Stephanie Aguilar

The conducting polymer polyaniline (PANI) has been considered to be a promising pseudocapacitive electrode material for supercapacitors due to its high specific capacitance, low cost, and environmental friendliness. However, the poor cycling stability of PANI during the charge–discharge processes limits its widespread practical application. Herein, a facile synthetic method is demonstrated for covalently grafting an aniline tetramer (TANI), the basic building block of PANI, onto 3D graphene networks via perfluorophenylazide coupling chemistry to create a hybrid electrode material for ultralong‐life supercapacitors. The design, which substitutes long‐chain PANI with short‐chain TANI and introduces covalent linkages between TANI and 3D graphene, greatly enhances the charge–discharge cycling stability of PANI‐based supercapacitors. The electrode material, as well as the fabricated symmetric all‐solid‐state supercapacitors, exhibit extraordinary long cycle life (>85% capacitance retention after 30 000 charge–discharge cycles). The capacitance can be further boosted through fast and reversible redox reactions on the electrode surface using a redox‐active electrolyte while maintaining outstanding cycling stability (82% capacitance retention after 100 000 cycles for a symmetric all‐solid‐state device). While conducting polymers are known to be limited by their poor cycling stability, this work provides an effective strategy to achieve enhanced cycle life for conducting polymer‐based energy storage devices.

Surface modification offers a straightforward means to alter and enhance the properties and performance of materials, such as nanofiltration membranes for water softening. Herein, we demonstrate how a membrane’s surface charge can be altered by grafting different electrostatically varying copolymers onto commercial membrane surfaces using perfluorophenylazide (PFPA) photochemistry for enhanced ion separation performance. The native membrane’s performance—i.e., in terms of divalent cation separation—with copolymer coatings containing a positively charged quaternary ammonium (−N(Me)₃⁺), a negatively charged sulfonate (−SO₃^–), and an essentially neutral zwitterion (sulfobetaine, −N(Me)₂R₂⁺, and −SO₃^–), respectively, indicates that: (a) the sulfonated polymer induces robust Coulombic exclusion of divalent anions as compared to the negatively charged native membrane surface on account of its higher negative charge; (b) the positively charged ammonium coating induces exclusion of cations more effectively than the native membrane; and significantly, (c) the zwitterion polymer coating, which reduces the surface roughness and improves wettability, in spite of its near-neutral charge enhances exclusion of both divalent cations and anions on account of aperture sieving by the compact zwitterion polymer that arises from its ability to limit the size of ions that transport through the polymer along with dielectric exclusion. The outcomes thereby inform new pathways to achieve size- and charge-based exclusion of ionic, molecular, and other species contained in liquid streams.

Conjugated polyaniline has shown anticorrosive, hydrophilic, antibacterial, pH-responsive, and pseudocapacitive properties making it of interest in many fields. However, in situ grafting of polyaniline without harsh chemical treatments is challenging. In this study, we report a simple, fast, and non-destructive surface modification method for grafting tetraaniline (TANI), the smallest conjugated repeat unit of polyaniline, onto several materials via perfluorophenylazide photochemistry. The new materials are characterized by nuclear magnetic resonance (NMR) and electrospray ionization (ESI) mass spectroscopy. TANI is shown to be covalently bonded to important carbon materials including graphite, carbon nanotubes (CNTs), and reduced graphene oxide (rGO), as confirmed by transmission electron microscopy (TEM). Furthermore, large area modifications on polyethylene terephthalate (PET) films through dip-coating or spray-coating demonstrate the potential applicability in biomedical applications where high transparency, patternability, and low bio-adhesion are needed. Another important application is preventing biofouling in membranes for water purification. Here we report the first oligoaniline grafted water filtration membranes by modifying commercially available polyethersulfone (PES) ultrafiltration (UF) membranes. The modified membranes are hydrophilic as demonstrated by captive bubble experiments and exhibit extraordinarily low bovine serum albumin (BSA) and Escherichia coli adhesions. Superior membrane performance in terms of flux, BSA rejection and flux recovery after biofouling are demonstrated using a cross-flow system and dead-end cells, showing excellent fouling resistance produced by the in situ modification.

Significance: Polyketides are a class of diverse natural products with well-documented bioactivity and medicinal importance. Enzymes known as aromatase/cyclases (ARO/CYCs) catalyze regiospecific cyclization and aromatization during type II polyketide biosynthesis. Understanding how ARO/CYCs catalyze cyclization and aromatization is critical for developing strategies for engineering biosynthetic pathways. This is the first study, to our knowledge, to use X-ray crystallography, bioinformatic and structural analysis, and in vitro functional assays to critically compare a reducing di-domain ARO/CYC (BexL) and a nonreducing di-domain ARO/CYC (StfQ). Together, these results fill in a missing link in the structural enzymology of polyketide biosynthesis and will have a direct effect on future biosynthetic engineering efforts and bioinformatic analysis of type II PKS gene clusters.