PEGDA hydrogel microspheres with encapsulated salt for versatile control of protein crystallization.

Due to their biocompatibility and adjustable chemical structure and morphology, hydrogels have great potential in many applications, and can be used to enhance protein crystal quality and crystallization efficiency, contributing to biomedicine manufacturing. Monodispersed PEGDA hydrogel microspheres (HMSs) were synthesized using a Lego-inspired microfluidic device. The generated droplets were then UV polymerized, partially hydrolyzed with 0.1 M NaOH solution to improve their absorption capacity, and soaked in a buffer solution containing 0, 0.5, 1, 2, and 4 M NaCl. Salt-loaded HMSs were used as the medium for the enhanced crystallization of hen egg white lysozyme from aqueous solutions. Different supersaturations were achieved in the protein solutions by releasing NaCl of different concentrations from HMSs, as confirmed by electrical conductivity measurements. HMSs with or without NaCl can both provide heterogeneous nucleation sites due to their nano-porous structure and wrinkled surface. The addition of NaCl-loaded HMSs to the protein solution can also increase or decrease the supersaturation in the whole solution or locally near the HMS, leading to controllable nucleation time and crystal size distribution dependent on the NaCl concentration loaded into HMSs.

Microfluidic Fabrication of Monodisperse and Recyclable TiO2-Poly(ethylene glycol) Diacrylate Hybrid Microgels for Removal of Methylene Blue from Aqueous Medium.

Nearly monodisperse titanium oxide-polyethylene glycol diacrylate [TiO2-P(EGDA)] hybrid microbeads containing 0.5 wt % TiO2 nanoparticles entrapped within a P(EGDA) cross-linked polymeric network were synthesized using a modular Lego-inspired glass capillary microfluidic device. TiO2-P(EGDA) hybrid microgels were characterized by optical microscopy, scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, and thermogravimetric analysis. The fabricated TiO2-P(EGDA) hybrid microgel system showed 100% removal efficiency of methylene blue (MB) from its 1-3 ppm aqueous solutions after 4 h of UV light irradiation at 0.2 mW/cm2 at the loading of 25 g/L photocatalyst beads in the reaction mixture, corresponding to the loading of naked TiO2 of just 0.025 g/L. No decrease in photocatalytic efficiency was observed in 10 repeated runs with recycled photocatalyst using a fresh 1 ppm MB solution in each cycle. The rate of photocatalytic degradation was controlled by the UV light irradiance, catalyst loading, and the initial dye concentration. Physical adsorption of MB onto the surface of composite microgel was also observed. The adsorption data was best fitted with the Langmuir adsorption isotherm and the Elovich kinetic model. TiO2-P(EGDA) microgel beads are biocompatible, can be prepared with a tunable size in the microfluidic device, and can easily be separated from the reaction mixture by gravity settling. The TiO2-P(EGDA) system can be used for the removal of other toxic dyes and micropollutants from industrial wastewater.

Selective Adsorption of Ionic Species Using Macroporous Monodispersed Polyethylene Glycol Diacrylate/Acrylic Acid Microgels with Tunable Negative Charge.

Monodispersed polyethylene glycol diacrylate (PEGDA)/acrylic acid (AA) microgels with a tuneable negative charge and macroporous internal structure have been produced using a Lego-inspired droplet microfluidic device. The surface charge of microgels was controlled by changing the content of AA in the monomer mixture from zero (for noncharged PEGDA beads) to 4 wt%. The macroporosity of the polymer matrix was introduced by adding 20 wt% of 600-MW polyethylene glycol (PEG) as a porogen material into the monomer mixture. The porogen was successfully leached out with acetone after UV-crosslinking, which resulted in micron-sized cylindrical pores with crater-like morphology, uniformly arranged on the microgel surface. Negatively charged PEGDA/AA beads showed improved adsorption capacity towards positively charged organic dyes (methylene blue and rhodamine B) compared to neutral PEGDA beads and high repulsion of negatively charged dye molecules (methyl orange and congo red). Macroporous microgels showed better adsorption properties than nonporous beads, with a maximum adsorption capacity towards methylene blue of 45 mg/g for macroporous PEGDA/AA microgels at pH 8.6, as compared to 23 mg/g for nonporous PEGDA/AA microgels at the same pH. More than 98% of Cu(II) ions were removed from 50 ppm solution at pH 6.7 using 2.7 mg/mL of macroporous PEGDA/AA microgel. The adsorption of cationic species was significantly improved when pH was increased from 3 to 9 due to a higher degree of ionization of AA monomeric units in the polymer network. The synthesized copolymer beads can be used in drug delivery to achieve improved loading capacity of positively charged therapeutic agents and in tissue engineering, where a negative charge of scaffolds coupled with porous structure can help to achieve improved permeability of high-molecular-weight metabolites and nutrients, and anti-fouling activity against negatively charged species.

