The use of natural compounds for preparing hybrid molecular films-such as surface coatings made from metal-phenolic networks (MPNs)-is of interest in areas ranging from catalysis and separations to biomedicine. However, to date, the film growth of MPNs has been observed to proceed in discrete steps (≈10 nm per step) where the coordination-driven interfacial assembly ceases beyond a finite time (≈1 min). Here, it is demonstrated that the assembly process for MPNs can be modulated from discrete to continuous by utilizing solid-state reactants (i.e., rusted iron objects). Gallic acid etches iron from rust and produces chelate complexes in solution that continuously assemble at the interface of solid substrates dispersed in the system. The result is stable, continuous growth of MPN films. The presented double dynamic process-that is, etching and self-assembly-provides new insights into the chemistry of MPN assembly while enabling control over the MPN film thickness by simply varying the reaction time.
Surface patterning of liquid metals (LMs) is a key processing step for LM‐based functional systems. Current patterning methods are substrate specific and largely suffer from undesired imperfections—restricting their widespread applications. Inspired by the universal catechol adhesion chemistry observed in nature, LM inks stabilized by the assembly of a naturally abundant polyphenol, tannic acid, has been developed. The intrinsic adhesive properties of tannic acid containing multiple catechol/gallol groups, allow the inks to be applied to a variety of substrates ranging from flexible to rigid, metallic to plastics and flat to curved, even using a ballpoint pen. This method can be further extended from hand‐written texts to complex conductive patterns using an automated setup. In addition, capacitive touch and hazardous heavy metal ion sensors have been patterned, leveraging from the synergistic combination of polyphenols and LMs. Overall, this strategy provides a unique platform to manipulate LMs from hand‐written pattern to complex designs onto the substrate of choice, that has remained challenging to achieve otherwise.
Hysteresis of wetting, like the Coulombic friction at solid/solid interface, impedes the motion of a liquid drop on a surface when subjected to an external field. Here, we present a counterintuitive example, where some amount of hysteresis enables a drop to move on a surface when it is subjected to a periodic but asymmetric vibration. Experiments show that a surface either with a negligible or high hysteresis is not conducive to any drop motion. Some finite hysteresis of contact angle is needed to break the periodic symmetry of the forcing function for the drift to occur. These experimental results are consistent with simulations, in which a drop is approximated as a linear harmonic oscillator. The experiment also sheds light on the effect of the drop size on flow reversal, where drops of different sizes move in opposite directions due to the difference in the phase of the oscillation of their center of mass.
Particle‐based pulmonary delivery has great potential for delivering inhalable therapeutics for local or systemic applications. The design of particles with enhanced aerodynamic properties can improve lung distribution and deposition, and hence the efficacy of encapsulated inhaled drugs. This study describes the nanoengineering and nebulization of metal–phenolic capsules as pulmonary carriers of small molecule drugs and macromolecular drugs in lung cell lines, a human lung model, and mice. Tuning the aerodynamic diameter by increasing the capsule shell thickness (from ≈100 to 200 nm in increments of ≈50 nm) through repeated film deposition on a sacrificial template allows precise control of capsule deposition in a human lung model, corresponding to a shift from the alveolar region to the bronchi as aerodynamic diameter increases. The capsules are biocompatible and biodegradable, as assessed following intratracheal administration in mice, showing >85% of the capsules in the lung after 20 h, but <4% remaining after 30 days without causing lung inflammation or toxicity. Single‐cell analysis from lung digests using mass cytometry shows association primarily with alveolar macrophages, with >90% of capsules remaining nonassociated with cells. The amenability to nebulization, capacity for loading, tunable aerodynamic properties, high biocompatibility, and biodegradability make these capsules attractive for controlled pulmonary delivery.
