Yu-Jane Sheng

Transport of a liquid water and methanol mixture through carbon nanotubes under a chemical potential gradient

In this work, we report a dual-control-volume grand canonical molecular dynamics simulation study of the transport of a water and methanol mixture under a fixed concentration gradient through nanotubes of various diameters and surface chemistries. Methanol and water are selected as fluid molecules since water represents a strongly polar molecule while methanol is intermediate between nonpolar and strongly polar molecules. Carboxyl acid (-COOH) groups are anchored onto the inner wall of a carbon nanotube to alter the hydrophobic surface into a hydrophilic one. Results show that the transport of the mixture through hydrophilic tubes is faster than through hydrophobic nanotubes although the diffusion of the mixture is slower inside hydrophilic than hydrophobic pores due to a hydrogen network. Thus, the transport of the liquid mixture through the nanotubes is controlled by the pore entrance effect for which hydrogen bonding plays an important role.

Superhydrophilicity to superhydrophobicity transition of CuO nanowire films

The surface of CuO is known for its hydrophilicity and exhibits superhydrophilic nature as nanowires are present. When exposed in the air at room temperature or treated by low temperature annealing, however, transition from superhydrophilicity to superhydrophobicity of the CuO nanowire films are observed. Since the chemical structure of the films after treatment remains the same as CuO according to x-ray photoelectron spectroscopy spectra, the superhydrophobicity may be attributed to partial deoxidation of the upmost layer of CuO surfaces into Cu2O-like hydrophobic surfaces. Nonetheless, superhydrophilicity is recovered if the superhydrophobic CuO film is subject to high temperature annealing.

Hydration of "nonfouling" functional groups.

The prevention of nonspecific protein adsorption to synthetic materials and devices presents a major design challenge in the biomedical community. While some chemical groups can resist nonspecific protein adsorption from simple solutions for limited contact times, there remains a need for new nonfouling functional groups and surface coatings that prevent protein adsorption from complex media like blood or in harsh environments like seawater. Recent studies of the molecular mechanisms of nonfouling surfaces have identified a strong correlation between surface hydration and resistance to nonspecific protein adsorption. In this work, we describe a simple experimental method for evaluating the intrinsic hydration capacity of model surface coating functional groups based on the partial molal volume at infinite dilution. In order to evaluate a range of hydration capacity and nonfouling performance, solutes were selected from three classes: ethylene glycols, sugar alcohols, and glycine analogues. The number of hydrating water molecules bound to a solute was estimated by comparing the molecular volume at infinite dilution to the solute van der Waals molecular volume. The number of water molecules associated with each solute was further validated by constant pressure and temperature molecular dynamics simulations. Finally, a size-normalized molecular volume was correlated to previously observed protein adsorption experiments to relate the intrinsic hydration capacity of functional groups to their known nonfouling abilities.

Morphologies of multicompartment micelles formed by triblock copolymers

Multicompartment micelles are desirable for advanced applications such as drug delivery. Recently, core-shell-corona (CSC) and segmented-worm (SW) micelles formed by ABC triblock terpolymers with three mutually immiscible blocks are observed in experiments. We have performed dissipative particle dynamics simulations to study the effects of molecular architecture, block length, and solution concentration on the morphologies of ABC triblock terpolymers. The formation of CSC and SW micelles for linear and miktoarm star ABC terpolymers is confirmed in this work. In addition, we predict that different multicompartment micellar morphologies (e.g., incomplete skin-layered micelles and segmented worms) can be formed by linear copolymer with different arrangements of the three blocks.

High contact angle hysteresis of superhydrophobic surfaces: Hydrophobic defects

A typical superhydrophobic surface is essentially nonadhesive and exhibits very low water contact angle (CA) hysteresis, so-called Lotus effect. However, leaves of some plants such as scallion and garlic with an advancing angle exceeding 150° show very serious CA hysteresis. Although surface roughness and epicuticular wax can explain the very high advancing CA, our analysis indicates that the unusual hydrophobic defect, diallyl disulfide, is the key element responsible for contact line pinning on allium leaves. After smearing diallyl disulfide on an extended polytetrafluoroethylene (PTFE) film, which is originally absent of CA hysteresis, the surface remains superhydrophobic but becomes highly adhesive.

Evaporation Stains: Suppressing the Coffee-Ring Effect by Contact Angle Hysteresis

A ring-shaped stain is frequently left on a substrate by a drying drop containing colloids as a result of contact line pinning and outward flow. In this work, however, different patterns are observed for drying drops containing small solutes or polymers on various hydrophilic substrates. Depending on the surface activity of solutes and the contact angle hysteresis (CAH) of substrates, the pattern of the evaporation stain varies, including a concentrated stain, a ringlike deposit, and a combined structure. For small surface-inactive solutes, the concentrated stain is formed on substrates with weak CAH, for example, copper sulfate solution on silica glass. On the contrary, a ringlike deposit is developed on substrates with strong CAH, for example, a copper sulfate solution on graphite. For surface-active solutes, however, the wetting property can be significantly altered and the ringlike stain is always visible, for example, Brij-35 solution on polycarbonate. For a mixture of surface-active and surface-inactive solutes, a combined pattern of a ringlike and concentrated stain can appear. For various polymer solutions on polycarbonate, similar results are observed. Concentrated stains are formed for weak CAH such as sodium polysulfonate, and ring-shaped patterns are developed for strong CAH such as poly(vinyl pyrrolidone). The stain pattern is actually determined by the competition between the time scales associated with contact line retreat and solute precipitation. The suppression of the coffee-ring effect can thus be acquired by the control of CAH.

