CN104107734B - A kind of method of micro-fluidic chip and self assembly - Google Patents

A kind of method of micro-fluidic chip and self assembly Download PDF

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CN104107734B
CN104107734B CN201410345989.XA CN201410345989A CN104107734B CN 104107734 B CN104107734 B CN 104107734B CN 201410345989 A CN201410345989 A CN 201410345989A CN 104107734 B CN104107734 B CN 104107734B
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micro
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CN104107734A (en
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水玲玲
王娟
金名亮
阿尔伯特·范登伯格
周国富
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Shenzhen Guohua Optoelectronics Co Ltd
Academy of Shenzhen Guohua Optoelectronics
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SHENZHEN GUOHUA PHOTOELECTRIC Research INSTITUTE
South China Normal University
Shenzhen Guohua Optoelectronics Co Ltd
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Abstract

The invention discloses a kind of method of micro-fluidic chip and self assembly, the present invention is by providing a kind of micro-fluidic chip, comprise first passage, second channel, third channel, four-way and some side chain passages, liquid enters from first passage and second channel respectively, converge in the crosspoint of first passage, second channel and third channel, by adjusting the flow velocity of fluid, after making liquid joint, form monodispersed microlayer model particle, then by four-way, utilize branched structure, carry out being separated of particle and liquid, realize particle self assembly in four-way.By regulation and control flow rate of liquid, the size changing passage can obtain the particle of different-grain diameter, realizes the self-assembled structures of the ordered composite of individual layer/bilayer/multi-layer three-dimension solid.The present invention can be used for the self assembly of particle.

Description

A kind of method of micro-fluidic chip and self assembly
Technical field
The present invention relates to microflow control technique, relate to a kind of micro-fluidic chip for self assembly specifically and utilize this chip to realize the technology of monodisperse particles self assembly.
Background technology
Microflow control technique comes across the beginning of the eighties in last century, is an emerging field having gathered engineering science, physics, chemistry, biotechnology, micro-fabrication technique.Microflow control technique, by the chip of a few centimeter square, effectively precisely controls and handles minute yardstick fluid, especially refering in particular to micron to submicrometer structure, so micro-fluidic chip is the main platform that it realizes.Utilize microflow control technique can to produce a large amount of micro-liquid pearls (speed can reach 1Hz ~ 10 online within even shorter time a few minutes 4hz), the liquid pearl of generation can carry out the controlled adjustment of original position in the position of specifying, and reaches the object being self-assembled into ordered structure.Therefore, can by the method binding function material (polymeric, solid particle, liquid particles, bubble etc.) for three-dimensional self-assembling method and technology, make corresponding device, be applied to photonic bandgap material (photonic crystal), colored display, catalysis, sensing, chemical/biological separation and energy storage etc.
Self assembly SAM (Self-assembledmonolayers) refers to that a disordered system is not having, under outside intervention, by the interaction between individual part, and to form an organized configuration process.As a kind of new technique, self-assembling technique can design the structure of molecule on a molecular scale, obtains excellent properties and specific function, because it has highly sensitive, selective good advantage.Particles self assemble, general process can experience: prepare particle, screening particle, and in a solvent, external force drives the lower several process of particles self assemble to discrete particles.Fluid mixture containing particle carries out self assembly and generally removes decentralized photo medium by evaporation, microwave catalysis volatilization or the means such as dialysis, thus particle is tightly packed and form periodic regular texture; Or the solution-air adopting chemistry to drive and cause, the change of liquid-liquid interface energy, makes particle in interface self assembly.
But these existing self-assembling methods exist following shortcoming: first, the particle for self assembly needs preparation separately, and the difference due to preparation method can cause the dispersiveness of particle and size to be difficult to control; Secondly, because Granular composite is in solvent (i.e. continuous phase), a large amount of decentralized photos is needed to disperse, need to consume a large amount of decentralized photos, the particle in decentralized photo is made to carry out self assembly by the change of molecular separating force, chemical potential, the change etc. of pH, this process need consumes long time, and needs special experiment condition and equipment support, because which limit the wide model application of self-assembled material in fields such as photonic crystal, acoustics, micro-manufacturing system, insoluble drug release, sensings.
Summary of the invention
The technical problem to be solved in the present invention is: for solving the problem of above-mentioned prior art in particles self assemble, the invention provides a kind of micro-fluidic chip, and utilizes this chip to realize the method for monodisperse particles self assembly.
The solution that the present invention solves its technical problem is: provide a kind of micro-fluidic chip, comprises first passage, second channel, third channel, four-way and some side chain passages; Liquid enters from first passage and second channel respectively, converge in the crosspoint of first passage, second channel and third channel and flow into through third channel in four-way, side chain passage, wherein four-way is connected with some side chain passages respectively, and described third channel width is less than the width of described first passage, second channel and four-way.
