CN107573523B - A kind of eccentric structure polymer microballoon and preparation method thereof - Google Patents
A kind of eccentric structure polymer microballoon and preparation method thereof Download PDFInfo
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- CN107573523B CN107573523B CN201710826627.6A CN201710826627A CN107573523B CN 107573523 B CN107573523 B CN 107573523B CN 201710826627 A CN201710826627 A CN 201710826627A CN 107573523 B CN107573523 B CN 107573523B
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Abstract
A kind of eccentric structure polymer microballoon and preparation method thereof, relates generally to field of high polymer material processing.After this method is by being organically combined microflow control technique and electrospray techniques, with the eccentric structure polymer microballoon that monodispersed, size and morphology controllable have been prepared with interior phase solution appropriate and external solution；By the adjustment to relevant parameter, the opposite regulation of microballoon shell thick, eccentric area, eccentric degree, size is realized.Therefore, above-mentioned eccentric structure polymer microballoon is due to its unique structure and controllable preparation method, makes it have good biocompatibility, medicine controlled releasing ability and the ability for loading close and distant water substance, therefore it is with important application value.
Description
Technical field
The present invention relates to field of high polymer material processing, in particular to a kind of eccentric structure polymer microballoon and its
Preparation method.
Background technique
Electric jet technology refers to the process of that polymer melt or solution form microballoon under the action of high-voltage electrostatic field.Due to
Microballoon monodispersity, high carrying drug ratio and high repeatability with higher obtained, furthermore electric jet technology is at low cost, and easily
It in operation and improves, is widely used in preparing the nano-medicament carrier, micro-capsule for carrying double growth factors, multi-chamber carrier, red thin
Fields of biomedicine and other research fields such as microsphere supported of born of the same parents' size.
However, the current existing method for preparing microballoon has, preparation process is relative complex, operability and controllability phase
To poor, this has influenced the structure and service performance of final microballoon.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of eccentric structure polymer microballoon, polymerize in eccentric structure
In the preparation process of object microballoon, the use of surfactant and the preparation process of stable emulsion early period is omitted, makes operability
It is improved with controllability, the mutually separation for later period micro emulsion drop provides condition.
Another object of the present invention is to provide a kind of eccentric structure polymer microballoons, with good bio-compatible
Property, medicine controlled releasing ability, the ability and degradability for loading close and distant water substance.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of preparation method of eccentric structure polymer microballoon comprising following steps:
External solution and interior phase solution are pushed into respectively in the corresponding sample feeding pipe of micro fluidic device, water-in-oil type EFI is made
Mist solution；Wherein, the speed that pushes away of interior phase solution is controlled in 0.2-1mL/h, and external solution pushes away speed control in 0.4-2mL/h, also,
When interior phase solution push away speed be 0.2-0.6mL/h when, external solution push away speed control in 0.6-1mL/h, when the stream of interior phase solution
When speed increases to 0.6-1mL/h, the speed that pushes away of external solution is maintained at 1-2mL/h；
Apply high-pressure electrostatic at the nozzle of micro fluidic device, makes water-in-oil type EFI liquid that jet atomization occur, splitting, consolidate
After change or solvent volatilization, is stood and mutually separated.
The present invention also proposes a kind of eccentric structure polymer microballoon, is according to above-mentioned eccentric structure polymer microballoon
Preparation method is made.
The beneficial effect of eccentric structure polymer microballoon provided in an embodiment of the present invention and preparation method thereof is: by will be micro-
After fluidics and electrospray techniques are organically combined, with being prepared single point with interior phase solution appropriate and external solution
Scattered, size and morphology controllable eccentric structure polymer microballoon；Compared with traditional lotion EFI, surfactant is omitted
Use and stable emulsion early period preparation process, improve operability and controllability, and be the phase of later period microemulsion point
From providing condition；In addition, being defined and controlling by the speed that pushes away of internal phase solution and external solution, it is microcosmic to realize microballoon
The opposite regulation of structure.Therefore, the polymer microballoon provided in an embodiment of the present invention with eccentric structure is due to its unique knot
Structure and controllable preparation method make it have good biocompatibility, medicine controlled releasing ability and the energy for loading close and distant water substance
Power.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the preparation method schematic diagram of eccentric structure polymer microballoon provided in an embodiment of the present invention；
Fig. 2 provides capillary glass tube micro fluidic device schematic internal view for the embodiment of the present invention；
Fig. 3 provides micro-fluidic electric injection device for the embodiment of the present invention and prepares eccentric structure polymer microballoon schematic diagram；
Fig. 4 is that test example of the present invention carries out the resulting fluorogram of fluorescence analysis test.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Fig. 1 is please referred to, eccentric structure polymer microballoon of the embodiment of the present invention and preparation method thereof is carried out below specific
Explanation.
