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David J Banner,1 Emre Firlar,1,2 Justas Jakubonis,1 Yusuf Baggia,1 Jodi K Osborn,1 Reza Shahbazian-Yassar,2 Constantine M Megaridis,2 Tolou Shokuhfar1,2 1Department of Bioengineering, University of Illinois at Chicago, Chicago, IL 60607, USA; 2Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, IL 60607, USACorrespondence: Tolou ShokuhfarDepartment of Bioengineering (MC 063), University of Illinois at Chicago, 851 S. Morgan St, SEO 218, Chicago, IL 60607, USATel +1 312 996-2335Fax +1 312 996-5291Email tolou@uic.eduBackground: Nanoscale surface roughness has been suggested to have antibacterial and antifouling properties. Several existing models have attempted to explain the antibacterial mechanism of nanoscale rough surfaces without direct observation. Here, conventional and liquid-cell TEM are implemented to observe nanoscale bacteria/surface roughness interaction. The visualization of such interactions enables the inference of possible antibacterial mechanisms.Methods and Results: Nanotextures are synthesized on biocompatible polymer microparticles (MPs) via plasma etching. Both conventional and liquid-phase transmission electron microscopy observations suggest that these MPs may cause cell lysis via bacterial binding to a single protrusion of the nanotexture. The bacterium/protrusion interaction locally compromises the cell wall, thus causing bacterial death. This study suggests that local mechanical damage and leakage of the cytosol kill the bacteria first, with subsequent degradation of the cell envelope.Conclusion: Nanoscale surface roughness may act via a penetrative bactericidal mechanism. This insight suggests that future research may focus on optimizing bacterial binding to individual nanoscale projections in addition to stretching bacteria between nanopillars. Further, antibacterial nanotextures may find use in novel applications employing particles in addition to nanotextures on fibers or films.Keywords: liquid TEM, graphene liquid cell, antibacterial nanopatterns, antibacterial surface topology, antibacterial microparticles

The morphology of particulate soot formed in a liquid-fueled, complex- flow (i.e., turbulent, recirculating) combustor has been studied using thermophoretic sampling and transmission electron microscopy. Soot size information was obtained via computer-aided image analysis. Particle morphology was observed to be similar to that found in other combustion devices (i.e., nearly spherical primary particles fused into aggregate chains and clusters). Axial regions where soot nucleation, growth, agglomeration, and oxidation occur were identified. Primary particle size was observed to increase with combustor height, but the largest primary size reached is small compared to that observed in laminar diffusion flames. From calculated estimates of the specific soot surface growth and oxidation rates, the growth rate was found to be lower and the oxidation rate comparable to those for laminar diffusion flames. Aggregate sizes were also observed to increase with cambustor axial location, and were found to be distributed in a lognormal manner during the particle inception and growth stages. Fractal dimensions for characteristic aggregate populations were determined to be around 1.8, and were independent of combustor axial location. The results suggest that cluster-to-cluster aggregation-and not surface growth-is the dominant soot aggregate growth mechanism in the complex-flow reactor. Comparisons with more traditional methods for soot size determination were made with moderate success.

Background: Humans emit approximately 30 million microbial cells per hour into their immediate vicinity. However, sampling of aerosolized microbial taxa (aerobiome) remains largely uncharacterized due to the complexity and limitations of sampling techniques, which are highly susceptible to low biomass and rapid sample degradation. Recently, there has been an interest in developing technology that collects naturally occurring water from the atmosphere, even within the built environment. Here, we analyze the feasibility of indoor aerosol condensation collection as a method to capture and analyze the aerobiome., Methods: Aerosols were collected via condensation or active impingement in a laboratory setting over the course of 8 h. Microbial DNA was extracted from collected samples and sequenced (16S rRNA) to analyze microbial diversity and community composition. Dimensional reduction and multivariate statistics were employed to identify significant (p < 0.05) differences in relative abundances of specific microbial taxa observed between the two sampling platforms., Results: Aerosol condensation capture is highly efficient with a yield greater than 95% when compared to expected values. Compared to air impingement, aerosol condensation showed no significant difference (ANOVA, p > 0.05) in microbial diversity. Among identified taxa, Streptophyta and Pseudomonadales comprised approximately 70% of the microbial community composition., Conclusion: The results suggest that condensation of atmospheric humidity is a suitable method for the capture of airborne microbial taxa reflected by microbial community similarity between devices. Future investigation of aerosol condensation may provide insight into the efficacy and viability of this new tool to investigate airborne microorganisms., Importance: On average, humans shed approximately 30 million microbial cells each hour into their immediate environment making humans the primary contributor to shaping the microbiome found within the built environment. In addition, recent events have highlighted the importance of understanding how microorganisms within the built environment are aerosolized and dispersed, but more importantly, the lack in development of technology that is capable of actively sampling the ever-changing aerosolized microbiome, i.e., aerobiome. This research highlights the capability of sampling the aerobiome by taking advantage of naturally occurring atmospheric humidity. Our novel approach reproduces the biological content in the atmosphere and can provide insight into the environmental microbiology of indoor spaces. Video Abstract., (© 2023. The Author(s).)

The study of ice nucleation and growth at the nanoscale is of utmost importance in geological and atmospheric sciences. However, existing transmission electron microscopy (TEM) approaches have been unsuccessful in imaging ice formation directly. Herein, we demonstrate how radical scavengers - such as TiO 2 - encased with water in graphene liquid cells (GLCs) facilitate the observation of ice nucleation phenomena at low temperatures. Atomic-resolution imaging reveals the nucleation and growth of cubic ice-phase crystals at close proximity to TiO 2 -water nanointerfaces at low temperatures. Interestingly, both heterogeneously and homogeneously nucleated ice crystals exhibited this cubic phase. Ice crystal nuclei were observed to be more stable at the TiO 2 -water nanointerface, as compared with crystals in the bulk liquid (homogeneous nucleation), suggesting the radical scavenging efficacy of TiO 2 nanoparticles mitigating the electron beam by-products. The present work demonstrates that the use of radical scavengers in GLC TEM shows great promise towards unveiling the nanoscale pathways for ice nucleation and growth dynamic events.

