bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractBioorthogonalized 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

AbstractThe 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.
Conformer‐Mediated Helical Chirality in 2D Layered Hybrid Perovskites
Authors: Dutta Taniya , Swain Diptikanta , Nag Angshuman 
Published: December 2024

AbstractTwo‐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

AbstractNa4Fe3(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

AbstractPeptide 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

AbstractNanoimprint 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

AbstractThe 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

AbstractImperfections 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

AbstractControlling 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

AbstractCircularly 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

AbstractSulfurized 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

AbstractThe 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

AbstractSluggish 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.