Effects of geometrical characteristics of surface roughness on droplet wetting

Surface roughness is known to alter the wettability on a solid substrate. In general, either Wenzel or Cassie-Baxter theory is adopted to describe the apparent contact angle. Following the minimum free energy pathway associated with the imbibition process, we have derived a generalized expression for the apparent contact angle on a textured surface and the liquid-gas contact area within the groove that plays a key role. Depending on the geometrical characteristics of the grooves, the surface wetting falls into three regimes: (i) single stable state which is either Wenzel (completely wetted roughness) or Cassie-Baxter (completely nonwetted roughness) state, (ii) two stable states (Wenzel and Cassie-Baxter) separated by an energy barrier, and (iii) single stable state with partially wetted roughness. The sufficient condition for each regime is derived and several groove geometries are given to show the free energy path. Alteration in the geometric parameters may lead to the wetting crossover. We also show that the Cassie-Baxter can occur at a hydrophilic surface for particular pore shapes.

Superiority of Branched Side Chains in Spontaneous Nanowire Formation: Exemplified by Poly(3-2-methylbutylthiophene) for High-Performance Solar Cells

One-dimensional nanostructures containing heterojunctions by conjugated polymers, such as nanowires, are expected to greatly facilitate efficient charge transfer in bulk-heterojunction (BHJ) solar cells. Thus, a combined theoretical and experimental approach is pursued to explore spontaneous nanowire formation. A dissipative particle dynamics simulation is first performed to study the morphologies formed by rodlike polymers with various side-chain structures. The results surprisingly predict that conjugated polymers with branched side chains are well suited to form thermodynamically stable nanowires. Proof of this concept is provided via the design and synthesis of a branched polymer of regioregular poly(3-2-methylbutylthiophene) (P3MBT), which successfully demonstrates highly dense nanowire formation free from any stringent conditions and stratagies. In BHJ solar cells fabricated using a blend of P3MBT and [6,6]-phenyl-C71-butyric acid methyl ester (PC(71) BM), P3MBT polymers are self-organized into highly crystalline nanowires with a d(100) spacing of 13.30 Å. The hole mobility of the P3MBT:PC(71) BM (1:0.5 by weight) blend film reaches 3.83 × 10(-4) cm(2) V(-1) s(-1) , and the maximum incident photon-to-current efficiency reaches 68%. The results unambiguously prove the spontaneous formation of nanowires using solution-processable conjugated polymers with branched alkyl side chains in BHJ solar cells.

Anomalous Contact Angle Hysteresis of a Captive Bubble: Advancing Contact Line Pinning

Contact angle hysteresis of a sessile drop on a substrate consists of continuous invasion of liquid phase with the advancing angle (θ(a)) and contact line pinning of liquid phase retreat until the receding angle (θ(r)) is reached. Receding pinning is generally attributed to localized defects that are more wettable than the rest of the surface. However, the defect model cannot explain advancing pinning of liquid phase invasion driven by a deflating bubble and continuous retreat of liquid phase driven by the inflating bubble. A simple thermodynamic model based on adhesion hysteresis is proposed to explain anomalous contact angle hysteresis of a captive bubble quantitatively. The adhesion model involves two solid–liquid interfacial tensions (γ(sl) > γ(sl)′). Young’s equation with γ(sl) gives the advancing angle θ(a) while that with γ(sl)′ due to surface rearrangement yields the receding angle θ(r). Our analytical analysis indicates that contact line pinning represents frustration in surface free energy, and the equilibrium shape corresponds to a nondifferential minimum instead of a local minimum. On the basis of our thermodynamic model, Surface Evolver simulations are performed to reproduce both advancing and receding behavior associated with a captive bubble on the acrylic glass.

Size-Dependent Properties of Small Unilamellar Vesicles Formed by Model Lipids

The size-dependent behavior of small unilamellar vesicles is explored by dissipative particle dynamics, including the membrane characteristics and mechanical properties. The spontaneously formed vesicles are in the metastable state and the vesicle size is controlled by the concentration of model lipids. As the vesicle size decreases, the bilayer gets thinner and the area density of heads declines. Nonetheless, the area density in the inner leaflet is higher than that in the outer. The packing parameters are calculated for both leaflets. The result indicates that the shape of lipid in the outer leaflet is like a truncated cone but that in the inner leaflet resembles an inverted truncated cone. Based on a local order parameter, our simulations indication that the orientation order of lipid molecules decreases as the size of the vesicle reduces and this fact reveals that the bilayer becoming thinner for smaller vesicle is mainly attributed to the orientation disorder of the lipids. The membrane tension can be obtained through the Young-Laplace equation. The tension is found to grow with reducing vesicle size. Therefore, small vesicles are less stable against fusion. Using the inflation method, the area stretching and bending moduli can be determined and those moduli are found to grow with reducing size. Nonetheless, a general equation with a single numerical constant can relate bending modulus, area stretching modulus, and bilayer thickness irrespective of the vesicle size. Finally, a simple metastable model is proposed to explain the size-dependent behavior of bilayer thickness, orientation, and tension.