CN204269553U - In-situ SERS detects with micro-fluidic array load sample device - Google Patents
In-situ SERS detects with micro-fluidic array load sample device Download PDFInfo
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- CN204269553U CN204269553U CN201420749550.9U CN201420749550U CN204269553U CN 204269553 U CN204269553 U CN 204269553U CN 201420749550 U CN201420749550 U CN 201420749550U CN 204269553 U CN204269553 U CN 204269553U
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Abstract
The utility model In-situ SERS detects with micro-fluidic array load sample device, containing load sample main body, pretreating device and connecting pipe, described load sample body is load sample body, containing printing opacity envelope and plate and plastic layer: be provided with groove and through hole on plastic layer, it and printing opacity to be sealed and plate bonded energy is formed with the load sample main body of load sample passage and entrance and exit thereof, inflatable matrix material in load sample passage; Described pretreating device structure is Microfluidic array chip, formed by two layers of plastic layer bonding: on the first plastic layer, be provided with groove and through hole, it and the second plastic layer bonded energy are formed with the pretreating device of mixed structure and entrance thereof, flow dividing structure and outlet thereof; Adopt connecting pipe pretreating device and load sample main body can be coupled together.The utility model adopts micro-fluidic chip, can reduce the consumption of matrix material and sample, meet the detection of small size measuring samples; Testing process is simple, and the spectrum stability of acquisition and reappearance are all good.
Description
Technical field
The utility model relates to Surface enhanced raman spectroscopy pick-up unit technical field, particularly, is the micro-fluidic array load sample device that a kind of In-situ SERS detects.
Background technology
Raman spectrum is a kind of scattering spectrum.Due to the existence of Raman scattering effect, analysis is carried out to the scattering spectrum different from incident light frequency and can obtain molecular vibration, rotation aspect information, and the research of molecular structure can be applied to.But, because Raman scattering only accounts for 10 in whole optical radiation energy
-6~ 10
-10, thus its spectral intensity is extremely faint, conventional Raman scattering analytical approach cannot realize the detection of the sample to low concentration, and the application of Raman spectrum is very limited., Fleischmann(Fo Laiximan in 1974) etc. people find, the Pyridine Molecules being adsorbed on the Ag electrode surface of roughening has huge Raman scattering phenomenon, and the sensitivity of Raman scattering can be made to improve 10
3~ 10
7doubly.After this, a kind of novel Raman scattering and Surface enhanced raman spectroscopy (SERS) method are grown up.
Surface enhanced raman spectroscopy (SERS) mainly due to the compound that is adsorbed on roughening metal surfaces because surperficial local plasmon excimer is excited the cluster on caused Electromagnetic enhancement and rough surface and adsorb the active site that the molecular composition Raman on it strengthens, the effect of both makes the Raman scattering of determinand produce great enhancement effect.Meanwhile, active carrier surface adsorption selection molecule produces inhibiting effect to fluorescent emission, and the signal to noise ratio (S/N ratio) of Laser Roman spectroscopic analysis of composition is improved greatly.
At present, when adopting Surface Enhanced Raman Scattering Spectrum to carry out sample analysis, normally sample is mixed with noble metal colloidal sol (such as aurosol, silver sol etc.), then drip and directly carry out Surface enhanced raman spectroscopy analysis on slide.But, such operation can bring the error of more manual operation into, the abundant degree such as mixed, to control adding matrix material and sample size etc., and the reappearance analyzed can be caused greatly to reduce due to the difference of the matrix material prepared at every turn, thus limit the application of Surface enhanced raman spectroscopy technology in sample amounts is analyzed.
Utility model content
The purpose of this utility model is to solve the problem, there is provided a kind of In-situ SERS detection micro-fluidic array load sample device, it uses micro-fluidic chip, can reduce the consumption of matrix material, the consumption of sample can be reduced again, meet the detection needs of small size measuring samples; Adopt the mode of a fluid injecting to carry out the in-situ polymerization of matrix material, the difference of manual operation different batches can be avoided; Major part operation is completed by little instruments such as syringe pumps and simplifies manual operation; The reappearance that Surface Enhanced Raman Scattering Spectrum carries out in sample analysis can be improved.
For achieving the above object, the utility model takes following technical scheme.