Continuous Manipulation and Characterization of Colloidal Beads and Liposomes via Diffusiophoresis in Single- and Double-Junction Microchannels.

We reveal a physical mechanism that enables the preconcentration, sorting, and characterization of charged polystyrene nanobeads and liposomes dispersed in a continuous flow within a straight micron-sized channel. Initially, a single Ψ-junction microfluidic chip is used to generate a steady-state salt concentration gradient in the direction perpendicular to the flow. As a result, fluorescent nanobeads dispersed in the electrolyte solutions accumulate into symmetric regions of the channel, appearing as two distinct symmetric stripes when the channel is observed from the top via epi-fluorescence microscopy. Depending on the electrolyte flow configuration and, thus, the direction of the salt concentration gradient field, the fluorescent stripes get closer to or apart from each other as the distance from the inlet increases. Our numerical and experimental analysis shows that although nanoparticle diffusiophoresis and hydrodynamic effects are involved in the accumulation process, diffusio-osmosis along the top and bottom channel walls plays a crucial role in the observed particles dynamics. In addition, we developed a proof-of-concept double Ψ-junction microfluidic device that exploits this accumulation mechanism for the size-based separation and size detection of nanobeads as well as for the measurement of zeta potential and charged lipid composition of liposomes under continuous flow settings. This device is also used to investigate the effect of fluid-like or gel-like states of the lipid membranes on the liposome diffusiophoretic response. The proposed strategy for solute-driven manipulation and characterization of colloids has great potential for microfluidic bioanalytical testing applications, including bioparticle preconcentration, sorting, sensing, and analysis.

Lego-Inspired Glass Capillary Microfluidic Device: A Technique for Bespoke Microencapsulation of Phase Change Materials.

We report a Lego-inspired glass capillary microfluidic device capable of encapsulating both organic and aqueous phase change materials (PCMs) with high reproducibility and 100% PCM yield. Oil-in-oil-in-water (O/O/W) and water-in-oil-in-water (W/O/W) core-shell double emulsion droplets were formed to encapsulate hexadecane (HD, an organic PCM) and salt hydrate SP21EK (an aqueous PCM) in a UV-curable polymeric shell, Norland Optical Adhesive (NOA). The double emulsions were consolidated through on-the-fly polymerization, which followed thiol-ene click chemistry for photoinitiation. The particle diameters and shell thicknesses of the microcapsules were controlled by manipulating the geometry of glass capillaries and fluid flow rates. The microcapsules were monodispersed and exhibited the highest encapsulation efficiencies of 65.4 and 44.3% for HD and SP21EK-based materials, respectively, as determined using differential scanning calorimetry (DSC). The thermogravimetric (TGA) analysis confirmed much higher thermal stability of both encapsulated PCMs compared to pure PCMs. Polarization microscopy revealed that microcapsules could sustain over 100 melting-crystallization cycles without any structural changes. Bifunctional microcapsules with remarkable photocatalytic activity along with thermal energy storage performance were produced after the addition of 1 wt % titanium dioxide (TiO2) nanoparticles (NPs) into the polymeric shell. The presence of TiO2 NPs in the shell was confirmed by higher opacity and whiteness of these microcapsules and was quantified by energy dispersive X-ray (EDX) spectroscopy. Young's modulus of HD-based microcapsules estimated using micromanipulation analysis increased from 58.5 to 224 MPa after TiO2 incorporation in the shell.

