Wetting-dewetting Transition Research Articles

PH and potential-controlled multi-modal mass transport in block copolymer nanochannel membranes

Inspired by the hydrophobic gating for achieving fast and selective ion/molecular transport in cell membranes, wetting/dewetting transition in solid-state nanopores controlled by external stimuli such as voltage, pH, electrostatics, and light have attracted increasing attention. For an accurate and better understanding, a single nanopore or low-density array of nanopores was preferred to investigate the wetting and dewetting transitions owing to their well-defined chemical functions and physical structures. However, high-density nanochannel membranes capable of processing high-throughput and multi-modal mass transport are more beneficial with the aim of practical use. In this regard, pH- and potential-responsive nanochannel membranes consisting of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) are prepared to demonstrate a multi-modal transport system with high-throughput capability. At pH < pKa(P4VP) (pKa ∼ 4.8), the cylindrical P4VP nanodomains are hydrophilic and positively charged, acting as an anion-exchange membrane. In contrast, at pH > pKa(P4VP), the P4VP domains switch to be charge-neutral and hydrophobic, naturally blocking the mass transport through the nanochannels. Applying a sufficiently positive potential to a BCP membrane-coated electrode may induce oxidative wetting in the hydrophobic nanochannels to facilitate mass transport across the membrane with no charge-selectivity. Releasing the bias makes the hydrophobic nanochannel membranes retrieve the original dewetted state, blocking the transport again. In addition, direct observation of the wetting-dewetting transition dynamics in the hydrophobic nanochannels is investigated by monitoring potential-correlated electrochemiluminescence (ECL) signals arising from Ru(bpy)32+ and co-reactant tripropylamine (TPA) under potential modulations. ECL signals tend to decrease with increasing membrane thickness ranging from 0 nm to 820 nm because it requires higher potentials to induce wetting in the nanochannels due to elongated hydrophobic nanochannels. The multi-modal transport system developed in the present work will be useful for applications such as water treatment, biosensors, and smart valve systems like controlled drug release/delivery.

Mechanism of hydrophobic gating in the acetylcholine receptor channel pore.

Neuromuscular acetylcholine receptors (AChRs) are hetero-pentameric, ligand-gated ion channels. The binding of the neurotransmitter acetylcholine (ACh) to two target sites promotes a global conformational change of the receptor that opens the channel and allows ion conduction through the channel pore. Here, by measuring free-energy changes from single-channel current recordings and using molecular dynamics simulations, we elucidate how a constricted hydrophobic region acts as a "gate" to regulate the channel opening in the pore of AChRs. Mutations of gate residues, including those implicated in congenital myasthenia syndrome, lower the permeation barrier of the channel substantially and increase the unliganded gating equilibrium constant (constitutive channel openings). Correlations between hydrophobicity and the observed free-energy changes, supported by calculations of water densities in the wild-type versus mutant channel pores, provide evidence for hydrophobic wetting-dewetting transition at the gate. The analysis of a coupled interaction network provides insight into the molecular mechanism of closed- versus open-state conformational changes at the gate. Studies of the transition state by "phi"(φ)-value analysis indicate that agonist binding serves to stabilize both the transition and the open state. Intersubunit interaction energy measurements and molecular dynamics simulations suggest that channel opening involves tilting of the pore-lining M2 helices, asymmetric outward rotation of amino acid side chains, and wetting transition of the gate region that lowers the barrier to ion permeation and stabilizes the channel open conformation. Our work provides new insight into the hydrophobic gate opening and shows why the gate mutations result in constitutive AChR channel activity.

What Can Probing Liquid-Air Menisci Inside Nanopores Teach Us About Macroscopic Wetting Phenomena?