A kind of In-situ SERS detects with micro-fluidic array load sample device, at least comprises a load sample body, a Microfluidic array chip, described load sample body is provided with load sample region, it is characterized in that, described load sample body adopts load sample agent structure; Described Microfluidic array chip adopts pretreating device structure; Described load sample main body contains printing opacity envelope and plate and plastic layer: on described plastic layer, be provided with the through hole that can become load sample feeder connection and load sample channel outlet, in the inside of described plastic layer, be namely provided with groove between described two through holes, described plastic layer and described printing opacity are sealed and namely plate bonding is formed with the load sample main body of load sample passage, load sample feeder connection and load sample channel outlet, described load sample passage is described load sample region; Described pretreating device is formed by two layers of plastic layer bonding: suppressed the groove structure that can form mixed structure, flow dividing structure by template in the inside of ground floor plastic layer, arranges the through hole that can become mixed structure entrance and flow dividing structure outlet at the two ends of described groove structure; Second layer plastic layer is slab construction (formation for passage); Described ground floor plastic layer is bonded in the pretreating device namely described second layer plastic layer being formed with the outlet of mixed structure, flow dividing structure, mixed structure entrance and flow dividing structure; Described pretreating device can be coupled together with the load sample feeder connection of described load sample main body by its flow dividing structure outlet connecting pipe.
Further, described bonding is the bonding pattern adopting oxygen gas plasma process.
Further, described load sample passage is single channel, and containing a load sample feeder connection, a load sample channel outlet, described single pass size is less than the size of mixed structure in described pretreating device.
Further, described load sample passage contains seven passages, and every root passage has a load sample feeder connection, a load sample channel outlet.Number of channels can increase and decrease as required.
Further, described mixed structure is the structure (the abundant mixing for matrix material) that herring-bone form interlocks.
Further, described flow dividing structure contains seven passages, and the front end of described seven passages is connected with described mixed structure, and the rear end of described seven passages is respectively by the seven piece expanding channels of respective flow dividing structure outlet by seven connecting pipes and described load sample passage.
Further, described connecting pipe is teflon pipeline.
Further, described printing opacity envelope and plate are the glass sheet that 1mm is thick.
Further, the plastic layer of described load sample main body and the two layers of plastic layer of described pretreating device are polymethyl methacrylate layers.
The good effect of the utility model In-situ SERS detection micro-fluidic array load sample device is:
(1) the utility model adopts micro-fluidic chip, not only reduces the consumption of matrix material, and decreases the consumption of sample, meet the detection needs of small size measuring samples.
(2) the utility model adopts the mode of a fluid injecting to carry out the in-situ polymerization of matrix material, avoid the difference causing matrix material due to the difference of different batches manual operation, overcome the shortcoming that same sample SPECTRAL DIVERSITY in repetitive measurement is large, the homogeneity of matrix material improves greatly, the stability of spectrum and favorable reproducibility.
(3) the utility model adopts single channel detection arrays, greatly can improve the flux of detection; Meanwhile, because major part operation is completed by little instruments such as syringe pumps, manual operation is simplified.
(4) micro-fluidic array load sample device of the present utility model is when the Surface enhanced raman spectroscopy being applied to sample is analyzed, pretreating device can be utilized to be mixed fully by matrix material and be diverted in load sample main body, make the matrix material in load sample main body completely the same; And the testing process of sample is simple, the spectrum stability of acquisition and reappearance are all good.
Accompanying drawing explanation
Fig. 1 is the structural representation of the utility model In-situ SERS detection micro-fluidic array load sample device.
Fig. 2 is the structural representation after Fig. 1 in-situ polymerization matrix material.
Fig. 3 is the spectrogram that Fig. 2 carries out four kinds of aromatic amine surface-enhanced Ramans detections.
Label in figure is respectively:
1, load sample main body; 11, printing opacity envelope and plate; 12, plastic layer;
13, load sample passage; 14, load sample feeder connection; 15, load sample channel outlet;
16, matrix material; 2, pretreating device; 21, mixed structure;
22, flow dividing structure; 23, mixed structure entrance; 24, flow dividing structure outlet;
3, connecting pipe.
Embodiment
Introduce the embodiment of the utility model In-situ SERS detection micro-fluidic array load sample device below in conjunction with accompanying drawing, but it is noted that enforcement of the present utility model is not limited to following embodiment.
See Fig. 1.A kind of In-situ SERS detects with micro-fluidic array load sample device, containing load sample main body 1, pretreating device 2 and connecting pipe 3.Described load sample main body 1 is load sample body, containing printing opacity envelope and plate 11 and plastic layer 12: the glass sheet that described printing opacity seals and plate 11 selects 1mm thick, its role is to the complete formation of load sample passage 13 and the detection of Raman spectrum; Described plastic layer 12 adopts polymethyl methacrylate layers.
Described plastic layer 12 is arranged the through hole that can become load sample feeder connection 14 and load sample channel outlet 15 by the mode of mold pressing; In the inside of described plastic layer 12, namely between described two through holes, groove is set.Again described plastic layer 12 and described printing opacity are sealed and plate 11 by bonding after oxygen gas plasma process: namely two through holes become load sample feeder connection 14 and load sample channel outlet 15, and namely described groove becomes load sample passage 13; Form the load sample main body 1 with load sample passage 13, load sample feeder connection 14 and load sample channel outlet 15.
