Carlos J. Martinez

Designer emulsions using microfluidics

We describe new developments for the controlled fabrication of monodisperse emulsions using microfluidics. We use glass capillary devices to generate single, double, and higher order emulsions with exceptional precision. These emulsions can serve as ideal templates for generating well-defined particles and functional vesicles. Polydimethylsiloxane microfluidic devices are also used to generate picoliter-scale water-in-oil emulsions at rates as high as 10 000 drops per second. These emulsions have great potential as individual microvessels in high-throughput screening applications, where each drop serves to encapsulate single cells, genes, or reactants.

Assembly of Colloidal Silica Crystals Inside Double Emulsion Drops

We investigated the assembly of colloidal silica crystals inside double emulsion drops generated in microcapillary microfluidic devices. The double emulsions are composed of an aqueous suspension of monodisperse silica particles in the inner drop surrounded by a PDMS oil drop that acts as a semipermeable membrane for the diffusion of water into or out of the inner drop in the presence of an osmotic gradient. Imposing a high osmotic pressure in the continuous phase induces water diffusion out of the inner drop, increasing the silica volume fraction (φ(silica)) and leading to the formation of a spherical colloidal silica crystal. Silica suspensions with no salt or low salt concentration (<10(-3) M) formed colloidal crystals with φ(silica) up to 0.68. Monodisperse spherical colloidal silica crystals with sizes ranging from 16 to 133 μm were generated by varying the device geometry, flow-rate ratios, and initial silica fraction. At salt concentrations > 10(-3) M, the electrostatic repulsion is reduced, and crystallization is suppressed. Crystals were preserved in a hydrogel matrix or inside a silicone rubber shell. This study demonstrates a robust path for controlled colloidal assembly inside double emulsion drops.

Synthesis and Characterization of Microencapsulated Phase Change Materials with Poly(urea−urethane) Shells Containing Cellulose Nanocrystals

The main objective of this study is to develop microencapsulation technology for thermal energy storage incorporating a phase change material (PCM) in a composite wall shell, which can be used to create a stable environment and allow the PCM to undergo phase change without any outside influence. Surface modification of cellulose nanocrystals (CNCs) was conducted by grafting poly(lactic acid) oligomers and oleic acid to improve the dispersion of nanoparticles in a polymeric shell. A microencapsulated phase change material (methyl laurate) with poly(urea-urethane) (PU) composite shells containing the hydrophobized cellulose nanocrystals (hCNCs) was fabricated using an in situ emulsion interfacial polymerization process. The encapsulation process of the PCMs with subsequent interfacial hCNC-PU to form composite microcapsules as well as their morphology, composition, thermal properties, and release rates was examined in this study. Oil soluble Sudan II dye solution in methyl laurate was used as a model hydrophobic fill, representing other latent fills with low partition coefficients, and their encapsulation efficiency as well as dye release rates were measured spectroscopically in a water medium. The influence of polyol content in the PU polymer matrix of microcapsules was investigated. An increase in polyol contents leads to an increase in the mean size of microcapsules but a decrease in the gel content (degree of cross-linking density) and permeability of their shell structure. The encapsulated PCMs for thermal energy storage demonstrated here exhibited promising performance for possible use in building or paving materials in terms of released heat, desired phase transformation temperature, chemical and physical stability, and concrete durability during placement.

Sustained Dye Release Using Poly(urea–urethane)/Cellulose Nanocrystal Composite Microcapsules

The aim of this study is to develop methods to reinforce polymeric microspheres with cellulose nanocrystals (CNCs) to make eco-friendly microcapsules for a variety of applications such as medicines, perfumes, nutrients, pesticides, and phase change materials. Surface hydrophobization treatments for CNCs were performed by grafting poly(lactic acid) oligomers and fatty acids (FAs) to enhance the dispersion of nanoparticles in the polymeric shell. Then, a straightforward process is demonstrated to design sustained release microcapsules by the incorporation of the modified CNCs (mCNCs) in the shell structure. The combination of the mCNC dispersion with subsequent interfacial polyurea (PU) to form composite capsules as well as their morphology, composition, mechanical properties, and release rates were examined in this study. The PU microcapsules embedded with the mCNC were characterized by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The morphologies of the microcapsules were characterized by optical microscopy (OM) and scanning electron microscope (SEM). The rupture stress and failure behavior of the microcapsules were determined through single-capsule compression tests. Oil-soluble Sudan II dye solution in mineral oil was utilized as a model hydrophobic fill, representing other latent fills with low partition coefficients, and their encapsulation efficiency was measured spectroscopically. The release rates of the encapsulated dye from the microcapsules were examined spectroscopically by both ethanol and 2-ethyl-1-hexanol medium at room temperature. The concentration of released dye was determined by using UV-vis absorption spectrometry (UV-vis). The mCNC embedded poly(urea-urethane) capsules have strong and dense walls, which function as excellent barriers against leakage due to their extended diffusion path length and ensure enough mechanical strength from rupture for handling or postprocessing.

Altering Colloidal Surface Functionalization Using DNA Encapsulated Inside Monodisperse Gelatin Microsphere Templates

Soluble oligonucleotides are typically introduced to bulk solution to promote hybridization activity on DNA-functionalized surfaces. Here, an alternative approach is explored by encapsulating secondary target strands inside semipermeable colloidal satellite assemblies, then triggering their release at 37 °C for subsequent surface hybridization activity. To prepare DNA-loaded satellite assemblies, uniform gelatin microspheres are fabricated using microfluidics, loaded with 15 base-long secondary DNA targets, capped with a polyelectrolyte bilayer, and finally coated with a monolayer of polystyrene microspheres functionalized with duplexes comprised of immobilized probes and soluble, 13 base-long hybridization partner strands. Once warmed to 37 °C, secondary DNA targets are released from the gelatin template and then competitively displace the shorter, original hybridization partners on the polystyrene microspheres.

Nanoparticle-mediated assembly of colloidal crystals on patterned substrates

Through fundamental studies of the phase behavior and structure of binary mixtures of attractive colloidal microspheres and highly charged nanoparticles, we have discovered a new colloidal stabilization mechanism known as nanoparticle haloing.