A Bioinspired Hierarchical Underwater Superoleophobic Surface with Reversible pH Response

The development of oil-repellent surfaces in liquid environments has received considerable attention because of the urgent demand for antifouling coatings in marine industry. Inspired by the unique nanostructure surface of filefish scale, hierarchical films that consist of poly(pentafluorophenyl acrylate) free standing micropillars grafted with pH responsive poly(methacrylic acid) nanobrushes are fabricated by anodic aluminum oxide templating method combined with a subsequent post-polymerization modification strategy. The obtained films exhibit constantly underwater superoleophobicity, furthermore, a pH sensitive functionality, which enables reversible switching between low and high oil adhesion as a result of the adjustable oil sliding angle. This particular study provides a very mild method for the facile fabrication of bioinspired nanostructures with excellent oil-repellent performance and switchable oil-adhesion properties, thus paving the way toward novel functional materials with smart structures for promising applications, such as smart microfluidics, controllable bioadhesion, and intelligent materials for oil removal treatment and marine antifouling

A CO2_{2}-gated anodic aluminum oxide based nanocomposite membrane for de-emulsification

A carbon-dioxide-responsive organic–inorganic nanocomposite membrane based on a through-hole anodic aluminum oxide (AAO) template was constructed. The composite was prepared via a surface-initiated reversible addition–fragmentation chain-transfer (SI-RAFT) polymerization strategy to achieve the grafting of poly(methyl methacrylate-co-2-(diethylamino)ethyl methacrylate) brushes on the AAO membrane. The grafted polymer chain length could be controlled based on the feed ratio between the free chain transfer agent (CTA) and reactive monomer, e.g., methyl methacrylate and 2-(diethylamino)ethyl methacrylate, resulting in a membrane that features adjustable water permeability. Importantly, the membrane pore size and surface wettability could be switched from hydrophobic to hydrophilic upon the introduction of carbon dioxide and nitrogen gases. This allowed for the nanocomposite membrane to be utilized for controlled water flux and oil/water emulsion separation. The simple fabrication methodology as well as sustainable gaseous stimulus will be useful for the construction of future smart membranes

Inherently UV Photodegradable Poly(methacrylate) Gels

Organogels (hydrophobic polymer gels) are soft materials based on polymeric networks swollen in organic solvents. They are hydrophobic and possess a high content of solvent and low surface adhesion, rendering them interesting in applications such as encapsulants, drug delivery, actuators, slippery surfaces (self-cleaning, anti-waxing, anti-bacterial), or for oil-water separation. To design functional organogels, strategies to control their shape and surface structure are required. Herein, the inherent UV photodegradability of poly(methacrylate) organogels is reported. No additional photosensitizers are required to efficiently degrade organogels (d ≈ 1 mm) on the minute scale. A low UV absorbance and a high swelling ability of the solvent infusing the organogel are found to be beneficial for fast photodegradation, which is expected to be transferrable to other gel photochemistry. Organogel arrays, films, and structured organogel surfaces are prepared, and their extraction ability and slippery properties are examined. Films of inherently photodegradable organogels on copper circuit boards serve as the first ever positive gel photoresist. Spatially photodegraded organogel films protect or reveal copper surfaces against an etchant (FeCl3 aq.)

Polymer-Based Batteries — Flexible and Thin Energy Storage Systems

Batteries have become an integral part of everyday life—from small coin cells to batteries for mobile phones, as well as batteries for electric vehicles and an increasing number of stationary energy storage applications. There is a large variety of standardized battery sizes (e.g., the familiar AA‐battery or AAA‐battery). Interestingly, all these battery systems are based on a huge number of different cell chemistries depending on the application and the corresponding requirements. There is not one single battery type fulfilling all demands for all imaginable applications. One battery class that has been gaining significant interest in recent years is polymer‐based batteries. These batteries utilize organic materials as the active parts within the electrodes without utilizing metals (and their compounds) as the redox‐active materials. Such polymer‐based batteries feature a number of interesting properties, like high power densities and flexible batteries fabrication, among many more

Inverse Vulcanization of Norbornenylsilanes: Soluble Polymers with Controllable Molecular Properties via Siloxane Bonds

