Difference between revisions of "Fabrication of Polymersomes using Double-Emulsion Templates in Glass-Coated Stamped Microfluidic Devices"

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== Keywords ==
 
== Keywords ==
Coassembly, colloidal assembly, crack-free films, inverse opals, nanoporous
+
double emulsions, glass-coatings, PDMS microfluidics, polymersomes
  
 
== Overview ==
 
== Overview ==
 +
Since copolymer precipitates cannot be easily removed during emulsion generation a microfluidic design that combines the ability to form double emulsions with the ability to inject and mix two organic solvents is desirable. A convenient fabrication technique is soft lithography using
 +
poly(dimethylsiloxane) (PDMS) and depositing a glasslike coating using sol-gel chemistry can prevent the PDMS from swelling when it comes in contact with organic solvents.  This paper presents double-emulsion-templated polymersomes in stamped microfluidic devices.
  
 
== Results and Discussion ==
 
== Results and Discussion ==
 
[[Image:Thiele 1.jpg|300px|thumb|left|]] [[Image:Thiele 2.jpg|300px|thumb|right|]]
 
[[Image:Thiele 1.jpg|300px|thumb|left|]] [[Image:Thiele 2.jpg|300px|thumb|right|]]
[[Image:Thiele 3.jpg|800px|thumb|right|]]
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[[Image:Thiele 3.jpg|600px|thumb|left|]]
 
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Devices are evenly coated with a sol–gel to produce a durable glasslike layer with tailored surface properties which increases the resistance
The advantage of the presented process is that the infiltration of a preassembled porous structure is avoided, thus preventing the film from cracking during the drying step since cracking in "[...]conventional opal and inverse opal films tends to occur upon drying both at the colloidal assembly stage and at the infiltration stage due to a combination of dehydration and/or polymerization-induced contraction and associated local capillary forces". Indeed, the fabrication technique consists only of two steps (Fig. 1): 1) Polymer colloids (e.g. polystyrene (PS) or poly methyl methacrylate (PMMA)) assemble in a sol-gel precursor solution (e.g. <math> \mathrm {Si(OH_4), Ti(OH_4), Ge(OH_4)}</math>) during an evaporative deposition resulting in an opal film. 2) The template is removed.
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of the channel walls against organic solvents. Two streams of organic solvents can be injected to form the shell of the
If the PMMA spheres are deposited from a hydrolyzed tetraethoxy silane (TEOS) solution, the interstitial spaces of the polymeric opal film are filled with silica gel matrix material which results in an inverse opal silica structure (I-<math> \mathrm {SiO_2}</math>). In that way defects as cracking, formation of domain boundaries and colloidal vacancies which are a main problem in conventionally assembled films can be omitted over a cm length scale.
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double emulsion in the presented device configuration which 1) prevents clogging and 2) enables controlling the ratio of the solvents having different volatilities and thus controlling the evaporation rate of the solvents.
 
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Double emulsions are produced in an array of three flow-focusing cross-junctions with different wettability. The first two junctions allow for injection of solvents enabling manipulation of the composition of the shell phase of double
Several observations were made:
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emulsions. Drops formed in the first two junctions enter the third junction where they are encapsulated to create double emulsions (Fig. 1). In this way formation of copolymer-stabilized double emulsions is guaranteed. Diblock copolymers are dissolved in the organic solvent stream injected at the first junction. The second organic solvent injected at the second crossjunction is miscible with the copolymer-loaded solvent.
There's a critical TEOS-to-colloid ratio (approximately 0.15 mL TEOS solution per 20 mL PMMA suspension) beyond which crackfree films can be expected. Figure 2 shows a highly ordered crackfree film which was fabricated in optimized conditions: 1) suspending a vertically oriented glass slide in a mixture comprised of 0.15 mL of a 28.6 wt% TEOS solution with a 20 mL suspension of 280 nm diameter PMMA spheres (approximately 0.125 vol%), 2) allowing the solvent to slowly evaporate at 65 °C (deposition rate = 2 cm/day), and 3) treating the composite structure at 500 °C for 5 h in air.  
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Scanning electron micrographs of the glass coated microchannels are shown in Figure 2. The glass coating provides also the ability to spatially control the wettability of the surface by functionalizing the intrinsically hydrophobic sol–gel with
 