Microfluidic Fabrication and Applications of Microgels and Hybrid Microgels.

Smart microgels have gained much attention because of their wide range of applications in the field of biomedical, environmental, nanotechnological and catalysis sciences. Most of the applications of microgels are strongly affected by their morphology, size and size distribution. Various methodologies have been adopted to obtain polymer microgel particles. Droplet microfluidic techniques have been widely reported for the fabrication of highly monodisperse microgel particles to be used for various applications. Monodisperse microgel particles of required size and morphology can be achieved via droplet microfluidic techniques by simple polymerization of monomers in the presence of suitable crosslinker or by gelation of high molecular weight polymers. This report gives recent research progress in fabrication, characterization, properties and applications of microgel particles synthesized by microfluidic methods.

Enhanced Accumulation of Colloidal Particles in Microgrooved Channels via Diffusiophoresis and Steady-State Electrolyte Flows.

The delivery of colloidal particles in dead-end microstructures is very challenging, since these geometries do not allow net flows of particle-laden fluids; meanwhile, diffusive transport is slow and inefficient. Recently, we introduced a novel particle manipulation strategy, based on diffusiophoresis, whereby the salt concentration gradient between parallel electrolyte streams in a microgrooved channel induces the rapid (i.e., within minutes) and reversible accumulation, retention, and removal of colloidal particles in the microgrooves. In this study, we investigated the effects of salt contrast and groove depth on the accumulation process in silicon microgrooves and determined the experimental conditions that lead to a particle concentration peak of more than four times the concentration in the channel bulk. Also, we achieved an average particle concentration in the grooves of more than twice the concentration in the flowing streams and almost 2 orders of magnitude larger than the average concentration in the grooves in the absence of a salt concentration gradient. Analytical sufficient and necessary conditions for particle accumulation are also derived. Finally, we successfully tested the accumulation process in polydimethylsiloxane microgrooved channels, as they are less expensive to fabricate than silicon microgrooved substrates. The controlled and enhanced accumulation of colloidal particles in dead-end structures by solute concentration gradients has potential applications in soft matter and living systems, such as drug delivery, synthetic biology, and on-chip diagnostics.

Hierarchical Assembly of a Micro- and Macroporous Hydrogen-Bonded Organic Framework with Tailored Single-Crystal Size.

Porous organic molecular materials represent an emergent field of research in Chemistry and Materials Science due to their unique combination of properties. To enhance their performance and expand the number of applications, the incorporation of hierarchical porosity is required, as exclusive microporosity entails several limitations. However, the integration of macropores in porous organic molecular materials is still an outstanding challenge. Herein, we report the first example of a hydrogen-bonded organic framework (MM-TPY) with hierarchical skeletal morphology, containing stable micro- and macroporosity. The crystal size, from micro to centimetre scale, can be controlled in a single step without using additives or templates. The mechanism of assembly during the crystal formation is compatible with a skeletal crystal growth. As proof of concept, we employed the hierarchical porosity as a platform for the dual, sequential and selective co-recognition of molecular species and microparticles.

Monodispersed Sirolimus-Loaded PLGA Microspheres with a Controlled Degree of Drug-Polymer Phase Separation for Drug-Coated Implantable Medical Devices and Subcutaneous Injection.