Solid surfaces with excellent nonwetting ability have drawn significant interest from interfacial scientists and engineers. While much effort was devoted to investigating macroscopic wetting phenomena on nonwetting surfaces, the otherwise microscopic wetting has received less attention, and the surface/interface properties at the microscopic scale are not well resolved and correlated with the macroscopic wetting behavior. Herein, we first characterize the nanoscopic morphology and effective stiffness of liquid-air interfaces inside nanopores (nanomenisci) on diverse nonwetting nanoporous surfaces underneath water droplets using atomic force microscopy. Detailed three-dimensional imaging of the droplet-surface contact region reveals that water only slightly penetrates into the nanopores, allowing for quantitative prediction of the macroscopic contact angle using the Cassie-Baxter model. By gradually increasing the scanning force, we observe incrementally wetting of nanopores by water, and dewetting occurs when the force is lowered again, exhibiting reversible wetting-dewetting transitions. Further, nanoindentation measurements demonstrate that the nanomenisci show apparent elastic deformation and size-dependent effective stiffness at small indenting forces. Finally, we correlate the effective stiffness of the nanomenisci with the transition from complete rebound to partial rebound for impinging droplets on nanoporous surfaces. Our study suggests that probing the physical properties of the liquid-air menisci at the nanoscale is essential to rationalize macroscopic static and dynamic wetting phenomena on structured surfaces.

Fingering instability in spreading epithelial monolayers: roles of cell polarisation, substrate friction and contractile stresses.

Collective cell migration plays a crucial role in many developmental processes that underlie morphogenesis, wound healing, or cancer progression. In such coordinated behaviours, cells are organised in coherent structures and actively migrate to serve different biological purposes. In some contexts, namely during epithelial wound healing, it is well known that a migrating free-edge monolayer develops finger-like instabilities, yet the onset is still under debate. Here, by means of theory and numerical simulations, we shed light on the main mechanisms driving the instability process, analysing the linear and nonlinear dynamics of a continuum compressible polar fluid. In particular, we assess the role of cell polarisation, substrate friction, and contractile stresses. Linear theory shows that it is crucial to analyse the perturbation transient dynamics, since we unravel a plethora of crossovers between different exponential growth rates during the linear regime. Numerical simulations suggest that cell-substrate friction could be the mechanism responsible for the formation of complex finger-like structures at the edge, since it triggers secondary fingering instabilities and tip-splitting phenomena. Finally, we obtain a critical contractile stress that depends on cell-substrate friction and the initial-to-nematic length ratio, characterising an active wetting-dewetting transition. In the dewetting scenario, the monolayer retracts and becomes stable without developing finger-like structures.

A Novel Method to Measure the Effective Change of the Interfacial Energy due to Kinetic Self-Assembly of Amyloid Fibrils.

Adsorbates growing a self-assembled layer on a solid-liquid interface can significantly change the effective interfacial energy at the solid surface. However, measuring the changes in the effective surface energy while these adsorbates accumulate is challenging, as static contact angle measurements can be affected by the motion and accumulation of these adsorbates at the droplet's boundary (coffee stain effects). In this report, we utilize a novel method that takes advantage of spin-induced dewetting to measure the change in the effective surface energy as the self-assembly progresses. We use a previously well-studied model system of self-assembled fibrils of amyloid-β (Aβ) peptides on the mica substrate to demonstrate the feasibility of this method. Using variations of terminal spin speeds and acceleration rates, we measure the terminal spin speed at which a wetting-dewetting transition (WDT) occurs on a surface that hosts self-assembled Aβ12-28 fibrils. By comparing this speed with the WDT speed on the bare mica substrate, we can quantify the spreading coefficient and thus the effective change of the substrate's interfacial energy due to the adsorption of mobile peptides at various stages of the self-assembly. These measurements show that the surface becomes more hydrophilic as the self-assembly progresses and thus can explain previous observations that the self-assembly of this particular peptide system is self-limiting and stops before full surface coverage.

