bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Direct Air Capture in Industrial Cooling Towers Mediated by Electrochemical CO2 Release
Authors: Zheng Ao‐Chuan , Zou Ye‐Bin , Du Lin , Zhang Qiang , Daasbjerg Kim , Hu Xin‐Ming
Published: December 2024

Direct air capture (DAC) is a promising technology for mitigating global climate change but suffers from low efficiency, small scale, and high cost due to the dilute atmospheric CO2, limited size of air contactors, and heat‐driven CO2 release. Here, we propose combining DAC with widely used industrial cooling towers to extract CO2 from the air and using electrolysis to release the captured CO2 at room temperature. We first prepare a buffered absorbent solution consisting of sodium glycinate, glycine, and sodium chloride for effective CO2 capture from the air, solving the incompatibility problem of the cooling towers with conventional absorbents. Next, we employ a three‐chamber electrolyzer for efficient release (≥95 %) of the captured CO2 with high purity (≥98 %) by constant current electrolysis at room temperature, bypassing the conventional energy‐intensive heating process. The entire DAC system can operate stably for multiple cycles, and the mechanism for consecutive CO2 capture and release is uncovered. This work reveals the great potential of running DAC in industrial cooling towers coupled with electrochemically‐driven CO2 release, opening up new avenues for curbing the increasingly severe climate change.
A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries
Authors: Deng Tao , Wang Changhong , Wan Hongli , Li Ai‐Min , He Xinzi , Wang Zeyi , Cao Longsheng , Fan Xiulin , Wang Chunsheng
Published: December 2024

All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li6PS5Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm−2 with excellent cycling stability at 1.0 mA cm−2. The ASSLBs paring with Ni‐rich LiNi0.6Mn0.2Co0.2O2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.
Sugar Auxiliary Group Assisted Diversity‐Oriented Enzymatic Modular Synthesis of 0‐Series Ganglioside Glycans
Authors: Ye Jinfeng , Zhong Kan , Hu Zhi‐Fei , Liu Chang‐Cheng , Li Ming , Wu Peng , Cao Hongzhi
Published: December 2024

Owing to the inaccessibility of β1–4‐N‐acetylgalactosaminyltransferase for direct glycan chain elongation, the enzymatic synthesis of 0‐series gangliosides with extended backbones has not been explored. In this study, sialic acid was enzymatically introduced as an auxiliary group to overcome the limitation of substrate specificity of Campylobacter jejuni β1–4‐N‐acetylgalactosaminyltransferase (CjCgtA) to achieve the synthesis of desired extended 0‐series ganglioside core structures, and the sialic acid auxiliary group could be removed by sialidase at appropriate stages. A bacterial α2–6‐sialyltransferase from Photobacterium damselae (Pd2,6ST) exhibited unexpected acceptor substrate specificity for 0‐series ganglioside core structures, providing ready access to complex gangliosides bearing the sialyl N‐acetylgalactosamine unit. The 0‐series ganglioside core structures as the key acceptor substrates were further diversified by sequential enzymatic modular assembly to generate a collection of 31 complex 0‐series ganglioside glycans after removal of the sugar auxiliary group of sialic acid at the appropriate stage.
Liquid Crystalline Nanorods by Synchronized Polymerization, Self‐Assembly and Oriented Attachment for Utilization in Magnetically Responsive Displays
Authors: Wang Xiao , Lu Jiawei , Shi An‐Chang , Liu Bing
Published: December 2024

The creation of anisotropic nanoparticles (NPs) by polymerization and/or self‐assembly (SA) has significantly promoted the applications of polymer nanomaterials in many fields. However, polymer nanorods are not easily accessible via conventional polymerization or SA. Here we report a one‐step route to synthesize single‐domain smectic liquid crystalline (LC) nanorods utilizing oriented attachment (OA) that was usually found in the synthesis of inorganic NPs, synchronized with polymerization and SA. The synchronization was achieved by developing a novel stabilizer derived from a thermo‐responsive polyelectrolyte system. Mechanistic studies reveal that controlling the thermo‐responsive behavior and the distribution of stabilizers on NPs enabled OA. The LC nanorods can further form hierarchical colloidal LCs, which show much larger light transmittance than that of non‐LC nanorods. Moreover, we demonstrate that this LC system can be manipulated by an external magnetic field, thus providing a candidate material for magnetic‐responsive display.
Self‐Healing 2D Anion‐Organic Frameworks for Low‐Temperature Water Release
Authors: Li Zhong‐Qiu , Shao Jiang‐Yang , Gong Zhong‐Liang , Liang Tongling , Hao Xiang , Yao Jiannian , Zhong Yu‐Wu
Published: December 2024

Molecular frameworks have recently shown a great potential in atmospheric water harvesting, in which the water release at low temperatures is challenging. Anion‐organic frameworks based on anion‐coordination chemistry are presented herein to meet this challenge. These frameworks are prepared as tubular single crystals in pure water from the in situ protonation and crystallization of pyridine‐terminated triphenylamine derivatives with hydrochloric or hydrobromic acid. They possess a 2D honeycombed porous structure and carry halogen anions confined within 1D hexagonal nanochannels with a modular size of 1.7–2.3 nm. They exhibit a high water uptake of up to 0.87 g g−1 and a water release onset temperature as low as −90 °C. The water uptake and release induce significant changes in the crystal morphology and absorption and emission properties of these framework crystals, providing a visual indication of their hydration states over a wide temperature range. The kinetics of dehydration at subglacial temperatures is successfully determined by emission spectral shifts. These framework crystals show a high water‐stability and can be used for repeated water capture and release thanks to a rapid and robust self‐healing capability. This discovery opens opportunities for the design and synthesis of flexible and self‐healing frameworks for porosity‐related applications.
Access to Polyhydroxyalkanoates with Diverse Syndiotacticity via Polymerization by Spiro‐Salen Complexes and Insights into the Stereocontrol Mechanism
Authors: Huang Hao‐Yi , Ren Bai‐Hao , Xie Min , Huang Yu‐Ting , Li Kun , Cai Zhongzheng , Lu Xiao‐Bing , Zhu Jian‐Bo
Published: December 2024

