bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modulating the Inner Helmholtz Plane towards Stable Solid Electrolyte Interphase by Anion‐π Interactions for High‐Performance Anode‐Free Lithium Metal Batteries
Authors: Ma Shaobo , Zhao Jingteng , Xiao Huang , Gao Qixin , Li Fang , Song Congying , Li Guoxing 
Published: September 2024

AbstractAnode‐free lithium (Li) metal batteries (AFLBs) featured high energy density are viewed as the viable future energy storage technology. However, the irregular Li deposition and unstable solid electrolyte interphase (SEI) on anode current collectors reduce their cycling performance. Here, we propose a concept of anion‐recognition electrodes enabled by anion‐π interactions to regulate the inner Helmholtz plane (IHP) and electrolyte solvation chemistry for high‐performance AFLBs. By engineering the electrodes with electron‐deficient aromatic‐π systems that possess high permanent quadrupole moment (Qzz), the anion‐π interactions can be generated to concentrate the anions on the electrode surface and tune the IHP structure to construct a stable anion‐derived SEI layer, thus achieving highly reversible Li plating/stripping process. Through designing various current collectors with different Qzz values, the intimate correlations among the surface charge of the electrode, competitive adsorption of the IHP, and SEI structures are demonstrated. Particularly, the modified carbon cloth current collector with a high Qzz value (+35.1) delivers a high average Li stripping/plating Coulombic efficiency of 99.1 % over 230 cycles in the carbonated electrolyte, enabling a long lifespan and high capacity retention of LiNi0.8Co0.1Mn0.1O2‐based AFLBs with a commercial‐level areal capacity (4.1 mAh cm−2).
Stapled Peptides as Inhibitors of mRNA Deadenylation
Authors: Pal Sunit , Gordijenko Ilja , Schmeing Stefan , Biswas Somarghya , Akbulut Yasemin , Gasper Raphael , 't Hart Peter 
Published: September 2024

AbstractTherapeutic intervention targeting mRNA typically aims at reducing the levels of disease‐causing sequences. Achieving the opposite effect of blocking the destruction of beneficial mRNA remains underexplored. The degradation of mRNA starts with the removal of poly(A) tails, reducing their stability and translational activity, which is mainly regulated by the CCR4‐NOT complex. The subunit NOT9 binds various RNA binding proteins, that recruit mRNA in a sequence‐specific manner to the CCR4‐NOT complex to promote their deadenylation. These RNA binding proteins interact with NOT9 through a helical NOT9 binding motif, which we used as a starting point for development of the hydrocarbon stapled peptide NIP‐2. The peptide (KD=60.4 nM) was able to inhibit RNA‐binding (IC50=333 nM) as well as the deadenylation activity of the CCR4‐NOT complex in vitro while being cell‐permeable (cell‐permeability EC50=2.44 μM). A co‐crystal structure of NIP‐2 bound to NOT9 allowed further optimization of the peptide through point mutation leading to NIP‐2‐H27A‐N3 (KD=122 nM) with high cell permeability (cell‐permeability EC50=0.34 μM). The optimized peptide was able to inhibit deadenylation of target mRNAs when used in HeLa cells at a concentration of 100 μM, demonstrating the feasibility of increasing mRNA stability.
Dinuclear Cyclometalated Pincer Nickel(II) Complexes with Metal‐Metal‐to‐Ligand Charge Transfer Excited States and Near‐Infrared Emission
Authors: Gao Mengyue , To Wai‐Pong , Tong Glenna So Ming , Du Lili , Low Kam‐Hung , Tang Zhou , Lu Wei , Che Chi‐Ming 
Published: September 2024