Porous organic cages embedded in a lipid membrane for water desalination: A molecular simulation study

We report a molecular simulation study on porous organic cages (POCs) embedded in a lipid membrane for water desalination by reverse osmosis (RO). Four types of POC channels are examined namely straight, tilted, tilted with 3-openings and crystalline. The flow rates of water are found to increase in the order of tilted < straight < 3-opening < crystalline channel. With 3D interconnected morphology, the crystalline channel possesses the highest flow rate about 6.86 water molecules per ns. Both Na+ and Cl− ions cannot pass through the four channels with 100% salt rejection. The activation energy for water flow through the POC channels is approximately 12 – 13 kJ/mol, much lower than 22 – 26 kJ/mol through aromatic polyamide membranes. Due to confinement effect, the number of hydrogen bonds formed by water molecules in the channels is lower than in bulk water. Wetting-dewetting transition is observed in the straight, tilted and 3-opening channels, but not in the crystalline channel. This work highlights the important role of channel alignment, opening and morphology in water flow, and provides microscopic understanding of water structure and dynamics in the POC channels.

Inorganic Surface Coating with Fast Wetting-Dewetting Transitions for Liquid Manipulations.

Liquid manipulation is a fundamental issue for microfluidics and miniaturized sensors. Fast wetting-state transitions by optical methods have proven being efficient for liquid manipulations by organic surface coatings, however rarely been achieved by using inorganic coatings. Here, we report a fast optical-induced wetting-state transition surface achieved by inorganic coating, enabling tens of second transitions for a wetting-dewetting cycle, shortened from an hour, as typically reported. Here, we demonstrate a gravity-driven microfluidic reactor and switch it to a mixer after a second-step exposure in a minimum of within 80 s of UV exposure. The fast wetting-dewetting transition surfaces enable the fast switchable or erasable smart surfaces for water collection, miniature chemical reaction, or sensing systems by using inorganic surface coatings.

Humidity-Responsive Single-Nanoparticle-Layer Plasmonic Films.

2D materials possess many interesting properties, and have shown great application potentials. In this work, the development of humidity-responsive, 2D plasmonic nanostructures with switchable chromogenic properties upon wetting-dewetting transitions is reported. By exploiting DNA hybridization-directed anchoring of gold nanoparticles (AuNPs) on substrates, a series of single-nanoparticle-layer (SNL) plasmonic films is fabricated. Due to the collective plasmonic responses in SNL, these ultrathin 2D films display rapid and reversible red-blue color change upon the wetting-dewetting transition, suggesting that hydration-induced microscopic plasmonic coupling between AuNPs is replicated in the macroscopic, centimeter-scale films. It is also found that hydration finely tunes the electric field distribution between AuNPs in the SNL film, based on which responsive surface-enhanced Raman scattering substrates with spatially homogeneous hot spots are developed. Thus it is expected that DNA-mediated 2D SNL structures open new avenues for designing miniaturized plasmonic nanodevices with various applications.

Dewetting and spreading transitions for active matter on random pinning substrates.

We show that sterically interacting self-propelled disks in the presence of random pinning substrates exhibit transitions among a variety of different states. In particular, from a phase separated cluster state, the disks can spread out and homogeneously cover the substrate in what can be viewed as an example of an active matter wetting transition. We map the location of this transition as a function of activity, disk density, and substrate strength, and we also identify other phases including a cluster state, coexistence between a cluster and a labyrinth wetted phase, and a pinned liquid. Convenient measures of these phases include the cluster size, which dips at the wetting-dewetting transition, and the fraction of sixfold coordinated particles, which drops when dewetting occurs.

Stability of Polymer Grafted Nanoparticle Monolayers: Impact of Architecture and Polymer-Substrate Interactions on Dewetting.

The stability of polymer thin films is crucial to a broad range of technologies, including sensors, energy storage, filtration, and lithography. Recently, the demonstration of rapid deposition on solid substrates of ordered monolayers of polymer grafted nanoparticles (PGN) has increased potential for inks to additively manufacture such components. Herein, enhanced stability against dewetting of these self-assembled PGN films (gold nanoparticle functionalized with polystyrene (AuNP-PS)) is discussed in context to linear polystyrene (PS) analogues using high throughput surface gradients: surface energy (20-45 mN/m) and temperature (90-160 °C). PGNs exhibit a lower surface (γp) and interfacial (γsp) energy relative to linear polymers, which results in increased thermal and energetic stability by 10-25 °C and 5-15 mN/m, respectively. This enhanced wetting-dewetting transition is qualitatively consistent with the behavior of star macromolecules and depends on the architecture of the polymer canopy. Increased film stability through canopy architecture expands the manufacturability of thin film hybrids and refines postprocessing conditions to maximize local PGN order.

