CN106345545A - Multinuclear emulsion drip preparation chip and modification method - Google Patents
Multinuclear emulsion drip preparation chip and modification method Download PDFInfo
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- CN106345545A CN106345545A CN201610850459.XA CN201610850459A CN106345545A CN 106345545 A CN106345545 A CN 106345545A CN 201610850459 A CN201610850459 A CN 201610850459A CN 106345545 A CN106345545 A CN 106345545A
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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
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- 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
- B01L3/502707—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 characterised by the manufacture of the container or its components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- 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
- B01L3/502769—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 characterised by multiphase flow arrangements
-
- 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
-
- 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
- B01L2300/08—Geometry, shape and general structure
- B01L2300/0861—Configuration of multiple channels and/or chambers in a single devices
Abstract
The invention discloses a multinuclear emulsion drip preparation chip and a modification method. The chip comprises a glass substrate, and a micro-channel formed in the glass substrate, wherein the micro-channel comprises a main channel; one end of the main channel is respectively communicated with an oil phase O sample introduction first channel, an oil phase O sample introduction second channel and a water phase W1 sample introduction channel; the other end of the main channel is communicated to a cross-shaped fluid confocal cutting channel; one opening of the fluid confocal cutting channel is communicated to the main channel; the other three openings are respectively communicated to a water phase W2 sample introduction first channel, a water phase W2 sample introduction second channel and an outlet channel; the cross area of the fluid confocal cutting channel is smaller than that of the main channel. According to the multinuclear emulsion drip preparation chip and the modification method provided by the invention, through accurately controlling the flow velocity of fluid, a modifier and other fluid form hedging, so that a standard glass chip is locally modified, and the modified micro-fluidic chip is used for preparing multinuclear emulsion drips, and has the characteristics of remarkable modification effect, simplicity in operation and the like.
Description
Technical field
The application belongs to micro fluidic chip technical field, and more particularly to a kind of multinuclear emulsion droplets prepare chip and modification side
Method, the multinuclear drop of preparation can be used for pharmaceutical carrier and enzyme is fixed, the protection of cosmetics key component, internal encapsulating and streaming thin
Born of the same parents' art etc..
Background technology
The preparation of emulsion droplets is one important application of micro-fluidic chip, and drop type microflow control technique is to adopt drop
There is chip, by unique MCA and fluid flow rate the adjustment of design, using fluid between shearing force and stream
The viscous force of body and capillary interaction are so that dispersed phase fluid produces velocity gradient under continuous phase separation, and then quilt
Cut into microlayer model, the microemulsion drop of generation is distributed evenly in continuous phase, and advantage is to manipulate batch drop, drop
Stable homogeneous, and experimental provision is simple.Generally, the microfluidic channel structure preparing drop mainly has t type structure and fluid altogether
Focus type.
The making material of micro-fluidic chip has silicon, glass, an organic material, and the wherein research of glass micro-fluidic chips is nearly ten
Paid close attention within several years, compared with other materials, the advantage of glass-chip is: material is readily available, making apparatus with tradition
Ic process equipment compatibility good, be readily available fine perfect passage, chemical stability preferably, can through ripe cutting technique
Obtain standard size, be easy to be connected with other systems.
Multinuclear drop be mainly used in encapsulating and discharge active substance, prepare micelle, as microreactor, such as prepare mesoporous
Hydroxyapatite, prepare the microparticle of morphology controllable as template.Double emulsion (w/o/w or o/w/o) protections are also environmentally sensitive
Active component, therefore double emulsions have wide practical use in medicine, food, cosmetic field.
The chip preparing double-core drop of glass micro-fluidic technology preparation is mainly based upon capillary glass tube, but its repeatability
Difference, preparation process is loaded down with trivial details, need process instrument more, be difficult to industrialization.In addition, by designing glass-chip, being based on poly- diformazan
Epoxide siloxanes (pdms) chip, polymethyl methacrylate (pmma) chip channel equally can prepare multistage emulsion, but due to
Multistage emulsion is related to multiphase and has the fluid of different hydrophilic and hydrophobics it is therefore desirable to passage is carried out local hydrophobe modification.However,
At present the chip of the above-mentioned material of report carries out that partial modification process is extremely complex, and application is greatly limited.
For the above-mentioned problems in the prior art, this area is good in the urgent need to developing simple to operate, modified effect
Partial modification method.
Content of the invention
It is an object of the invention to provide a kind of multinuclear emulsion droplets prepare chip and method of modifying, to overcome in prior art
Deficiency.
