Nanofilament-Coated Superhydrophobic Membranes Show Enhanced Flux and Fouling Resistance in Membrane Distillation.

Membrane distillation (MD) is an important technique for brine desalination and wastewater treatment that may utilize waste or solar heat. To increase the distillation rate and minimize membrane wetting and fouling, we deposit a layer of polysiloxane nanofilaments on microporous membranes. In this way, composite membranes with multiscale pore sizes are created. The performance of these membranes in the air gap and direct contact membrane distillation was investigated in the presence of salt solutions, solutions containing bovine serum albumin, and solutions containing the surfactant sodium dodecyl sulfate. In comparison to conventional hydrophobic membranes, our multiscale porous membranes exhibit superior fouling resistance while attaining a higher distillation flux without using fluorinated compounds. This study demonstrates a viable method for optimizing MD processes for wastewater and saltwater treatment.

A super liquid-repellent hierarchical porous membrane for enhanced membrane distillation.

Membrane distillation (MD) is an emerging desalination technology that exploits phase change to separate water vapor from saline based on low-grade energy. As MD membranes come into contact with saline for days or weeks during desalination, membrane pores have to be sufficiently small (typically <0.2 µm) to avoid saline wetting into the membrane. However, in order to achieve high distillation flux, the pore size should be large enough to maximize transmembrane vapor transfer. These conflicting requirements of pore geometry pose a challenge to membrane design and currently hinder broader applications of MD. To address this fundamental challenge, we developed a super liquid-repellent membrane with hierarchical porous structures by coating a polysiloxane nanofilament network on a commercial micro-porous polyethersulfone membrane matrix. The fluorine-free nanofilament coating effectively prevents membrane wetting under high hydrostatic pressure (>11.5 bar) without compromising vapor transport. With large inner micro-porous structures, the nanofilament-coated membrane improves the distillation flux by up to 60% over the widely used commercially available membranes, while showing excellent salt rejection and operating stability. Our approach will allow the fabrication of high-performance composite membranes with multi-scale porous structures that have wide-ranging applications beyond desalination, such as in cleaning wastewater.

Hierarchically Branched Siloxane Brushes for Efficient Harvesting of Atmospheric Water.

Atmospheric water harvesting is considered a viable source of freshwater to alleviate water scarcity in an arid climate. Water condensation tends to be more efficient on superhydrophobic surfaces as the spontaneous coalescence-induced droplet jumping on superhydrophobic surfaces enables faster condensate removal. However, poor water nucleation on these surfaces leads to meager water harvest. A conventional approach to the problem is to fabricate micro- and nanoscale biphilic structures. Nonetheless, the process is complex, expensive, and difficult to scale. Here, the authors present an inexpensive and scalable method based on manipulating the water-repellent coatings of superhydrophobic surfaces. Flexible siloxane can facilitate water nucleation, while a branched structure promotes efficient droplet jumping. Moreover, ToF-SIMS analysis indicated that branched siloxane provides a better water-repellent coating coverage than linear siloxane and the siloxanes comprise hydrophilic and hydrophobic molecular segments. Thus, the as-prepared superhydrophobic surface, TiO2 nanorods coated with branched siloxanes harvested eight times more water than a typical fluoroalkylsilane (FAS)-coated surface under a low 30% relative humidity and performed better than most reported biphasic materials.

Plasma-Induced Superhydrophobicity as a Green Technology for Enhanced Air Gap Membrane Distillation.