Polyhydroxyalkanoates (PHAs) have attracted broad interest as promising sustainable materials to address plastic pollution and resource scarcity. However, the chemical synthesis of stereoregular PHAs via ring‐opening polymerization (ROP) has long been an elusive endeavor. In this contribution, we exploited a robust spiro‐salen yttrium complex (Y3) as the catalyst to successfully prepare syndiotactic PHAs with diverse pendent groups. Simply altering the ratio of enantiomeric catalysts allowed to access of PHAs with diverse syndiotacticity (Pr=0.5–0.99, from sticky oil to tough materials), delivering tunable thermal properties (glass transition temperature, Tg from −52 to 70 °C and melting transition temperature, Tm from 38 to 223 °C). A combined experimental and computational study suggested a polymeric exchange mechanism could boost the polymerization activity and control the syndioselectivity.
Promoting Photocatalytic Hydrogen Evolution by Stabilization of Excited Triplet States and Enhancement of Internal Electric Field at Dye/PCN Interface
Authors: Chen Yanting , Jiang Changzun , Liu Siwei , Yuan Wentao , Li Qianqian , Li Zhen
Published: December 2024

The heterojunction photocatalysts composed of organic dyes and polymeric carbon nitride (PCN) have great potential for photocatalytic hydrogen evolution (PHE). However, serious charge recombination exists at the dye/PCN interface for the large gaps in time scales and the poor driving force of charge transfer process. Herein, both the excited triplet states of organic dyes with long lifetimes and strong internal electric fields (IEF) as charge transfer driving forces are achieved by the construction of high dipole moments with aromatic‐core engineering, and modulation of dye aggregates by alkyl modification. Accordingly, PHE efficiency can achieve up to 833.49 μmol/h, over 36‐fold that of PCN/Pt (23.34 μmol/h) under the same conditions. The relationship between molecular structures and PHE performance has been systematically investigated by the photophysical properties of organic dyes and the strength of IEF at dye/PCN interface. It afforded an efficient strategy to balance the charge transfer process in PHE systems, which can guide the molecular design of organic dyes with optimized aggregated behaviors and stable excited triplet states.
Achieving Photocatalytic Overall Nitrogen Fixation via an Enzymatic Pathway on a Distorted CoP4 Configuration
Authors: Wang Xin , Zhao Yuqi , Wu Xi , Zhang Bin , Tian Jian , Wong Wai‐Yeung , Zhang Fuxiang
Published: December 2024

Photocatalytic nitrogen (N2) fixation over semiconductors has always suffered from poor conversion efficiency owing to weak N2 adsorption and the difficulty of N≡N triple bond dissociation. Herein, a Co single‐atom catalyst (SAC) model with a C‐defect‐evoked CoP4 distorted configuration was fabricated using a selective phosphidation strategy, wherein P‐doping and C defects co‐regulate the local electronic structure of Co sites. Comprehensive experiments and theoretical calculations revealed that the distorted CoP4 configuration caused a strong charge redistribution between the Co atoms and adjacent C atoms, minimizing their electronegativity difference. Consequently, the N2 adsorption pattern switched from an “end‐on” to a “side‐on” mode with a high N2 adsorption energy of −1.40 eV and an elongated N−N bond length of 1.20 Å, notably decreasing the N2 adsorption/activation energy barrier. In the absence of sacrificial agents, the Co SAC achieved excellent photocatalytic overall N2 fixation performance via an enzymatic pathway. The NH3 yielding rate peaked at 1249.5 μmol h−1 g−1 with an apparent quantum yield of 3.51 % at 365 nm. Moreover, the selective phosphidation strategy has universality for synthesizing other SACs, such as those containing Ni and Fe. This study offers new insight into co‐regulating the electronic structure of SACs for efficient photocatalytic overall N2 fixation.
Breaking the Stability‐Activity Trade‐off of Oxygen Electrocatalyst by Gallium Bilateral‐Regulation for High‐Performance Zinc‐Air Batteries
Authors: Li Yunrui , Xu Jiaqi , Lan Fan , Wang Yao , Jiang Hairong , Wu Xueke , Huang Ya , Li Run , Jiang Qinyuan , Gao Di , Zhu Ping , Zhao Siming , Zhao Yanlong , Wang Fei , Zhang Libo , Zhang Longgui , Zhang Rufan
Published: December 2024