For achieving the above object, the following technical scheme of present invention offer:
The embodiment of the present application discloses a kind of multinuclear emulsion droplets and prepares chip, including glass baseplate and be formed at glass base
Microchannel on material, described microchannel includes main channel, one end of this main channel be respectively communicated with oil phase o sample introduction first passage,
Oil phase o sample introduction second channel and aqueous phase w1Sample intake passage, described oil phase o sample introduction first passage, oil phase o sample introduction second channel are respectively
Positioned at the both sides of described main channel, the other end of described main channel is communicated in a criss-cross fluid copolymerization burnt shearing passage, should
In described main channel, the other three opening is respectively communicated with aqueous phase w one open communication of fluid copolymerization burnt shearing passage2Sample introduction
First passage, aqueous phase w2Sample introduction second channel and exit passageway, described aqueous phase w2Sample introduction first passage, aqueous phase w2Sample introduction second leads to
Road is located at the both sides of described main channel respectively, and the sectional area of described fluid copolymerization burnt shearing passage is less than described main channel.
Preferably, prepare in chip in above-mentioned multinuclear emulsion droplets, described oil phase o sample introduction first passage and oil phase o sample introduction
Second channel is respectively perpendicular to described main channel.
Preferably, prepare in chip in above-mentioned multinuclear emulsion droplets, described aqueous phase w1Sample intake passage and exit passageway and institute
State main channel to extend in the same direction.
Preferably, prepare in chip in above-mentioned multinuclear emulsion droplets, described oil phase o sample introduction first passage, oil phase o sample introduction
Two passages and aqueous phase w1Sample intake passage inner wall surface is formed with hydrophobic modifier.
Preferably, prepare in chip in above-mentioned multinuclear emulsion droplets, described hydrophobic modifier is selected from chlorosilane or silicon fluoride.
The embodiment of the present application also discloses a kind of multinuclear emulsion droplets and prepares chip method of modifying, comprising:
S1, aqueous phase w2Sample introduction first passage and aqueous phase w2Sample introduction second channel is passed through water, and exit passageway is passed through oil;
S2, aqueous phase w1Sample intake passage is passed through modifying agent, and oil phase o sample introduction first passage, oil phase o sample introduction second channel are as liquid
Body flow pass;
In s3, operating process, it is gradually increased the flow velocity of modifying agent, reduce aqueous phase w simultaneously2Sample introduction first passage, aqueous phase w2Enter
The sample introduction flow velocity of sample second channel and exit passageway is so that two side liquids are in oil phase o sample introduction first passage, oil phase o sample introduction second
Formed in passage and liquidate.
In another embodiment, disclosed herein as well is a kind of multinuclear emulsion droplets prepare chip method of modifying, comprising:
S1, it is passed through modifying agent, to microchannel all passages modifying surface;
S2, by alkaline solution remove aqueous phase w2Sample introduction first passage, aqueous phase w2Sample introduction second channel and exit passageway surface
Modifying agent.
Preferably, prepare in chip method of modifying in above-mentioned multinuclear emulsion droplets, described alkaline solution is sodium hydroxide.
Compared with prior art, it is an advantage of the current invention that:
The flow velocity by accurate control of fluid for the present invention, makes modifying agent form " liquidating " with other fluids, realizes to standard
Glass-chip carries out partial modification modification, and the micro-fluidic chip after modified modification is used for preparing multinuclear emulsion droplets, has modification
The features such as effect is obvious, simple to operate.
Brief description
In order to be illustrated more clearly that the embodiment of the present application or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments described in application, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 show the top view that multinuclear emulsion droplets in the specific embodiment of the invention prepare chip.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouching is carried out to the technical scheme in the embodiment of the present invention
State it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the present invention
In embodiment, the every other enforcement that those of ordinary skill in the art are obtained on the premise of not making creative work
Example, broadly falls into the scope of protection of the invention.
In conjunction with shown in Fig. 1, multinuclear emulsion droplets prepare chip, including glass baseplate 1 and be formed at micro- on glass baseplate
Passage, microchannel includes main channel 201, and one end of this main channel 201 has been respectively communicated with oil phase o sample introduction first passage 202, oil phase
O sample introduction second channel 203 and aqueous phase w1 sample intake passage 204, oil phase o sample introduction first passage 202, oil phase o sample introduction second channel 203
It is located at the both sides of main channel 201 respectively, the other end of main channel 201 is communicated in a criss-cross fluid copolymerization burnt shearing passage
205, in main channel 201, the other three opening is respectively communicated with water an open communication of this fluid copolymerization burnt shearing passage 205
Phase w2 sample introduction first passage 206, aqueous phase w2 sample introduction second channel 207 and exit passageway 208, aqueous phase w2 sample introduction first passage 206,
Aqueous phase w2 sample introduction second channel 207 is located at the both sides of main channel 201 respectively, and the sectional area of fluid copolymerization burnt shearing passage 205 is little
In main channel 201.