Hypothesis: The interfacial energy γ sl between a solid and a liquid designates the affinity between these two phases, and in turn, the macroscopic wettability of the surface by the fluid. This property is needed for precise control of fluid-transport phenomena that affect the operation/quality of commercial devices/products. Although several indirect or theoretical approaches can quantify the solid/liquid interfacial energy, no direct experimental procedure exists to measure this property for realistic (i.e. rough) surfaces. Makkonen hypothesized that the frictional resistance force per unit contact-line length is equal to the interfacial energy on smooth surfaces, which, however, are rarely found in practice. Consequently, the hypothesis that Makkonen's assumption may also hold for rough surfaces (which are far more common in practice) arises naturally. If so, a reliable and simple experimental methodology of obtaining γ sl for rough surfaces can be put forth. This is accomplished by performing dynamic contact-angle experiments on rough surfaces that quantify the relationship between the frictional resistance force per unit contact-line length acting on an advancing liquid (F p,a ) and the surface roughness in wetting configurations., Experiment: We perform static and advancing contact-line experiments with aqueous and organic liquids on different hydrophilic surfaces (Al, Cu, Si) with varying Wenzel roughnesses in the range 1-2. These parameters are combined with the liquid's known surface tension to determine F p,a ., Findings: F p,a rises linearly with the surface roughness. Analysis based on existing theories of wetting and contact-angle hysteresis reveals that the slope of F p,a vs.Wenzel roughness is equal to the solid/liquid interfacial energy, which is thus determined experimentally with the present measurements. Interfacial energies obtained with this experimental approach are within 12% of theoretically predicted values for several solid/liquid pairs, thereby validating this methodology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Inc.)

Effective manipulation of liquids on open surfaces without external energy input is indispensable for the advancement of point-of-care diagnostic devices. Open-surface microfluidics has the potential to benefit health care, especially in the developing world. This review highlights the prospects for harnessing capillary forces on surface-microfluidic platforms, chiefly by inducing smooth gradients or sharp steps of wettability on substrates, to elicit passive liquid transport and higher-order fluidic manipulations without off-the-chip energy sources. A broad spectrum of the recent progress in the emerging field of passive surface microfluidics is highlighted, and its promise for developing facile, low-cost, easy-to-operate microfluidic devices is discussed in light of recent applications, not only in the domain of biomedical microfluidics but also in the general areas of energy and water conservation.

The extreme liquid transport properties of carbon nanotubes present new opportunities for surpassing conventional technologies in water filtration and purification. We demonstrate that carbon nanotubes with wettability surface patterns act as nanopumps for the ultrafast transport of picoliter water droplets without requiring externally imposed pressure gradients. Large-scale molecular dynamics simulations evidence unprecedented speeds and accelerations on the order of 10 10 g of droplet propulsion caused by interfacial energy gradients. This phenomenon is persistent for nanotubes of varying sizes, stepwise pattern configurations, and initial conditions. We present a scaling law for water transport as a function of wettability gradients through simple models for the droplet dynamic contact angle and friction coefficient. Our results show that patterned nanotubes are energy-efficient nanopumps offering a realistic path toward ultrafast water nanofiltration and precision drug delivery.

The persisting outbreak of SARS-CoV-2 has posed an enormous threat to global health. The sustained human-to-human transmission of SARS-CoV-2 via respiratory droplets makes the medical procedures around the perioral area vulnerable to the spread of the disease. Such procedures include the ultrasonic dental cleaning method, which occurs within the oral cavity and involves cavitation-induced sprays, thus increasing the risk of pathogen transmission via advection. To understand the associated health and safety risks for patients and clinicians, it is critical to understand the flow pattern of the spray cloud around the operating region, the size and velocity distribution of the emitted droplets, and the extent of fluid dispersion until ultimate deposit on surfaces or escape through air vents. In this work, the droplet size and velocity distributions of the spray emerging from the tip of a free-standing common ultrasonic dental cleaning device were characterized via high-speed imaging. Deionized water and 1.5% and 3% aqueous hydrogen peroxide (H 2 O 2 ) solutions were used as working fluids, with the H 2 O 2 -an established oxidizing agent-intended to curb the survival of virus released in aerosols generated from dental procedures. The measurements reveal that the presence of H 2 O 2 in the working fluid increases the mean droplet size and ejection velocity. Detailed computational fluid dynamic simulations with multiphase flow models reveal benefits of adding small amounts of H 2 O 2 in the feed stream of the ultrasonic cleaner; this practice causes larger droplets with shorter residence times inside the clinic before settling down or escaping through air vents. The results suggest optimal benefits (in terms of fluid spread) of adding 1.5% H 2 O 2 in the feed stream during dental procedures involving ultrasonic tools. The present findings are not specific to the COVID-19 pandemic but should also apply to future outbreaks caused by airborne droplet transmission.

Surfaces with extreme wettability (too low, superhydrophobic; too high, superhydrophilic) have attracted considerable attention over the past two decades. Titanium dioxide (TiO 2 ) has been one of the most popular components for generating superhydrophobic/hydrophilic coatings. Combining TiO 2 with ethanol and a commercial fluoroacrylic copolymer dispersion, known as PMC, can produce coatings with water contact angles approaching 170°. Another property of interest for this specific TiO 2 formulation is its photocatalytic behavior, which causes the contact angle of water to be gradually reduced with rising timed exposure to UV light. While this formulation has been employed in many studies, there exists no quantitative guidance to determine or tune the contact angle (and thus wettability) with the composition of the coating and UV exposure time. In this article, machine learning models are employed to predict the required UV exposure time for any specified TiO 2 /PMC coating composition to attain a certain wettability (UV-reduced contact angle). For that purpose, eight different coating compositions were applied to glass slides and exposed to UV light for different time intervals. The collected contact-angle data was supplied to different regression models to designate the best method to predict the required UV exposure time for a prespecified wettability. Two types of machine learning models were used: (1) parametric and (2) nonparametric. The results showed a nonlinear behavior between the coating formulation and its contact angle attained after timed UV exposure. Nonparametric methods showed high accuracy and stability with general regression neural network (GRNN) performing best with an accuracy of 0.971, 0.977, and 0.933 on the test, train, and unseen data set, respectively. The present study not only provides quantitative guidance for producing coatings of specified wettability, but also presents a generalized methodology that could be employed for other functional coatings in technological applications requiring precise fluid/surface interactions.

Liquid-jet impact on porous, relatively thin solids has a variety of applications in heat transfer, filtration, liquid-fuel atomization, incontinence products, and solid-substrate erosion, among others. Many prior studies focused on liquid-jet impact on impermeable substrates, and some have investigated the hydraulic jump phenomenon. In the present work, the liquid jet strikes a superhydrophobic, permeable, metal mesh orthogonally, and the radial spreading and throughflow of the liquid are characterized. The prebreakthrough hydraulic jump, the breakthrough velocity, and the postbreakthrough spatial distributions of the liquid are investigated by varying the liquid properties (density, surface tension, and viscosity) and the openness of the metal mesh. The hydraulic jump radius in the prebreakthrough regime increases with jet velocity and is independent of the liquid properties and mesh geometry (pore size, wire diameter and pitch). The breakthrough velocity increases with surface tension of the liquid and decreases with the mesh opening diameter and liquid viscosity. A simple analytical model predicts the jet breakthrough velocity; its predictions are in accordance with the experimental observations. In the postbreakthrough regime, as the jet velocity increases, the liquid flow rate penetrating the mesh shows an initially steep increase, followed by a plateau, which is attributed to a Cassie-Baxter-to-Wenzel transition at the impact area of the mesh.

