Programmable Self‐Assembly from Two‐Dimensional Nanosheets to Spiral, Twisted and Branched NanostructuresHu, Haohui; Jiang, Wei; Han, Xiao; Wu, Geng; Wang, Haoran; Shi, Yi; He, Dayin; Ma, Xianhui; Hong, Xun
doi: 10.1002/anie.202416624pmid: 39686877
Self‐assembly of nanomaterials into hierarchical structure is of great interest to fabricate functional materials. However, programmable design of the assembled structures remains a great challenge. Herein, we reported a programmable self‐assembly strategy to customize the assembled structure. The self‐assembly strategy is designed to orderly transform the two‐dimensional (2D) Ca ions assembled F127 nanosheets (Ca‐F127 NSs) into spiral nanosheet structures (S‐Ca‐F127 NSs), branched nanosheet structures (B‐Ca‐F127 NSs), branched‐spiral nanosheet structures (B‐S‐Ca‐F127 NSs), and twisted‐branched structures (T‐Ca‐F127 NBs). Wide‐angle X‐ray scattering (WAXS) and X‐ray absorption spectroscopy (XAS) indicate that these different structures maintain the same orthorhombic phase and Ca‐O octahedral coordination structure. Selected area electron diffraction (SAED) in the double‐tilt liquid nitrogen cooling holder identifies the Eshelby twist in the twisted structures, demonstrating the spiral structure are formed by screw dislocation growth. Cryo‐electron microscopy (cryo‐EM) proves the oriented epitaxial growth in the B‐Ca‐F127 NSs. Furthermore, the formation mechanisms of spiral structure and branched structure can be recombined to form complex hierarchical structures. The epitaxial growth along screw dislocation can lead to the formation of B‐S‐Ca‐F127 NSs, while the twisted epitaxial growth in the screw dislocation can lead to the formation of T‐Ca F127 NBs.
Spontaneous Emergence of Lipid Vesicles in a Coacervate‐Based Compartmentalized SystemYin, Chengying; Yu, Xinran; Wu, Baohu; Tian, Liangfei
doi: 10.1002/anie.202414372pmid: 39656166
The spontaneous emergence of lipid vesicles in the absence of evolved biological machinery represents a major challenge for bottom‐up synthetic biology. We show that coacervate microdroplets could create a compartmentalized environment that enriches lipid molecules and facilitates their spontaneous assembly into lipid vesicles. These vesicles can escape from the coacervate microdroplets in a continuous process under non‐equilibrium conditions, resembling a constant production process akin to a “primitive enzyme” factory assembly line. These findings significantly extend our understanding of the intricate interaction between lipid molecules and coacervate microdroplets, shedding light on the emergence of cellular systems and offering a new perspective on the conditions necessary for the development of life on Earth.
Mesoporous Electrodes Enhance the Electrocatalytic Performance of [FeFe]‐HydrogenaseWebb, Sophie; Veliju, Astrit; Maroni, Plinio; Apfel, Ulf‐Peter; Happe, Thomas; Milton, Ross D.
doi: 10.1002/anie.202416658pmid: 39530332
The metalloenzyme [FeFe]‐hydrogenase is of interest to future biotechnologies targeting the production of “green” hydrogen (H2). We recently developed a simple two‐step functionalized procedure to immobilize the [FeFe]‐hydrogenase from Clostridium pasteurianum (“CpI”) on mesoporous indium tin oxide (ITO) electrodes to achieve elevated H2 production with high operational stability and current densities of 8 mA cm−2. Here, we use a combination of atomic force microscopy (AFM), scanning electron microscopy (SEM) and electrochemical quartz crystal microbalance (EQCM) to understand how mesoporous ITO stabilizes and activates CpI for electroenzymatic H2 production. Examination of the topography and morphology of the mesoporous ITO surface revealed a hierarchical morphology containing cavities and well‐defined nanoparticle agglomerates. Any potential effect of mesoporosity was investigated by comparing the stability and electroenzymatic activity of CpI on mesoporous ‘nanoITO’ and planar ITO, where we determined that CpI has a higher turnover frequency and adsorbs with greater stability (with respect to electroenzymatic activity over time) to nanoITO surfaces.
