Abstract The cap’n’collar family of bZIP transcription factors, including NRF1 and NRF2, execute essential protective transcriptional programs in response to cellular stressors and are thus of high interest to harness with pharmacological tools. From a high throughput screen of a covalently acting small molecule library, we identified the furanyl-acrylamide, exemplified by analog WC1, as a chemical scaffold capable of activating both NRF1 and NRF2 transcription programs. Chemical proteomic guided target identification work indicated that WC1 covalently modifies C160 of SKP1, an adaptor protein of the SKP1-CUL1-F-box E3 ubiquitin ligase complex, leading to decreased interactions with the F-box protein βTrCP, a shared regulator of NRF1 and NRF2 ubiquitination. This work identifies a novel mechanism of action to concurrently activate the NRF1 and NRF2 transcriptional programs and suggests a potential pharmacological route toward programming the activities of F-box containing proteins.
Abstract Mesoporous materials have attracted great research attention since their first advent in 1990s; however, the self-assembly of soft micelles can generate only unary periodicity. A feasible strategy capable of building multinary pore structures remains scarcely explored due to huge synthetic difficulty. Herein, we explore a cooperative dual-template assembly route, which allows for compatible interaction of Pluronic P123 and L64 in solution, to successfully construct a type of mesoporous carbon nanospheres with bimodal mesopores. The key to such construction of hierarchical mesopores from a pure soft-template process without recruitment of a hard template mainly relies on the formation of composite micelles with both suitable mutual interactions and individually stabilized condensed states. The resultant mesoporous carbon spheres possess good uniformity in morphology and mesoporosity, including a mean particle size at ∼200 nm, a high surface area of 537 m2 g–1, and an interconnected bimodal mesopore size centered at 11.1 and 4.2 nm along with a massive amount of micropores. Moreover, this dual-template assembly strategy allows for precise structural regulation over the pore curvature and pore size through tailoring the reaction conditions. As a proof of concept, the fabricated bimodal mesoporous carbon, as an ammonium-ion battery anode, showcases excellent electrochemical performances owing to its permeable and gradient porous structure for fast mass and charge transfer. Our study underscores a facile and extendable toolbox for synthesizing complex or hierarchical mesostructures as advanced energy model materials.
Abstract Earth-abundant transition-metal electrocatalysts often degrade in acidic or neutral media due to reconstruction and leaching, hindering their use for deep electrooxidation processes like the conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a key monomer for sustainable plastics. Here, we report that under nonalkaline conditions, cobalt ions (Co2+) and electrodeposited cobalt (oxy)hydroxide surfaces, maintained in a dynamic dissolution/deposition equilibrium, act synergistically to drive efficient HMF oxidation. Carboxylate anions, particularly propionate, stabilize dissolved Co2+ as active complexes that are enriched at the electrode interface, while the heterogeneous surfaces facilitate substrate adsorption. This cooperative mechanism enables deep oxidation to FDCA. By optimizing this equilibrium with a potassium propionate electrolyte, we achieved a 93.3% FDCA yield using only 1 mM Co2+. Coupling this anodic process with the oxygen reduction reaction (ORR) allows for low-voltage FDCA production from which FDCA precipitates directly at high concentrations without acidification. This synergy between homogeneous complexes and heterogeneous surfaces offers a new paradigm for stable and efficient electrocatalysis under mild conditions.
Abstract Next-generation optical devices for beam shaping, spatial light modulation, and information storage will benefit from scalable methods to program molecular anisotropy in processable soft materials. Liquid crystal polymers (LCPs) are attractive platforms for this purpose because they combine orientational mobility and long-range order with the processability of polymeric materials, yet a general strategy for high-fidelity grayscale control of molecular order in single-layer LCP films remains an unmet challenge. Here, we address this challenge through molecular design of an azobenzene/cyanobiphenyl side-chain LCP, where a small fraction of photoisomerizable azobenzene units transduces visible light into bulk alignment of a birefringent cyanobiphenyl-rich matrix. This chemically amplified photoalignment strategy preserves light penetration while producing order parameters up to S ≈ 0.58. Excitation intensity controls molecular order through a thresholded and saturating response, captured by an empirical calibration that enables grayscale projections to be translated into spatial maps of molecular alignment along a specific axis. Photomask-free digital projections produced high-fidelity birefringent features down to ∼10 μm and an effective optical bit-depth exceeding 6 bits. Intensity-to-response correction improved grayscale fidelity in complex images and was transferable from microscale to centimeter-scale projection areas. This approach provides a scalable route to programming coupled opacity and polarization-dependent optical behavior in solid LCP films.