COVID-19, caused by the SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2) virus, has been rapidly spreading worldwide since December 2019, causing a public health crisis. Recent studies showed SARS-CoV-2's ability to infect humans via airborne routes. These motivated the study of aerosol and airborne droplet transmission in a variety of settings. This study performs a large-scale numerical simulation of a real-world dentistry clinic that contains aerosol-generating procedures. The simulation tracks the dispersion of evaporating droplets emitted during ultrasonic dental scaling procedures. The simulation considers 25 patient treatment cubicles in an open plan dentistry clinic. The droplets are modeled as having a volatile (evaporating) and nonvolatile fraction composed of virions, saliva, and impurities from the irrigant water supply. The simulated clinic's boundary and flow conditions are validated against experimental measurements of the real clinic. The results evaluate the behavior of large droplets and aerosols. We investigate droplet residence time and travel distance for different droplet diameters, surface contamination due to droplet settling and deposition, airborne aerosol mass concentration, and the quantity of droplets that escape through ventilation. The simulation results raise concerns due to the aerosols' long residence times (averaging up to 7.31 min) and travel distances (averaging up to 24.45 m) that exceed social distancing guidelines. Finally, the results show that contamination extends beyond the immediate patient treatment areas, requiring additional surface disinfection in the clinic. The results presented in this research may be used to establish safer dental clinic operating procedures, especially if paired with future supplementary material concerning the aerosol viral load generated by ultrasonic scaling and the viral load thresholds required to infect humans., (© 2021 Author(s).)

Hypothesis: Quantitative characterization of surface wettability through contact angle (CA) measurement using the sessile droplet (SD) or captive bubble (CB) methods is often limited by the intrinsic wetting properties of the substrate. Situations may arise when an extreme surface wettability may preclude using one of the two methods for predicting the behaviors of droplets or bubbles on the surface. This warrants a relationship between the dynamic CAs measured via the SD and CB methods. While the two dynamic CAs (e.g., the advancing CA of SD and receding CA of CB) add up to 180° on a smooth surface, the simple geometric supplementary principle may not apply for rough surfaces., Experiments: We perform a systematic wettability characterization of solid substrates with varying degrees of roughness using the sessile-droplet and captive-bubble methods, and interpret the experimental observations using a theoretical model., Findings: The dynamic contact angles measured by the sessile-droplet and captive-bubble methods deviate from the supplementary principle as the surface roughness is increased. We present a theoretical explanation for this disparity and predict the values of the contact angles using prevalent thermodynamic models of wetting and contact-angle hysteresis on rough substrates. The theoretical prediction is in good agreement with the experimental observations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Spreading of liquid droplets on wettability-confined paths has attracted considerable attention in the past decade. On the other hand, the inverse scenario of a gas bubble spreading on a submerged, wettability-confined track has rarely been studied. In the present work, an experimental investigation of the spreading of millimetric gas bubbles on horizontally submerged, textured, wettability-confined tracks is carried out. The width of the track is kept fixed along its entire length, and the spreading behavior of a gas bubble, dispensed at one end of the track, is studied. The effects of varying track width, bubble diameter, and ambient liquid are investigated. Post-contact, the gas bubble spreads along the track at a linear rate with time, while remaining pinned at its back end; the recorded spreading speed is O (0.5 m/s). An inertio-capillary force balance describes the experimentally observed spreading dynamics with excellent agreement.

The interaction of rising gas bubbles with submerged air-repelling or air-attracting surfaces is relevant to various technological applications that rely on gas-microvolume handling or removal. This work demonstrates how submerged metal meshes with super air-attracting/repelling properties can be employed to manipulate microvolumes of air, rising buoyantly in the form of bubbles in water. Superaerophobic meshes are observed to selectively allow the passage of air bubbles depending on the mesh pore size, the bubble volume-equivalent diameter, and the bubble impact velocity on the mesh. On the other hand, superaerophilic meshes reduce or amplify the volume captured from a train of incoming bubbles. Finally, a spatial wettability pattern on the mesh is used to control the size of the outgoing bubble, and an empirical relation is formulated to predict the released gas volume. The study demonstrates how porous materials with controlled wettability can be used to precisely modulate and control the outcome of bubble/mesh interactions.

The outbreak of unknown viral pneumonia in Wuhan China in December 2019 led to a new coronavirus (SARS-CoV-2), which attracted worldwide attention, with the related COVID-19 disease quickly becoming a global pandemic. In about 5 months, this disease has led to ~ 4 million cases and claimed more than 200 k deaths as a result of its highly contagious nature. The present understanding is that SARS-CoV-2 is a type of influenza virus that can be transmitted through respiratory droplets and aerosols; Lewis (Nature 580:175, 2020). The primary methodology to prevent the spreading of this disease has been "social distancing" and usage of personal protective equipment (PPE) at the front lines of healthcare and other critical operations. The scale of the disease has led to unprecedented demand for PPEs and increased functionality of the same. This paper focuses on improving PPE functionality in a scalable manner by surface treatment and coating with appropriate materials and other functional enhancements, such as exposure to UV rays or other sterilizing agents (e.g., hydrogen peroxide)., (© Indian National Academy of Engineering 2020.)

With the rapid spread of COVID-19 worldwide, the demand for appropriate face masks in the market has also skyrocketed. To ease strain on the supply of masks to the essential healthcare sector, it has become imperative that ordinary people rely more on home-made masks that can be easily put together using commonly available materials, while at the same time performing reasonably at arresting the ingress or egress of airborne droplets. Here, we propose a simple do-it-yourself (DIY) method for preparing a three-layered face mask that deploys two hydrophobic polypropylene nonwoven layers interspaced with a hydrophilic cellulosic cloth. The first hydrophobic layer, facing the user, allows high-momentum droplets (e.g., expelled by a sneeze or cough) to pass through and get absorbed in the next hydrophilic layer, thereby keeping the skin in contact with the mask dry and comfortable. The third (outermost) hydrophobic layer prevents penetration of the liquids from the middle layer to the outside, and also arrests any airborne droplets on its exterior. Simple tests show that our masks perform better in arresting the droplet transmission as compared to surgical masks available in the market., (© Indian National Academy of Engineering 2020.)

The impact of liquid droplets on permeable substrates is important for a number of applications, such as fog collection, liquid atomization, and interaction of liquids with filters and textiles. When a water droplet impacts a wettable mesh, it penetrates the mesh easily with a part of the liquid remaining pinned. On the other hand, when striking a superhydrophobic mesh, part of the water droplet may penetrate and detach from the parent droplet, depending upon the impact velocity and the relative length scales of the droplet and the mesh. In most cases, the remaining droplet would rebound from the top of the superhydrophobic mesh. In this work, we study the impact of a water droplet on a wettability-patterned mesh, with the droplet centrally impacting the wettability-contrast line between the superhydrophobic and superhydrophilic semi-infinite domains. Half of the droplet seeing the superhydrophobic domain responds to it in a fashion that differs from the half hitting the superhydrophilic mesh side. This creates a wide range of post-impact scenarios, depending on the impact conditions and the relative characteristics of the droplet and the mesh. The difference in mesh wettability leads to a net unbalanced surface-tension force that makes the droplet rebound with a horizontal momentum component directed from the non-wettable to the wettable side. Some part of the droplet may even detach during such directional rebounding (i.e., vectoring). Along with the experimental results, a simplified analytical model is presented, which differentiates the cases of detachment or no detachment during vectoring.