Preferably, described micro-fluidic chip also comprises the wing passage with some side chain channel connections, like this from the liquid that side chain passage flows out, can unify to collect after approaching side passage, need not respectively at each side chain channel setting fluid collection device.
Preferably, described first passage and second channel have inlet respectively; Described four-way and wing passage have liquid outlet respectively, are convenient to liquid like this and inject and self assembly sample collection.
Preferably, described first passage is that axial symmetry is arranged with second channel; Described side chain passage and wing passage are with four-way for axial symmetry is arranged, and side chain channel vertical is in four-way.Better can eliminate the interference of other factors to fluid like this, be more conducive to accurately control self assembling process.Described first passage is that axial symmetry is arranged with second channel, refers to that first passage has many, and symmetrical is distributed in second channel both sides, and these first passages can have same inlet, also can have independent inlet separately.
Further preferably, the width of described third channel is 10 ~ 100 μm, and the width of described four-way is 100 ~ 400 μm, and the width of described side chain passage is 10 ~ 100 μm.
Present invention also offers a kind of method utilizing this micro-fluidic chip to carry out self assembly, the method comprises the following steps:
(1) two immiscible liquid A phases and B phase is selected;
(2) under room temperature, A phase is injected first passage, B phase injects second channel;
(3) regulate two-phase fluid speed, make when two-phase converge enter third channel time, B phase liquid forms uniform and stable monodisperse particles and is scattered in A phase liquid;
(4) mixed liquor of A phase liquid and B phase liquid particles enters four-way, and A phase liquid flows out after entering the side chain passage of micro-fluidic chip, and B phase liquid particles is self-assembled into close-packed structure in the four-way of micro-fluidic chip;
(5) in-situ solidifying self-assembled structures collecting.
The invention has the beneficial effects as follows: the present invention is by providing a kind of micro-fluidic chip, comprise first passage, second channel, third channel, four-way and some side chain passages, liquid enters from first passage and second channel respectively, converge in the crosspoint of first passage, second channel and third channel, by adjusting the flow velocity of fluid, make liquid after converging, form monodispersed microlayer model particle, then four-way is entered, utilize its branched structure, realize being separated of particle and liquid, particle carries out self assembly in four-way.Described micro-fluidic chip has integrated height, manipulates easy, to be easy to control advantage; Its method of carrying out self assembly is used to have the homogeneous advantage of condition controllable precise, granule-morphology; By regulation and control flow rate of liquid, the size changing passage can obtain the particle of different-grain diameter, realizes the self-assembled structures of the ordered composite of individual layer/bilayer/multi-layer three-dimension solid.The present invention can be used for the self assembly of particle.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described.Obviously, described accompanying drawing is a part of embodiment of the present invention, instead of whole embodiment, and those skilled in the art, under the prerequisite not paying creative work, can also obtain other designs and accompanying drawing according to these accompanying drawings.
Fig. 1 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 1;
Fig. 2 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 2;
Fig. 3 is the structural representation of the micro-fluidic chip of the embodiment of the present invention 3.
Detailed description of the invention
Clear, complete description is carried out, to understand object of the present invention, characteristic sum effect fully below with reference to embodiment and the accompanying drawing technique effect to design of the present invention, concrete structure and generation.Obviously; described embodiment is a part of embodiment of the present invention, instead of whole embodiment, based on embodiments of the invention; other embodiments that those skilled in the art obtains under the prerequisite not paying creative work, all belong to the scope of protection of the invention.Each technical characteristic in the invention, can combination of interactions under the prerequisite of not conflicting conflict.
The manufacture craft of micro-fluidic chip is the technology of current comparative maturity, the professional knowledge that those skilled in the art can have according to it selects suitable technique to realize, and glass, silicon materials or macromolecular material such as dimethyl silicone polymer, epoxy resin, polyurethane etc. can be used to be used as the material of micro-fluidic chip.Preferably, use the material with waterproof or grease proofness as the material of micro-fluidic chip.When adopting glass material to do chip, first make mask plate, its model is etched on solid substrate by method such as recycling photoetching, etching etc., then carries out device package.When using macromolecular material as chip material, manufacturing process is: mask blank, and photoetching copies template, finally by the macromolecule chip attach that obtains on slide, namely obtain particles self assemble micro-fluidic chip of the present invention.Passage on described micro-fluidic chip is connected with fluid pump by plastic tube, glass tube etc., and flow rate of liquid is controlled by fluid pump.