S1, oil-soluble polymers are dissolved in organic solvent, water-soluble substances are dissolved in deionized water, and being respectively formed has centainly
The external solution of viscosity and interior phase solution.
Further, oil-soluble polymers provided in an embodiment of the present invention include polylactic acid, poly lactic-co-glycolic acid copolymerization
Object, PLA-PEG copolymer or polycaprolactone, organic solvent include dimethyl carbonate or ethyl acetate；Water-soluble object
Matter includes polyethylene glycol, sodium alginate, gelatin, polyvinyl alcohol, glucan, chitosan or glycerol.It should be noted that of the invention
The above-mentioned oil-soluble polymers and water-soluble substances that embodiment provides, except respectively as the molten of external solution and interior phase solution
Matter provides other than material conditions for the eccentric structure polymer microballoon of monodispersed, size and morphology controllable is prepared, also
Because it is with good biocompatibility and degradability, so that it has the advantage harmless to human body and Environmental security.
Specifically, the configuration process of external solution of the embodiment of the present invention are as follows: by wherein one in above-mentioned oil-soluble polymers
Kind is dissolved in corresponding one of organic solvent according to a certain percentage and carries out magnetic agitation 6-12h, obtains quality volume
Than the external solution for 10-30%；The configuration process of interior phase solution provided in an embodiment of the present invention are as follows: by above-mentioned water-soluble substances
One of which be dissolved in deionized water according to a certain percentage, carry out magnetic agitation 2-12h, obtain mass volume ratio be 5-
30% interior phase solution.It should be noted that the embodiment of the present invention is preferably, the time of magnetic agitation is controlled in 12h；In addition,
Why the concentration of external solution and interior phase solution is defined and is controlled, is primarily due to external solution and interior
The concentration of phase solution is excessive or the too small formation for being unfavorable for its eccentric structure polymer microballoon.
S2, external solution and interior phase solution are pushed into respectively in the corresponding sample feeding pipe of micro fluidic device, water-in-oil type is made
Electron spray solution.Wherein, the speed that pushes away of interior phase solution is controlled in 0.2-1mL/h, and external solution pushes away speed control in 0.4-2mL/h.
Further, in the embodiment of the present invention, external solution and interior phase solution push away speed ratio can be controlled in for 2:1,3:1,
4:1 or 5:1.Specifically push away speed control when: when interior phase solution push away speed be 0.2-0.6mL/h when, external solution pushes away fast control
In 0.6-1mL/h；When the flow velocity of interior phase solution increases to 0.6-1mL/h, the speed that pushes away of external solution is maintained at 1-2mL/h.It needs
It is noted that being defined and controlling by the speed that pushes away of internal phase solution and external solution in the embodiment of the present invention, realize
Opposite regulation to micro-sphere structure.
Further, incorporated by reference to referring to Fig. 2 and Fig. 3, micro fluidic device provided in an embodiment of the present invention is by square tube, two
Root round tube, a piece of glass slide and two dispensing needle heads are constituted, wherein the internal diameter of square tube is 1000 μm, and outer diameter is 1300 μm；Two
The internal diameter of round tube is 550 μm, and outer diameter is 1000 μm, and in two round tubes wherein one with draw needle instrument be drawn into one end
For the capillary of conical opening, then with forging needle instrument conical opening is handled, makes 80 μm of diameter of conical opening.
Further, the speed that pushes away of interior phase solution and external solution regulates and controls in the following manner: interior phase solution and foreign minister
Solution is contained in syringe respectively, and the needle point of syringe is connected to the polyfluortetraethylene pipe that two outer diameters are 2mm
The sample introduction end at end and micro fluidic device；Syringe and miniflow pump are connected again after the completion of connection, thus accuracy controlling external solution
Speed is pushed away with interior phase solution.
Further, external solution and interior phase solution pass through polyfluortetraethylene pipe, and it is corresponding to be directed respectively into micro fluidic device
Injection port, immiscible external solution and interior phase solution meets at the conical opening of round tube, and under the action of shear force
Water-in-oil type single emulsion is formed, water-in-oil type single emulsion flows through the nozzle progress EFI that outlet instantaneously enters electric injection device.