Superhydrophobicity has only recently become a requirement in membrane fabrication and modification. Superhydrophobic membranes have shown improved flux performance and scaling resistance in long-term membrane distillation (MD) operations compared to simply hydrophobic membranes. Here, we introduce plasma micro- and nanotexturing followed by plasma deposition as a novel, dry, and green method for superhydrophobic membrane fabrication. Using plasma micro- and nanotexturing, commercial membranes, both hydrophobic and hydrophilic, are transformed to superhydrophobic featuring water static contact angles (WSCA) greater than 150° and contact angle hysteresis lower than 10°. To this direction, hydrophobic polytetrafluoroethylene (PTFE) and hydrophilic cellulose acetate (CA) membranes are transformed to superhydrophobic. The superhydrophobic PTFE membranes showed enhanced water flux in standard air gap membrane distillation and more stable performance compared to the commercial ones for at least 48 h continuous operation, with salt rejection >99.99%. Additionally, their performance and high salt rejection remained stable, when low surface tension solutions containing sodium dodecyl sulfate (SDS) and NaCl (down to 35 mN/m) were used, showcasing their antiwetting properties. The improved performance is attributed to superhydrophobicity and increased pore size after plasma micro- and nanotexturing. More importantly, CA membranes, which are initially unsuitable for MD due to their hydrophilic nature (WSCA ≈ 40°), showed excellent performance with stable flux and salt rejection >99.2% again for at least 48 h, demonstrating the effectiveness of the proposed method for wetting control in membranes regardless of their initial wetting properties.

Vapor Lubrication for Reducing Water and Ice Adhesion on Poly(dimethylsiloxane) Brushes.

Fast removal of small water drops from surfaces is a challenging issue in heat transfer, water collection, or anti-icing. Poly(dimethylsiloxane) (PDMS) brushes show good prospects to reach this goal because of their low adhesion to liquids. To further reduce adhesion of water drops, here, the surface to the vapor of organic solvents such as toluene or n-hexane is exposed. In the presence of such vapors, water drops slide at lower tilt angle and move faster. This is mainly caused by the physisorption of vapor and swelling of the PDMS brushes, which serves as a lubricating layer. Enhanced by the toluene vapor lubrication, the limit departure volume of water drop on PDMS brushes decreases by one order of magnitude compared to that in air. As a result, the water harvesting efficiency in toluene vapor increases by 65%. Benefits of vapor lubrication are further demonstrated for de-icing: driven by gravity, frozen water drops slide down the vertical PDMS brush surface in the presence of vapor.

Tunable Water Harvesting Surfaces Consisting of Biphilic Nanoscale Topography.

Water scarcity has become a global issue of severe concern. Great efforts have been undertaken to develop low-cost and highly efficient condensation strategies to relieve water shortages in arid regions. However, the rationale for design of an ideal condensing surface remains lacking due to the conflicting requirements for water nucleation and transport. In this work, we demonstrate that a biphilic nanoscale topography created by a scalable surface engineering method can achieve an ultraefficient water harvesting performance. With hydrophilic nanobumps on top of a superhydrophobic substrate, this biphilic topography combines the merits of biological surfaces with distinct wetting features (e.g., fog-basking beetles and water-repellent lotus), which enables a tunable water nucleation phenomenon, in contrast to the random condensation mode on their counterparts. By adjusting the contrasting wetting features, the characteristic water nucleation spacing can be tuned to balance the nucleation enhancement and water transport to cope with various environments. Guided by our nucleation density model, we show an optimal biphilic topography by tuning the nanoscale hydrophilic structure density, which allows an ∼349% water collection rate and ∼184% heat transfer coefficient as compared to the state-of-the-art superhydrophobic surface in a moisture-lacking atmosphere, offering a very promising strategy for improving the efficiency of water harvesting in drought areas.

Controllable Formation of Monodisperse Polymer Microbubbles as Ultrasound Contrast Agents.

Microbubbles have been widely used as ultrasound contrast agents in clinical diagnosis and hold great potential for ultrasound-mediated therapy. However, polydispersed population and short half-life time (<10 min) of the microbubbles still limit their applications in imaging and therapy. To tackle these problems, we develop a microfluidic flow-focusing approach to produce monodisperse microbubbles stabilized by Poly(lactic-co-glycolic acid) (PLGA) as the polymer shell. The size of PLGA microbubbles can be tightly controlled from ∼600 nm to ∼7 µm with a coefficient of variation less than 4% in size distribution for ensuring highly homogeneous echogenic behavior of PLGA polymer microbubbles in ultrasound fields. Both in vitro and in vivo experiments showed that the monodisperse PLGA microbubbles had excellent echogenicity and elongated sonographic duration time (>3 times) for ultrasound imaging in comparison with the commercial lipid microbubbles.

