Modeling the Transition between Localized and Extended Deposition in Flow Networks through Packings of Glass Beads.

We use a theoretical model to explore how fluid dynamics, in particular, the pressure gradient and wall shear stress in a channel, affect the deposition of particles flowing in a microfluidic network. Experiments on transport of colloidal particles in pressure-driven systems of packed beads have shown that at lower pressure drop, particles deposit locally at the inlet, while at higher pressure drop, they deposit uniformly along the direction of flow. We develop a mathematical model and use agent-based simulations to capture these essential qualitative features observed in experiments. We explore the deposition profile over a two-dimensional phase diagram defined in terms of the pressure and shear stress threshold, and show that two distinct phases exist. We explain this apparent phase transition by drawing an analogy to simple one-dimensional mass-aggregation models in which the phase transition is calculated analytically.

Hysteresis in the thermally induced phase transition of cellulose ethers.

Functionalized cellulosics have shown promise as naturally derived thermoresponsive gelling agents. However, the dynamics of thermally induced phase transitions of these polymers at the lower critical solution temperature (LCST) are not fully understood. Here, with experiments and theoretical considerations, we address how molecular architecture dictates the mechanisms and dynamics of phase transitions for cellulose ethers. Above the LCST, we show that hydroxypropyl substituents favor the spontaneous formation of liquid droplets, whereas methyl substituents induce fibril formation through diffusive growth. In celluloses which contain both methyl and hydroxypropyl substituents, fibrillation initiates after liquid droplet formation, suppressing the fibril growth to a sub-diffusive rate. Unlike for liquid droplets, the dissolution of fibrils back into the solvated state occurs with significant thermal hysteresis. We tune this hysteresis by altering the content of substituted hydroxypropyl moieties. This work provides a systematic study to decouple competing mechanisms during the phase transition of multi-functionalized macromolecules.

Nanoparticle-stabilised emulsions: droplet armouring vs. droplet bridging.

We speculate that the ability of small nanoparticles to stabilise emulsions via droplet bridging is controlled by the balance between an energy increase, due to the interaction between two oil-water interfaces in close proximity through surface forces, and an energy decrease due to the adsorption of a bridging particle on two oil-water interfaces. For nanoparticles of diameter greater than about 10 nm, tuning this interaction may render bridging possible, whereas nanoparticles smaller than 10 nm may stabilise emulsions only via the formation of dense layers of adsorbed particles on droplets. Both predictions are experimentally testable.

Ethyl Cellulose Nanoparticles at the Alkane-Water Interface and the Making of Pickering Emulsions.

Pickering emulsions stabilized by nanoparticles have recently received great attention for their remarkable stability, in part a consequence of irreversible adsorption. In this study, we generate Pickering oil-in-water emulsions stabilized by ethyl cellulose (EC) nanoparticles without the addition of surfactants. Over a range of ionic strength and EC nanoparticle concentrations, a series of dynamic interfacial tension (IFT) measurements complemented by extended DLVO theoretical computations are conducted to quantitatively describe the behavior of EC nanoparticles at the interface of water with different alkanes. Regardless of ionic strength, there is no barrier against the adsorption of EC nanoparticles at the alkane-water interfaces studied and the particles tightly cover these interfaces with near maximal coverage (i.e., 91%). Remarkably, the rate of approach to maximum coverage of the alkane-water interface by EC nanoparticles during the later stages of adsorption is accelerated in the presence of salt at concentrations below the critical coagulation concentration (CCC), unlike the air-water interface. Above the CCC, alkane-water interfaces behave similar to air-water interfaces, showing decay in the adsorption flux which is attributed to an increase in surface blocking originating from the attachment of nanoparticles to nanoparticles already adsorbed at the interface. These findings shed light on particle-particle and particle-interface colloidal interactions at and near fluid-fluid interfaces, thereby improving our ability to use hydrophobic EC nanoparticles as emulsion stabilizers.

Dynamics of ethyl cellulose nanoparticle self-assembly at the interface of a nematic liquid crystal droplet.