Embodiment 1
With reference to Fig. 1, the structural representation of the micro-fluidic chip of the preferred embodiment of the present invention, liquid converges after entering first passage 1 and second channel 2 respectively and enters third channel 3, the some side chain passages 5 entering four-way 4 after flowing through third channel and be communicated with four-way, chip also comprises the wing passage 6 with side chain channel connection, the width of third channel 3 is less than first passage 1, the width of second channel 2 and four-way 4, first passage 1 with second channel 2 for axial symmetry distribution, side chain passage 5 and wing passage 6 with four-way 4 for axial symmetry distribution, and side chain passage 5 vertical connection is in four-way 4, first passage 1 and second channel 2 have inlet a respectively, b, four-way 4 and wing passage 6 have liquid outlet c respectively, d.
In practice, the various factors such as particle diameter and fluid properties of particle should be prepared as required, select suitable channel width, according to test, the width of described third channel 3 can be made to be 10 ~ 100 μm, the width of described four-way 4 is 100 ~ 400 μm, and the width of described side chain passage 5 is that more than 10 ~ 100 μm number ranges are comparatively suitable.
The micro-fluidic chip of the present embodiment can carry out self assembly by following steps:
(1) select immiscible two-phase liquid, be denoted as A phase and B phase respectively; Preferably, described immiscible two-phase liquid, wherein one is oil-soluble organic solvent mutually, and another is that the aqueous solution comprises: the aqueous solution of distilled water, running water, deionized water or other materials mutually.Described oil-soluble organic solvent is the one or more kinds of mixing in dodecane, hexadecane, dimethicone, kerosene, mineral oil, vegetable oil; The described aqueous solution is the one in the polyethyleneglycol diacrylate aqueous solution, acrylonitrile compolymer acrylamide aqueous solution, the NIPA aqueous solution, inorganic salt solution etc., described inorganic salts can be any one in common inorganic salts, as villaumite, carbonate, nitrate, sulfate, sulfonate, carbonate, bicarbonate, disulfate, phosphate, hydrophosphate, dihydrogen sulfate salt etc.Particularly, as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ferric nitrate, ferrous nitrate, sodium sulphate, sodium sulfonate, potassium sulfate, calcium sulfate, sodium carbonate, potash, magnesium carbonate etc.
Further, in order to regulate the interfacial tension of two-phase liquid, making stable generation particle and stable existence carries out self assembly, in described two-phase liquid, can surfactant be added.Preferably, described surfactant is the one or more kinds of mixing in lauryl sodium sulfate, tween (Tween), Qu Latong (Triton), sapn (Span), polyvinyl alcohol (PVA), cetyl polyethylene/polypropylene glycol-10/1 dimethyl siloxane (EM90).Wherein tween refers to TWEEN Series, comprises polysorbas20 (Tween-20), tween 21(Tween-21), polysorbate40 (Tween-40), polysorbate60 (Tween-60), Tween61 (Tween-61), Tween 80 (Tween-80), sorbimacrogol oleate100 (Tween-81), polysorbate85 (Tween-85) etc.; Equally, Qu Latong, sapn also refer to respectively Qu Latong series and Span series, comprise triton x-100 (TritonX-100), Qu Latong X-114(TritonX-114 respectively) etc. with span 20 (Span20), span 40 (Span40), sorbester p18 (Span60), sorbester p38 (Span65), sorbester p17 (Span80), sorbester p37 (Span85) etc.
(2), under room temperature, A phase is injected first passage 1, B phase by inlet a and injects second channel 2 by inlet b, can the introducings such as fluid pump be adopted.
(3) regulate two-phase fluid speed, make when two-phase converge enter third channel 3 time, B phase liquid forms uniform and stable monodisperse particles and is scattered in A phase liquid; General A phase flow rate of liquid is at 40 ~ 1500 μ L/h, B phase flow rate of liquid is at 15 ~ 600 μ L/h, according to the speed size of two-phase fluid, and the width of third channel can be observed like several patterns such as stopper, bead, injection thread or linear flows at meet, these four kinds of patterns are formed based on different mechanism (extruding, drip, line spray, linear flow) accordingly.
(4) mixed liquor enters four-way 4, due to impact and the passage geometry designs of flow velocity, four-way 4 and side chain passage 5 have pressure differential, such A phase liquid is taken away by the side chain passage 5 of micro-fluidic chip, flowed out by liquid outlet d through wing passage 6, B phase liquid particles concentration becomes large, because maximum energy criterion is self-assembled into close-packed structure in the four-way 4 of micro-fluidic chip, A phase liquid can be taken away by wing passage within several seconds even shorter time, the ordered arrangement that only remaining B phase liquid particles is spontaneous forms individual layer, double-deck, the regular close-packed structure of multilayer, it is self-assembled into one dimension, two dimension, three-dimensional closs packing stereochemical structure depends on the character of two-phase fluid, the grain diameter size produced, the flow rate of fluid, the factor of each side such as the geometry designs of passage.