The rational design of metal oxide catalysts with enhanced oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance is crucial for the practical application of aqueous rechargeable zinc‐air batteries (a‐r‐ZABs). Precisely regulating the electronic environment of metal‐oxygen (M−O) active species is critical yet challenging for improving their activity and stability toward OER and ORR. Herein, we propose an atomic‐level bilateral regulation strategy by introducing atomically dispersed Ga for continuously tuning the electronic environment of Ru−O and Mn−O in the Ga/MnRuO2 catalyst. The Ga/MnRuO2 catalyst breaks the stability‐activity restriction, showing remarkable bifunctional performance with a low potential gap (ΔE) of 0.605 V and super durability with negligible performance degradation (300,000 ORR cycles or 30,000 OER cycles). The theoretical calculations revealed that the strong coupling electron interactions between Ga and Ru−O/Mn−O tuned the valence state distribution of the metal center, effectively modulating the adsorption behavior of *O/*OH, thus optimizing the reaction pathways and reducing the reaction barriers. The a‐r‐ZABs based on Ga/MnRuO2 catalysts exhibited excellent performance with a wide working temperature range of −20–60 °C and a long lifetime of 2308 hours (i.e., 13,848 cycles) under a current density of 5 mA cm−2 at −20 °C.
A Three‐Tiered Golf Anode towards Ultralong‐Life Zn−Mn Aqueous Batteries
Authors: Hu Qiang , Wang Xinrui , Cui Jiuzhi , Hou Jiabing , Liu Xingquan , Yang Jia‐Lin , Gu Zhen‐Yi , Zhao Jingxin , Xu Bingang , Wu Xing‐Long
Published: December 2024

Zn−Mn aqueous batteries (ZMABs) are widely recognized as a promising candidate for large‐scale energy storage due to their cost‐effectiveness, high safety and environmental friendliness. However, the practical application of ZMABs is hindered by inherent electrical contact loss, hydrogen evolution and dendrite growth on traditional anodes. Here, a three‐tiered golf anode with high conductivity is developed to simultaneously enhance the reversibility of Zn and Mn metals. The three‐tiered golf anode is achieved by inner zinc powder, intermediate carbon and outer bismuth layer, which can effectively enhance the Gibbs free energy and mitigate the volume change of the anode, thus enabling stable Zn−Mn cycling. As a proof of concept, Zn−Mn full cells (coupled to CNT@MnO2) achieve an ultralong cycle life with 94.6 % capacity retention at 2 A g−1 after 16,000 cycles. This study presents valuable insights into the structural design of anodes aimed at enhancing the stability and durability of ZMABs.
Conditional Relay Activation of Theranostic Prodrug by Pretargeting Bioorthogonal Trigger and Fluorescence‐Guided Visible Light Irradiation
Authors: Li Shihong , Pang Jing , Sun Yuanjun , Zhang Yuchen , Long Ya‐Qiu
Published: December 2024

Bioorthogonalized light‐responsive click‐and‐uncage platform has enabled precise cell surface engineering and timed payload release, but most of such photoactivatable prodrugs have “always‐on” photoactivity leading to the dark toxicity. On the other hand, the conditionally activatable photocage is limited to the application of fluorogenic probe/photosensitizer liberation. Herein, we devise a conditionally activatable theranostic platform based on the tetrazine (Tz)‐boron‐dipyrromethene (BODIPY) construct, in which tetrazine serves as a quencher motif to disable both the fluorescence and photoresponsivity of BODIPY. The uncaged BODIPY upon the bioorthogonal transformation of the tetrazine reinstates fluorescence on‐target to guide the subsequent visible light irradiation thereby releasing the therapeutic payload in situ. The proof of concept for such “light where is lit up”‐activated theranostics was demonstrated by the tetrazine‐BODIPY conjugated SN‐38 (1) with masked fluorescence, up to 70 times‐reduced cytotoxicity, and good photostability. Upon an inverse electron‐demand Diels–Alder (IEDDA) reaction between tetrazine unit on 1 and a biotinylated trans‐cyclooctene (biotin‐TCO) as a pretargeted trigger on tumor cell surface, the green fluorescence from BODIPY was fully restored for cell‐selective imaging, which guided the green light irradiation (500–520 nm) to activate the caged drug SN‐38 exerting potent cytotoxicity against tumor cells, offering high spatiotemporal precision of disease diagnosis and therapy.
Highly Selective Construction of Unique Cyclic [4]Catenanes Induced by Multiple Noncovalent Interactions
Authors: Dang Li‐Long , Zheng Jie , Tian Dan , Chai Yin‐Hang , Wu Tian‐Tian , Yang Jian‐Xin , Wang Peng , Zhao Ying , Aznarez Francisco , Ma Lu‐Fang
Published: December 2024

The synthesis of high‐ordered mechanically interlocked supramolecular structures is an extremely challenging topic. Only two linear [4]catenanes have been reported so far and there is no defined strategy to obtain cyclic [4]catenane. Herein, two unprecedented cyclic [4]catenanes, 1 and 2, were prepared in high yields. The syntheses rely on the strategic selection of naphthalenediimide (NDI) based Cp*Rh/Ir building blocks E1/E2 (Cp*=pentamethyl‐cyclopentadienyl) and nonlinear diimidazole ligand precursor L1, exhibiting large conjugate plane, appropriate coordination angles, and freely rotating imidazole units, thereby enabling multiple π⋅⋅⋅π stacking interactions to maintain the supramolecular structures. The use of other Cp*Rh building blocks E3, E4 or E5 featuring slightly shorter metal‐to‐metal distances than E1/E2 and different chemical properties led to the formation of a complex 3 and two metallamacrocycles 4 or 5, respectively. The structures of these assemblies were confirmed by X‐ray crystallographic analysis, ESI‐TOF‐MS and NMR spectroscopy. Complex 1, exhibiting a broad‐band absorption in the UV/Vis to NIR regions and a remarkable photothermal conversion was thereafter used to build the new 1 membrane. The solar power‐induced water steam generation performance of 1 membrane was investigated, reaching a value of 2.37 kg ⋅ m−2 ⋅ h−1, making it suitable for collection of fresh water via desalination and wastewater.
Arraying and Guest Inclusion of Soluble Metal‐Organic Nanotubes Composed of Macrocyclic Paddle‐Wheel Metal Complexes
Authors: Kawano Shin-ichiro , Sasaki Ako , Tanaka Kentaro
Published: December 2024

