While nature has optimized its antifouling strategies over millions of years, synthetic antifouling coatings have not yet reached technological maturity. For an antifouling coating to become technically feasible, it should fulfill many requirements: high effectiveness, long‐term stability, durability, ecofriendliness, large‐scale applicability, and more. It is therefore not surprising that the search for the perfect antifouling coating has been going on for decades. With the discovery of metal‐based antifouling paints in the 1970s, fouling was thought to be a problem of the past, yet its untargeted toxicity led to serious ecological concern, and its use became prohibited. As a response, research shifted focus toward a biocompatible alternative: polymer‐based antifouling coatings. This has resulted in numerous advanced and innovative antifouling strategies, including fouling‐resistant, fouling‐release, and fouling‐degrading coatings. Here, these novel and exciting discoveries are highlighted while simultaneously assessing their antifouling performance and practical feasibility.
Quartz crystal microbalance with dissipation monitoring (QCMD) is a well-established technique for studying soft films. It can provide gravimetric as well as nongravimetric information about a film, such as its thickness and mechanical properties. The interpretation of sets of overtone-normalized frequency shifts, Δf/n, and overtone-normalized shifts in half-bandwidth, ΔΓ/n, provided by QCMD relies on a model that, in general, contains five independent parameters that are needed to describe film thickness and frequency-dependent viscoelastic properties. Here, we examine how noise inherent in experimental data affects the determination of these parameters. There are certain conditions where noise prevents the reliable determination of film thickness and the loss tangent. On the other hand, we show that there are conditions where it is possible to determine all five parameters. We relate these conditions to the mathematical properties of the model in terms of simple conceptual diagrams that can help users understand the model’s behavior. Finally, we present new open source software for QCMD data analysis written in Python, PyQTM.
Despite recent developments in controlled polymerization techniques, the straightforward synthesis of block copolymers that feature both strong anionic and charge-neutral segments remains a difficult endeavor. In particular, solubility issues may arise during the direct synthesis of strong amphiphiles and typical postpolymerization deprotection often requires harsh conditions. To overcome these challenges, we employed Cu(0)mediated reversible deactivation radical polymerization (Cu(0)-RDRP) on a hydrophobic isobutoxy-protected 3-sulfopropyl acrylate. Cu(0)-RDRP enables the rapid synthesis of the polymer, reaching high conversions and low dispersities while using a single solvent system and low amounts of copper species. These macromolecules are straightforward to characterize and can subsequently be deprotected in a mild yet highly efficient fashion to expose their strongly charged nature. Furthermore, a protected sulfonate segment could be grown from a variety of charge-neutral macroinitiators to produce, after the use of the same deprotection chemistry, a library of amphiphilic, double-hydrophilic as well as thermoresponsive block copolymers (BCPs). The ability of these various BCPs to self-assemble in aqueous media was further studied by dynamic light scattering, ζ-potential measurements as well as atomic force and electron microscopy.
Fouling remains a widespread challenge as its nonspecific and uncontrollable character limits the performance of materials and devices in numerous applications. Although many promising antifouling coatings have been developed to reduce or even prevent this undesirable adhesion process, most of them suffer from serious limitations, specifically in scalability. Whereas scalability can be particularly problematic for covalently bound antifouling polymer coatings, replacement by physisorbed systems remains complicated as it often results in less effective, low-density films. In this work, we introduce a two-step adsorption strategy to fabricate high-density block copolymer-based antifouling coatings on hydrophobic surfaces, which exhibit superior properties compared to one-step adsorbed coatings. The obtained hybrid coating manages to effectively suppress the attachment of both lysozyme and bovine serum albumin, which can be explained by its dense and homogeneous surface structure as well as the desired polymer conformation. In addition, the intrinsic reversibility of the adhered complex coacervate core micelles allows for the successful triggered release and regeneration of the hybrid coating, resulting in full recovery of its antifouling properties. The simplicity and reversibility make this a unique and promising antifouling strategy for large-scale underwater applications.
We report spin-singlet formation in an organic-inorganic hybrid identified as CH 3 NH 3 Cu 2 Cl 5 . The hybrid adopts a layered structure in which Cu 2 Cl 5 − layers are separated by CH 3 NH 3 + layers. The inorganic layers consist of corner-and edge-sharing CuCl 6 octahedra, forming edge-sharing tetramers. Magnetic susceptibility measurements indicate strong antiferromagnetic interactions within the tetramers, whereas the coupling between the tetramers is weak. Low-temperature magnetic susceptibility data as well as electron spin resonance measurements suggest a nonmagnetic ground state with a large spin gap of ∼130 K, in apparent contradiction with ferromagnetic interactions between nearest-neighbor spins. We discuss a spin-tetramer model in which antiferromagnetic next-nearest-neighbor interactions lead to a spin-singlet state.
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