Monodispersed sirolimus (SRL)-loaded poly(lactic-co-glycolic acid) microspheres with a diameter of 1.8, 3.8, and 8.5 µm were produced by high-throughput microfluidic step emulsification─solvent evaporation using single crystal silicon chips consisted of 540-1710 terraced microchannels with a depth of 2, 4, or 5 µm arranged in 10 parallel arrays. Uniform sized droplets were generated over 25 h across all channels. Nearly 15% of the total drug was released by the initial burst release during an accelerated drug release testing performed at 37 °C using a hydrotropic solution containing 5.8 M N,N-diethylnicotinamide. After 24 h, 71% of the drug was still entrapped in the particles. The internal morphology of microspheres was investigated by fluorescence microscopy using Nile red as a selective fluorescent stain with higher binding affinity toward SRL. By increasing the drug loading from 33 to 50 wt %, the particle morphology evolved from homogeneous microspheres, in which the drug and polymer were perfectly mixed, to patchy particles, with amorphous drug patches embedded within a polymer matrix to anisotropic patchy Janus particles. Janus particles with fully segregated drug and polymer regions were achieved by pre-saturating the aqueous phase with the organic solvent, which decreased the rate of solvent evaporation and allowed enough time for complete phase separation. This approach to manufacturing drug-loaded monodisperse microparticles can enable the development of more effective implantable drug-delivery devices and improved methods for subcutaneous drug administration, which can lead to better therapeutic treatments.

Facile Microfluidic Fabrication of Biocompatible Hydrogel Microspheres in a Novel Microfluidic Device.

Poly(ethylene glycol) diacrylate (PEGDA) microgels with tuneable size and porosity find applications as extracellular matrix mimics for tissue-engineering scaffolds, biosensors, and drug carriers. Monodispersed PEGDA microgels were produced by modular droplet microfluidics using the dispersed phase with 49-99 wt% PEGDA, 1 wt% Darocur 2959, and 0-50 wt% water, while the continuous phase was 3.5 wt% silicone-based surfactant dissolved in silicone oil. Pure PEGDA droplets were fully cured within 60 s at the UV light intensity of 75 mW/cm2. The droplets with higher water content required more time for curing. Due to oxygen inhibition, the polymerisation started in the droplet centre and advanced towards the edge, leading to a temporary solid core/liquid shell morphology, confirmed by tracking the Brownian motion of fluorescent latex nanoparticles within a droplet. A volumetric shrinkage during polymerisation was 1-4% for pure PEGDA droplets and 20-32% for the droplets containing 10-40 wt% water. The particle volume increased by 36-50% after swelling in deionised water. The surface smoothness and sphericity of the particles decreased with increasing water content in the dispersed phase. The porosity of swollen particles was controlled from 29.7% to 41.6% by changing the water content in the dispersed phase from 10 wt% to 40 wt%.

Novel glass capillary microfluidic devices for the flexible and simple production of multi-cored double emulsions.

HYPOTHESIS: Double emulsions with many monodispersed internal droplets are required for the fabrication of multicompartment microcapsules and tissue-like synthetic materials. These double emulsions can also help to optically resolve different coalescence mechanisms contributing to double emulsion destabilization. Up to date microfluidic double emulsions are limited to either core-shell droplets or droplets with eight or less inner droplets. By applying a two-step jet break-up within one setup, double emulsion droplets filled with up to several hundred monodispersed inner droplets can be achieved. EXPERIMENTS: Modular interconnected CNC-milled Lego®-inspired blocks were used to create two separated droplet break-up points within coaxial glass capillaries. Inner droplets were formed by countercurrent flow focusing within a small inner capillary, while outer droplets were formed by co-flow in an outer capillary. The size of inner and outer droplets was independently controlled since the two droplet break-up processes were decoupled. FINDINGS: With the developed setup W/O/W and O/W/O double emulsions were produced with different surfactants, oils, and viscosity modifiers to encapsulate 25-400 inner droplets in each outer drop with a volume percentage of inner phase between 7% and 50%. From these emulsions monodispersed multicompartment microcapsules were obtained. The report offers insights on the relationship between the coalescence of internal droplets and their release.

Crosslinking Strategies for the Microfluidic Production of Microgels.