Covalent Folding of Fluorinated Polyphenylene by Sulfur Fluorine Annulative SubstitutionZhu, Yanpeng; Lin, Chaojun; Zhao, Chaoqun; Ou, Yiqiang; Li, Zhongshu; Zhu, Kelong; Wang, Jiaobing
doi: 10.1002/anie.202420073pmid: 39545719
We report that fluorinated polyphenylene P50 undergoes folding‐like sulfur fluorine annulative substitution (SFAS) to form a well‐defined tubular helix H50. This is achieved with atomic precision in an exceptionally efficient manner, involving the simultaneous transformation of 98 C−F bonds with the yield per reaction site approaching 99.9 %. The desired product H50 features a fully fused dibenzothiophene skeleton of 5.8 helical turns in total. It is truly monodisperse (Đ=1.0) in nature, allowing for thorough spectroscopic characterizations. Unambiguous single crystal X‐ray structure, distinct chiroptical properties, and intriguing through‐cavity threading complexation are described. These results, in addition to those of H50’s lower congeners, H34 and H18, illustrate the great potential of folding‐like SFAS in shaping random‐coiled polymer chains into higher‐order functional structures.
Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic AcidChang, Jinquan; Wang, Sikai; Hülsey, Max J.; Zhang, Sheng; Nee Lou, Shi; Ma, Xinbin; Yan, Ning
doi: 10.1002/anie.202417251pmid: 39460653
Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2‐O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45
μmolgPTA-1h-1
${\mu mol\ {g}_{PTA}^{-1}{h}^{-1}}$
with approximately 20.3 % overall electron yield. Under continuous operation, we achieved 19.90
μmolgPTA-1h-1
${\mu mol\ {g}_{PTA}^{-1}{h}^{-1}}$
catalytic activity, over 74.3 % methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo‐ and electrochemical methane oxidation at ambient conditions.
Activation and C−C Coupling of Aryl Iodides via Bismuth PhotocatalysisMato, Mauro; Stamoulis, Alexios; Cleto Bruzzese, Paolo; Cornella, Josep
doi: 10.1002/anie.202418367pmid: 39436157
Within the emerging field of bismuth redox catalysis, the catalytic formation of C−C bonds using aryl halides would be highly desirable; yet such a process remains a synthetic challenge. Herein, we present a chemoselective bismuth‐photocatalyzed activation and subsequent coupling of (hetero)aryl iodides with pyrrole derivatives to access C(sp2)−C(sp2) linkages through C−H functionalization. This unique reactivity is the result of the bismuth complex featuring two redox state‐dependent interactions with light, which 1) activates the Bi(I) complex for oxidative addition via MLCT, and 2) promotes the homolytic cleavage of aryl Bi(III) intermediates through a LLCT process.
Ultra‐Wide Modulation and Reversible Reconfiguration of a Flexible Organic Crystalline Optical Waveguide Between 645 and 731 nmChen, Quanliang; Tang, Baolei; Ye, Kaiqi; Hu, Hanlin; Zhang, Hongyu
doi: 10.1002/anie.202417459pmid: 39299918
Flexible organic crystalline optical waveguides, which deliver input or self‐emit light through various dynamic organic crystals, have attracted increasing attention in the past decade. However, the modulation of the waveguide output relies on chemical design and substituent modification, being time‐consuming and laborious. Here we report an elastic organic crystal that displays long‐distance light transduction up to 2.0 cm and an ultra‐wide modulation of crystalline optical waveguides between red (645 nm) and near infrared (731 nm) in both the pristine and the elastically bent states based on a pre‐designed self‐absorption effect. The flexible organic crystalline optical waveguides can be precisely and reversibly reconfigured by controlling the irradiation point. In addition, deep‐red amplified spontaneous emission (ASE) that is able to transduce through a 5.0 mm bent crystal with an ultra‐low optical loss coefficient of 0.093 dB/mm has been attained. To the best of our knowledge, this is the first report of flexible organic ASE waveguides. The present study not only provides a simple yet effective strategy to remarkably modulate flexible organic crystalline optical waveguides but also demonstrates the superiority of lasing over normal emission as flexible optical communication elements.