Suppressing Ice Nucleation of Supercooled Condensate with Biphilic Topography.

Preventing or minimizing ice formation in supercooled water is of prominent importance in many infrastructures, transportation, and cooling systems. The overall phase change heat transfer on icephobic surfaces, in general, is intentionally sacrificed to suppress the nucleation of water and ice. However, in a condensation frosting process, inhibiting freezing without compromising the water condensation has been an unsolved challenge. Here we show that this conflict between anti-icing and efficient condensation cooling can be resolved by utilizing biphilic topography with patterned high-contrast wettability. By creating a varying interfacial thermal barrier underneath the supercooled condensate, the biphilic structures tune the nucleation rates of water and ice in the sequential condensation-to-freezing process. Our experimental and theoretical investigation of condensate freezing dynamics further unravels the correlation between the onset of droplet freezing and its characteristic radius, offering a new insight for controlling the multiphase transitions among vapor, water, and ice in supercooled conditions.

Tunable Confinement for Bridging Single-Cell Manipulation and Single-Molecule DNA Linearization.

DNA linearization by nanoconfinement has offered a new avenue toward large-scale genome mapping. The ability to smoothly interface the widely different length scales from cell manipulation to DNA linearization is critical to the development of single-cell genomic mapping or sequencing technologies. Conventional nanochannel technologies for DNA analysis suffer from complex fabrication procedures, DNA stacking at the nanochannel entrance, and inefficient solution exchange. In this work, a dynamic and tunable confinement strategy is developed to manipulate and linearize genomic-length DNA molecules from a single cell. By leveraging pneumatic microvalve control and elastomeric collapse, an array of nanochannels with confining dimension down to 20 nm and length up to sub-millimeter is created and can be dynamically tuned in size. The curved edges of the microvalve form gradual transitions from microscale to nanoscale confinement, smoothly facilitating DNA entry into the nanochannels. A unified micro/nanofluidic device that integrates single-cell trapping and lysis, DNA extraction, purification, labeling, and linearization is developed based on dynamically controllable nanochannels. Mbp-long DNA molecules are extracted directly from a single cell and in situ linearized in the nanochannels. The device provides a facile and promising platform to achieve the ultimate goal of single-cell, single-genome analysis.

High aspect ratio induced spontaneous generation of monodisperse picolitre droplets for digital PCR.

Droplet microfluidics, which involves micrometer-sized emulsion droplets on a microfabricated platform, has been demonstrated as a unique system for many biological and chemical applications. Robust and scalable generation of monodisperse droplets at high throughput is of fundamental importance for droplet microfluidics. Classic designs for droplet generation employ shear fluid dynamics to induce the breakup of droplets in a two-phase flow and the droplet size is sensitive to flow rate fluctuations, often resulting in polydispersity. In this paper, we show spontaneous emulsification by a high aspect ratio (>3.5) rectangular nozzle structure. Due to the confinement and abrupt change of the structure, a Laplace pressure difference is generated between the dispersed and continuous phases, and causes the thread thinning and droplet pinch-off without the need to precisely control external flow conditions. A high-throughput droplet generator was developed by parallelization of a massive number of the basic structures. This device enabled facile and rapid partition of aqueous samples into millions of uniform picolitre droplets in oil. Using this device, on-chip droplet-based digital polymerase chain reaction (PCR) was performed for absolute quantification of rare genes with a wide dynamic range.

Microfluidic production of nanoscale perfluorocarbon droplets as liquid contrast agents for ultrasound imaging.

