Designer polymer-based microcapsules made using microfluidics.

Filled microcapsules made from double emulsion templates in microfluidic devices are attractive delivery systems for a variety of applications. The microfluidic approach allows facile tailoring of the microcapsules through a large number of variables, which in turn makes these systems more challenging to predict. To elucidate these dependencies, we start from earlier theoretical predictions for the size of double emulsions and present quantitative design maps that correlate parameters such as fluid flow rates and device geometry with the size and shell thickness of monodisperse polymer-based capsules produced in microcapillary devices. The microcapsules are obtained through in situ photopolymerization of the middle oil phase of water-in-oil-in-water double emulsions. Using polymers with selected glass transition temperatures as the shell material, we show through single capsule compression testing that hollow capsules can be prepared with tunable mechanical properties ranging from elastomeric to brittle. A quantitative statistical analysis of the load at rupture of brittle capsules is also provided to evaluate the variability of the microfluidic route and assist the design of capsules in applications involving mechanically triggered release. Finally, we demonstrate that the permeability and microstructure of the capsule shell can also be tailored through the addition of cross-linkers and silica nanoparticles in the middle phase of the double emulsion templates.

[1]  H. Möhwald,et al.  Magnetic colloidosomes derived from nanoparticle interfacial self-assembly. , 2005, Nano letters.

[2]  Liang-Yin Chu,et al.  Controllable monodisperse multiple emulsions. , 2007, Angewandte Chemie.

[3]  Daeyeon Lee,et al.  Double Emulsion‐Templated Nanoparticle Colloidosomes with Selective Permeability , 2008 .

[4]  R. K. Shah,et al.  Fabrication of Monodisperse Thermosensitive Microgels and Gel Capsules in Microfluidic Devices Highlight Www.rsc.org/softmatter | Soft Matter , 2022 .

[5]  J. Lyklema,et al.  Adsorption of polyvinyl alcohol on the paraffin—water interface. I. Interfacial tension as a function of time and concentration , 1972 .

[6]  A. Studart,et al.  Monodisperse functional colloidosomes with tailored nanoparticle shells. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[7]  Daeyeon Lee,et al.  Double emulsion templated monodisperse phospholipid vesicles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[8]  Randall M. Erb,et al.  Predicting sizes of droplets made by microfluidic flow-induced dripping , 2011 .

[9]  Zhibing Zhang,et al.  Silica-shell/oil-core microcapsules with controlled shell thickness and their breakage stress. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[10]  Sang Hoon Lee,et al.  Hydrodynamic micro-encapsulation of aqueous fluids and cells via ‘on the fly’ photopolymerization , 2006 .

[11]  F. Caruso,et al.  Tunable UV-Responsive Organic−Inorganic Hybrid Capsules , 2009 .

[12]  Sébastien Gouin,et al.  Microencapsulation: industrial appraisal of existing technologies and trends , 2004 .

[13]  Paolo Colombo,et al.  Ceramic microparticles and capsules via microfluidic processing of a preceramic polymer , 2010, Journal of The Royal Society Interface.

[14]  N. Sottos,et al.  Autonomic healing of polymer composites , 2001, Nature.

[15]  Henrik Bruus,et al.  Equilibrium and nonequilibrium states in microfluidic double emulsions. , 2008, Physical review letters.

[16]  Ilke Akartuna,et al.  General route for the assembly of functional inorganic capsules. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[17]  Nancy R. Sottos,et al.  Mechanical Properties of Microcapsules Used in a Self-Healing Polymer , 2006 .

[18]  W. Weibull A statistical theory of the strength of materials , 1939 .

[19]  Dae Kun Hwang,et al.  Microfluidic-based synthesis of non-spherical magnetic hydrogel microparticles. , 2008, Lab on a chip.

[20]  P. Tabeling,et al.  Synthesizing microcapsules with controlled geometrical and mechanical properties with microfluidic double emulsion technology. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[21]  N. Sottos,et al.  In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene , 2003 .

[22]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

[23]  D. Weitz,et al.  Monodisperse Double Emulsions Generated from a Microcapillary Device , 2005, Science.

[24]  F. Shahidi,et al.  Encapsulation of food ingredients. , 1993, Critical reviews in food science and nutrition.

[25]  L. Gauckler,et al.  Ceramic forming using enzyme catalyzed reactions , 1999 .

[26]  Liang-Yin Chu,et al.  Designer emulsions using microfluidics , 2008 .

[27]  D A Weitz,et al.  Generation of polymerosomes from double-emulsions. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[28]  K Tsuji,et al.  Microencapsulation of pesticides and their improved handling safety , 2001, Journal of microencapsulation.

[29]  H. Chang,et al.  Microencapsulation of microbial cells. , 2000, Biotechnology advances.

[30]  A. R. Bausch,et al.  Colloidosomes: Selectively Permeable Capsules Composed of Colloidal Particles , 2002, Science.

[31]  Ilke Akartuna,et al.  Stabilization of oil-in-water emulsions by colloidal particles modified with short amphiphiles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[32]  J. McIntosh,et al.  Patterning of functional antibodies and other proteins by photolithography of silane monolayers. , 1996, Proceedings of the National Academy of Sciences of the United States of America.