Design and fabrication of many next-generation liquid crystal (LC)-based devices rely on nematic LC domains in the form of drops or emulsions. In addition to surfactants, solid nanoparticles may be used to stabilize LC-in-water Pickering emulsions, possibly adding new dimensions to device functionality. In this work we quantitatively study the adsorption of ethyl cellulose (EC) nanoparticles, as a colloid model system, on the 4-cyano-4'-pentylbiphenyl (5CB)-water interface via a series of dynamic interfacial tension measurements. It is found that the planar alignment of 5CB molecules at the interface with water is unaffected by particle adsorption, but a significant reduction of the interfacial tension over time occurs. It is also found that adsorption of EC nanoparticles to the LC-water interface is irreversible and results in close hexagonal packing. This study demonstrates a systematic approach to quantitatively investigate the effect of nanoparticles on the stabilization of LC emulsions.

Effects of Ionic Strength on the Colloidal Stability and Interfacial Assembly of Hydrophobic Ethyl Cellulose Nanoparticles.

Nanoparticle attachment at a fluid interface is a process that often takes place concurrently with nanoparticle aggregation in the bulk of the suspension. Here we investigate systematically the coupling of these processes with reference to the adsorption of aqueous suspensions of ethyl cellulose (EC) nanoparticles at the air-water interface. The suspension stability is optimal at neutral pH and in the absence of salt, conditions under which the electrostatic repulsion among EC nanoparticles is maximized. Nonetheless, hydrophobic attraction dominates particle-interface interactions, resulting in the irreversible adsorption of EC nanoparticles at the air-water interface. The addition of salt weakens the particle-particle and particle-interface repulsive electrostatic forces. This leads to destabilization of the suspension at ionic strengths of 0.05 M or greater but does not affect nanoparticle adsorption. The energy of adsorption, the surface tension and interface coverage at steady state, and the particle contact angle at the interface all remain unchanged by the addition of salt. These findings contribute to the fundamental understanding of colloidal systems and inform the utilization of EC nanocolloids, in particular for the stabilization of foams and emulsions.

Irreversible adsorption-driven assembly of nanoparticles at fluid interfaces revealed by a dynamic surface tension probe.

Adsorption-driven self-assembly of nanoparticles at fluid interfaces is a promising bottom-up approach for the preparation of advanced functional materials and devices. Full realization of its potential requires quantitative understanding of the parameters controlling the self-assembly, the structure of nanoparticles at the interface, the barrier properties of the assembly, and the rate of particle attachment. We argue that models of dynamic surface or interfacial tension (DST) appropriate for molecular species break down when the adsorption energy greatly exceeds the mean energy of thermal fluctuations and validate alternative models extending the application of generalized random sequential adsorption theory to nanoparticle adsorption at fluid interfaces. Using a model colloidal system of hydrophobic, charge-stabilized ethyl cellulose nanoparticles at neutral pH, we demonstrate the potential of DST measurements to reveal information on the energy of adsorption, the adsorption rate constant, and the energy of particle-interface interaction at different degrees of nanoparticle coverage of the interface. These findings have significant implications for the quantitative description of nanoparticle adsorption at fluid interfaces.

Synthesizing Lipid Nanoparticles by Turbulent Flow in Confined Impinging Jet Mixers.

Lipid nanoparticles (LNPs) have demonstrated their enormous potential as therapeutic delivery vehicles, as evidenced by the approval and global usage of two COVID-19 messenger RNA (mRNA) vaccines. On a small scale, LNPs are often made using microfluidics; however, the limitations of these devices preclude their use on a large scale. The COVID-19 vaccines are manufactured in large quantities using confined impinging jet (CIJ) turbulent mixers. CIJ technology enables production at a laboratory scale with the confidence that it can be scaled to production volumes. The key concepts in CIJ mixing are that the mixing length and time scale are determined by the turbulence intensity in the mixing cavity and that the nanoparticle formation occurs away from walls, eliminating the problem of deposition on surfaces and fouling. This work demonstrates the process of making LNPs using confined impinging jet mixer technology with two geometries: the two-jet CIJ and the four-jet multi-inlet vortex mixer (MIVM). The advantages and disadvantages of each mixing geometry are discussed. In these geometries, LNPs are formed by rapid mixing of an organic solvent stream (usually ethanol containing the ionizable lipids, co-lipids, and stabilizing PEG-lipids) with an aqueous anti-solvent stream (aqueous buffer containing RNA or DNA). The operating parameters for the CIJ and MIVM mixers are presented to prepare reproducible LNPs with controlled size, zeta potential, stability, and transfection effectiveness. The differences between LNPs made with poor mixing (pipetting solutions) compared to CIJ mixing are also presented.