A fast and effective approach for reversible wetting-dewetting transitions on ZnO nanowires.

Here, we demonstrate a facile approach for the preparation of ZnO nanowires (NWs) with tunable surface wettability that can be manipulated reversibly in a controlled manner from a superhydrophilic state to a superhydrophobic state. The as-synthesized ZnO NWs obtained by a chemical vapor deposition method are superhydrophilic with a contact angle (CA) value of ~0°. After H2 gas annealing at 300 °C for 90 minutes, ZnO NWs display superhydrophobic behavior with a roll-off angle less than 5°. However, O2 gas annealing converts these superhydrophobic ZnO NWs into a superhydrophilic state. For switching from superhydrophobic to superhydrophilic state and vice versa in cyclic manner, H2 and O2 gas annealing treatment was used, respectively. A model based on density functional theory indicates that the oxygen-related defects are responsible for CA switching. The water resistant properties of the ZnO NWs coating is found to be durable and can be applied to a variety of substrates including glass, metals, semiconductors, paper and even flexible polymers.

Highly Permeable Artificial Water Channels that Self-Assemble into Two-Dimensional Arrays

Artificial nanoscale water channels are the future of cheap, low-power water filtration and desalinization. Biological water channels such as the aquaporin membrane protein selectively pass water across the cell membranes of living creatures, but are prohibitively difficult to incorporate into large-scale technological applications. In response to these challenges, many artificial channels have been designed to imitate the function of aquaporins, including a new single-molecule water channel we introduce here, peptide-appended pillar[5]arene (PAP). PAP is comprised of a single benzyl ring decorated by hydrophobic phenylalanine amino acid arms. Stopped-flow light scattering measurements combined with fluorescence correlation spectroscopy accurately characterized single channel PAP permeability as near to that of aquaporin itself, orders of magnitude better than first-generation artificial water channels. Molecular dynamics simulation supported this assessment and further predicted wetting-dewetting transitions to occur in individual PAP channels on the nanosecond timescale. Molecular dynamics simulation also predicted PAP self-assembly into two-dimentional arrays of lattice size 21 Å, driven by hydrogen bonds among the channel's peptide arms. Aggregation and lattice size were verified to within 1 Å by cryo-electron microscopy. The self-assembly of individual, highly permeable water channels into densely packed two-dimensional arrays can be potentially utilized to design a new generation of high-flux water filtration membranes. Furthermore, as the phenylalanine arms of PAP can be switched out for other amino acids, the individual channels and their self-assembly can be programmed to enable selective transmembrane transport.

Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability.

The stability or wettability of thin polymer films on solids is of vital interest in traditional technologies as well as in new emerging nanotechnologies. We report here that nanoscale structures of polymer chains adsorbed onto a solid surface play a crucial role in the thermal stability of the film. In this study, polystyrene (PS) spin-cast films (20 nm in thickness) with eight different molecular weights prepared on silicon (Si) substrates were used as a model. When low molecular weight (Mw≤ 50 kDa) PS films were subjected to thermal annealing at temperatures far above the bulk glass transition temperature, dewetting occurred promptly, while high molecular weight (Mw≥ 123 kDa) PS films were stable for at least 6 weeks at 150 °C. We reveal a strong correlation between the film stability and the two different interfacial structures of the adsorbed polymer chains: their opposing wettability against chemically identical free polymer chains results in a wetting-dewetting transition at the adsorbed polymer-free polymer interface. This is a unique aspect of the stability of polymer thin films and may be generalizable to other polymer systems regardless of the magnitude of solid-polymer attractive interactions.

Wetting-Dewetting and Dispersion-Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix.