We study the stochastic motion of a small solid block or a small water drop on a flat solid support in the presence of an external noise and a bias. The bias is caused either by inclining the plane of the support, as is the case with the solid block, or by creating a gradient of wettability, as is the case with a water drop. Both the solid block and the water drop exhibit drifted Brownian-like motion. There are, however, differences between the motion described here and that of a classical drifted Brownian motion, in that the Coulombic friction (for solid on solid) or wetting hysteresis (for water drops on a solid) accounts for a significant resistance to motion in addition to the kinematic friction. Although the displacement distribution here is non-Gaussian, the variance of the distribution increases with time, indicating that the overall motion follows simple diffusion. The diffusivity and the mobility of the solid object are considerably lower than the values expected when the diffusion is governed by only kinematic friction. The experimental diffusivity increases with the power of the noise with an exponent of 1.61, which is close to that (1.74) of an analysis based on the Langevin equation when the Coulombic friction is taken into account in addition to the kinematic friction. The ratio of diffusivity and mobility increases slightly sublinearly with the power of the noise with an exponent of about 0.8. The experimentally observed relaxation time of the process is, however, considerably smaller than the Langevin relaxation time. When the experimental ratio of diffusivity and mobility is taken into account in the distribution function of the displacement, the later quantity becomes amenable to an analysis that is similar to the conventional fluctuation relations.
It is well known that a liquid drop with a low contact angle (approximately 45 degrees ) and low wetting hysteresis moves toward the colder region of a temperature gradient substrate as a result of the thermal Marangoni force. A moderately sized water drop, however, usually does not move on such a surface because of the overwhelming effect of hysteresis. The water drop can, however, be forced to move when it is vibrated on a temperature gradient surface with its velocity exhibiting maxima at the respective Rayleigh frequencies. A simple model is presented that captures the dependence of drop velocity on hysteresis, vibration amplitude, and the forcing and resonance frequencies of vibration.
The synthesis of hybrid functional materials using the coordination-driven assembly of metal-phenolic networks (MPNs) is of interest in diverse areas of materials science. To date, MPN assembly has been explored as monoligand systems (i.e., containing a single type of phenolic ligand) where the phenolic components are primarily obtained from natural sources via extraction, isolation, and purification processes. Herein, we demonstrate the fabrication of MPNs from a readily available, crude phenolic source-green tea (GT) infusions. We employ our recently introduced rust-mediated continuous assembly strategy to prepare these GT MPN systems. The resulting hollow MPN capsules contain multiple phenolic ligands and have a shell thickness that can be controlled through the reaction time. These multiligand MPN systems have different properties compared to the analogous MPN systems reported previously. For example, the Young's modulus (as determined using colloidal-probe atomic force microscopy) of the GT MPN system presented herein is less than half that of MPN systems prepared using tannic acid and iron salt solutions, and the disassembly kinetics are faster (∼50%) than other, comparable MPN systems under identical disassembly conditions. Additionally, the use of rust-mediated assembly enables the formation of stable capsules under conditions where the conventional approach (i.e., using iron salt solutions) results in colloidally unstable dispersions. These differences highlight how the choice of phenolic ligand and its source, as well as the assembly protocol (e.g., using solution-based or solid-state iron sources), can be used to tune the properties of MPNs. The strategy presented herein expands the toolbox of MPN assembly while also providing new insights into the nature and robustness of metal-phenolic interfacial assembly when using solution-based or solid-state metal sources.
Relaxation of the three phase contact line of a sessile drop of water on a low energy surface is studied by subjecting it to a white noise vibration. While a spring force acts on the contact line whenever the contact angle deviates from its equilibrium value, it is opposed by hysteresis. The drop, therefore, remains pinned at a metastable state. With an appropriate amount of vibration, the drop can reach a global equilibrium state irrespective of its initial state, be it advanced or retreated. While the end state is free of hysteresis, the current study sheds light on the dynamics of relaxation that is analyzed in conjunction with a modified Langevin equation. Instead of exhibiting a smooth relaxation as predicted by the Langevin equation with a smooth background potential, stepwise relaxation is observed in most cases. These stepwise relaxations can be explained if the background potential is made slightly corrugated that signifies the existence of metastable states of a drop on a surface. The fluctuation of the displacement of the contact line is highly non-Gaussian. It is shown that an exponential distribution of the displacement fluctuation arises due to the nonlinear hysteresis term in the Langevin equation. The observations of stick-slip motion, the large time of relaxation, and the anomalous displacement fluctuation suggest that hysteresis is present during the relaxation process of the drop even though the final state reached by the drop is free of hysteresis. Finally, we compare the displacement fluctuations of the contact line on two different surfaces: a silicone rubber and a fluorocarbon monolayer. Although the displacement fluctuation is exponential in both cases, the later surface exhibits a greater variance of the distribution than the former plausibly due to differences in hysteresis. This result indicates that the fluctuation of displacement may be used as a tool to study the surface property of a low energy substrate.
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