This article provides a systematic review of the crosslinking strategies used to produce microgel particles in microfluidic chips. Various ionic crosslinking methods for the gelation of charged polymers are discussed, including external gelation via crosslinkers dissolved or dispersed in the oil phase; internal gelation methods using crosslinkers added to the dispersed phase in their non-active forms, such as chelating agents, photo-acid generators, sparingly soluble or slowly hydrolyzing compounds, and methods involving competitive ligand exchange; rapid mixing of polymer and crosslinking streams; and merging polymer and crosslinker droplets. Covalent crosslinking methods using enzymatic oxidation of modified biopolymers, photo-polymerization of crosslinkable monomers or polymers, and thiol-ene "click" reactions are also discussed, as well as methods based on the sol-gel transitions of stimuli responsive polymers triggered by pH or temperature change. In addition to homogeneous microgel particles, the production of structurally heterogeneous particles such as composite hydrogel particles entrapping droplet interface bilayers, core-shell particles, organoids, and Janus particles are also discussed. Microfluidics offers the ability to precisely tune the chemical composition, size, shape, surface morphology, and internal structure of microgels by bringing multiple fluid streams in contact in a highly controlled fashion using versatile channel geometries and flow configurations, and allowing for controlled crosslinking.

Droplet breakup mechanisms in premix membrane emulsification and related microfluidic channels.

Premix membrane emulsification (PME) is a pressure driven process of droplet breakup, caused by their motion through membrane pores. The process is widely used for high-throughput production of sized-controlled emulsion droplets and microparticles using low energy inputs. The resultant droplet size depends on numerous process, membrane, and formulation factors such as flow velocity in pores, number of extrusions, initial droplet size, internal membrane geometry, wettability of pore walls, and physical properties of emulsion. This paper provides a comprehensive review of different mechanisms of droplet deformation and breakup in membranes with versatile pore morphologies including sintered glass and ceramic filters, SPG and polymeric membranes with sponge-like structures, micro-engineered metallic membranes with ordered straight-through pore arrays, and dynamic membranes composed of unconsolidated particles. Fundamental aspects of droplet motion and breakup in idealized pore networks have also been covered including droplet disruption in T-junctions, channel constrictions, and obstructed channels. The breakup mechanisms due to shear interactions with pore walls and localized shear (direct breaking) or due to interfacial tension effects and Rayleigh-Plateau instability (indirect breaking) are systematically discussed based on recent experimental and numerical studies. Non-dimensional droplet size correlations based on capillary, Weber, and Ohnesorge numbers are also presented.

Highly Porous Magnetic Janus Microparticles with Asymmetric Surface Topology.

Monodispersed magnetic Janus particles composed of a porous polystyrene portion and a nonporous poly(vinyl acetate) portion with embedded oleic acid-coated magnetic nanoparticles were generated using microfluidic emulsification followed by two distinct phase separation events triggered by solvent evaporation. The template droplets were composed of 2 wt % polystyrene, 2 wt % poly(vinyl acetate), and 0.5-2 wt % n-heptane-based magnetic fluid dissolved in dichloromethane (DCM). The porosity of polystyrene compartments was the result of phase separation between a nonvolatile nonsolvent (n-heptane) and a volatile solvent (DCM) within polystyrene-rich phase. The focused ion beam cross-sectioning and scanning electron microscopy (SEM) imaging revealed high surface porosity of polystyrene compartments with negligible porosity of poly(vinyl acetate) parts, which can be exploited to increase the wettability contrast between the two polymers and enhance bubble generation in bubble-driven micromotors. The porosity of the polystyrene portion was controlled by varying the fraction of n-heptane in the dispersed phase. The particle composition was confirmed by scanning electron microscopy-energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The fabricated particles were successfully magnetized when subjected to an external magnetic field, which led to their aggregation into regular 2D assemblies. The particle clusters composed of two to four individual particles could be rotated with a rotating magnetic field. Microfluidic generation of highly porous Janus particles with compositional, topological, and magnetic asymmetry provides a cost-effective, easy-to-implement yet highly robust and versatile strategy for the manufacturing of multifunctional smart particles.

Reversible Trapping of Colloids in Microgrooved Channels via Diffusiophoresis under Steady-State Solute Gradients.

