positioned on the glass slide at a specified speed until the nano porous silver structure is exposed out of the water surface, thus obtaining the nano porous silver structure with the surface modified by the monolayer lipid film.
8. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 6, wherein the step of modifying the surface of the nanoporous silver structure by a single lipid film comprises:
dropping a certain amount of lipid solution on the water surface through a Hamilton micro-injector until the lipid solution is evaporated to form a lipid membrane;
pressing the lipid membrane at a preset speed until the lipid membrane is subjected to a target surface pressure;
pulling up the glass slide positioned in the water and the nano porous silver structure positioned on the glass slide at a designated speed until the nano porous silver structure is exposed out of the water surface;
and inserting the nano-porous silver structure into the water again to realize the nano-porous silver structure with the surface modified by the double lipid films.
9. The detecting device applied to the multi-channel SERS microfluidic chip as recited in claim 2, wherein the reducing agent is a sodium borohydride solution.
10. The detecting device applied to the multi-channel SERS micro-fluidic chip as recited in claim 1, wherein an input pipeline end of the micro-fluidic pipeline is configured as a Y-shaped pipeline, a cavity where the sample solution to be detected is located is communicated with a first port of the Y-shaped pipeline, and a second port of the Y-shaped pipeline is communicated with a cavity where a cleaning solution for cleaning the micro-fluidic pipeline is located.
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