The fog-basking behavior of the Onymacris unguicularis , a beetle species living in the coastal regions of the Namibian desert, has recently caught the attention of the engineering community, as suggesting a viable biomimetic approach to address the problem of harvesting water in arid regions of the globe. Previous research has focused on observation and analysis of the beetle's elytron properties and how these affect fog-collection rates. The head stance taken by the Onymacris unguicularis when fog basking is well documented. However, how this stance affects droplet collection has not been studied up to now. The present paper addresses this problem from a computational fluid dynamics perspective, where three-dimensional numerical simulations are used to characterize the fog flow properties around a simplified geometry mimicking the beetle's body. The simulations employ two-way coupling between the gas flow and the dispersed fog phase to account for feedback effects of fog droplets on the carrier fluid (air), and assume that droplets are captured after hitting the elytron surface. The study considers several combinations of free-stream velocity and droplet volume fraction. The analysis reveals that there is a range of head-stance angles, corresponding to an inclination of the beetle between 35 deg and 45 deg with respect to the horizon, that maximizes water collection on the beetle's back, in qualitative agreement with observations in nature and laboratory experiments. A rationale is proposed to explain this phenomenon, finding that the specific head stance corresponds to the maximum residence time of fluid particles above the beetle's elytron surface. This, in turn, designates the maximum likelihood for water droplets to be captured in the boundary layer developing over the beetle and subsequently hit the surface where they get captured. The results reveal the importance of the fluid flow pattern around the beetle's body in addition to the microphysical properties of the elytron when reliable predictions of the water droplet collection efficiency are sought.

The directed transport of liquids at the nanoscale is of great importance for nanotechnology applications ranging from water filtration to the cooling of electronics and precision medicine. Here we demonstrate such unidirectional, pumpless transport of water nanodroplets on graphene sheets patterned with hydrophilic/phobic areas inspired by natural systems. We find that spatially varying patterning of the graphene surfaces can lead to water transport at ultrafast velocities, far exceeding macroscale estimates. We perform extensive molecular dynamics simulations to show that such high transport velocities ( O(10 2 m/s)) are due to differences of the advancing and receding contact angles of the moving droplet. This contact angle hysteresis and the ensuing transport depend on the surface pattern and the droplet size. We present a scaling law for the driving capillary and resisting friction forces on the water droplet and use it to predict nanodroplet trajectories on a wedge-patterned graphene sheet. The present results demonstrate that graphene with spatially variable wettability is a potent material for fast and precise transport of nanodroplets with significant potential for directed nanoscale liquid transport and precision drug delivery.

Water is ubiquitous in natural systems, ranging from the vast oceans to the nanocapillaries in the earth crust or cellular organelles. In bulk or in intimate contact with solid surfaces, water molecules arrange themselves according to their hydrogen (H) bonding, which critically affects their short- and long-range molecular structures. Formation of H-bonds among water molecules designates the energy levels of certain nonbonding molecular orbitals of water, which are quantifiable by spectroscopic techniques. While the molecular architecture of water in nanoenclosures is of particular interest to both science and industry, it requires fine spectroscopic probes with nanometer spatial resolution and sub-eV energy sensitivity. Graphene liquid cells (GLCs), which feature opposing closely spaced sheets of hydrophobic graphene, facilitate high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) measurements of attoliter water volumes encapsulated tightly in the GLC nanovessels. We perform in situ TEM and EELS analysis of water encased in thin GLCs exposed to room and cryogenic temperatures to examine the nanoscale arrangement of the contained water molecules. Simultaneous quantification of GLC thickness leads to the conclusion that H-bonding strengthens under increased water confinement. The present results demonstrate the feasibility of nanoscale chemical characterization of aqueous fluids trapped in GLC nanovessels and offer insights on water molecule arrangement under high-confinement conditions.

Porous substrates have the ability to transport liquids not only laterally on their open surfaces but also transversally through their thickness. Directionality of the fluid transport can be achieved through spatial wettability patterning of these substrates. Different designs of wettability patterns are implemented herein to attain different schemes (modes) of three-dimensional transport in a high-density paper towel, which acts as a thin porous matrix directing the fluid. All schemes facilitate precise transport of metered liquid microvolumes (dispensed as droplets) on the surface and through the substrate. One selected mode features lateral fluid transport along the bottom surface of the substrate, with the top surface remaining dry, except at the initial droplet dispension point. This configuration is investigated in further detail, and an analytical model is developed to predict the temporal variation of the penetrating drop shape. The analysis and respective measurements agree within the experimental error limits, thus confirming the model's ability to account for the main transport mechanisms.

Liquid jet impingement on porous materials is particularly important in many applications of heat transfer, filtration, or in incontinence products. Generally, it is desired that the liquid not penetrate the substrate at or near the point of jet impact, but rather be distributed over a wider area before reaching the back side. A facile wettability-patterning technique is presented, whereby a water jet impinging orthogonally on a wettability-patterned nonwoven substrate is distributed on the top surface and through the porous matrix, and ultimately dispensed from prespecified points underneath the sample. A systematic approach is adopted to identify the optimum design that allows for a uniform distribution of the liquid on horizontally mounted substrates of ∼50 cm 2 area, with minimal or no spilling over the sample edges at jet flow rates exceeding 1 L/min. The effect of the location of jet impingement on liquid distribution is also studied, and the design is observed to perform well even under offset jet impact conditions.

Spontaneous pumpless transport of droplets on wettability-confined tracks is important for various applications, such as rapid transport and mixing of fluid droplets, enhanced dropwise condensation, biomedical devices, and so forth. Recent studies have shown that on an open surface, a superhydrophilic track of diverging width, laid on a superhydrophobic background, facilitates the transport of water from the narrower end to the wider end at unprecedented rates (up to 40 cm/s) without external actuation. The spreading behavior on such surfaces, however, has only been characterized for water. Keeping in mind that such designs play a key role for a diverse range of applications, such as handling organic liquids and in point-of-care devices, the importance of characterizing the spreading behavior of viscous liquids on such surfaces cannot be overemphasized. In the present work, the spreading behavior on the aforementioned wettability-patterned diverging tracks was observed for fluids of different viscosities. Two dimensionless variables were identified, and a comprehensive relationship was obtained. Three distinct temporal regimes of droplet spreading were established: I), a Washburn-type slow spreading, II) a much faster Laplace pressure-driven spreading, and III), a sluggish density-augmented Tanner-type film spreading. The results offer design guidance for tracks that can pumplessly manage fluids of various viscosities and surface tensions.