The controlled transport of colloids in dead-end structures is a key capability that can enable a wide range of applications, such as biochemical analysis, drug delivery, and underground oil recovery. This Letter presents a new trapping mechanism that allows the fast (i.e., within a few minutes) and reversible accumulation of submicron particles within dead-end microgrooves by means of parallel streams with different salinity level. For the first time, particle focusing in dead-end structures is achieved under steady-state gradients. Confocal microscopy analysis and numerical investigations show that the particles are trapped at a flow recirculation region within the grooves due to a combination of diffusiophoresis transport and hydrodynamic effects. Counterintuitively, the particle velocity at the focusing point is not vanishing and, hence, the particles are continuously transported in and out of the focusing point. The accumulation process is also reversible and one can cyclically trap and release the colloids by controlling the salt concentration of the streams via a flow switching valve.

Versatile reconfigurable glass capillary microfluidic devices with Lego® inspired blocks for drop generation and micromixing.

Novel cost effective, versatile, reconfigurable, reusable and easy to assemble glass capillary microfluidic devices were developed and used to generate micro/nano-materials with controlled size and morphology. The devices are composed of coaxial assemblies of glass capillaries held between two interchangeable plastic blocks fabricated from chemically inert polyoxymethylene copolymer using computer numerical control (CNC) machining. Three different blocks were combined and locked together using Lego® inspired stud-and-hole coupling system to achieve different flow configurations. The device allows a truly axisymmetric round capillary inside a round capillary geometry and self-alignment of capillaries. The synthesis of polyvinylpyrrolidone capped gold nanoparticles and liposomes of controlled size was demonstrated in the co-flow device by mixing the contents of two parallel laminar streams. The flow focusing device was used to generate piroxicam monohydrate crystals of controlled size (10-29 µm) by antisolvent crystallisation. Silver nanoparticles with tailored size (40-90 nm) were prepared in the three-phase device by merging silver nitrate and tannic acid/citrate streams inside droplets. The same device was used to prepare fluorescently labelled double emulsion droplets with controlled number of inner droplets. The droplet morphology was modified and tuned during operation by adjusting the distance between the inner capillaries. Water-in-oil emulsions consisted of Eudragit S100 solution at pH > 7 dispersed in Miglyol® 840 were prepared and gellified in situ over 6 h without fouling. The setup time of the novel devices was reduced from ∼30 min in manually made capillary devices to just several minutes.

3D Arrays of Super-Hydrophobic Microtubes from Polypore Mushrooms as Naturally-Derived Systems for Oil Absorption.

Porous materials derived from natural resources, such as Luffa sponges, pomelo peel and jute fibres, have recently emerged as oil adsorbents for water purification, due to their suitability, low environmental impact, biodegradability and low cost. Here we show, for the first time, that the porosity of the fruiting body of polypore mushrooms can be used to absorb oils and organic solvents while repelling water. We engineered the surface properties of Ganoderma applanatum fungi, of which the fruiting body consists of a regular array of long capillaries embedded in a fibrous matrix, with paraffin wax, octadecyltrichlorosilane (OTS) and trichloro(1H,1H,2H,2H-perfluorooctyl)silane. Morphological and wettability analyses of the modified fungus revealed that the OTS treatment was effective in preserving the 3D porosity of the natural material, inducing super-hydrophobicity (water contact angle higher than 150°) and improving oil sorption capacity (1.8⁻3.1 g/g). The treated fungus was also inserted into fluidic networks as a filtration element, and its ability to separate water from chloroform was demonstrated.

Nanoencapsulation of Bacteriophages in Liposomes Prepared Using Microfluidic Hydrodynamic Flow Focusing.