A new series of metal‐organic nanotubes was constructed through one‐dimensional assembly using molecular triangles or molecular squares composed of paddlewheel dirhodium complexes and bidentate axial ligands. The metal‐organic nanotubes were significantly different from conventional solid metal‐organic framework (MOF) motifs. They exhibit good solubility owing to the branched side chains at their periphery and demonstrate high orientation capabilities in thin films owing to their anisotropic structure. Furthermore, the nanotubes can accommodate guest molecules in nanochannels and orient them on a large scale on a glass substrate.
Conformer‐Mediated Helical Chirality in 2D Layered Hybrid Perovskites
Authors: Dutta Taniya , Swain Diptikanta , Nag Angshuman
Published: December 2024

Two‐dimensional (2D) chiral hybrid perovskites A2PbI4 (A: chiral organic ion) enable chirality controlled optoelectronic and spin‐based properties. A+ organic sublattice induces chirality into the semiconducting [PbI4]2− inorganic sublattice through non‐covalent interactions at organic–inorganic interface. Often, the A+ cations in the lattice have different orientations, leading to asymmetry in the non‐covalent interactions. In a novel approach, we use different conformers of A+ cations to create asymmetry in the non‐covalent interactions, thereby, achieving chiral perovskites with rare helical enantiomorphic structures. We prepared (R‐IdPA)2PbI4 and (S‐IdPA)2PbI4 (IdPA: 1‐iodopropan‐2‐ammonium) which crystallize in the helical enantiomorphic space groups P43212 and P41212, respectively. The gauche‐ and anti‐conformers of IdPA+ are arranged alternatively in the hybrid structure. Importantly, the anti‐conformer of IdPA+ ion have significantly stronger electrostatic, N−H⋅⋅⋅I hydrogen bonding, and I⋅⋅⋅I halogen bonding interactions with the [PbI4]2− sublattice, compared to the gauche‐conformer. This periodic asymmetry in non‐covalent interactions caused by the alternative arrangement of gauche‐ and anti‐conformers induces chirality in the inorganic sublattice with four‐fold screw axes (43 and 41). The enantiomers (R‐/S‐IdPA)2PbI4 show mirror‐image like circular dichroism from excitonic absorption of the inorganic sublattice. This conformer‐based design of chiral hybrid perovskites in helical space groups broadens material choices for advanced optoelectronic applications.
Cephalopod‐Inspired MXene‐Integrated Mechanochromic Cholesteric Liquid Crystal Elastomers for Visible‐Infrared‐Radar Multispectral Camouflage
Authors: Wang Ling , Liu Yuan , Bi Ran , Zhang Xuan , Chen Yuanhao , Valenzuela Cristian , Yang Yanzhao , Liu Huan , Yang Le , Feng Wei
Published: December 2024

Multispectral camouflage materials play a vital role in sophisticated multi‐band electromagnetic (EM) applications. However, conventional single‐band stealth is difficult to align with the growing demand for multi‐band compatibility and intelligent adaptation. Herein, we report the design and synthesis of cephalopod‐inspired MXene‐integrated cholesteric liquid crystal elastomers (MXene‐CLCEs) with multispectral camouflage capability, which was fabricated through in situ thiol‐acrylate Michael addition and free‐radical photopolymerization of CLCE precursor and isocyanate‐mediated robust covalent chemical bonding of MXene nanocoating at the interface. The resulting MXene‐CLCE exhibits dynamic structural color changes, tunable infrared radiation, and switchable microwave shielding across wide ranges upon mechanical stretching, with its infrared stealth and microwave shielding properties being realized through the reconfiguration of surface morphology from planar to cracked states via mechanical actuation. A visible‐to‐infrared camouflage octopus‐patterned MXene‐CLCE is demonstrated to achieve a stealth effect across the visible‐infrared spectrum upon mechanical stretching. As an illustration, proof‐of‐concept pneumatic‐driven octopus‐inspired soft models are demonstrated, which enables dynamic visible‐infrared camouflage and microwave shielding switching between two compatible states. The research herein can offer new perspectives on the development of bioinspired smart camouflage materials and their application in smart optical stealth, dynamic thermal management, and switchable electromagnetic devices.
Spherical Mg/Cu Co‐Doped Na4Fe3(PO4)2P2O7 Cathode Materials with Mitigated Diffusion‐Induced Stresses and Enhanced Cyclic Stability
Authors: Peng Fan , Dong Pengyuan , Chen Changdong , Chu Youqi , Min Wenxue , Lai Anjie , Wang Hao , Yang Chenghao
Published: December 2024

Na4Fe3(PO4)2P2O7 (NFPP) has been regarded as the promising cathode material for sodium‐ion batteries (SIBs). However, the practical applications of NFPP are hindered by its high‐volume changes, poor intrinsic electron conductivity and sluggish Na+ ions diffusion kinetics. Herein, a spray‐drying and solid‐state reaction method have been utilized to fabricate the spherical trace amount Mg/Cu co‐doped Na4Fe3(PO4)2P2O7 (NFMCPP). The Mg/Cu co‐doping can effectively mitigate the lattice volume change and promote the electronic conductivity of NFMCPP by reducing band gap between the conduction and valence bands. While, the unique spherical structured NFMCPP with a carbon film even coated on its surface ensures rapid electron transport. Moreover, small NFMCPP particles with spherical geometry demonstrate an alleviated diffusion‐induced stress and enhanced structural stability, due to the high sphericity structure enables fluent Na+ extraction/insertion, leads to a low high‐stress concentration and uniform stress/strain distribution during extensive (de)sodiation process. Consequently, the optimized spherical NFMCPP cathode materials exhibit an excellent rate capability and cyclic stability.
Guanidinium‐Stapled Helical Peptides for Targeting Protein‐Protein Interactions
Authors: Perdriau Camille , Luton Anaïs , Zimmeter Katharina , Neuville Maxime , Saragaglia Claire , Peluso‐Iltis Carole , Osz Judit , Kauffmann Brice , Collie Gavin W. , Rochel Natacha , Guichard Gilles , Pasco Morgane
Published: December 2024