S3, apply high-pressure electrostatic at the nozzle of micro fluidic device, make water-in-oil type EFI liquid that jet atomization occur, split
Split, solidify or solvent volatilization after, stood and mutually separated.
Further, when applying high-pressure electrostatic at nozzle, in 18-24KV, temperature is controlled at 20-30 DEG C for voltage control,
Distance controlling is received in 15-20cm.It should be noted that in the embodiment of the present invention why to voltage, temperature, receive distance into
Row control, and regulated and controled previously for the speed ratio that pushes away of external solution and interior phase solution, it is for realizing to final microballoon
The control of pattern, size and monodispersity.
It needs further exist for illustrating, water-in-oil type single emulsion forms the process of polymer microballoon are as follows: water-in-oil type
Single emulsion is delivered to be split under the electric field force effect of high-pressure electrostatic as lesser emulsion droplet, emulsion droplet arrival reception device at nozzle
Before glass plate organic solvent portion volatilization solidification, the emulsion droplet not being fully cured in glass plate with the passage of time (2-12h), because of phase
Separation gradually forms the polymer microballoon of eccentric structure.
It is to utilize above-mentioned eccentric structure polymer microballoon the present invention also provides a kind of eccentric structure polymer microballoon
Preparation method be made, the eccentric structure polymer microballoon monodispersity is good, size and morphology controllable, has eccentric structure, and
And also with good biocompatibility, medicine controlled releasing ability and the ability for loading close and distant water substance.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, preparation process is as follows:
Firstly, 2mL glycerol is dissolved in 0.5mL deionized water, magnetic agitation 12h mixes it uniformly, and interior phase solution is made.
2g poly lactide-glycolide acid is dissolved in 10mL dimethyl carbonate, magnetic agitation 12h mixes it uniformly, and foreign minister is made
Solution.
Then, interior phase and foreign minister respectively with 0.2mL/h, 0.6mL/h push away speed be pushed into respectively through polyfluortetraethylene pipe it is micro-
The corresponding injection port of flow control apparatus forms water-in-oil type EFI liquid under the action of shear force.It can going out in micro fluidic device
The emulsion droplet that size is uniform, spacing is equal is observed at mouth pipe.Wherein, the size and spacing of emulsion droplet can be by pushing away inside and outside two-phase
The adjusting of speed regulates and controls.
Finally, applying high-voltage electrostatic field, water-in-oil type emulsion droplet is by mist at the nozzle of micro-fluidic exit, that is, electric injection device
Change, splitting, solidification, and eventually passes through to stand mutually to separate and form eccentric structure polymer microballoon.Wherein, voltage 18KV, temperature
Degree is 25 DEG C, reception distance is 15cm.
The present embodiment also provides a kind of eccentric structure polymer microballoon, and a diameter of 3 μm or so, be through this embodiment
The preparation method of the eccentric structure polymer microballoon of offer prepares gained.It specifically, is obtained by water-in-oil type list cream EFI.
The micro emulsion drop that EFI is formed has nucleocapsid structure, and the mutually separation inside micro emulsion drop is completed over time, ultimately forms tool
There is the microballoon of eccentric structure.
Embodiment 2
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is copolymerized using 1g poly lactic-co-glycolic acid
Object is dissolved in 10mL dimethyl carbonate, and magnetic agitation 12h is uniformly mixed, external solution is made.
Further, there are also the difference is that the interior phase solution of the present embodiment and the speed that pushes away of external solution are distinguished with embodiment 1
For 0.2mL/h, 0.8mL/h.It should be noted that remaining parameter and preparation method process of the present embodiment and embodiment 1 are homogeneous
Together.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 3
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is copolymerized using 2g polylactic acid-polyglycol
Object is dissolved in 10mL dimethyl carbonate, and magnetic agitation 12h is uniformly mixed, external solution is made.It should be noted that this reality
Apply example remaining parameter and preparation method process and embodiment 1 it is all the same.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 4
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is dissolved in 1mL deionization using 2mL glycerol
Water, magnetic agitation 12h are uniformly mixed, interior phase solution is made.