The inverse vulcanization produces high sulfur content polymers from alkenes and elemental sulfur. Control over properties such as the molar mass or the solubility of polymers is not well established, and existing strategies lack predictability or require large variations of the composition. Systematic design principles are sought to allow for a targeted design of materials. Herein, we report on the inverse vulcanization of norbornenylsilanes (NBS), with a different number of hydrolysable groups at the silicon atom. Inverse vulcanization of mixtures of NBS followed by polycondensation yielded soluble high sulfur content copolymers (50 wt % S) with controllable weight average molar mass (M$_{W}$), polydispersity (Đ), glass transition temperature (TG), or zero-shear viscosity (η$_{0}$). Polycondensation was conducted in the melt with HCl as a catalyst, abolishing the need for a solvent. Purification by precipitation afforded polymers with a greatly reduced amount of low molar mass species

Hydrophobically Modified Sulfobetaine Copolymers with Tunable Aqueous UCST through Postpolymerization Modification of Poly(pentafluorophenyl acrylate)

Polysulfobetaines, polymers carrying highly polar zwitterionic side chains, present a promising research field by virtue of their antifouling properties, hemocompatibility, and stimulus-responsive behavior. However, limited synthetic approaches exist to produce sulfobetaine copolymers comprising hydrophobic components. Postpolymerization modification of an activated ester precursor, poly(pentafluorophenyl acrylate), employing a zwitterionic amine, 3-((3-aminopropyl)dimethylammonio)propane-1-sulfonate, ADPS, is presented as a novel, one-step synthetic concept toward sulfobetaine (co)polymers. Modifications were performed in homogeneous solution using propylene carbonate as solvent with mixtures of ADPS and pentylamine, benzylamine, and dodecylamine producing a series of well-defined statistical acrylamido sulfobetaine copolymers containing hydrophobic pentyl, benzyl, or dodecylacrylamide comonomers with well-controllable molar composition as evidenced by NMR and FT-IR spectroscopy and size exclusion chromatography.This synthetic strategy was exploited to investigate, for the first time, the influence of hydrophobic modification on the upper critical solution temperature (UCST) of sulfobetaine copolymers in aqueous solution. Surprisingly, incorporation of pentyl groups was found to increase solubility over a wide composition range, whereas benzyl groups decreased solubility—an effect attributed to different entropic and enthalpic contributions of both functional groups. While UCST transitions of polysulfobetaines are typically limited to higher molar mass samples, incorporation of 0–65 mol % of benzyl groups into copolymers with molar masses of 25.5–34.5 kg/mol enabled sharp, reversible transitions from 6 to 82 °C in solutions containing up to 76 mM NaCl, as observed by optical transmittance and dynamic light scattering. Both synthesis and systematic UCST increase of sulfobetaine copolymers presented here are expected to expand the scope and applicability of these smart materials

Versatile synthesis of functional gold nanoparticles: Grafting polymers from and onto

Functionalized gold nanoparticles have been prepared in an organic solvent by a two-phase reduction method in ethyl acetate and water using bis(6-hydroxyhexyl) disulfide bis(2-bromoisobutyl) ester, bis(6-acetyloxyhexyl) disulfide, and bis(5-carboxypentyl) disulfide bis(pentafluorophenyl) ester as stabilizing ligands. This procedure features the advantages that no phase transfer agent was necessary during the preparation of the gold nanoparticles and that the reducing conditions were mild enough to utilize functional disulfide ligands. The obtained gold nanoparticles with typical sizes between 2 and 5 nm could be precipitated and redispersed without any irreversible aggregation. Using these nanoparticles the stimuli-responsive polymers poly(N-isopropylacrylamide) and poly(N-cyclopropylacrylamide) could be grafted from the surface. Also, the grafting of polymers onto gold nanoparticles could be demonstrated with nanoparticles featuring pentafluorophenyl ester groups. The reactive character of gold nanoparticles featuring a pentafluorophenyl ester groups on the surface could also be applied in the preparation of multilayers on the basis of covalent bonds between the gold nanoparticles and polyallylamine