Peptide stapling has emerged as a versatile approach in drug discovery to reinforce secondary structure elements especially α‐helices and improve properties of linear bioactive peptides. Inspired by the prevalence of arginine in protein‐protein and protein‐DNA interfaces, we investigated guanidinium‐stapling as a means to constrain helical peptides. Guanidinium stapling was readily achieved on solid support, utilizing two orthogonally protected lysine or unatural α‐amino acid residues with an amino function. This method allows for easy modulation of the nature and size of the staple as well as helix propensity. Evaluating a set of guanidinium‐stapled peptides for their interaction with different protein targets identified several binders with increased target affinity. X‐ray structure determination of four complexes revealed that all stapled peptides adopt a helical conformation upon protein binding. Notably, the disubstituted guanidinium generally exhibits a distinct cis/trans conformation and, in one instance, retains a conserved hydrogen bond with the protein surface. By identifying, for the first time, the guanidinium moiety as an effective helical peptide stapling group, this research significantly expands the repertoire of α‐helix stapling techniques for the creation of useful protein mimics.
Polymer Films’ Residual Stress Attenuation from the Supramolecular Complexation with Ultra‐Small Nanoparticles for High Resolution Nanoimprint Lithography
Authors: Chen Jiadong , Yao Shenglin , Wang Bin , Yu Qiang , Xue Binghui , Yin Panchao
Published: December 2024

Nanoimprint lithography (NIL) has been broadly applied in the fabrication of nano‐patterned polymer films for cost‐efficiency and high through‐put; however, the intrinsic tradeoff between mechanical strength and residual stress of polymer films significantly limits the NIL resolution while the harsh processing conditions limit its versatile applications to different substrates. Herein, 1 nm metal oxide cluster, phosphotungstic acid (PTA), is used to complex with polyvinyl alcohol (PVA) for high‐resolution NIL that can be operated at large‐scale and mild conditions. The ultra‐small size of PTA enables dense supramolecular interaction with PVA for the diminished crystallinity and accelerated chain dynamics that help relax the residual stress during film casting. Meanwhile, the PTAs serve as supramolecular crosslinkers for the increased modulus of the films (ca. 2 GPa), providing promising dimensional stability required for high‐resolution NIL. Simple casting the aqueous blend on a master mold successfully gives a residual stress‐free film with sub‐2 nm resolution at wafer scale (>100 cm2). The mild processing at ambient condition permits broad NIL applications to diverse substrates, e.g., integrated circuit chips, compact discs, PET nano gratings and even delicate bio‐surfaces.
Current‐Regulated Selective Nickel‐Catalyzed Electroreductive Cross‐Electrophile Carbonylation to β/γ‐Hydroxy Ketones
Authors: Xie Shentong , Lu Ming , Wang Pengcheng , Shi Renyi
Published: December 2024

The nickel catalyzed multi‐component cross‐electrophile carbonylation which emerges as a powerful and efficient method for constructing diverse ketones has attracted increasing attention of organic chemists. However, the selectivity of this reaction poses a significant challenge. In this work, we have developed a current‐regulated selective nickel‐catalyzed electroreductive cross‐electrophile carbonylation, which offers a direct convergent synthesis of β/γ‐hydroxy ketones, which represent pivotal structural motifs found in numerous natural products, bioactive molecules, pharmaceutical compounds, and essential building blocks. A diverse range of multi‐substituted β/γ‐hydroxyketones can be accessed with high chemo‐ and regioselectivity from epoxides, aryl iodides, and a simple CO source (ClCO2Pr). This electroreductive carbonylation strategy exhibits high functional group tolerance and can be applied in late‐stage derivatization of drugs and natural products. Notably, chiral epoxides can be employed as reactants with chirality retention, enabling the synthesis of asymmetric β‐hydroxy ketones. Our approach demonstrates a novel electrochemical selectivity‐controlled strategy in multi‐component cross‐electrophile coupling.
Imperfections Immobilization and Regeneration in Perovskite with Redox‐Active Supramolecular Assembly for Stable Solar Cells
Authors: Fang Zihan , Mu Xijiao , Xiao Guo‐Bin , Cao Jing
Published: December 2024