Diblock Copolymer Targeted Lipid Nanoparticles: Next-Generation Nucleic Acid Delivery System Produced by Confined Impinging Jet Mixers.

Despite the recent advances and clinical demonstration of lipid nanoparticles (LNPs) for therapeutic and prophylactic applications, the extrahepatic delivery of nucleic acids remains a significant challenge in the field. This limitation arises from the rapid desorption of lipid-PEG in the bloodstream and clearance to the liver, which hinders extrahepatic delivery. In response, we explore the substitution of lipid-PEG with biodegradable block copolymers (BCPs), specifically poly(ε-caprolactone)-block-poly(ethylene glycol) (PCL-b-PEG). BCPs offer strong anchoring for large macromolecules, potentially enhancing cell-specific targeting. To develop and optimize BCP-stabilized LNPs (BCP-LNPs), we employed a Design of Experiment (DOE) approach. Through a systematic exploration, we identified optimal formulations for BCP-LNPs, achieving desirable physicochemical properties and encapsulation efficiency. Notably, BCP-LNPs exhibit surprising trends in transfection efficiency, with certain formulations showing up to a 40-fold increase in transfection in Hela cells, while maintaining minimal cytotoxicity. The lipid compositions that optimized PCL-b-PEG LNP transfection were different from the compositions that optimized PEG-lipid LNP transfection. Furthermore, our study confirms the versatility of BCP-LNPs in encapsulating and delivering both mRNA and pDNA, demonstrating their cargo-agnostic nature. Lastly, we showcased the targeted BCP-LNPs using a Cetuximab-conjugated formulation. These targeted LNPs show significant promise in delivering cargo specific to EGFR-overexpressing cells (A549 cells), with up to 2.4 times higher transfection compared to nontargeted LNPs. This finding underscores the potential of BCP-LNPs in targeted gene therapy, especially in challenging scenarios such as tumor targeting. Overall, our study establishes the viability of BCP-LNPs as a versatile, efficient, and targeted delivery platform for nucleic acids, opening avenues for advanced therapeutic applications.

Quick-Release Antifouling Hydrogels for Solar-Driven Water Purification.

Hydrogels are promising soft materials for energy and environmental applications, including sustainable and off-grid water purification and harvesting. A current impediment to technology translation is the low water production rate well below daily human demand. To overcome this challenge, we designed a rapid-response, antifouling, loofah-inspired solar absorber gel (LSAG) capable of producing potable water from various contaminated sources at a rate of ∼26 kg m-2 h-1, which is sufficient to meet daily water demand. The LSAG-produced at room temperature via aqueous processing using an ethylene glycol (EG)-water mixture-uniquely integrates the attributes of poly(N-isopropylacrylamide) (PNIPAm), polydopamine (PDA), and poly(sulfobetaine methacrylate) (PSBMA) to enable off-grid water purification with enhanced photothermal response and the capacity to prevent oil fouling and biofouling. The use of the EG-water mixture was critical to forming the loofah-like structure with enhanced water transport. Remarkably, under sunlight irradiations of 1 and 0.5 sun, the LSAG required only 10 and 20 min to release ∼70% of its stored liquid water, respectively. Equally important, we demonstrate the ability of LSAG to purify water from various harmful sources, including those containing small molecules, oils, metals, and microplastics.

A Bioinspired Elastic Hydrogel for Solar-Driven Water Purification.

