CN105548135A - Surface enhanced Raman scattering-based micro-fluidic chip and detection system containing same - Google Patents
Surface enhanced Raman scattering-based micro-fluidic chip and detection system containing same Download PDFInfo
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- 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
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- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention discloses a surface enhanced Raman scattering-based micro-fluidic chip. The chip comprises a chip substrate and a chip cover plate just covering the chip substrate, wherein the chip cover plate is provided with a first micro-channel, a second micro-channel, a third micro-channel, a liquid feeding channel and a liquid discharging channel. The invention also discloses a detection system containing the chip. The detection system comprises a leading-in optical fiber arranged at the end of the surface enhanced Raman scattering-based micro-fluidic chip and an optical fiber Bragg grating, wherein the surface enhanced Raman scattering-based micro-fluidic chip, the leading-in optical fiber and the optical fiber Bragg grating are detachably installed on a same base. The surface enhanced Raman scattering-based micro-fluidic chip employs a total-reflection liquid core waveguide to reduce transmission loss of a single and increase a transmission distance. When applied to the detection system, the surface enhanced Raman scattering-based micro-fluidic chip can improve detection sensitivity of Raman signals and improves repeatability of the Raman signals by using mean action of the liquid core waveguide on long-distance transmission. The invention also provides a preparation method for the chip.
Description
Technical field
The invention belongs to optics and micro-fluidic field, be specifically related to a kind of surface-enhanced Raman micro-fluidic chip and comprise the detection system of this chip.
Background technology
Along with development that is economic and society, Dynamic Non-Destruction Measurement is widely used each technical field, as geology archaeology, Gemstone Identification, biochemical analysis, biomedicine, food security, environment measuring etc.
Wherein, Surface enhanced raman spectroscopy technology is as the one of Non-Destructive Testing, its have untouchable, the non-destructive of test sample, detection time short, little without the need to sample pretreatment, sample aequum, be applicable to the features such as water sample solvent detection, can from the internal structural information of molecular level reflected sample more directly perceived, interface orientation and the conformation configuration of molecule can be differentiated, be widely used in study of surfaces, the research of adsorbate interfacial state, the biochemical large aspect such as molecular studies, analysis of the molecular structure; And detection sensitivity is high, resolution is high, disturb little, good stability, effectively can reduce the fluorescence background of sample molecule, detection limit lowly can reach nM or pM rank, can realize monomolecular detection, detection to bacterial cell, DNA and the detection of blood, the detection etc. of minimal residue agricultural chemicals, be the important testing tool in biochemical analysis, biomedicine, food security, the anti-probably field such as anti-riot.
At present, chip research based on Surface enhanced raman spectroscopy technology mainly concentrates on following three aspects: one is the surface-enhanced Raman chip research based on microchannel, the mode of many employings concentrating sample improves sensitivity and adopts the mode of single-point detection to collect signal, and signal repeatability is poor; Two is the surface-enhanced Raman chips based on photonic crystal fiber, adopts long-range detection mode to improve sensitivity, but integrated difficulty; Three is the surface-enhanced Raman chips based on solid waveguide, and the mode adopting prism-coupled, system is huge more.
Summary of the invention
The present invention aims to provide a kind of long range propagation that utilizes and strengthens Raman signal, utilizes the average effect of liquid flow to improve signal repeatability, and convenient and micro-fluidic integrated surface-enhanced Raman micro-fluidic chip, and comprise the detection system of this chip, in addition, present invention also offers the preparation method of this chip.