In enforcement, described load sample passage 13 can be set to single channel, containing a load sample feeder connection 14, load sample channel outlet 15, described single pass size should be less than the size of mixed structure 21 in pretreating device 2.
Or be arranged to by described load sample passage 13 containing seven passages (as in-situ polymerization matrix material and spectral detection), every root passage is provided with a load sample feeder connection 14 and a load sample channel outlet 15.
Described pretreating device 2 is micro-fluidic chip array, is formed by two layers of plastic layer (ground floor plastic layer and second layer plastic layer) bonding.Described ground floor plastic layer and second layer plastic layer adopt polymethyl methacrylate layers.
Suppressed the groove structure that can form mixed structure 21, flow dividing structure 22 in the inside of ground floor plastic layer by template, the through hole that can become mixed structure entrance 23 and flow dividing structure outlet 24 is set at the two ends of described groove structure.Second layer plastic layer can adopt slab construction, is mainly used in the formation of passage.Namely the second layer plastic layer described ground floor plastic layer being bonded in slab construction is formed with the pretreating device 2 of mixed structure 21, flow dividing structure 22, mixed structure entrance 23 and flow dividing structure outlet 24.
The structure that described mixed structure 21 can adopt herring-bone form staggered, for the abundant mixing of matrix material.
Described flow dividing structure 22 should be consistent with the load sample passage 13 of load sample main body 1: if described load sample passage 13 is provided with seven passages, and so described flow dividing structure 22 also should contain seven passages.Described flow dividing structure 22 7 passages
beforeend should be connected with described mixed structure 21, described flow dividing structure 22 7 passages
afterhold and be connected by the load sample feeder connection 14 of seven connecting pipes 3 and described load sample passage 13 7 passages respectively by respective flow dividing structure outlet 24.Described mixed structure 21, flow dividing structure 22 are described micro-fluidic chip array.
In concrete enforcement, the thickness of described load sample main body 1 and described pretreating device 2 can adjust as required.What adopt due to the utility model is micro-fluidic chip, and for the analysis of small samples, therefore, in described load sample main body 1 and described pretreating device 2, the height of passage is generally between 100 ~ 500 μm.
When needing, can connecting pipe 3 be adopted to couple together with the load sample feeder connection 14 of load sample main body 1 by its flow dividing structure outlet 24 described pretreating device 2.Described connecting pipe 3 can adopt teflon pipeline.
In enforcement, can select described load sample main body 1 to be connected with described pretreating device 2 or to disconnect according to the needs of different step: being generally when carrying out in-situ polymerization matrix material, both are connected, when carrying out surface-enhanced Raman detection, both being disconnected.
The use-pattern of the utility model In-situ SERS detection micro-fluidic array load sample device is:
(1) described load sample main body 1 and the described connecting pipe 3 of described pretreating device 2 are connected together; By glycidyl methacrylate, ethene dimethylacrylate, ring ethanol, dodecanol and benzoyl peroxide in mass ratio 1:0.6:2:0.4:0.02 be mixed into matrix material solution.
(2) with syringe pump, a small amount of described matrix material solution is injected described pretreating device 2 by mixed structure entrance 23, treat that described matrix material solution arrives load sample main body 1 by described pretreating device 2.
(3) matrix material solution is removed, again by ejection of syringe pump air, order about described matrix material solution by air and be full of (described matrix material solution can only rest in the load sample passage 13 of load sample main body 1) in all load sample passages of load sample main body 1 13, in described pretreating device 1 and described connecting pipe 3, should not retain any matrix material solution.
(4) described load sample main body 1 is placed in thermostatic drier to place 24 hours at 65 DEG C of temperature, makes the matrix material solution in all load sample passages 13 become matrix material 16(see Fig. 2).
(5) pass into a certain amount of ammoniacal liquor in the whole load sample passages 13 in the load sample main body 1 after being polymerized in position, make described load sample passage 13 soak 4 hours in 70 DEG C of temperature in ammoniacal liquor, complete the amino modified of matrix material 16.
(6) in load sample body passageways 13, pass into the gold nano colloidal sol prepared in advance again, react 10 hours, complete the modification of hyperchannel gold nano grain to matrix material by the self assembly between the amino on matrix material 16 and nm of gold.
To the detection of the utility model In-situ SERS detection with micro-fluidic array load sample device:
Sample after a certain amount of dissolving is injected arbitrary load sample passage 13 of load sample main body 1 prepared by the utility model embodiment by syringe pump and keeps certain hour (as 10 minutes), making sample adsorption on matrix material 16, is that the portable micro-Raman spectroscopy of 785nm detects with exciting light.