AbstractFacile non‐radiative decay of low‐lying metal‐centered (MC) dd excited states has been well documented to pose a significant obstacle to the development of phosphorescent NiII complexes due to substantial structural distortions between the dd excited state and the ground state. Herein, we prepared a series of dinuclear Ni2II,II complexes by using strong σ‐donating carbene‐phenyl‐carbene (CNHC Cphenyl CNHC) pincer ligands, and prepared their dinuclear Pt2II,II and Pd2II,II analogues. Dinuclear Ni2II,II complexes bridged by formamidinate/α‐carbolinato ligand exhibit short Ni−Ni distances of 2.947–3.054 Å and singlet metal‐metal‐to‐ligand charge transfer (1MMLCT) transitions at 500–550 nm. Their 1MMLCT absorption energies are red‐shifted relative to the Pt2II,II and Pd2II,II analogues at ~450 nm and ≤420 nm respectively. One‐electron oxidation of these Ni2II,II complexes produces valence‐trapped dinuclear Ni2II,III species, which are characterized by EPR spectroscopy. Upon photoexcitation, these Ni2II,II complexes display phosphorescence (τ=2.6–8.6 μs) in the NIR (800–1400 nm) spectral region in 2‐MeTHF and in the solid state at 77 K, which is insensitive to π‐conjugation of the coordinated [CNHC Cphenyl CNHC] ligand. Combined with DFT calculations, the NIR emission is assigned to originate from the 3dd excited state. Studies have found that the dinuclear Ni2II,II complex can sensitize the formation of singlet oxygen and catalyze the oxidation of cyclo‐dienes under light irradiation.
Inner Side Chain Modification of Small Molecule Acceptors Enables Lower Energy Loss and High Efficiency of Organic Solar Cells Processed with Non‐halogenated Solvents
Authors: Wu Xiangxi , Gong Yufei , Li Xiaojun , Qin Shucheng , He Haozhe , Chen Zekun , Liang Tongling , Wang Caixuan , Deng Dan , Bi Zhaozhao , Ma Wei , Meng Lei , Li Yongfang 
Published: September 2024

AbstractOrganic solar cells (OSCs) processed with non‐halogenated solvents usually suffer from excessive self‐aggregation of small molecule acceptors (SMAs), severe phase separation and higher energy loss (Eloss), leading to reduced open‐circuit voltage (Voc) and power conversion efficiency (PCE). Regulating the intermolecular interaction to disperse the aggregation and further improve the molecular packing order of SMAs would be an effective strategy to solve this problem. Here, we designed and synthesized two SMAs L8‐PhF and L8‐PhMe by introducing different substituents (fluorine for L8‐PhF and methyl for L8‐PhMe) on the phenyl end group of the inner side chains of L8‐Ph, and investigated the effect of the substituents on the intermolecular interaction of SMAs, Eloss and performance of OSCs processed with non‐halogenated solvents. Through single crystal analysis and theoretical calculations, it is found that compared with L8‐PhF, which possesses strong and abundant intermolecular interactions but downgraded molecular packing order, L8‐PhMe with the methyl substituent possesses more effective non‐covalent interactions, which improves the tightness and order of molecular packing. When blending the SMAs with polymer donor PM6, the differences in intermolecular interactions of the SMAs influenced the film formation process and phase separation of the blend films. The L8‐PhMe based blend film exhibits shorten film formation and more homogeneous phase separation than those of the L8‐PhF and L8‐Ph based ones. Especially, the OSCs based on L8‐PhMe show reduced non‐radiative energy loss and enhanced Voc than the devices based on the other two SMAs. Consequently, the L8‐PhMe based device processed with o‐xylene (o‐XY) and using 2PACz as the hole transport layer (HTL) shows an outstanding PCE of 19.27 %. This study highlights that the Eloss of OSCs processed with non‐halogenated solvents could be decreased through regulating the intermolecular interactions of SMAs by inner side chain modification, and also emphasize the importance of effectivity rather than intensity of non‐covalent interactions introduced in SMAs on the molecular packing, morphology and PCE of OSCs.
f–π* Back‐Bonding Orbital Induced by a Lutetium‐Based Conducting Metal–Organic Framework Promotes Highly Selective CO2‐to‐CH4 Conversion at Low Potential
Authors: Yu Fuqing , Zhang Guangyao , Shu Minxing , Wang Hongming 
Published: September 2024