Imperfections in metal halide perovskites, such as those induced by light exposure or thermal stress, compromise device performance and stability. A key challenge is immobilizing volatile iodine produced by iodide oxidation and regenerating impurities like elemental lead and iodine. Here, we address this by integrating a redox‐active supramolecular assembly of nickel octaethylporphyrin into perovskite film, functioning as both an immobilizer and redox shuttle. Decorated ethyl groups in porphyrin distorts the π ring, increasing the axial ligand adsorption capacity of central metal ion, while reducing intermolecular interactions and promoting iodine adsorption achieving a maximum uptake of 3.83 mg mg−1 to iodine. Adsorbed iodine transfers more electrons to Ni ions, leading to a weakened interaction within I−I bond and facilitating the production of iodide ions. Such a situation further enables selective oxidation of metallic lead defects to Pb2+. Porphyrin supramolecule facilitates hole transport across perovskite grain boundaries, leading to a champion device efficiency of 25.37 % for a 0.10 cm2 active area, outperforms the value of control device being 23.96 %. Modified devices without encapsulation exhibit significantly enhanced stability, maintaining over 90 % of its initial performance after 1,000 hours of continuous 1‐sun illumination at maximum power point at 65 °C.
Conduction Band and Defect Engineering for the Prominent Visible‐Light Responsive Photocatalysts
Authors: Yamakata Akira , Kato Kosaku , Ogawa Takafumi , Ogawa Kanta , Ogawa Makoto , Kato Daichi , Zhong Chengchao , Kuwabara Akihide , Abe Ryu , Kageyama Hiroshi
Published: December 2024

Controlling trap depth is crucial to improve photocatalytic activity, but designing such crystal structures has been challenging. In this study, we discovered that in 2D materials like BiOCl and Bi4NbO8Cl, composed of interleaved [Bi2O2]2+ and Cl‐ slabs, the trap depth can be controlled by manipulating the slab stacking structure. In BiOCl, oxygen vacancies (VO) create deep electron traps, while chlorine vacancies (VCl) produce shallow traps. The depth is determined by the coordination around anion vacancies: VO forms strong σ bonds with Bi‐6p dangling bonds below the conduction band minimum (CBM), while those around Cl are parallel, forming weak π‐bonding. The strong re‐hybridization makes the trap depth deeper. In Bi4NbO8Cl, VCl also creates shallow traps, but VO does not produce deep traps although Bi‐6p orbitals are also forming strong σ bonding. This difference is attributed to the difference of the energy level of CBM. In both cases, the CBM consists of Bi‐6p orbitals extending into the Cl layers. However, these orbitals are isolated in BiOCl, but those in Bi4NbO8Cl are bonded with each other between neighboring [Bi2O2]2+ layers. This unique bonding‐based CBM prevents the formation of deep electron traps, and significantly enhances H2 evolution activity by prolonging the lifetime of highly reactive free electrons.
Dynamic Covalent Bonds‐Mediated Color‐Switchable Circularly Polarized Luminescence in Helical Assemblies of Achiral Liquid Crystal Block Copolymer Films
Authors: Yuan Jianan , He Xiaojie , Chen Lianjie , Lu Xuemin , Lu Qinghua
Published: December 2024

Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three‐dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non‐contact modulation of CPL remain challenging. In this work, color‐switchable homochiral CPL films with high luminescence asymmetry factor (glum~0.11) were constructed based on the co‐assembly of a liquid crystal block copolymer (poly (ethylene oxide)‐b‐poly (methyl methacrylate) bearing cyanostilbene group) with axial chiral dinaphthalene diamine derivatives (R/S‐DINBPA). Mechanistic investigation revealed that the efficient stacking of R/S‐DINBPA with cyanostilbene groups and the liquid crystal field provide the driving force for chiral transfer and amplification. The dynamic covalent bonds of the cyanostilbene groups endow the film with chiral fixation ability and enable precise modulation of CPL luminescence bands under UV light irradiation, making it suitable for chiral patterned anti‐counterfeit encryption. This facile strategy provides a general platform for designing intelligent chiroptical materials.
Stabilizing SPAN in Non‐Flammable Acetonitrile Electrolytes for Long‐Life Graphite||SPAN Batteries
Authors: Li Yan , Qi Xiaoqun , Zhou Han , Yang Fengyi , Jin Xiaoyu , Jiang Ruining , Zhu Zhenglu , Liang Chaofan , Li Zhen , Yuan Lixia , Qie Long , Huang Yunhui
Published: December 2024

Sulfurized polyacrylonitrile (SPAN) presents an opportunity to replace elemental sulfur as a “shuttle‐free” cathode for secondary Li−S batteries, which can be an ideal choice for stationary energy storage due to its abundance, low cost, and sustainability. The electrolyte options for the state‐of‐the‐art SPAN batteries have been limited to the flammable carbonate and ether ones, which raises safety concerns. Here, we explored the use of a non‐flammable acetonitrile (AN) electrolyte for SPAN battery for the first time and identified the irreversible cleavage of C−S bonds of SPAN as the main reason for the failure of SPAN in AN electrolyte. Fortunately, by introducing 10 wt % fluoroethylene carbonate into the AN electrolyte, the bond cleavage in SPAN is suppressed and a stable cathode electrolyte interface is formed, both contributing to stabilizing the structure of SPAN during electrochemical process. Consequently, we achieved a stable cycling for 900 cycles in Li||SPAN cells. Moreover, by pairing with a pre‐lithiated graphite (pGr) anode, the newly formulated electrolyte enables extended cycle life for 1500 cycles with a capacity retention of 91 % and superb safety in pGr||SPAN full cell. The present exploitation broadens the electrolyte choices of SPAN‐based batteries and paves the way for future applications for these batteries.
Excited‐State Engineering of Chalcogen‐Bridged Chiral Molecules for Efficient OLEDs with Diverse Luminescence Mechanisms
Authors: Li Mengke , Li Zhizhi , Peng Xiaomei , Liu Denghui , Chen Zijian , Xie Wentao , Liu Kunkun , Su Shi‐Jian
Published: December 2024