(5) in-situ solidifying, obtains self-assembly equipments, and collects at four-way exit c.The method of solidification comprises UV solidification, chemosetting, heat cure etc.
In above-mentioned steps, in order to control the speed of fluid, tackifier can be added wherein, so that regulate fluid rate, realizing the self assembly effect needed.In addition, also light trigger, crosslinking agent etc. can be added, so that the solidification of self-assembled structures.
Utilize the micro-fluidic chip of embodiment 1, the specific embodiment carrying out particles self assemble is as follows:
Embodiment A
A phase is hexadecane, wherein add 2.5wt%Span80 as surfactant, B phase is deionized water, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, and when A phase flow velocity is 40 ~ 100 μ L/h, B phase flow velocity is 15 ~ 50 μ L/h, the micro-liquid pearl of the B phase obtained is of a size of 30 ~ 48 μm, the one dimension close-packed structure that self assembly is formed.When A phase flow velocity is 100 ~ 400 μ L/h, B phase flow velocity is 50 ~ 100 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 25 ~ 30 μm, the two-dimentional close-packed structure that self assembly is formed.
When A phase flow velocity is 400 ~ 600 μ L/h, B phase flow velocity is 100 ~ 200 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 20 ~ 30 μm, the three-dimensional close-packed structure that self assembly is formed.
Embodiment B
A phase is hexadecane, add 2.5wt%Span80 as surfactant, B phase is the 6wt%N-N-isopropylacrylamide aqueous solution, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, and regulate A phase flow velocity to be 900 ~ 1200 μ L/h, B phase flow velocity is 400 ~ 600 μ L/h, the B phase micro-liquid pearl size 18 ~ 30 μm obtained, the one dimension close-packed structure that self assembly is formed.
Embodiment C
A phase is mineral oil, add 10wt%EM90 as surfactant, B phase is the 18wt%N-N-isopropylacrylamide aqueous solution, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, and regulate A phase flow velocity to be 40 ~ 250 μ L/h, B phase flow velocity is 15 ~ 60 μ L/h, the B phase micro-liquid pearl size 8 ~ 30 μm obtained, the one dimension close-packed structure that self assembly is formed.
Embodiment D
A phase is hexadecane, add 2.6wt%Span80 as surfactant, B phase is the 15wt%N-N-isopropylacrylamide aqueous solution, wherein containing light trigger 1.5wt%, crosslinking agent 3wt%, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, regulates A phase flow velocity to be 80 ~ 180 μ L/h, fixing B phase flow velocity is 20 μ L/h, the B phase micro-liquid pearl size 8 ~ 15 μm obtained, the three-dimensional close-packed structure of the peacekeeping that self assembly is formed.In A phase speed less than or equal to 120 μ L/h, obtain one dimension close-packed structure, when A phase speed is higher than 120 μ L/h, obtain 3 D stereo close-packed structure, liquid bead footpath is little of 8 μm.
Embodiment E
A phase is mineral oil, add 10wt%EM90 as surfactant, B phase is the 40wt%N-N-isopropylacrylamide aqueous solution, wherein containing light trigger 0.5wt%, crosslinking agent 2wt%, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, and regulate A phase flow velocity to be 20 ~ 80 μ L/h, B phase flow velocity is 20 ~ 30 μ L/h, the B phase micro-liquid pearl size 23 ~ 47 μm obtained, the one dimension close-packed structure that self assembly is formed.
Embodiment F
A phase is 0.3% sodium dodecyl sulfate aqueous solution, and B phase is dodecane, adopts fluid pump, and A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b,
When A phase flow velocity is 10 ~ 50 μ L/h, B phase flow velocity is 10 ~ 15 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 40 ~ 50 μm, the one dimension close-packed structure that self assembly is formed.
When A phase flow velocity is 50 ~ 80 μ L/h, B phase flow velocity is 15 ~ 25 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 20 ~ 40 μm, the two-dimentional close-packed structure that self assembly is formed.
When A phase flow velocity is 80 ~ 100 μ L/h, B phase flow velocity is 25 ~ 30 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 5 ~ 25 μm, the three-dimensional close-packed structure that self assembly is formed.