Thermal Brownian motors (TBMs) are nanoscale machines that exploit thermal fluctuations to provide useful work. We introduce a TBM-based nanopump which enables continuous water flow through a carbon nanotube (CNT) by imposing an axial thermal gradient along its surface. We impose spatial asymmetry along the CNT by immobilizing certain points on its surface. We study the performance of this molecular motor using molecular dynamics (MD) simulations. From the MD trajectories, we compute the net water flow and the induced velocity profiles for various imposed thermal gradients. We find that spatial asymmetry modifies the vibrational modes of the CNT induced by the thermal gradient, resulting in a net water flow against the thermal gradient. Moreover, the kinetic energy associated with the thermal oscillations rectifies the Brownian motion of the water molecules, driving the flow in a preferred direction. For imposed thermal gradients of 0.5-3.3 K/nm, we observe continuous net flow with average velocities up to 5 m/s inside CNTs with diameters of 0.94, 1.4, and 2.0 nm. The results indicate that the CNT-based asymmetric thermal motor can provide a controllable and robust system for delivery of continuous water flow with potential applications in integrated nanofluidic devices.

Self-driven surface micromixers (SDSM) relying on patterned-wettability technology provide an elegant solution for low-cost, point-of-care (POC) devices and lab-on-a-chip (LOC) applications. We present a SDSM fabricated by strategically patterning three wettable wedge-shaped tracks onto a non-wettable, flat surface. This SDSM operates by harnessing the wettability contrast and the geometry of the patterns to promote mixing of small liquid volumes (µL droplets) through a combination of coalescence and Laplace pressure-driven flow. Liquid droplets dispensed on two juxtaposed branches are transported to a coalescence station, where they merge after the accumulated volumes exceed a threshold. Further mixing occurs during capillary-driven, advective transport of the combined liquid over the third wettable track. Planar, non-wettable "islands" of different shapes are also laid on this third track to alter the flow in such a way that mixing is augmented. Several SDSM designs, each with a unique combination of island shapes and positions, are tested, providing a greater understanding of the different mixing regimes on these surfaces. The study offers design insights for developing low-cost surface microfluidic mixing devices on open substrates.

Frost formation is omnipresent when suitable environmental conditions are met. A good portion of research on combating frost formation has revolved around the passive properties of superhydrophobic (SHPO) and slippery lubricant-impregnated porous (SLIP) surfaces. Despite much progress, the need for surfaces that can effectively combat frost formation over prolonged periods still remains. In this work, we report, for the first time, the use of electrically conductive SHPO/SLIP surfaces for active mitigation of frost formation. First, we demonstrate the failure of these surfaces to passively avert prolonged (several hours) frosting. Next, we make use of their electroconductive property for active Joule heating, which results in the removal of any formed frost. We study the role of the impregnating lubricant in the heat transfer across the interface, the surface, and the ambient. We show that, even though the thermal properties of the impregnating lubricant may vary drastically, the lubricant type does not noticeably affect the defrosting behavior of the surface. We attribute this outcome to the dominant thermal resistance of the thick frost layer formed on the cooled surface. We support this claim by drawing parallels between the present system and heat transfer through a one-dimensional (1D) composite medium, and solving the appropriate transient transport equations. Lastly, we propose periodic thermal defrosting for averting frost formation altogether. This methodology utilizes the coating's passive repellent capabilities, while eliminating the dominant effect of thick deposited frost layers. The periodic heating approach takes advantage of lubricants with higher thermal conductivities, which effectively enhance heat transfer through the porous multiphase surface that forms the first line of defense against frosting.

Rapid advances in modern electronics place ever-accelerating demands on innovation towards more robust and versatile functional components. In the flexible electronics domain, novel material solutions often involve creative uses of common materials to reduce cost, while maintaining uncompromised performance. Here we combine a commercially available paraffin wax-polyolefin thermoplastic blend (elastomer matrix binder) with bulk-produced carbon nanofibres (charge percolation network for electron transport, and for imparting nanoscale roughness) to fabricate adherent thin-film composite electrodes. The simple wet-based process produces composite films capable of sustained ultra-high strain (500%) with resilient electrical performance (resistances of the order of 10(1)-10(2) Ω sq(-1)). The composites are also designed to be superhydrophobic for long-term corrosion protection, even maintaining extreme liquid repellency at severe strain. Comprised of inexpensive common materials applied in a single step, the present scalable approach eliminates manufacturing obstacles for commercially viable wearable electronics, flexible power storage devices and corrosion-resistant circuits.

Rough surfaces immersed under water remain practically dry if the liquid-solid contact is on roughness peaks, while the roughness valleys are filled with gas. Mechanisms that prevent water from invading the valleys are well studied. However, to remain practically dry under water, additional mechanisms need consideration. This is because trapped gas (e.g. air) in the roughness valleys can dissolve into the water pool, leading to invasion. Additionally, water vapor can also occupy the roughness valleys of immersed surfaces. If water vapor condenses, that too leads to invasion. These effects have not been investigated, and are critically important to maintain surfaces dry under water. In this work, we identify the critical roughness scale, below which it is possible to sustain the vapor phase of water and/or trapped gases in roughness valleys - thus keeping the immersed surface dry. Theoretical predictions are consistent with molecular dynamics simulations and experiments.

Marine oil spills seriously endanger sea ecosystems and coastal environments, resulting in a loss of energy resources. Environmental and economic demands emphasize the need for new methods of effectively separating oil-water mixtures, while collecting oil content at the same time. A new surface-tension-driven, gravity-assisted, one-step, oil-water separation method is presented for sustained filtration and collection of oil from a floating spill. A benchtop prototype oil collection device uses selective-wettability (superhydrophobic and superoleophilic) stainless steel mesh that attracts the floating oil, simultaneously separating it from water and collecting it in a container, requiring no preseparation pumping or pouring. The collection efficiencies for oils with wide ranging kinematic viscosities (0.32-70.4 cSt at 40 °C) are above 94%, including motor oil and heavy mineral oil. The prototype device showed high stability and functionality over repeated use, and can be easily scaled for efficient cleanup of large oil spills on seawater. In addition, a brief consolidation of separation requirements for oil-water mixtures of various oil densities is presented to demonstrate the versatility of the material system developed herein.

Driven by its importance in nature and technology, droplet impact on solid surfaces has been studied for decades. To date, research on control of droplet impact outcome has focused on optimizing pre-impact parameters, e.g., droplet size and velocity. Here we follow a different, post-impact, surface engineering approach yielding controlled vectoring and morphing of droplets during and after impact. Surfaces with patterned domains of extreme wettability (high or low) are fabricated and implemented for controlling the impact process during and even after rebound--a previously neglected aspect of impact studies on non-wetting surfaces. For non-rebound cases, droplets can be morphed from spheres to complex shapes--without unwanted loss of liquid. The procedure relies on competition between surface tension and fluid inertial forces, and harnesses the naturally occurring contact-line pinning mechanisms at sharp wettability changes to create viable dry regions in the spread liquid volume. Utilizing the same forces central to morphing, we demonstrate the ability to rebound orthogonally-impacting droplets with an additional non-orthogonal velocity component. We theoretically analyze this capability and derive a We(-.25) dependence of the lateral restitution coefficient. This study offers wettability-engineered surfaces as a new approach to manipulate impacting droplet microvolumes, with ramifications for surface microfluidics and fluid-assisted templating applications.