The global demand for clean and safe water will continue to grow well into the 21st century. Moving forward, the lack of access to clean water, which threatens human health and strains precious energy resources, will worsen as the climate changes. Therefore, future innovations that produce potable water from contaminated sources must be sustainable. Inspired by nature, a solar absorber gel (SAG) is developed to purify water from contaminated sources using only natural sunlight. The SAG is composed of an elastic thermoresponsive poly(N-isopropylacrylamide) (PNIPAm) hydrogel, a photothermal polydopamine (PDA) layer, and a sodium alginate (SA) network. Production of the SAG is facile; all processing is aqueous-based and occurs at room temperature. Remarkably, the SAG can purify water from various harmful reservoirs containing small molecules, oils, metals, and pathogens, using only sunlight. The SAG relies on solar energy to drive a hydrophilic/hydrophobic phase transformation at the lower critical solution temperature. Since the purification mechanism does not require water evaporation, an energy-intensive process, the passive solar water-purification rate is the highest reported. This discovery can be transformative in the sustainable production of clean water to improve the quality of human life.

Evolution of Polymer Colloid Structure During Precipitation and Phase Separation.

Polymer colloids arise in a variety of contexts ranging from synthetic to natural systems. The structure of polymeric colloids is crucial to their function and application. Hence, understanding the mechanism of structure formation in polymer colloids is important to enabling advances in their production and subsequent use as enabling materials in new technologies. Here, we demonstrate how the specific pathway from precipitation to vitrification dictates the resulting morphology of colloids fabricated from polymer blends. Through continuum simulations, free energy calculations, and experiments, we reveal how colloid structure changes with the trajectory taken through the phase diagram. We demonstrate that during solvent exchange, polymer-solvent phase separation of a homogeneous condensate can precede polymer-polymer phase separation for blends of polymers that possess some degree of miscibility. For less-miscible, higher-molecular-weight blends, phase separation and kinetic arrest compete to determine the final morphology. Such an understanding of the pathways from precipitation to vitrification is critical to designing functional structured polymer colloids.

Multiscale dynamics of colloidal deposition and erosion in porous media.

Diverse processes-e.g., environmental pollution, groundwater remediation, oil recovery, filtration, and drug delivery-involve the transport of colloidal particles in porous media. Using confocal microscopy, we directly visualize this process in situ and thereby identify the fundamental mechanisms by which particles are distributed throughout a medium. At high injection pressures, hydrodynamic stresses cause particles to be continually deposited on and eroded from the solid matrix-notably, forcing them to be distributed throughout the entire medium. By contrast, at low injection pressures, the relative influence of erosion is suppressed, causing particles to localize near the inlet of the medium. Unexpectedly, these macroscopic distribution behaviors depend on imposed pressure in similar ways for particles of different charges, although the pore-scale distribution of deposition is sensitive to particle charge. These results reveal how the multiscale interactions between fluid, particles, and the solid matrix control how colloids are distributed in a porous medium.

In Silico Design Enables the Rapid Production of Surface-Active Colloidal Amphiphiles.

A new technology platform built on the integration of theory and experiments to enable the design of Janus colloids with precision control of surface anisotropy and amphiphilicity could lead to a disruptive transformation in the next generation of surfactants, photonic or phononic materials, and coatings. Here, we exploit molecular dynamics (MD) simulations to guide the rational design of amphiphilic polymer Janus colloids by Flash NanoPrecipitation (FNP), a method capable of the production of colloids with complex structure without the compromise of reduced scalability. Aided by in silico design, we show in experiments that amphiphilic Janus colloids can be produced using a unique blend of hydrophobic homopolymers and the addition of an amphiphilic block copolymer. The final structure of the colloids depends on the mass fraction of each homopolymer as well as the concentration and composition of the block copolymer additive. To confirm the surface activity of the colloids, we demonstrate their potential to stabilize Pickering emulsions. This hybrid approach of simulations and experiments provides a pathway to designing and manufacturing complex polymeric colloids on an industrial scale.