The exploration of circularly polarized luminescence is important for advancing display and lighting technologies. Herein, by utilizing isomeric molecular engineering, a novel series of chiral molecules are designed to exploit both thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP) mechanisms for efficient luminescence. The cooperation of a small singlet‐triplet energy gap, moderate spin‐orbital coupling (SOC), and large oscillator strength enables efficient TADF emission, with photoluminescence quantum yields exceeding 90 %. By altering the symmetry of molecular structures, it is demonstrated that the intrinsic electronic SOC and vibrational SOC effects can be greatly enhanced to facilitate RTP emission. Notably, through modulating simultaneous TADF and RTP emissions, single‐molecule white emission is successfully achieved. Accordingly, the TADF‐based organic light‐emitting diode (OLED) achieves a maximum external quantum efficiency up to 30 %, representing exceptional performance of non‐aromatic amine‐based emitters. Furthermore, the first single‐molecule white OLED based on TADF and RTP dual‐emissive chiral material is developed, establishing a benchmark for the development of advanced display and lighting technologies.
Cooperation of Multifunctional Redox Mediator and Separator Modification to Enhance Li‐S Batteries Performance under Low Electrolyte/Sulfur Ratios
Authors: Jin Weihua , Guo Yunpeng , Gan Taorong , Shen Zhengyuan , Zhu Xuebing , Zhang Peng , Zhao Yong
Published: December 2024

Sluggish reaction kinetics of sulfur species fundamentally trigger the incomplete conversion of S8↔Li2S and restricted lifespan of lithium‐sulfur batteries, especially under high sulfur loading and/or low electrolyte/sulfur (E/S) ratios. Developing redox mediators (RMs) is an effective strategy to boost the battery reaction kinetics, yet their multifunctionality and shuttle inhibition are still not available. Here, a unique ethyl viologen (EtV2+) RM with two highly reversible redox couples (EtV2+/EtV+, EtV+/EtV0) is demonstrated to well match the redox chemistry of sulfur species, in terms of accelerating the electron transfer in S8 reduction, Li2S nucleation and the Li2S oxidation. When coupling with a functionalized separator with electronegative ‐SO3Li groups, a synergetic chemistry is established to ensure the substantial inhibition of the shuttle effect and the acceleration of charge transfer. As a result, the activation energies during sulfur species conversion (S8→Li2S4→Li2S/Li2S2→Li2S4→S8) are decreased, especially for Li2S nucleation step. The correspond lithium‐sulfur batteries achieve a high specific capacity of 1006.9 mAh g−1 (0.1 C; sulfur loading of 5 mg cm−2; E/S ratios of 6 μL mgs−1), and an outstanding cycling stability. This study provides a paradigm of solving complex problems via multifunctional molecule engineering and strategic cooperation towards Li−S batteries and other battery communities.
A Self‐Reinforced “Microglia Energy Modulator” for Synergistic Amyloid‐β Clearance in Alzheimer's Disease Model
Authors: Ma Mengmeng , Wang Jing , Guo Kaiming , Zhong Wenbin , Cheng Yu , Lin Li , Zhao Yanli
Published: December 2024

Microglial phagocytosis is a highly energy‐consuming process that plays critical roles in clearing neurotoxic amyloid‐β (Aβ) in Alzheimer's disease (AD). However, microglial metabolism is defective overall in AD, thereby undermining microglial phagocytic functions. Herein, we repurpose the existing antineoplastic drug lonidamine (LND) conjugated with hollow mesoporous Prussian blue (HMPB) as a “microglial energy modulator” (termed LND@HMPB‐T7) for safe and synergistic Aβ clearance. The modified blood–brain barrier penetrating heptapeptide (T7) enables efficient transport of LND@HMPB‐T7 to the AD brain. LND in LND@HMPB‐T7 could fuel Aβ phagocytosis by stimulating microglial adenosine triphosphate (ATP) production, whereas HMPB with catalase and superoxide dismutase‐mimicking activities substantially alleviates the mitochondrial side effects commonly associated with LND and thus further enhances ATP production. The synergism of LND and nanozyme affords a high microglial Aβ clearance efficacy without triggering mitochondrial dysfunction. In vivo experiments ascertain that LND@HMPB‐T7 could synergistically promote phagocytic clearance of Aβ, relieve neuroinflammation and ameliorate cognitive function in AD mice. These findings indicate that LND@HMPB‐T7 holds tremendous clinical potential as a repurposed drug for AD treatment.
Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis
Authors: Su Zhifang , Liu Kang-Kai , Xu Yu-Qi , Yan Bing , Wang Shuangyin , Guan Zong-Jie , Zou Yuqin , Fang Yu
Published: December 2024

Electrocatalytic synthesis of high‐value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO3‐) to ammonia (NH3), known as NO3RR, and the oxidation of 5‐hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NO3RR and HMFOR. We have synthesized a range of porous coordination cages (PCCs) that share the same topology and Co/Ni metal centers but incorporate different charged moeities, imparting them with distinct surface net charges. Electrocatalytic evaluations revealed that PCC‐Co demonstrated a voltage‐dependent activity in NO3RR. Conversely, PCC‐Ni exhibited a precisely adjustable product selectivity in HMFOR, contingent upon the cage's charge state. In‐situ analysis and Density functional theory (DFT) calculations underscored the profound impact of catalyst charge on the differential adsorption of reaction intermediates and the lowest free energy change (ΔG) during the pivotal reaction step, resulting in alterations to both activity and selectivity. These discoveries provide invaluable insights into the "structure‐performance relationship" of NO3RR/HMFOR catalysts, highlighting PCCs as promising contenders for advanced electrocatalysts.
Hybrid Enzyme‐Electrocatalyst Cascade Modified Gas‐Diffusion Electrodes for Methanol Formation from Carbon Dioxide
Authors: Wang Panpan , Wang Xin , Chandra Shubhadeep , Lielpetere Anna , Quast Thomas , Conzuelo Felipe , Schuhmann Wolfgang
Published: December 2024