Fig. 3 is the Raman spectrogram that two adjacent chlorodiphenyl amine methane (MOCA) of variable concentrations record; MOCA concentration is wherein respectively 1 from a to f, 5,10,20,40,50ppb.
Needed for one-time detection, the amount of sample is about a few microlitre.The spectral results of 5 replicate determinations is with 1603cm
-1relation between the raman spectrum strength at place and concentration is mapped, and finds that it has good linear relationship, related coefficient (R
2) reach 0.9852.
When the Surface enhanced raman spectroscopy adopting proof gold colloidal sol to carry out two adjacent chlorodiphenyl amine methane (MOCA) measures, only could certain Raman signal be produced when sample concentration is greater than 10ppm, and the non-constant of reappearance.
Therefore, adopt micro-fluidic array load sample device of the present utility model, when greatly reducing test amount of samples, test effect has had very large lifting than adopting proof gold colloidal sol Detection results.
Claims (9)
1. an In-situ SERS detects with micro-fluidic array load sample device, at least comprise a load sample body, a Microfluidic array chip, described load sample body is provided with load sample region, it is characterized in that, described load sample body adopts load sample main body (1) structure; Described Microfluidic array chip adopts pretreating device (2) structure; Described load sample main body (1) is containing printing opacity envelope and plate (11) and plastic layer (12): on described plastic layer (12), be provided with the through hole that can become load sample feeder connection (14) and load sample channel outlet (15), described plastic layer (12) the inside, be namely provided with groove between described two through holes, described plastic layer (12) and described printing opacity sealed and namely plate (11) bonding is formed with the load sample main body (1) of load sample passage (13), load sample feeder connection (14) and load sample channel outlet (15), described load sample passage (13) is described load sample region;
Described pretreating device (2) is formed by two layers of plastic layer bonding: suppressed the groove structure that can form mixed structure (21), flow dividing structure (22) by template in the inside of ground floor plastic layer, arranges the through hole that can become mixed structure entrance (23) and flow dividing structure outlet (24) at the two ends of described groove structure; Second layer plastic layer is slab construction; Described ground floor plastic layer is bonded in the pretreating device (2) namely described second layer plastic layer being formed with mixed structure (21), flow dividing structure (22), mixed structure entrance (23) and flow dividing structure outlet (24); Described pretreating device (2) can be coupled together with the load sample feeder connection (14) of connecting pipe (3) with described load sample main body (1) by its flow dividing structure outlet (24).
2. In-situ SERS detection micro-fluidic array load sample device according to claim 1, is characterized in that, described bonding is the bonding pattern adopting oxygen gas plasma process.
3. In-situ SERS detection micro-fluidic array load sample device according to claim 1, it is characterized in that, described load sample passage (13) is single channel, containing a load sample feeder connection (14), a load sample channel outlet (15), described single pass size is less than the size of mixed structure (21) in described pretreating device (2).
4. In-situ SERS detection micro-fluidic array load sample device according to claim 1, it is characterized in that, described load sample passage (13) is containing seven passages, and every root passage is provided with a load sample feeder connection (14), a load sample channel outlet (15).
5. In-situ SERS detection micro-fluidic array load sample device according to claim 1, is characterized in that, the structure that described mixed structure (21) interlocks for herring-bone form.
6. the micro-fluidic array load sample device of the In-situ SERS detection according to claim 1 or 4, it is characterized in that, described flow dividing structure (22) is containing seven passages, the front end of described seven passages is connected with described mixed structure (21), and the rear end of described seven passages exports (24) by the seven piece expanding channels of seven connecting pipes (3) with described load sample passage (13) respectively by respective flow dividing structure.
7. In-situ SERS detection micro-fluidic array load sample device according to claim 1, it is characterized in that, described connecting pipe (3) is teflon pipeline.
8. In-situ SERS detection micro-fluidic array load sample device according to claim 1, is characterized in that, described printing opacity envelope and plate (11) are the thick glass sheet of 1mm.
9. In-situ SERS detection micro-fluidic array load sample device according to claim 1, it is characterized in that, the plastic layer (12) of described load sample main body (1) and the two layers of plastic layer of described pretreating device (2) are polymethyl methacrylate layers.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108709880A (en) * | 2018-05-28 | 2018-10-26 | 中国工程物理研究院化工材料研究所 | Reusable high throughput SERS micro-fluidic chips and its application |
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| CN108709880A (en) * | 2018-05-28 | 2018-10-26 | 中国工程物理研究院化工材料研究所 | Reusable high throughput SERS micro-fluidic chips and its application |
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