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photoreactive silanes and subsequent conversion of the surface chemistry to hydrophilicity via using a photochemical surface treatment. The first and second cross-junctions are made hydrophobic while the third junction is made hydrophilic; this allows water drops to be dispersed in a continuous phase of organic solvents at the first and second junctions, while the continuous water phase required for the double emulsion is injected at the third,
The film thickness (number of layers) is linearly proportional to the colloidal volume fraction for a given TEOS-to-PMMA ratio. There were no crack formation observed beyond a 20 layers. For thicker films crack free domains were as large as 100<math>/mu m</math> (Fig. 3A).
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hydrophilic junction. Poly(ethylene-glycol)-<math>b</math>-poly(lactid acid),PEG<math>_{5000}-b</math>-PLA<math>_{5000}</math>, polymer vesicles are formed in this way. Diblock copolymers are first dissolved in the organic solvent chloroform (first junction). In order to lower the density of the organic phase, toluene is added to the copolymer containing chloroform as a second organic solvent. Balancing osmolarities of the inner and outer phases of the double-emulsion template is guaranteed via adding glucose to the inner phase and polyvinyl alcohol (PVA) to the outer phase of the double emulsion. Thus, toluene is added at the second droplet making junction while PVA is used for emulsifying the
 
+
organic solvent phase that contains aqueous inner drops at the third junction.The three phases are fed into the device shown in Figure 2a.
The growth direction was found to be along <110> direction as opposed to conventional film growth along <112> direction (Fig. 3C) and shows a fcc structure. Adding the silicate in the process seems to change the preferential growth direction along <110> and induces a "self-healing" of domains with a temporary different growth direction.  
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The highest pore density in fcc films occurs along {111} planes where crack formation is most probable, which is confirmed for films with a thickness < 5<math>/mu m</math> (when cleaved). But for films > 5<math>/mu m</math> the formation occurs along <110> planes.
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Since sol–gel coatings often consist of a nanoporous structure chloroform and toluene can overcome the sol–gel barrier into the
 
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PDMS. But chloroform evaporates faster, resulting in a lower chloroform fraction in the solvent mixture. As the solubility of PEG-<math>b</math>-PLA in toluene is significantly lower than in chloroform, the diblock copolymer forms precipitates after the more volatile chloroform starts to evaporate in the microfluidic device which leads to a buildup of a thick layer of copolymers on the channel walls (Fig. 2b) and can even result in destabilization of the double-emulsion drops (Fig. 2c). Even in this new device geometry, where chloroform with PEG-b-PLA and toluene are injected separately precipitation of the copolymer can still take place at the chloroform/toluene interface if sufficient diffusive mixing is allowed. Thus, elevated flow rates are used, and the microchannel between the second nozzle, and the
 
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third cross-junction is shortened. Optimal flow rates were 1000<math> \mathrm{\mu L/h}</math> for toluene and
When explaining the effect of this new crackfree formation of films the authors refer to the phenomenon of the formation of large single crystals of calcite patterned at the micron scale: "[...]the transformation of the amorphous <math> \mathrm {CaCO_3}</math> film into a defect-free, porous calcite crystal is facilitated by the micropatterned substrate that not only determines the pattern of porosity of the final single crystal, but also provides interfacial sites for stress and impurity release during the amorphous-to-crystalline transition. Similarly in the current system, the formation of a colloidal crystal and the associated interfaces between the polymerizing sol-gel solution and the assembling colloidal spheres may provide sites for the relaxation of tensile stresses encountered during the gelation process. Controlled solvent release during the polycondensation reaction can also occur at these interfaces and be channeled through the interconnected porous network to evaporate at the surface."
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500<math> \mathrm{\mu L/h}</math> for chloroform.  
 
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The different wetting states of the double emulsion are shown in Figure 3. First, the organic solvent mixture wets the entire inner drop and is homogenously distributed on its surface, (Fig. 3a,b). Second, it dewets from the inner phase due to evaporation of the volatile organic solvents as well as due to the relative high surface energy between the inner and outer
This evaporative deposition is also suitable for multifilm inverse opal structures of different pore sizes as well as deposition on curved surfaces (Fig. 4). The multifilm is created via multiple depostions of template/matrix layers.
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phase (Fig. 3c). The result is a state of partial wetting where the
 
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double emulsions adopt an acornlike, asymmetric structure.
The I-<math> \mathrm {SiO_2}</math> films were also replicated in Si/MgO, Si and <math> \mathrm {TiO_2}</math> while maintaining the porous structure and minor cracking in some cases.
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Having the optimized volumetric ratio of toluene and chloroform,
 +
the diblock copolymer molecules at the two interfaces of the
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shell self-assemble into a membrane.
 +
Upon dewetting, the bulb of the acornlike dewetted drop which
 +
contains the excess diblock copolymer and homo polymer,
 +
remains on the surface of the polymersome. After evaporation
 +
of the organic solvents, a polymeric aggregate of these polymers
 +
remains attached to the surface of the polymersomes, as shown
 +
in Figure 3d. The aggregate can also detach from the
 +
polymersome (Fig. 3e). Double-emulsion templates of
 +
approximately 100–150mm in diameter, corresponding to
 +
a polymersome diameter of approximately 50–100 mm were formed.