In this technical scheme, oil phase o sample introduction first passage 202, oil phase o sample introduction second channel 203, aqueous phase w1 sample intake passage
204 and main channel intersect at same point formed fluid copolymerization Jiao shear constitution 209.In a preferred embodiment, oil phase o sample introduction
One passage 202 and oil phase o sample introduction second channel 203 are respectively perpendicular to main channel 201, and intersection location forms criss-cross fluid altogether
Focus on shear constitution.
Fluid copolymerization burnt shearing passage 205 is machined with closing in, and closing in size is at least below main channel size.Its closing in size
It is also less than the size of aqueous phase w2 sample introduction first passage 206, aqueous phase w2 sample introduction second channel 207 and exit passageway 208 further.
Fluid copolymerization Jiao's shear constitution 209 positioned at main channel one end passes through in order to form single emulsion 3, the single emulsion of formation
Another shear constitution 205 forms double emulsions 4.
Microchannel is shaped as t type or fluid focus type altogether, and two shear constitutions can be double t- types, two-fluid focus type altogether
Or t- type focus type common with fluid combines.
Microchannel can be connected with outside dynamical system, and dynamical system includes syringe pump, constant pressure pump etc..
Further, aqueous phase w1 sample intake passage 204 and exit passageway 208 are extended in the same direction with main channel 201.
Further, oil phase o sample introduction first passage 202, oil phase o sample introduction second channel 203 and aqueous phase w1Sample intake passage
Inner wall surface is formed with hydrophobic modifier.Hydrophobic modifier is selected from chlorosilane or silicon fluoride.
The multinuclear emulsion droplets being obtained prepare chip as normal glass micro-fluidic chip, and size and thickness are fixed, and hard
Matter micro-fluidic chip clamp connects use.
In the first embodiment, prepared by multinuclear emulsion droplets with what chip was modified method, comprising:
S1, pretreatment is carried out to glass-chip, choose modifying agent chlorosilane or silicon fluoride simultaneously;
S2, normal glass chip is connected with hard micro-fluidic chip clamp, syringe pump passes through ptfe pipe jockey;
S3, aqueous phase w2 sample introduction first passage 206 and aqueous phase w2 sample introduction second channel 207 are passed through water, and exit passageway 208 is passed through
Oil;
S4, aqueous phase w1 sample intake passage 204 are passed through modifying agent, oil phase o sample introduction first passage 202, oil phase o sample introduction second channel
203 as liquid outflow channel;
In s5, operating process, it is gradually increased the flow velocity of modifying agent, reduce aqueous phase w2 sample introduction first passage 206, aqueous phase simultaneously
The sample introduction flow velocity of w2 sample introduction second channel 207 and exit passageway 208 so that two side liquids oil phase o sample introduction first passage 202,
Formed in oil phase o sample introduction second channel 203 and liquidate;
After the completion of s6, modification, change sample introduction fluid, you can carry out the preparation of double emulsions.
During need to keep modifying agent ratio be to the greatest extent in oil phase o sample introduction first passage 202, oil phase o sample introduction second channel 203
May be big, this process need to continue~2h, fully modified to ensure passage.
By the flow velocity of regulated fluid, multinuclear emulsion droplets can be obtained, and controllable emulsion droplets kernel and outer core size
And preparation efficiency.
In a second embodiment, prepared by multinuclear emulsion droplets with what chip was modified method, comprising:
S1, it is passed through modifying agent, to microchannel all passages modifying surface;
S2, by alkaline solution remove aqueous phase w2 sample introduction first passage 206, aqueous phase w2 sample introduction second channel 207 and outlet
The modifying agent on passage 208 surface.Detailed process is: alkaline solution is entered by exit passageway, from aqueous phase w2 sample introduction first passage,
W2 sample introduction second channel flows out.
Alkaline solution is the aqueous solution that can dissolve modifying agent, such as sodium hydroxide solution.
Processed by Modifiers Surface, glazing channel surface and the contact angle of water can be made to be more than 90 °.
Multinuclear drop in this case, is double emulsion, such as w1/o/w2、o1/w/o2, including monokaryon, double-core, three cores etc., can lead to
The velocity ratio crossing change fluid is adjusted obtaining.
In sum, advantages of the present invention at least includes:
1. system is installed simply, fast;
2. modified effect is obvious, process is simple;
3. the method can one step generate stable homogeneous multinuclear emulsion droplets;
4. the emulsion droplets adjustable extent of the method preparation is larger;
5. the method can control emulsion droplets kernel and outer core size and preparation efficiency by changing rate of flow of fluid.
6. this system is standard size, can be connected with other systems, application is wider.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation are made a distinction with another entity or operation, and not necessarily require or imply these entities or deposit between operating
In any this actual relation or order.And, term " inclusion ", "comprising" or its any other variant are intended to
Comprising of nonexcludability, wants so that including a series of process of key elements, method, article or equipment and not only including those
Element, but also include other key elements being not expressly set out, or also include for this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element that limited by sentence "including a ..." it is not excluded that
Also there is other identical element including in the process of described key element, method, article or equipment.