Liquid perfluorocarbon (PFC) nanodroplets may have a better chance to extravasate through inter-endothelial gaps (400-800 nm) into tumor interstitium for extravascular imaging, which holds promise as an innovative strategy for imaging-guided drug delivery, early diagnosis of cancer and minimally invasive treatment of cancer. Currently available emulsion technologies still face challenges in reducing droplet sizes from the microscale to the nanoscale. To control size and ensure monodispersity of PFC nanodroplets, we developed a flame-shaped glass capillary and polydimethylsiloxane (PDMS) hybrid device that creates a concentric flow of the dispersed phase enclosed by the focusing continuous phase at the cross-junction. Through adjustment of the pressure applied, a stable tip-streaming mode can be obtained for PFC nanodroplet generation. Using this device, we synthesized various kinds of PFC nanodroplets as small as 200 nm in diameter with polydispersity index (PDI) <0.04. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were carried out for the characterization of the PFC nanodroplets. Finally, ultrasound imaging was conducted to demonstrate that the liquid PFC nanodroplets can be used for enhancing the ultrasound contrast upon vaporization.

In vitro epithelial organoid generation induced by substrate nanotopography.

The extracellular matrix (ECM) exhibits tissue-specific topography and composition and plays a crucial role in initiating the biochemical and biomechanical signaling required for organizing cells into distinct tissues during development. How single cells assemble into structures featuring specific shapes in response to external cues is poorly understood. We examined the effect of substrate nanotopography on the morphogenesis of several types of epithelial cells and found that in response to the topography, Calu-3 and MDCK-II cells formed organoids that closely resemble their morphology in vivo. This finding represents the first demonstration that substrate nanotopography, one of the first physical cues detected by cells, can by itself induce epithelial tissue-like organization. Our results provide insights, in terms of a new aspect of ECM topography, into the design of future tissue-engineering systems and the study of mechanosignaling in the epithelium during normal development and tumor progression.

An on-demand nanofluidic concentrator.

Preconcentration of biomolecules by electrokinetic trapping at the nano/microfluidic interface has been extensively studied due to its significant efficiency. Conventionally, sample preconcentration takes place in continuous flow and therefore suffers from diffusion and dispersion. Encapsulation of the preconcentrated sample into isolated droplets offers a superior way to preserve the sample concentration for further analysis. Nevertheless, the rationale for an optimal design to obviate the sample dilution prior to encapsulation is still lacking. Herein, we propose a pressure-assisted strategy for positioning the concentrated sample plug directly at the ejecting nozzle, which greatly eliminates the concentration decline during sample ejection. A distinctive mechanism for this plug localization was elucidated by two-dimensional numerical simulations. Based on the simulation results, we developed an on-demand nanofluidic concentrator in which the nanochannels were facilely generated through lithography-free nanocracking on a polystyrene substrate. By wisely implementing an on-demand droplet generation module, our system can adaptively encapsulate the highly concentrated sample and effectively enhance the long-term stability. We experimentally demonstrated the preconcentration of a fluorescently labelled biomolecule, bovine serum albumin (BSA), by using an amplification factor of 10(4). We showed that, by adjusting the applied voltage, accumulation time, and pulsed pressure imposed on the control microchannel, our system can generate a droplet of the desired volume with a target sample concentration at a prescribed time. This study not only provides insights into the previously unidentified role of assisted pressure in sample positioning, but also offers an avenue for varied requirements in low-abundance biomolecule detection and analysis.

Recurrent filmwise and dropwise condensation on a beetle mimetic surface.

Vapor condensation plays a key role in a wide range of industrial applications including power generation, thermal management, water harvesting and desalination. Fast droplet nucleation and efficient droplet departure as well as low interfacial thermal resistance are important factors that determine the thermal performances of condensation; however, these properties have conflicting requirements on the structural roughness and surface chemistry of the condensing surface or condensation modes (e.g., filmwise vs dropwise). Despite intensive efforts over the past few decades, almost all studies have focused on the dropwise condensation enabled by superhydrophobic surfaces. In this work, we report the development of a bioinspired hybrid surface with high wetting contrast that allows for seamless integration of filmwise and dropwise condensation modes. We show that the synergistic cooperation in the observed recurrent condensation modes leads to improvements in all aspects of heat transfer properties including droplet nucleation density, growth rate, and self-removal, as well as overall heat transfer coefficient. Moreover, we propose an analytical model to optimize the surface morphological features for dramatic heat transfer enhancement.