Embodiment G
A phase is the olive oil of 60v% and the mixed liquor of 40v% sunflower oil, adding 1.5wt%Tween60 with 1wt%Span40 is the 18wt%N-N-isopropylacrylamide aqueous solution as surfactant B mutually, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, A phase flow velocity is regulated to be 300 ~ 500 μ L/h, B phase flow velocity is 50 ~ 150 μ L/h, and the micro-liquid pearl of the B phase obtained is of a size of 15-50 μm, the two-dimentional close-packed structure that self assembly is formed.
Embodiment H
A phase is the mixed liquor of the dodecane of 30v%, 20v% hexadecane and 50v% mineral oil, add 1.5wt%PVA as surfactant, B phase is the polyethyleneglycol diacrylate aqueous solution, adopt fluid pump, A, B two-phase is introduced first passage 1 and second channel 2 respectively by inlet a, b, regulates A phase flow velocity to be 800 ~ 1200 μ L/h, B phase flow velocity 300 ~ 600 μ L/h, the micro-liquid pearl of the B phase obtained is of a size of 5-15 μm, the three-dimensional close-packed structure that self assembly is formed.
Embodiment 2
As Fig. 2, give the structural representation of the embodiment 2 of micro-fluidic chip of the present invention, the difference of the chip of itself and embodiment 1 is only: two first passages 1 have independently inlet a respectively.
Embodiment 3
Fig. 3 gives the structural representation of the embodiment 3 of micro-fluidic chip of the present invention, and the difference of the chip of itself and embodiment 1 is: first passage 1, second channel 2 form y-type structure with third channel 3, and side chain passage 5 tilts to be communicated in four-way 4.
About utilizing the chip of embodiment 2 and enforcement 3 to carry out the method for self assembly for composing a piece of writing succinctly, do not repeat them here.
Above better embodiment of the present invention is illustrated, but the invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modifications or replacement under the prerequisite without prejudice to spirit of the present invention, and these equivalent modification or replacement are all included in the application's claim limited range.

Claims (10)

1. a micro-fluidic chip, is characterized in that: comprise first passage, second channel, third channel, four-way and some side chain passages; Liquid enters from first passage and second channel respectively, and converge in the crosspoint of first passage, second channel and third channel and flow into through third channel in four-way, side chain passage, wherein four-way is connected with some side chain passages respectively; Described third channel width is less than the width of described first passage, second channel and four-way.
2. micro-fluidic chip according to claim 1, is characterized in that: also comprise the wing passage with some side chain channel connections.
3. micro-fluidic chip according to claim 2, is characterized in that: described first passage and second channel have inlet respectively; Described four-way and wing passage have liquid outlet respectively.
4. micro-fluidic chip according to claim 2, is characterized in that: described first passage is that axial symmetry is arranged with second channel; Described side chain passage and wing passage with four-way for axial symmetry is arranged.
5. micro-fluidic chip according to claim 1, is characterized in that: the width of described third channel is 10 ~ 100 μm, and the width of described four-way is 100 ~ 400 μm, and the width of described side chain passage is 10 ~ 100 μm.
6. a method for the self assembly of the micro-fluidic chip according to any one of claim 1-5, the method comprises the steps:
(1) two immiscible liquid A phases and B phase is selected;
(2) under room temperature, A phase is injected first passage, B phase injects second channel;
(3) regulate two-phase fluid speed, make when two-phase converge enter third channel time, B phase liquid forms uniform and stable Granular composite in A phase liquid;
(4) mixed liquor of A phase liquid and B phase liquid particles enters four-way, third channel width is less than the width of first passage, second channel and four-way, A phase liquid flows out after entering the side chain passage of micro-fluidic chip, and B phase liquid particles is self-assembled into close-packed structure in the four-way of micro-fluidic chip;
(5) in-situ solidifying self-assembled structures collecting.
7. the method for self assembly according to claim 6, is characterized in that: described A phase and B phase liquid, and wherein one is oil-soluble organic solvent mutually, and another is distilled water, running water, deionized water or the aqueous solution mutually.
8. the method for self assembly according to claim 7, is characterized in that: described oil-soluble organic solvent is the one or more kinds of mixtures in dodecane, hexadecane, dimethicone, kerosene, mineral oil, vegetable oil; The described aqueous solution is the one in the polyethyleneglycol diacrylate aqueous solution, acrylonitrile compolymer acrylamide aqueous solution, the NIPA aqueous solution, inorganic salt solution.
9. the method for self assembly according to claim 6, is characterized in that: be added with surfactant in described A phase or B phase liquid.
10. self-assembling method according to claim 6, wherein the flow velocity of A phase liquid is 40 ~ 1500 μ L/h, and the flow velocity of B phase liquid is 15 ~ 600 μ L/h.
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