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

Dynamics of the wetting-induced nanowire reconstruction of Au/Ge(001)

We have used low-energy electron microscopy and scanning tunneling microscopy to visualize the dynamics of the formation of one-dimensional Au-induced nanowires on a Ge(001) substrate. At low temperature, the growth of nanowire domains is limited by the diffusion of Au. A wetting-dewetting transition occurs at a temperature of 665 K that transforms nanowire domains into three-dimensional Au clusters. Dewetting occurs at temperatures above 665 K and is fully reversible during repetitive heating and cooling cycles. The decay and growth rates of the nanowire domains below 665 K show intriguing dynamics, caused by the complex diffusion of gold. It correlates directly with the diffracted intensity of a reconstruction along the top of the nanowires, indicating a temperature-dependent potential landscape for the thermally activated diffusion of Au atoms across nanowire domains.

Role of wetting and nanoscale roughness on thermal conductance at liquid-solid interface

Using non-equilibrium molecular dynamics simulations in which a temperature gradient is imposed, we determine the thermal resistance of a model liquid-solid interface with and without nanoscale roughness. Our simulations reveal that in both cases the key factor controlling interfacial thermal conductance is the strength of the bonding between liquid and solid atoms. In addition, we show that in the case of rough surfaces, the nanoscopic wetting-dewetting transition has a strong signature in the interfacial thermal conductance. Interestingly, the smooth and rough interfaces, despite distinct geometry, show quantitatively the same dependence of the interfacial conductance on the value of the interfacial adhesion.

In situ atomic force microscopy studies of reversible light-induced switching of surface roughness and adhesion in azobenzene-containing PMMA films

Thin films in the range 40–80 nm of a blend of PMMA with an azobenzene derivative have been studied directly during UV and blue light irradiation by atomic force microscopy (AFM), revealing highly reversible changes in the surface roughness and the film adhesion. UV light induces an ≈80% increase in surface roughness, whereas illumination by blue light completely reverses these changes. Based on the observed surface topography and transition kinetics a reversible mass flow mechanisms is suggested, where the polarity changes upon switching trigger a wetting-dewetting transition in a surface segregation layer of the chromophore. Similar AFM measurements of the pull-off force indicate a decrease upon UV and an increase after blue light illumination with a complex kinetic behavior: a rapid initial change, attributed to the change in the cis isomer fraction of the azobenzene derivative, and a more gradual change, indicative of slow structural reorganization.

Surface Roughness-Hydrophobicity Coupling in Microchannel and Nanochannel Flows

An approach based on a lattice version of the Boltzmann kinetic equation for describing multiphase flows in nano- and microcorrugated devices is proposed. We specialize it to describe the wetting-dewetting transition of fluids in the presence of nanoscopic grooves etched on the boundaries. This approach permits us to retain the essential supramolecular details of fluid-solid interactions without surrendering--actually boosting--the computational efficiency of continuum methods. The method is used to analyze the importance of conspiring effects between hydrophobicity and roughness on the global mass flow rate of the microchannel. In particular we show that smart surfaces can be tailored to yield very different mass throughput by changing the bulk pressure. The mesoscopic method is also validated quantitatively against the molecular dynamics results of [Cottin-Bizonne, Nat. Mater. 2, 237 (2003)].

The wetting-dewetting transition of monolayer water on a hydrophobic metal surface observed by surface-state resonant second-harmonic generation

The isothermal adsorption and desorption of monolayer water on a Ag(110) surface in the temperature range of 130-137 K were characterized by monitoring second-harmonic (SH) generation from the silver surface. The SH intensity resonantly enhanced by the silver surface-state transition is highly sensitive to the amount of silver surface area covered by water and allows the observation of an abrupt change in the adsorption/desorption behavior at 133.5 K. At temperatures below 133.5 K water wets the Ag surface in a two-dimensional structure with a measured desorption energy of 25.0 (+/-3.3) kJ/mol. At temperatures greater than 133.5 K water desorbs from three-dimensional clusters with a measured desorption energy of 48.3 (+/-2.2) kJ/mol, in agreement with temperature-programmed desorption measurements. This wetting-dewetting transition of water adsorbed on the silver surface at 133.5 K is supported by classical nucleation theory calculations.