Dropwise condensation (DWC) heat transfer depends strongly on the maximum diameter (Dmax) of condensate droplets departing from the condenser surface. This study presents a facile technique implemented to gain control of Dmax in DWC within vapor/air atmospheres. We demonstrate how this approach can enhance the corresponding heat transfer rate by harnessing the capillary forces in the removal of the condensate from the surface. We examine various hydrophilic-superhydrophilic patterns, which, respectively, sustain and combine DWC and filmwise condensation on the substrate. The material system uses laser-patterned masking and chemical etching to achieve the desired wettability contrast and does not employ any hydrophobizing agent. By applying alternating straight parallel strips of hydrophilic (contact angle ∼78°) mirror-finish aluminum and superhydrophilic regions (etched aluminum) on the condensing surface, we show that the average maximum droplet size on the less-wettable domains is nearly 42% of the width of the corresponding strips. An overall improvement in the condensate collection rate, up to 19% (as compared to the control case of DWC on mirror-finish aluminum) was achieved by using an interdigitated superhydrophilic track pattern (on the mirror-finish hydrophilic surface) inspired by the vein network of plant leaves. The bioinspired interdigitated pattern is found to outperform the straight hydrophilic-superhydrophilic pattern design, particularly under higher humidity conditions in the presence of noncondensable gases (NCG), a condition that is more challenging for maintaining sustained DWC.

Many important applications in fluid management could benefit from unidirectional transport through porous media via a simple, large-area, low-cost coating treatment; in essence, a fluid diode demonstrated herein for water using common cellulosic paper substrates. In electronics, the diode is an electrical component with asymmetric current transfer characteristics. A light (<2 g/m(2)) superhydrophobic conformal coating applied onto one side of a porous substrate is shown to create a liquid transport function analogous to the electronic diode, facilitating fluid movement in one direction under negligible penetration pressures, but opposing it in reverse up to greater pressures. The phenomenon is driven by capillary action and can be observed using any similarly-thin fluid barrier applied on only one side (i.e., wettability contrast) of an absorbent porous matrix. Diodic action and liquid transport rates are shown to be highly tunable, determined by fiber diameter and spacing, in combination with coating deposition amount. As an example, the device is used to separate an oil/water mixture, relying upon the surface tension differences of the mixture constituents, and may be implemented in multicomponent fluid filtration/separation technologies.

Surface tension driven transport of liquids on open substrates offers an enabling tool for open micro total analysis systems that are becoming increasingly popular for low-cost biomedical diagnostic devices. The present study uses a facile wettability patterning method to produce open microfluidic tracks that - due to their shape, surface texture and chemistry - are capable of transporting a wide range of liquid volumes (~1-500 μL) on-chip, overcoming viscous and other opposing forces (e.g., gravity) at the pertinent length scales. Small volumes are handled as individual droplets, while larger volumes require repeated droplet transport. The concept is developed and demonstrated with coatings based on TiO2 filler particles, which, when present in adequate (~80 wt.%) quantities within a hydrophobic fluoroacrylic polymer matrix, form composites that are intrinsically superhydrophobic. Such composite coatings become superhydrophilic upon exposure to UV light (390 nm). A commercial laser printer-based photo-masking approach is used on the coating for spatially selective wettability conversion from superhydrophobic to superhydrophilic. Carefully designed wedge-patterned surface tension confined tracks on the open-air devices move liquid on them without power input, even when acting against gravity. Simple designs of wettability patterning are used on versatile substrates (e.g., metals, polymers, paper) to demonstrate complex droplet handling tasks, e.g., merging, splitting and metered dispensing, some of which occur in 3-D geometries. Fluid transport rates of up to 350 μL s(-1) are attained. Applicability of the design on metal substrates allows these devices to be used also for other microscale engineering applications, e.g., water management in fuel cells.

We demonstrate the fabrication of free-standing polymeric nanocomposite films, which present magnetic and electrically conductive anisotropic properties. Magnetically functionalized carbon nanofibers are dispersed in a polymeric solution and, upon casting under a weak external magnetic field, are easily oriented and permanently assembled in a head-to-tail orientation in the polymer film during solvent evaporation. Magnetic and conductive property studies reveal that the resulting films have a high degree of anisotropy in both cases, thus allowing their use in functional complex devices. As a proof of concept, we demonstrate the potential application of these films as flexible THz polarizers. The detailed study shows that very high attenuation values per unit film thickness and fiber mass concentration are achieved, paving thus the way for cost-effective fabrication of substrate-free systems that have advantage over conventional devices realized so far.

We present a facile approach for the fabrication of low-cost surface biomicrofluidic devices on superhydrophobic paper created by drop-casting a fluoroacrylic copolymer onto microtextured paper. Wettability patterning is performed with a common household printer, which produces regions of varying wettability by simply controlling the intensity of ink deposited over prespecified domains. The procedure produces surfaces that are capable of selective droplet sliding and adhesion, when inclined. Using this methodology, we demonstrate the ability to tune the sliding angles of 10 μL water droplets in the range from 13° to 40° by printing lines of constant ink intensity and varied width from 0.1 mm to 2 mm. We also formulate a simple model to predict the onset of droplet sliding on printed lines of known width and wettability. Experiments demonstrate open-air surface microfluidic devices that are capable of pumpless transport, mixing and rapid droplet sampling (~0.6 μL at 50 Hz). Lastly, post treatment of printed areas with pH indicator solutions exemplifies the utility of these substrates in point-of-care diagnostics, which are needed at geographical locations where access to sophisticated testing equipment is limited or non-existent.

Low-cost, large-area, superhydrophobic coating treatments are of high value to technological applications requiring efficient liquid repellency. While many applications are envisioned, only few are realizable in practice due to either the high cost or low durability of such treatments. Recently, spray deposition of polymer-particle dispersions has been demonstrated as an excellent means for producing low-cost, large-area, durable, superhydrophobic composite coatings/films; however, such dispersions generally contain harsh or volatile solvents, which are required for solution processing of polymers as well as for dispersing hydrophobic nanoparticles, thus inhibiting scalability due to the increased cost in chemical handling and environmental safety concerns. Moreover, such coatings usually contain fluoropolymers due to their inherent low surface energy, a requirement for superhydrophobicity, but concerns over their biopersistence has provided an impetus for eliminating these chemicals. For spray coating, the former problem can be overcome by replacing organic solvents with water, but this situation seems paradoxical: Producing a highly water-repellent coating from an aqueous dispersion. We report a water-based, nonfluorinated dispersion for the formation of superhydrophobic composite coatings applied by spray on a variety of substrates. We stabilize hydrophobic components (i.e., polymer, nanoparticles) in water, by utilizing chemicals containing acid functional groups (i.e., acrylic acid) that can become ionized in aqueous environments under proper pH control (pH > 7). The functional polymer utilized in this study is a copolymer of ethylene and acrylic acid, while the particle filler is exfoliated graphite nanoplatelet (xGnP), which contains functional groups at its periphery. Once spray deposited and dried, the components become insoluble in water, thus promoting liquid repellency. Such coatings can find a wide range of applications due to their benign processing nature as well as the variety of substrates on which they can be deposited.