Further, there are also the difference is that the interior phase solution of the present embodiment and the speed that pushes away of external solution are distinguished with embodiment 1
For 0.8mL/h, 1.5mL/h.It should be noted that remaining parameter and preparation method process of the present embodiment and embodiment 1 are homogeneous
Together.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 5
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is dissolved in 10mL using 2g polyethylene glycol
Ionized water, magnetic agitation 12h are uniformly mixed, interior phase solution is made.It should be noted that remaining parameter of the present embodiment
And preparation method process and embodiment 1 it is all the same.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 6
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is dissolved in 10mL using 2g polyethylene glycol
Ionized water, magnetic agitation 12h are uniformly mixed, interior phase solution is made.Also, by the way that 2g poly lactic-co-glycolic acid is total to
Polymers is dissolved in 10mL ethyl acetate, and magnetic agitation 12h is uniformly mixed, external solution is made.It should be noted that this reality
Apply example remaining parameter and preparation method process and embodiment 1 it is all the same.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 7
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment is dissolved in 10mL using 2g polyethylene glycol
Ionized water, magnetic agitation 12h are uniformly mixed, interior phase solution is made.Also, it is copolymerized using 2g polylactic acid-polyglycol
Object is dissolved in 10mL ethyl acetate, and magnetic agitation 12h is uniformly mixed, external solution is made.
In addition, further, pushing away for interior phase solution and external solution provided in this embodiment is fast also different, respectively
0.2mL/h,0.8mL/h.It should be noted that remaining parameter and preparation method process and embodiment 1 of the present embodiment are all the same.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
Embodiment 8
The present embodiment provides a kind of preparation method of eccentric structure polymer microballoon, the eccentric knot provided with embodiment 1
The preparation method of structure polymer microballoon is roughly the same, the difference is that, the present embodiment using 2g glucan be dissolved in 10mL go from
Sub- water, magnetic agitation 12h are uniformly mixed, interior phase solution is made.Also, 10mL carbonic acid diformazan is dissolved in using 2g polylactic acid
Ester, magnetic agitation 12h are uniformly mixed, external solution is made.It should be noted that remaining parameter and system of the present embodiment
Preparation Method process and embodiment 1 are all the same.
The present embodiment also provides a kind of eccentric structure polymer microballoon, is that the eccentric structure provided through this embodiment gathers
The preparation method for closing object microballoon prepares gained.
It is emphasized that in above-mentioned 8 embodiments provided by the invention, electrostatic spinning technique parameter are as follows: spinning voltage:
18-24KV；Spinning temperature: 20-30 DEG C；Spinning distance: 15-20cm.Microflow control technique parameter are as follows: interior phase (water phase) pushes away speed:
0.2-1mL/h；Foreign minister's (oily phase) pushes away speed: 0.4-2mL/h.
Test example
In order to verify to micro-sphere structure prepared by the embodiment of the present invention, the present invention selects the product of embodiment 1 to carry out
Fluorescence analysis.
Specifically, it is added to Nile red dyeing in poly lactide-glycolide acid (PLGA), is accepted in glass plate, uses
Laser co-focusing observation, as a result as shown in Figure 4.As shown in Figure 4, the stratum nucleare of microballoon is one side of black and the round shell of deviation,
Therefore demonstrate the successful preparation of nucleocapsid bias microballoon.
In conclusion eccentric structure polymer microballoon provided in an embodiment of the present invention and preparation method thereof, by by miniflow
Control technology and electrospray techniques organically combine, and the polymer microballoon of the size uniformity monodispersity with eccentric structure is made；It is logical
The adjustment to relevant parameter is crossed, the opposite regulation of microballoon shell thick, eccentric area, eccentric degree, size is realized.Therefore, this hair
The above-mentioned eccentric structure polymer microballoon that bright embodiment provides is made it have due to its unique structure and controllable preparation method
Good biocompatibility, medicine controlled releasing ability and the ability for loading close and distant water substance.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of eccentric structure polymer microballoon, which is characterized in that itself the following steps are included:
External solution and interior phase solution are pushed into respectively in the corresponding sample feeding pipe of micro fluidic device, it is molten that water-in-oil type electron spray is made
Liquid；Wherein, the speed that pushes away of the interior phase solution is controlled in 0.2-1mL/h, and the speed that pushes away of the external solution is controlled in 0.4-2mL/h,
Also, when the interior phase solution is when to push away speed be 0.2-0.6mL/h, the external solution pushes away speed control in 0.6-1mL/h, when
When the flow velocity of the interior phase solution increases to 0.6-1mL/h, the speed that pushes away of the external solution is maintained at 1-2mL/h；The foreign minister
Solution is made of oil-soluble polymers and organic solvent, and the mass volume ratio of the oil-soluble polymers and the organic solvent is
0.1-0.3g/mL；The interior phase solution is made of water-soluble substances and deionized water, the water-soluble substances and the deionization
The mass volume ratio of water is 0.05-0.3g/mL；
Applying high-pressure electrostatic at the nozzle of the micro fluidic device, in 18-24KV, temperature is controlled at 20-30 DEG C for voltage control,
Reception distance controlling is in 15-20cm, after making the water-in-oil type EFI liquid that jet atomization, splitting, solidification or solvent volatilization occur,
It is stood and is mutually separated.