We propose a hybrid electrocatalytic‐bioelectrocatalytic reaction cascade integrated on a gas diffusion electrode for CO2 reduction under selective formation of methanol. Ag‐Bi2O3 selectively reduces gaseous CO2 to formate at neutral pH conditions. A subsequent enzymatic cascade comprising formaldehyde dehydrogenase and alcohol dehydrogenase, which are both nicotinamide adenine dinucleotide (NAD)‐dependent, further reduce formate sequentially to formaldehyde and methanol. The enzymatically oxidized redox cofactor NAD+ is regenerated through the enzyme diaphorase which is electrochemically coupled to the electrode by embedding it into a cobaltocene‐based low‐potential redox polymer. Methanol formation is confirmed using a highly selective biosensor based on alcohol oxidase in combination with horseradish peroxidase integrated into a specifically adapted redox polymer. The proposed hybrid electrocatalytic‐bioelectrocatalytic cascade is an example for a general strategy for enhancing the selectivity of electrocatalytic reactions and/or to replace bioelectrochemically challenging steps such as the synthesis of formate from CO2 using highly oxygen‐sensitive formate dehydrogenases by more robust inorganic electrocatalysts.
Multifaceted Hidden Catalysis Revealed by Mechanistic Analysis of FeBr3‐Catalysed Arene Borylation
Authors: Britton Luke , Bage Andrew D. , McOnie Sarah L. , Thomas Stephen P.
Published: December 2024

Arene borylation reactions provide direct access to aryl organoboranes, including aryl boronic esters. Precious metals, namely Ir, Rh, Pt, remain the go‐to for metal‐catalysed borylation reactions, however, significant efforts have been expended in developing Earth‐abundant metal alternatives. The iron‐catalysed borylation of 2‐aryl pyridine derivatives with 9‐borabicyclo[3.3.1]nonane (H‐B‐9‐BBN) offers unique reactivity by using only FeBr3 as the catalyst, without added ligand(s). Mechanistic analysis of this borylation reaction revealed an alternative, hidden catalysis pathway whereby the iron salt acts not as a borylation catalyst, but as an initiator for the generation of a catalytically active haloborane, Br‐B‐9‐BBN. The roles of iron salt, Br‐B‐9‐BBN, and HBr in catalyst formation, the mode of catalytic turnover, and catalyst regeneration were all determined using single‐turnover and catalytic studies. The borylation reaction was found to proceed by a catalytic electrophilic borylation using, in situ generated, Br‐B‐9‐BBN. These studies highlight a new, orthogonal method of generating haloboranes and their previously unobserved role as hidden catalysts within arene borylation reactions.
Flavonoid‐Derived Probes for the Detection of Islet Amyloid Polypeptide Aggregates
Authors: Luo Zijie , Xu Yijia , Fan Jiayi , Lean Isabel E. , Davis Thomas P. , Javed Ibrahim , Kaur Amandeep
Published: December 2024

Type‐2 diabetes (T2D) is a growing global health crisis, with over 90% of diabetes cases attributed to this condition. Misfolding and aggregation of islet amyloid polypeptide (IAPP) is a hallmark of early T2D, contributing to pancreatic β‐cell dysfunction. While significant progress has been made in developing sensors for amyloids implicated in neurodegeneration, fluorescent probes for detecting IAPP aggregates remain limited. We report a series of flavonoid derivatives designed for enhanced IAPP fibril detection. The probes feature modifications, including methoxy substitution at C7 and varying amines at C4, which enhance their binding affinity for IAPP fibrils compared to the widely used Thioflavin T (ThT). The leading probes, F4 and MF1, exhibited over 10‐fold increased binding affinity compared to ThT, alongside ratiometric fluorescence due to excited‐state intramolecular proton transfer. F4 and MF1 were applied to image IAPP aggregates in pancreatic β‐cells and zebrafish tissue sections, where both probes demonstrated specific imaging of IAPP fibrils. These probes also demonstrated reduced fluorescence when IAPP monomers were incubated with inhibitors, indicating fibril disassembly. Our results position F4 and MF1 as promising tools for exploring the pathological role of IAPP aggregation in diabetes and for high‐throughput screening of IAPP aggregation inhibitors.
Poly(aminoamide) Based Fluorescent Microgel: A Functional Platform for Selective Detection and Discrimination of Cu2+ and Pb2+ Ions via Turn‐off/on Behavior in Water
Authors: Ghosh Soumen , Anand Aayush , Chattopadhyay Subrata
Published: December 2024

Selective detection of more than one metal ion contaminant in water using a single fluorescent probe is challenging. In this work, a one‐pot synthetic approach is presented to prepare fluorescent poly(aminoamide) microgel, which can detect simultaneously and selectively both Cu2+ and Pb2+ by fluorescent turn off and turn on at pH 7 and 12 respectively. Further, while testing water containing a mixture of both Cu2+ and Pb2+ as contaminants, the microgel can detect the characteristic presence of Cu2+ at pH 7 and Pb2+ at pH 12 via their respective turn‐off and on behavior. The mechanistic studies revealed that the dynamic quenching defines the fluorescent turn‐off behavior of the microgel in the presence of Cu2+. On the other hand, aggregation‐induced emission (AIE) is primarily responsible for the fluorescent turn‐on of the microgel in the presence of Pb2+. Additionally, applicability of microgels in real life industrial applications are checked by detecting the presence of both analytes in waste water sample collected from a local sewage treatment plant (STP water).