Carbon nanotube (CNT) membranes hold the promise of extraordinary fast water transport for applications such as energy efficient filtration and molecular level drug delivery. However, experiments and computations have reported flow rate enhancements over continuum hydrodynamics that contradict each other by orders of magnitude. We perform large scale molecular dynamics simulations emulating for the first time the micrometer thick CNTs membranes used in experiments. We find transport enhancement rates that are length dependent due to entrance and exit losses but asymptote to 2 orders of magnitude over the continuum predictions. These rates are far below those reported experimentally. The results suggest that the reported superfast water transport rates cannot be attributed to interactions of water with pristine CNTs alone.

Surface tension confined (STC) open tracks for pumpless transport of low-surface tension liquids (e.g., acetone, ethanol, hexadecane) on microfluidic chips are fabricated using a large-area, wet-processing technique. Wettable, paraffin-wax, submillimeter-wide tracks are applied by a fountain-pen procedure on superoleophobic, fluoroacrylic-carbon nanofiber (CNF) composite coatings. The fabricated anisotropic wetting patterns confine the low-surface-tension liquids onto the flow tracks, driving them with meniscus velocities up to 3.1 cm s(-1). Scaling arguments and Washburn's equation provide estimates of the liquid velocities measured in the STC tracks. These tracks are also shown to act as rails for directional sliding control of mm-sized water droplets. The present facile top-down patterned wettability approach can be extended to deposit micrometer-wide tracks, which bear promise for pumpless handling of low-surface tension liquids (e.g., aqueous solutions containing alcohols or surfactants) in lab-on-a-chip type applications or in low power, high-throughput bio-microfluidics for health care applications.

Surfaces patterned with alternating (binary) superhydrophobic-superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane-silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ∼100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie-Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications.

Ice formation can have catastrophic consequences for human activity on the ground and in the air. Here we investigate water freezing delays on untreated and coated surfaces ranging from hydrophilic to superhydrophobic and use these delays to evaluate icephobicity. Supercooled water microdroplets are inkjet-deposited and coalesce until spontaneous freezing of the accumulated mass occurs. Surfaces with nanometer-scale roughness and higher wettability display unexpectedly long freezing delays, at least 1 order of magnitude longer than typical superhydrophobic surfaces with larger hierarchical roughness and low wettability. Directly related to the main focus on heterogeneous nucleation and freezing delay of supercooled water droplets, the observed ensuing crystallization process consisted of two distinct phases: one very rapid recalescent partial solidification phase and a subsequent slower phase. Observations of the droplet collision process employed for the continuous liquid mass accumulation up to the point of ice formation reveal a previously unseen atmospheric-pressure, subfreezing-temperature regime for liquid-on-liquid bounce. On the basis of the entropy reduction of water near a solid surface, we formulate a modification to the classical heterogeneous nucleation theory, which predicts the observed freezing delay trends. Our results bring to question recent emphasis on super water-repellent surface formulations for ice formation retardation and suggest that anti-icing design must optimize the competing influences of both wettability and roughness.

This paper presents a solvent-based, mild method to prepare superhydrophobic, carbon nanofiber/PTFE-filled polymer composite coatings with high electrical conductivity and reports the first data on the effectiveness of such coatings as electromagnetic interference (EMI) shielding materials. The coatings are fabricated by spraying dispersions of carbon nanofibers and sub-micron PTFE particles in a polymer blend solution of poly(vinyledene fluoride) and poly(methyl methacrylate) on cellulosic substrates. Upon drying, coatings display static water contact angles as high as 158° (superhydrophobic) and droplet roll-off angles of 10° indicating self-cleaning ability along with high electrical conductivities (up to 309 S/m). 100 μm-thick coatings are characterized in terms of their EMI shielding effectiveness in the X-band (8.2-12.4 GHz). Results show up to 25 dB of shielding effectiveness, which changed little with frequency at a fixed composition, thus indicating the potential of these coatings for EMI shielding applications and other technologies requiring both extreme liquid repellency and high electrical conductivity., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Thermosensitive hydrogels are materials which globally shrink/swell in water when the surrounding temperature crosses the lower critical solution temperature (LCST). We demonstrate here a novel class of cross-linked polymeric materials, which do not shrink/swell in water globally, but nevertheless reveal a hydrogel-like, stimuli-responsive behavior. In particular, they demonstate a positive thermosensitive release of the embedded fluorescent dye significantly modulated when temperature crosses the LCST. Using staining with copper, transmission electron microscopy and energy dispersive X-ray analysis, we show that this effect is associated with nanogel "raisins" dispersed in such materials (e.g., polymer nanofibers). Shrinkage of individual nanogel "raisins" at elevated temperatures increases nanoporosity via increased exposure of the existing nanopores to water, or formation of new nanopores/nanocracks in the overstretched polymer matrix in the vicinity of shrinking nanogel "raisins". As a result, the release rate of the embedded dye from the nanofibers increases at elevated temperatures. We suggest that similar functional materials with embedded nanogel "raisins" will find applications in nanofluidics and as drug carriers for controlled drug release.

Super-repellent nanostructured composite coatings applied over large areas by spray and subsequent thermal treatment are reported. Solution blending of poly(vinylidene fluoride) and poly(ethyl 2-cyanoacrylate) is implemented to formulate filler particle dispersions used to apply these coatings. The wettability of these coatings is manipulated using hydrophobic poly(tetrafluoroethylene) and hydrophilic zinc oxide particle fillers or their combination. The resulting coatings feature contact angles up to 164 degrees for water and 154 degrees for a water and isopropyl alcohol mixture (9:1 weight ratio; surface tension approximately 40 mN/m). A self-cleaning ability is revealed by droplet roll-off angles below 10 degrees . The results show that the fillers affect the coating surface energy and surface roughness, in turn influencing the wettability of the coatings.