The above is only the specific embodiment of the application it is noted that ordinary skill people for the art
For member, on the premise of without departing from the application principle, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as the protection domain of the application.
Claims (8)
1. a kind of multinuclear emulsion droplets prepare chip it is characterised in that including glass baseplate and being formed at micro- on glass baseplate
Passage, described microchannel includes main channel, and one end of this main channel has been respectively communicated with oil phase o sample introduction first passage, oil phase o sample introduction
Second channel and aqueous phase w1Sample intake passage, described oil phase o sample introduction first passage, oil phase o sample introduction second channel are located at described respectively
The both sides of main channel, the other end of described main channel is communicated in a criss-cross fluid copolymerization burnt shearing passage, this fluid copolymerization
In described main channel, the other three opening is respectively communicated with aqueous phase w one open communication of burnt shearing passage2Sample introduction first leads to
Road, aqueous phase w2Sample introduction second channel and exit passageway, described aqueous phase w2Sample introduction first passage, aqueous phase w2Sample introduction second channel is respectively
Positioned at the both sides of described main channel, the sectional area of described fluid copolymerization burnt shearing passage is less than described main channel.
2. multinuclear emulsion droplets according to claim 1 prepare chip it is characterised in that: described oil phase o sample introduction first passage
It is respectively perpendicular to described main channel with oil phase o sample introduction second channel.
3. multinuclear emulsion droplets according to claim 1 prepare chip it is characterised in that: described aqueous phase w1Sample intake passage and going out
Mouth passage is extended in the same direction with described main channel.
4. multinuclear emulsion droplets according to claim 1 prepare chip it is characterised in that: described oil phase o sample introduction first passage,
Oil phase o sample introduction second channel and aqueous phase w1The inner wall surface of sample intake passage is formed with hydrophobic modifier.
5. multinuclear emulsion droplets according to claim 4 prepare chip it is characterised in that: described hydrophobic modifier be selected from chlorine silicon
Alkane or silicon fluoride.
6. the arbitrary described multinuclear emulsion droplets of claim 1 to 5 prepare chip method of modifying it is characterised in that including:
S1, aqueous phase w2Sample introduction first passage and aqueous phase w2Sample introduction second channel is passed through water, and exit passageway is passed through oil;
S2, aqueous phase w1Sample intake passage is passed through modifying agent, and oil phase o sample introduction first passage, oil phase o sample introduction second channel are as liquid flow
Go out passage;
In s3, operating process, it is gradually increased the flow velocity of modifying agent, reduce aqueous phase w simultaneously2Sample introduction first passage, aqueous phase w2Sample introduction
The sample introduction flow velocity of two passages and exit passageway is so that two side liquids are in oil phase o sample introduction first passage, oil phase o sample introduction second channel
Middle formation liquidates.
7. the arbitrary described multinuclear emulsion droplets of claim 1 to 5 prepare chip method of modifying it is characterised in that including:
S1, it is passed through modifying agent, to microchannel all passages modifying surface;
S2, by alkaline solution remove aqueous phase w2Sample introduction first passage, aqueous phase w2The changing of sample introduction second channel and exit passageway surface
Property agent.
8. multinuclear emulsion droplets according to claim 7 prepare chip method of modifying it is characterised in that: described alkaline solution is
Sodium hydroxide.
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CN109856300A (en) * | 2018-11-22 | 2019-06-07 | 天津大学 | A kind of preparation method of silica inverse opal hydrogel photonic crystal microballoon |
CN111889148A (en) * | 2019-05-05 | 2020-11-06 | 微纳芯 (苏州)科技有限公司 | Method and equipment for surface modification of microfluidic chip |
CN112852705A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Preparation method of double-liquid-core hydrogel microcapsule for single cell pairing |
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CN109856300A (en) * | 2018-11-22 | 2019-06-07 | 天津大学 | A kind of preparation method of silica inverse opal hydrogel photonic crystal microballoon |
CN111889148A (en) * | 2019-05-05 | 2020-11-06 | 微纳芯 (苏州)科技有限公司 | Method and equipment for surface modification of microfluidic chip |
CN112852705A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Preparation method of double-liquid-core hydrogel microcapsule for single cell pairing |
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CN112844259B (en) * | 2019-11-28 | 2022-09-16 | 中国科学院大连化学物理研究所 | Preparation method of double-liquid-core hydrogel microcapsule based on double aqueous phases |
CN115121306A (en) * | 2022-07-19 | 2022-09-30 | 华南农业大学 | Method for modifying PDMS chip based on microfluidic technology |
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