For this reason, the technical solution adopted in the present invention is: a kind of surface-enhanced Raman micro-fluidic chip, comprises chip base, and covers the chip cover plate directly over chip base; The bottom of described chip cover plate is provided with the first microchannel, the second microchannel and the 3rd microchannel, and described first microchannel is the through layout in left and right on chip cover plate; Described second one end, microchannel is communicated with the first microchannel, and the other end is connected with feed pathway; Described 3rd one end, microchannel is communicated with the first microchannel, and the other end is connected with liquid outlet channel; Described feed pathway and liquid outlet channel all extend outside chip cover plate; The material of described first, second, third microchannel is flexible polymer, and width is greater than 100 μm; The inwall of first, second, third microchannel is also provided with coat, and described coat refractive index is less than 1.33, and thickness is greater than 5 μm; Metal nanoparticle array structure is equipped with at coat inwall; Solution to be measured flows into from feed pathway, flows through the second microchannel, the first microchannel and the 3rd microchannel and forms liquid core waveguide.
Further, be staggeredly arranged about second, third microchannel described, and all perpendicular to the first microchannel; Described feed pathway is perpendicular to the second microchannel, and described liquid outlet channel is perpendicular to the 3rd microchannel, and feed pathway and liquid outlet channel paired linea angulata on chip cover plate is arranged, and is parallel to each other.
Further, the material of described coat is Teflon AF2400 or Teflon AF1600.
Further, the material of described metal nanoparticle array structure is Au, Ag, Cu or Pt, and single metal nanoparticle shape is spherical, triangle or square.Metal nanoparticle can amplify local fields, strengthens Raman signal.
On the basis of such scheme, the material of described first, second, third microchannel is PDMS, PDMA, PMMA, PVC soft glass or Zeonor.
Secondly, the invention still further relates to a kind of detection system of the surface-enhanced Raman micro-fluidic chip comprised in such scheme, described detection system also comprises and is arranged in importing optical fiber outside surface-enhanced Raman micro-fluidic chip and Fiber Bragg Grating FBG, and described surface-enhanced Raman micro-fluidic chip, imports optical fiber and Fiber Bragg Grating FBG is dismountable is arranged on same base; Described importing optical fiber extend in the first microchannel from one end of the first microchannel, for being imported in liquid core waveguide by exciting light, and utilizes long range propagation to strengthen Raman signal; Described Fiber Bragg Grating FBG extends in the first microchannel from the other end of the first microchannel, the exciting light transmitted can be reflected, transmission Raman light, realize the output to Raman light by liquid core waveguide.
In addition, the present invention also provides a kind of preparation method of surface-enhanced Raman micro-fluidic chip, and concrete steps are as follows:
Step one, processing formpiston: photoetching SU8 produces the formpiston of first, second, third bit port;
Step 2, preparation microchannel: get appropriate PDMS and hardening agent, be fully uniformly mixed, leave standstill to bubble free state, be cast on the formpiston made in step one, dry; Then the PDMS that takes a morsel bonds liquid inlet and outlet passage, dries; Demoulding, by feed pathway and the second microchannel, conducting between liquid outlet channel and the 3rd microchannel;
Step 3, bonding chip: chip cover plate and chip base are cleaned up rear bonding, naturally cools after drying;
Step 4, making coat: added in first, second, third microchannel by Teflon AF2400 solution and dry, make it form film at all microchannel interior walls, make coat;
Step 5, making metal nanoparticle array structure: use reduction of sodium citrate silver nitrate, configuration silver sol solution, then added in first, second, third microchannel by silver sol solution and dry, the coat inwall that metal nanoparticle is deposited on made by step 4 makes metal nanoparticle array structure.
On the basis of such scheme, the method making metal nanoparticle array structure in step 5 is sputtering, evaporates or self assembly.
The invention has the beneficial effects as follows:
(1), surface-enhanced Raman micro-fluidic chip of the present invention, total reflection liquid core waveguide is utilized to reduce the loss of Signal transmissions, increase transmission range, the cumulative function of long range propagation can improve the detection sensitivity of Raman signal, and utilizes the mean effort of liquid core waveguide long-haul transmission can improve Raman signal repeatability preferably.
(2) chip, importing optical fiber and Fiber Bragg Grating FBG are integrated on same base by the detection system, comprising surface-enhanced Raman micro-fluidic chip in the present invention, and adopt Fiber Bragg Grating FBG to export Raman signal, realize strengthening the microminiaturization of Raman chip, integrated, whole detection system has higher detection sensitivity and good repeatability, make simple, be convenient to real-time online detect, and portability is better.