Latest revision as of 16:39, 30 October 2010

Birgit Hausmann

Reference

J. Thiele et. al. "Fabrication of Polymersomes using Double-Emulsion Templates in Glass-Coated Stamped Microfluidic Devices", Small 6 (16), 1723–1727, (2010)

Keywords

double emulsions, glass-coatings, PDMS microfluidics, polymersomes

Overview

Since copolymer precipitates cannot be easily removed during emulsion generation a microfluidic design that combines the ability to form double emulsions with the ability to inject and mix two organic solvents is desirable. A convenient fabrication technique is soft lithography using poly(dimethylsiloxane) (PDMS) and depositing a glasslike coating using sol-gel chemistry can prevent the PDMS from swelling when it comes in contact with organic solvents. This paper presents double-emulsion-templated polymersomes in stamped microfluidic devices.

Results and Discussion

Thiele 1.jpg
Thiele 2.jpg
Thiele 3.jpg

Devices are evenly coated with a sol–gel to produce a durable glasslike layer with tailored surface properties which increases the resistance of the channel walls against organic solvents. Two streams of organic solvents can be injected to form the shell of the double emulsion in the presented device configuration which 1) prevents clogging and 2) enables controlling the ratio of the solvents having different volatilities and thus controlling the evaporation rate of the solvents. Double emulsions are produced in an array of three flow-focusing cross-junctions with different wettability. The first two junctions allow for injection of solvents enabling manipulation of the composition of the shell phase of double emulsions. Drops formed in the first two junctions enter the third junction where they are encapsulated to create double emulsions (Fig. 1). In this way formation of copolymer-stabilized double emulsions is guaranteed. Diblock copolymers are dissolved in the organic solvent stream injected at the first junction. The second organic solvent injected at the second crossjunction is miscible with the copolymer-loaded solvent. Scanning electron micrographs of the glass coated microchannels are shown in Figure 2. The glass coating provides also the ability to spatially control the wettability of the surface by functionalizing the intrinsically hydrophobic sol–gel with photoreactive silanes and subsequent conversion of the surface chemistry to hydrophilicity via using a photochemical surface treatment. The first and second cross-junctions are made hydrophobic while the third junction is made hydrophilic; this allows water drops to be dispersed in a continuous phase of organic solvents at the first and second junctions, while the continuous water phase required for the double emulsion is injected at the third, hydrophilic junction. Poly(ethylene-glycol)-<math>b</math>-poly(lactid acid),PEG<math>_{5000}-b</math>-PLA<math>_{5000}</math>, polymer vesicles are formed in this way. Diblock copolymers are first dissolved in the organic solvent chloroform (first junction). In order to lower the density of the organic phase, toluene is added to the copolymer containing chloroform as a second organic solvent. Balancing osmolarities of the inner and outer phases of the double-emulsion template is guaranteed via adding glucose to the inner phase and polyvinyl alcohol (PVA) to the outer phase of the double emulsion. Thus, toluene is added at the second droplet making junction while PVA is used for emulsifying the organic solvent phase that contains aqueous inner drops at the third junction.The three phases are fed into the device shown in Figure 2a.

Since sol–gel coatings often consist of a nanoporous structure chloroform and toluene can overcome the sol–gel barrier into the PDMS. But chloroform evaporates faster, resulting in a lower chloroform fraction in the solvent mixture. As the solubility of PEG-<math>b</math>-PLA in toluene is significantly lower than in chloroform, the diblock copolymer forms precipitates after the more volatile chloroform starts to evaporate in the microfluidic device which leads to a buildup of a thick layer of copolymers on the channel walls (Fig. 2b) and can even result in destabilization of the double-emulsion drops (Fig. 2c). Even in this new device geometry, where chloroform with PEG-b-PLA and toluene are injected separately precipitation of the copolymer can still take place at the chloroform/toluene interface if sufficient diffusive mixing is allowed. Thus, elevated flow rates are used, and the microchannel between the second nozzle, and the third cross-junction is shortened. Optimal flow rates were 1000<math> \mathrm{\mu L/h}</math> for toluene and 500<math> \mathrm{\mu L/h}</math> for chloroform. The different wetting states of the double emulsion are shown in Figure 3. First, the organic solvent mixture wets the entire inner drop and is homogenously distributed on its surface, (Fig. 3a,b). Second, it dewets from the inner phase due to evaporation of the volatile organic solvents as well as due to the relative high surface energy between the inner and outer phase (Fig. 3c). The result is a state of partial wetting where the double emulsions adopt an acornlike, asymmetric structure. Having the optimized volumetric ratio of toluene and chloroform, the diblock copolymer molecules at the two interfaces of the shell self-assemble into a membrane. Upon dewetting, the bulb of the acornlike dewetted drop which contains the excess diblock copolymer and homo polymer, remains on the surface of the polymersome. After evaporation of the organic solvents, a polymeric aggregate of these polymers remains attached to the surface of the polymersomes, as shown in Figure 3d. The aggregate can also detach from the polymersome (Fig. 3e). Double-emulsion templates of approximately 100–150mm in diameter, corresponding to a polymersome diameter of approximately 50–100 mm were formed.