2. the preparation method of eccentric structure polymer microballoon according to claim 1, which is characterized in that the oil-soluble is poly-
Closing object includes polylactic acid, poly lactide-glycolide acid, PLA-PEG copolymer or polycaprolactone；It is described organic
Solvent includes dimethyl carbonate or ethyl acetate；The oil-soluble polymers are dissolved in progress magnetic force in the organic solvent to stir
Mix 6-12h.
3. the preparation method of eccentric structure polymer microballoon according to claim 1, which is characterized in that the water solubility object
Matter includes polyethylene glycol, sodium alginate, gelatin, polyvinyl alcohol, glucan, chitosan or glycerol；The water-soluble substances are molten
Magnetic agitation 6-12h in deionized water described in Xie Yu.
4. the preparation method of eccentric structure polymer microballoon according to claim 1, which is characterized in that the micro-fluidic dress
It sets and is made of a square tube, two round tubes, a piece of glass slide and two dispensing needle heads, wherein the internal diameter of the square tube is 1000 μ
M, outer diameter are 1300 μm；The internal diameter of two round tubes is 550 μm, and outer diameter is 1000 μm, and in two round tubes
Wherein one handle the conical opening with drawing needle instrument to be drawn into the capillary that one end is conical opening, then with forging needle instrument, make described in
The diameter of conical opening is 80 μm.
5. the preparation method of eccentric structure polymer microballoon according to claim 4, which is characterized in that the interior phase solution
It is contained in syringe respectively with the external solution, and is connected to institute with the polyfluortetraethylene pipe that two outer diameters are 2mm
State the needle tip of syringe and the sample introduction end of the micro fluidic device；The syringe and miniflow pump are connected again after the completion of connection
It connects, so that external solution described in accuracy controlling and the interior phase solution push away speed.
6. the preparation method of eccentric structure polymer microballoon according to claim 5, which is characterized in that the external solution
Pass through the polyfluortetraethylene pipe with the interior phase solution, is directed respectively into the corresponding injection port of the micro fluidic device, mutually not
The external solution and the interior phase solution to mix meets at the conical opening of the round tube, and in the effect of shearing force
Lower formation water-in-oil type single emulsion, the water-in-oil type single emulsion flow through the nozzle progress that outlet instantaneously enters electric injection device
EFI；Push away speed ratio, voltage strength and the reception distance for regulating and controlling the external solution and the interior phase solution realize that size is uniform
Monodispersed microballoon EFI, wherein the speed ratio that pushes away is 2:1,3:1,4:1 or 5:1.
7. the preparation method of eccentric structure polymer microballoon according to claim 6, which is characterized in that the water-in-oil type
Single emulsion is delivered to be split under the electric field force effect of high-pressure electrostatic as lesser emulsion droplet, the emulsion droplet arrival at the nozzle
Before reception device glass plate organic solvent portion volatilization solidification, the emulsion droplet not being fully cured in the range of 2-12 hours with
The passage of time gradually forms the polymer microballoon of eccentric structure because mutually separating.
8. a kind of eccentric structure polymer microballoon, which is characterized in that the eccentric structure polymer microballoon according to claim 1-7
The preparation method of eccentric structure polymer microballoon described in any one is made.
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| CN101206207A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Multicenter electric spraying ion source for micro liquid phase separation system and mass spectrum |
| CN104262643A (en) * | 2014-10-21 | 2015-01-07 | 南京慧联生物科技有限公司 | Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof |
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| CN101206207A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Multicenter electric spraying ion source for micro liquid phase separation system and mass spectrum |
| CN104262643A (en) * | 2014-10-21 | 2015-01-07 | 南京慧联生物科技有限公司 | Supramolecular hydrogel microsphere prepared by taking liquid drop as template and preparation method thereof |
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