(3), the preparation method of surface-enhanced Raman micro-fluidic chip in the present invention, process is simple, easy to operate, to preparing environment and equipment requirement is not high, with low cost.
Accompanying drawing explanation
Fig. 1 is the front view that the present invention contains the detection system of surface-enhanced Raman micro-fluidic chip.
Fig. 2 is the vertical view that the present invention contains the detection system of surface-enhanced Raman micro-fluidic chip.
Fig. 3 is the cut-open view of Fig. 2.
Fig. 4 is the inner first Micro Channel Architecture schematic diagram of surface-enhanced Raman micro-fluidic chip of the present invention.
Embodiment
Below by embodiment also by reference to the accompanying drawings, the invention will be further described:
As shown in figures 1-4, a kind of surface-enhanced Raman micro-fluidic chip, primarily of chip base 1, and the chip cover plate 2 covered directly over chip base 1 forms.
The first microchannel 4, microchannel 3, second and the 3rd microchannel 3, microchannel 5, first through layout in left and right on chip cover plate is provided with in the bottom of chip cover plate 2; Second one end, microchannel 4 is communicated with the first microchannel 3, and the other end is connected with feed pathway 6; 3rd one end, microchannel 5 is communicated with the first microchannel 3, and the other end is connected with liquid outlet channel 7; Feed pathway 6 and liquid outlet channel 7 all extend outside chip cover plate 2; The material of the first microchannel 4, microchannel 3, second and the 3rd microchannel 5 is flexible polymer, and width is greater than 100 μm.Preferably, the material of the first microchannel 4, microchannel 3, second and the 3rd microchannel 5 is PDMS, PDMA, PMMA, PVC soft glass or Zeono; And the second microchannel 4 and the 3rd microchannel about 5 are staggeredly arranged, and all perpendicular to the first microchannel 3; Feed pathway 6 is perpendicular to the second microchannel 4, and liquid outlet channel 7 is perpendicular to the 3rd microchannel 5, and feed pathway 6 and liquid outlet channel 7 paired linea angulata on chip cover plate 2 is arranged, and is parallel to each other.
The inwall of the first microchannel 4, microchannel 3, second and the 3rd microchannel 5 is also provided with coat 8, and coat 8 refractive index is less than 1.33, and thickness is greater than 5 μm; Preferably, the material of coat 8 is Teflon AF2400 or Teflon AF1600.
Metal nanoparticle array structure 9 is equipped with at coat 8 inwall; Preferably, the material of metal nanoparticle array structure 9 is Au, Ag, Cu or Pt, and single metal nanoparticle shape is spherical, triangle or square.
When solution to be measured flows into from feed pathway 6, flow through the second microchannel 3, microchannel 4, first and the 3rd microchannel 5 forms liquid core waveguide.
As shown in Figures 1 to 3, a kind of detection system comprising above surface-enhanced Raman micro-fluidic chip, primarily of being arranged in surface-enhanced Raman micro-fluidic chip a, and the importing optical fiber b be arranged in outside surface-enhanced Raman micro-fluidic chip a and Fiber Bragg Grating FBG c forms, and surface-enhanced Raman micro-fluidic chip a, import that optical fiber b and Fiber Bragg Grating FBG c is dismountable is arranged on same base d; Importing optical fiber b extend in the first microchannel 3 from one end of the first microchannel 3, for being imported in liquid core waveguide by exciting light, and utilizes long range propagation to strengthen Raman signal; Fiber Bragg Grating FBG c extends in the first microchannel 3 from the other end of the first microchannel 3, the exciting light transmitted can be reflected, transmission Raman light, realize the output to Raman light by liquid core waveguide.
