Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest S of 1 151 m g) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m h bar.
Self-standing, flexible, continuous, and crack-free covalent-organic-framework membranes (COMs) are fabricated via a simple, scalable, and highly cost-effective methodology. The COMs show long-term durability, recyclability, and retain their structural integrity in water, organic solvents, and mineral acids. COMs are successfully used in challenging separation applications and recovery of valuable active pharmaceutical ingredients from organic solvents.
Covalent organic nanosheets (CONs) are a new class of porous thin two-dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene-based covalent organic framework (COF) to N-hexylmaleimide-functionalized CONs, to yield centimeter-sized free-standing thin films through layer-by-layer CON assembly at the air-water interface. The thin-layer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.
The free surface of a thin soft polymer film is often found to become unstable and self-organizes into various meso-scale structures. In this article we classify the instability of a thin polymer film into three broad categories, which are: category 1: instability of an ultra-thin (<100 nm) viscous film engendered by amplification of thermally excited surface capillary waves due to interfacial dispersive van der Waals forces; category 2: instability arising from the attractive inter-surface interactions between the free surface of a soft film exhibiting room temperature elasticity and another rigid surface in its contact proximity; and category 3: instability caused by an externally applied field such as an electric field or a thermal gradient, observed in both viscous and elastic films. We review the salient features of each instability class and highlight how characteristic length scales, feature morphologies, evolution pathways, etc. depend on initial properties such as film thickness, visco-elasticity (rheology), residual stress, and film preparation conditions. We emphasize various possible strategies for aligning and ordering of the otherwise isotropic structures by combining the essential concepts of bottom-up and top-down approaches. A perspective, including a possible future direction of research, novelty and limitations of the methods, particularly in comparison to the existing patterning techniques, is also presented for each setting.
Polyelectrolyte (PE) brushes are a special class of polymer brushes (PBs) containing charges. Polymer chains attain "brush"-like configuration when they are grafted or get localized at an interface (solid-fluid or liquid-fluid) with sufficiently close proximity between two-adjacent grafted polymer chains - such a proximity triggers a particular nature of interaction between the adjacent polymer molecules forcing them to stretch orthogonally to the grafting interface, instead of random-coil arrangement. In this review, we discuss the theory, synthesis, and applications of PE brushes. The theoretical discussion starts with the standard scaling concepts for polymer and PE brushes; following that, we shed light on the state of the art in continuum modelling approaches for polymer and PE brushes directed towards analysis beyond the scaling calculations. A special emphasis is laid in pinpointing the cases for which the PE electrostatic effects can be de-coupled from the PE entropic and excluded volume effects; such de-coupling is necessary to appropriately probe the complicated electrostatic effects arising from pH-dependent charging of the PE brushes and the use of these effects for driving liquid and ion transport at the interfaces covered with PE brushes. We also discuss the atomistic simulation approaches for polymer and PE brushes. Next we provide a detailed review of the existing approaches for the synthesis of polymer and PE brushes on interfaces, nanoparticles, and nanochannels, including mixed brushes and patterned brushes. Finally, we discuss some of the possible applications and future developments of polymer and PE brushes grafted on a variety of interfaces.
We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer-nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10-50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter approximately 3-4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3-6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where lambdaH approximately hn remains unchanged with NP concentration in regime 1 (n approximately 2) but increases in regime 2 with a change in the scaling relation (n approximately 3-3.5); (b) dynamics of instability and dewetting becomes progressively sluggish with an increase in the NP concentration; (c) there are distinct regimes of dewetting velocity at low NP concentrations; (d) force modulation AFM, as well as micro-Raman analysis, shows phase separation and aggregation of the gold nanoparticles within each dewetted polymer droplet leading to the formation of a metal core-polymer shell morphology. The polymer shell could be removed by washing in a selective solvent, thus exposing an array of bare gold nanoparticle aggregates.
The surface of a soft elastic film becomes unstable and forms a labyrinth pattern when a rigid flat plate is brought into adhesive contact, without application of any external pressure. These isotropic undulations have a characteristic wavelength, lambda approximately 3H, where H is the film thickness. We present here technique of ordering, aligning, and modulating these micro-labyrinth structures by using a patterned stamp, by varying the stamp-film inter-surface distance, by a lateral confinement of the instability and even by a simple shear motion of a flat stamp. Many complex structures, such as an array of femto-liter beakers and doubly periodic channels, are generated from a simple stamp consisting of parallel channels. The elastic nature of the patterns allows an in-situ tuning, manipulation, and reconfiguration of the microstructures. Regardless of their precise morphology, the structures continue to have the elastic length scale, lambda approximately 3H. The structures can also be made permanent as required by UV-ozone-induced oxidation of the structures. The underlying principles of the elastic contact instability presented here have the potential to develop into a new soft lithography technique-elastic contact lithography (ECL), allowing a simple, rapid and large area patterning of soft solids.
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