A wide array of technological applications requires localized high-rate delivery of dissolved compounds (in particular, biological ones), which can be achieved by forcing the solutions or suspensions of such compounds through nano or microtubes and their bundled assemblies. Using a water-soluble compound, the fluorescent dye Rhodamine 610 chloride, frequently used as a model drug release compound, it is shown that deposit buildup on the inner walls of the delivery channels and its adverse consequences pose a severe challenge to implementing pressure-driven long-term fluidic delivery through nano and microcapillaries, even in the case of such homogeneous solutions. Pressure-driven delivery (3-6 bar) of homogeneous dye solutions through macroscopically-long (approximately 1 cm) carbon nano and microtubes with inner diameters in the range 100 nm-1 microm and their bundled parallel assemblies is studied experimentally and theoretically. It is shown that the flow delivery gradually shifts from fast convection-dominated (unobstructed) to slow jammed convection, and ultimately to diffusion-limited transport through a porous deposit. The jamming/clogging phenomena appear to be rather generic: they were observed in a wide concentration range for two fluorescent dyes in carbon nano and microtubes, as well as in comparable transparent glass microcapillaries. The aim of the present work is to study the physics of jamming, rather than the chemical reasons for the affinity of dye molecules to the tube walls.

Cell differentiation, adhesion, and orientation are known to influence the functionality of both natural and engineered tissues, such as articular cartilage. Several attempts have been devised to regulate these important cellular behaviors, including application of inexpensive but efficient electrospinning that can produce patterned extracellular matrix (ECM) features. Electrospun and oriented polycaprolactone (PCL) scaffolds (500 or 3000 nm fiber diameter) were created, and human mesenchymal stem cells (hMSCs) were cultured on these scaffolds. Cell viability, morphology, and orientation on the fibrous scaffolds were quantitatively determined as a function of time. While the fiber-guided initial cell orientation was maintained even after 5 weeks, cells cultured in the chondrogenic media proliferated and differentiated into the chondrogenic lineage, suggesting that cell orientation is controlled by the physical cues and minimally influenced by the soluble factors. Based on assessment by the chondrogenic markers, use of the nanofibrous scaffold (500 nm) appears to enhance the chondrogenic differentiation. These findings indicate that hMSCs seeded on a controllable PCL scaffold may lead to an alternate methodology to mimic the cell and ECM organization that is found, for example, in the superficial zone of articular cartilage.

Therapeutic proteins have emerged as a significant class of pharmaceutical agents over the past several decades. The potency, rapid elimination, and systemic side effects have prompted the need of spatiotemporally controlled release for proteins maybe more than any other active therapeutic molecules. This work examines the release of two model protein compounds, bovine serum albumin (BSA) and an anti-integrin antibody (AI), from electrospun polycaprolactone (PCL) nanofiber mats. The anti-integrin antibody was chosen as a model of antibody therapy; in particular, anti-integrin antibodies are a promising class of therapeutic molecules for cancer and angiogenic diseases. The release kinetics were studied experimentally and interpreted in the framework of a recently published theory of desorption-limited drug release from nondegrading--or very slowly degrading--fibers. The results are consistent with a protein release mechanism dominated by desorption from the polymer surface, while the polycaprolactone nanofibers are not degrading at an appreciable rate.

A novel method of smoothing surfaces with nanoscale roughness is described, based on the Kelvin effect. The problem of vapor redistribution in cylindrical channels and over rough planar walls with nanoscale texture is posed and solved analytically. Vapor deposition (condensation) on the walls initially produces a deposit emulating the surface landscape. After a saturated state at the deposit surface is reached, the Kelvin effect should result in higher vapor pressure/ concentration near the convex sections of the wall and in lower vapor pressure/ concentration near the concave sections. As a result, local vapor fluxes should arise directed from the locally convex to the locally concave regions. Accordingly, the deposited layer at the wall should vaporize (or sublimate) at the convex sections due to depletion and vapor should condense at the concave sections, thus causing smoothing of physical surface unevenness. This mechanism of smoothing of nanoscale roughness has not been considered in detail or used before, even though the basic physics of the Kelvin effect is well known. In the present work, the smoothing kinetics is predicted and the characteristic timescales are calculated in the general case of axisymmetric and non-axisymmetric perturbations of the cylindrical channel walls, as well as for planar surfaces. In addition, experimental data are presented to show that the theoretically motivated approach is also practically realizable.

This work examines the release of a model water-soluble compound from electrospun polymer nanofiber assemblies. Such release attracts attention in relation to biomedical applications, such as controlled drug delivery. It is also important for stem cell attachment and differentiation on biocompatible electrospun nanofiber scaffolds containing growth factors, which have been encapsulated by means of electrospinning. Typically, the release mechanism has been attributed to solid-state diffusion of the encapsulated compound from the fibers into the surrounding aqueous bath. Under this assumption, a 100% release of the encapsulated compound is expected in a certain (long) time. The present work focuses on certain cases where complete release does not happen, which suggests that solid-state diffusion may not be the primary mechanism at play. We show that in such cases the release rate can be explained by desorption of the embedded compound from nanopores in the fibers or from the outer surface of the fibers in contact with the water bath. After release, the water-soluble compound rapidly diffuses in water, whereas the release rate is determined by the limiting desorption stage. A model system of Rhodamine 610 chloride fluorescent dye embedded in electrospun monolithic poly(methylmethacrylate) (PMMA) or poly(caprolactone) (PCL) nanofibers, in nanofibers electrospun from PMMA/PCL blends, or in core-shell PMMA/PCL nanofibers is studied. Both the experimental results and theory point at the above mentioned desorption-related mechanism, and the predicted characteristic time, release rate, and effective diffusion coefficient agree fairly well with the experimental data. A practically important outcome of this surface release mechanism is that only the compound on the fiber and pore surfaces can be released, whereas the material encapsulated in the bulk cannot be freed within the time scales characteristic of the present experiments (days to months). Consequently, in such cases, complete release is impossible. We also demonstrate how the release rate can be manipulated by the polymer content and molecular weight affecting nanoporosity and the desorption enthalpy, as well as by the nanofiber structure (monolithic fibers, fibers from polymer blends, and core-shell fibers). In particular, it is shown that, by manipulating the above parameters, release times from tens of hours to months can be attained.

The aim of this work is to demonstrate controlled flow through macroscopically long (approximately 1 cm) carbon tubes (0.5-1.8 microm in radius). A model, high-throughput, pressure-driven fluidic setup, which features a large number of parallel carbon tubes forming a bundle, is fabricated and tested. The carbon tubes are synthesized and self-assembled via co-electrospinning and subsequent carbonization. The setup accommodates pressure-driven flows with flow discharge rates of the order of 1 nL s(-1) (73 x 10(-11) kg s(-1)) for low-viscosity liquids and 30 nL s(-1) (36.3 x 10(-12) kg s(-1)) for gases into a water pool under imposed pressure drops below 4 bar. The measurements demonstrate the ability to sustain well-controlled laminar flows through these long carbon tube bundles and elucidate the main transport features. A novel procedure is also formulated to recover the flow-carrying tube inner-diameter distribution from the measured dependence of the fluid volumetric or mass flow rate on the imposed pressure drop.