Preferred as above-described embodiment, described second microchannel 4 and the 3rd microchannel about 5 are staggeredly arranged, and all perpendicular to the first microchannel 3; Feed pathway 6 perpendicular to the second microchannel 4, liquid outlet channel 7 perpendicular to the 3rd microchannel 5, and on feed pathway 6 and liquid outlet channel 7 chip cover plate 2 in pairs linea angulata arrange, and to be parallel to each other; Import the side that optical fiber b is arranged at close second microchannel 4, Fiber Bragg Grating FBG c is positioned at the side near the 3rd microchannel 5; Such layout makes chip more balance and stablize, and increases the sensitivity and reliability that detect.
In the present invention, additionally provide the preparation method of surface-enhanced Raman micro-fluidic chip in above-described embodiment, concrete steps are as follows:
Step one, processing formpiston: photoetching SU8 produces the formpiston of the first microchannel 4, microchannel 3, second and the 3rd microchannel 5.
Step 2, preparation microchannel: get PDMS and hardening agent, PDMS is flexible polymer, wherein the mass ratio of PDMS and hardening agent is 10:1 ~ 5:1, bi-material is fully uniformly mixed, leave standstill to bubble free state, be cast on the formpiston made in step one, dry, preferably 90 DEG C are dried 10 minutes; Then the PDMS that takes a morsel bonds out feed pathway 6 and liquid outlet channel 7, dries, and preferably 90 DEG C are dried 20 minutes; Demoulding, by feed pathway 6 and the second microchannel 4, conducting between liquid outlet channel 7 and the 3rd microchannel 5.Except above-mentioned PDMS, the material of preparation can also be PDMA, PMMA, PVC soft glass or Zeonor, mixes be prepared with hardening agent.
Preferably, in above-mentioned step 2, the optimum quality ratio of PDMS and hardening agent is 10:1, composite material using state at this time and performance best.
Step 3, bonding chip: chip cover plate 2 adopts flexible material, and itself has viscosity, can bond by nature after chip cover plate 2 and chip base 1 being cleaned up, dry, and preferably 120 DEG C are dried 5 minutes, then naturally cool.
Step 4, making coat: added by Teflon AF2400 solution in the first microchannel 4, microchannel 3, second and the 3rd microchannel 5 and dry, preferably 120 DEG C are dried 15 minutes, make it form film at all microchannel interior walls, make coat 8.
Preferably, in above-mentioned steps four, Teflon AF2400 solution weight concentration is 1% ~ 2%, preferably, use the Teflon AF2400 solution efficacy of 1% concentration best, when Teflon AF2400 solution concentration is more than 2%, coating effect is poor, possible blocking channel, causes bad.
Step 5, making metal nanoparticle array structure: use reduction of sodium citrate silver nitrate, configuration silver sol solution, then silver sol solution is added in the first microchannel 4, microchannel 3, second and the 3rd microchannel 5 and dry, preferably 100 DEG C are dried 5 minutes, and coat 8 inwall that metal nanoparticle is deposited on made by step 4 makes metal nanoparticle array structure 9.Preferably, the methods such as sputtering, evaporation or self assembly are adopted to make metal nanoparticle array structure 9.
Claims (8)
1. a surface-enhanced Raman micro-fluidic chip, is characterized in that: comprise chip base (1), and covers the chip cover plate (2) directly over chip base (1); The bottom of described chip cover plate (2) is provided with the first microchannel (3), the second microchannel (4) and the 3rd microchannel (5), described first microchannel (3) through layout in left and right on chip cover plate; Described second microchannel (4) one end is communicated with the first microchannel (3), and the other end is connected with feed pathway (6); Described 3rd microchannel (5) one end is communicated with the first microchannel (3), and the other end is connected with liquid outlet channel (7); Described feed pathway (6) and liquid outlet channel (7) all extend chip cover plate (2) outward; The material of described first, second, third microchannel (3,4,5) is flexible polymer, and width is greater than 100 μm; The inwall of first, second, third microchannel (3,4,5) is also provided with coat (8), and described coat (8) refractive index is less than 1.33, and thickness is greater than 5 μm; Metal nanoparticle array structure (9) is equipped with at coat (8) inwall; Solution to be measured flows into from feed pathway (6), flows through the second microchannel (4), the first microchannel (3) and the 3rd microchannel (5) and forms liquid core waveguide.