Increasing antibiotic resistance in pathogenic microorganisms has led to renewed interest in bacteriophage therapy in both humans and animals. A "Trojan Horse" approach utilizing liposome encapsulated phages may facilitate access to phagocytic cells infected with intracellular pathogens residing therein, e.g., to treat infections caused by Mycobacterium tuberculosis, Listeria, Salmonella, and Staphylococcus sp. Additionally, liposome encapsulated phages may adhere to and diffuse within mucosa harboring resistant bacteria which are challenges in treating respiratory and gastrointestinal infections. Orally delivered phages tend to have short residence times in the gastrointestinal tract due to clinical symptoms such as diarrhea; this may be addressed through mucoadhesion of liposomes. In the present study we have evaluated the use of a microfluidic based technique for the encapsulation of bacteriophages in liposomes having mean sizes between 100 and 300 nm. Encapsulation of two model phages was undertaken, an Escherichia coli T3 podovirus (size ~65 nm) and a myovirus Staphylococcus aureus phage K (capsid head ~80 nm and phage tail length ~200 nm). The yield of encapsulated T3 phages was 109 PFU/ml and for phage K was much lower at 105 PFU/ml. The encapsulation yield for E. coli T3 phages was affected by aggregation of T3 phages. S. aureus phage K was found to interact with the liposome lipid bilayer resulting in large numbers of phages bound to the outside of the formed liposomes instead of being trapped inside them. We were able to inactivate the liposome bound S. aureus K phages whilst retaining the activity of the encapsulated phages in order to estimate the yield of microfluidic encapsulation of large tailed phages. Previous published studies on phage encapsulation in liposomes may have overestimated the yield of encapsulated tailed phages. This overestimation may affect the efficacy of phage dose delivered at the site of infection. Externally bound phages would be inactivated in the stomach acid resulting in low doses of phages delivered at the site of infection further downstream in the gastrointestinal tract.

Microfluidic Production of Poly(1,6-hexanediol diacrylate)-Based Polymer Microspheres and Bifunctional Microcapsules with Embedded TiO2 Nanoparticles.

Application of TiO2 as a photocatalyst and UV protector is restricted by the difficulties in the recovery of TiO2 nanoparticles after water treatment. In this work, TiO2 nanoparticles (Degussa P25) were immobilised within easily recoverable poly(1,6-hexanediol diacrylate) poly(HDDA)-based polymer microspheres produced by on-the-fly photopolymerization of microfluidically generated droplets. Because of fast polymerization reaction, TiO2 was uniformly distributed within the polymer network. The transformation of double bonds in terminal vinyl groups of HDDA monomer into single bonds during photopolymerization was confirmed by Fourier transform infrared spectroscopy. The microspheres containing 0.5 wt % TiO2 embedded in a poly(HDDA) matrix degraded 80% of methylene blue from 1 ppm aqueous solution in 9 h under UV light irradiation of 0.9 mW/cm2 at 365 nm. The microspheres could easily be separated from water and used in repeated cycles without any loss in photocatalytic activity. The inclusion of TiO2 within a polymer matrix increased the thermal degradation temperature of the material from 364 to 389 °C. Bifunctional microcapsules consisting of aqueous or liquid paraffin core enclosed within a TiO2/poly(HDDA) composite polymer shell were also prepared. The fluorescent dye calcein was encapsulated in the core with 100% efficiency.

Preventing Crystal Agglomeration of Pharmaceutical Crystals Using Temperature Cycling and a Novel Membrane Crystallization Procedure for Seed Crystal Generation.

In this work, a novel membrane crystallization system was used to crystallize micro-sized seeds of piroxicam monohydrate by reverse antisolvent addition. Membrane crystallization seeds were compared with seeds produced by conventional antisolvent addition and polymorphic transformation of a fine powdered sample of piroxicam form I in water. The membrane crystallization process allowed for a consistent production of pure monohydrate crystals with narrow size distribution and without significant agglomeration. The seeds were grown in 350 g of 20:80 w/w acetone-water mixture. Different seeding loads were tested and temperature cycling was applied in order to avoid agglomeration of the growing crystals during the process. Focused beam reflectance measurement (FBRM); and particle vision and measurement (PVM) were used to monitor crystal growth; nucleation and agglomeration during the seeded experiments. Furthermore; Raman spectroscopy was used to monitor solute concentration and estimate the overall yield of the process. Membrane crystallization was proved to be the most convenient and consistent method to produce seeds of highly agglomerating compounds; which can be grown via cooling crystallization and temperature cycling.