2. surface-enhanced Raman micro-fluidic chip according to claim 1, is characterized in that: second, third microchannel described (4,5) left and right is staggeredly arranged, and all perpendicular to the first microchannel (3); Described feed pathway (6) is perpendicular to the second microchannel (4), described liquid outlet channel (7) is perpendicular to the 3rd microchannel (5), and feed pathway (6) and liquid outlet channel (7) are arranged at the upper paired linea angulata of chip cover plate (2), and be parallel to each other.
3. surface-enhanced Raman micro-fluidic chip according to claim 1, is characterized in that: the material of described coat (8) is Teflon AF2400 or Teflon AF1600.
4. surface-enhanced Raman micro-fluidic chip according to claim 1, is characterized in that: the material of described metal nanoparticle array structure (9) is Au, Ag, Cu or Pt, and single metal nanoparticle shape is spherical, triangle or square.
5. surface-enhanced Raman micro-fluidic chip according to claim 1, is characterized in that: the material of described first, second, third microchannel (3,4,5) is PDMS, PDMA, PMMA, PVC soft glass or Zeonor.
6. one kind comprises the detection system of surface-enhanced Raman micro-fluidic chip described in claim 1-5 any one, it is characterized in that: also comprise importing optical fiber (b) and Fiber Bragg Grating FBG (c) that are arranged in surface-enhanced Raman micro-fluidic chip (a) outside, and described surface-enhanced Raman micro-fluidic chip (a), import optical fiber (b) and Fiber Bragg Grating FBG (c) is dismountable is arranged on same base (d); Described importing optical fiber (b) extend in the first microchannel (3) from the one end of the first microchannel (3), for being imported in liquid core waveguide by exciting light, and utilizes long range propagation to strengthen Raman signal; Described Fiber Bragg Grating FBG (c) extends in the first microchannel (3) from the other end of the first microchannel (3), the exciting light transmitted by liquid core waveguide can be reflected, transmission Raman light, realizes the output to Raman light.
7. a preparation method for surface-enhanced Raman micro-fluidic chip, concrete steps are as follows:
Step one, processing formpiston: photoetching SU8 produces the formpiston of first, second, third bit port (3,4,5);
Step 2, preparation microchannel: get appropriate PDMS and hardening agent, be fully uniformly mixed, leave standstill to bubble free state, be cast on the formpiston made in step one, dry; Then the PDMS that takes a morsel bonds liquid inlet and outlet passage (6,7), dries; Demoulding, by feed pathway (6) and the second microchannel (4), conducting between liquid outlet channel (7) and the 3rd microchannel (5);
Step 3, bonding chip: chip cover plate (2) and chip base (1) are cleaned up rear bonding, naturally cools after drying;
Step 4, making coat: added by Teflon AF2400 solution in first, second, third microchannel (3,4,5) and dry, make it form film at all microchannel interior walls, make coat (8);
Step 5, making metal nanoparticle array structure: use reduction of sodium citrate silver nitrate, configuration silver sol solution, then added by silver sol solution in first, second, third microchannel (3,4,5) and dry, coat (8) inwall that metal nanoparticle is deposited on made by step 4 makes metal nanoparticle array structure (9).
8. the preparation method of surface-enhanced Raman micro-fluidic chip according to claim 7, is characterized in that: the method making metal nanoparticle array structure (9) in step 5 is sputtering, evaporation or self assembly.
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Cited By (2)
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| CN109781709A (en) * | 2019-03-19 | 2019-05-21 | 重庆大学 | Light amplification Raman spectrum detection system based on waveguiding structure |
| CN112697767A (en) * | 2020-12-03 | 2021-04-23 | 中国计量大学 | Detection device combining Raman spectrum with SPR (surface plasmon resonance) |
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