AbstractThe research on electrocatalytic carbon dioxide reduction (ECR) catalysts using renewable energy is particularly crucial in energy conversion studies, especially for viable hydrocarbon production. This study employs density functional theory calculations to screen a series of non‐radioactive lanthanide two‐dimensional metal–organic frameworks (MOFs) for product selectivity in ECR. Based on theoretical screening, our focus is on a lutetium (Lu)‐based conducting MOF (Lu‐HHTP), which exhibits a Faradaic efficiency of approximately 77 % for methane (CH4) production and maintains a stable current density of −280 mA/cm2 at −1.1 V vs. RHE. In situ electrochemical experiments and material characterization demonstrate that the Lu sites possess high coordination stability and structural recoverability during catalytic CO2 reduction, attributed to the overlap between Lu′s f‐orbitals and the π*‐orbitals of the ligand O, and the formation of back bonding orbitals between the f‐orbitals of Lu and the π* orbitals of CO contribute increasing CH4 selectivity and lowering the potential. This study leverages rare‐earth MOF‐type materials, offering a novel approach to addressing low conductivity and stabilizing rare‐earth materials, thereby establishing a theoretical framework for the conversion of linearly adsorbed *CO into hydrocarbons.
NIR‐Activable Charge Transfer Agents for Synergistic Photoimmunotherapy
Authors: Wang Chu , Zhong Wenbin , Sun Xiaohuan , Guo Jingjing , Chen Yun , Zhao Yue , Han Jie , Zhao Yanli 
Published: September 2024

AbstractThe combination of photothermal therapy (PTT) and photodynamic therapy (PDT) has become an attractive tumor treatment modality, yet the facile design of photoimmunotheranostic agents with efficient near infrared (NIR) light‐absorbing and immune‐activating capabilities remains a tremendous challenge. Herein, we developed a NIR‐activable organic charge transfer complex (CTC), with perylene (PER) as the electron donor and 4,5,9,10‐tetrabromoisochromeno [6,5,4‐def]isochromene‐1,3,6,8‐tetraone (Br4NDI) as the electron acceptor. Through further supramolecular assembly, the PER‐Br4NDI nanoparticle (PBND NP) for spatiotemporally controlled photoimmunotherapy was constructed. The PBND NP exhibits superb NIR absorption, robust intermolecular charge transfer, and enhanced intersystem crossing. Upon NIR photoirradiation, the PBND NP effectively exerts photothermal and photodynamic effects with a remarkable photothermal conversion efficiency of 63.5 % and a high reactive oxygen species generation capability, which not only directly ablates primary tumors, but also dramatically suppresses distant tumor growth via promoted immunogenic cell death. Moreover, programmed cell death protein 1 antibody acts synergistically to block immune evasion and ultimately enhances cancer treatment efficacy. This work therefore sheds light on the design of organic CTCs for synergistic photoimmunotherapy.
Emulating “Curvature‐Enhanced Adsorbate Coverage” for Superconformal and Orientated Zn Electrodeposition in Zinc‐ion‐Batteries
Authors: Wang Huibo , Liu Yi , Zhu Mengyu , Chen Yuejin , Chen Danling , Lin Zhimin , Wang Kexuan , Xu Zhu , Chen Shi , Xing Guichuan , Malyi Oleksandr I. , Tang Yuxin , Zhang Yanyan 
Published: September 2024

AbstractUneven Zn deposition and unfavorable side reactions have prevented the reversibility of the Zn anode. Herein, we design a rearranged (002) textured Zn anode inspired by a traditional curvature‐enhanced adsorbate coverage (CEAC) process to realize the highly reversible Zn anode. The rearranged (002) textured structure directs superconformal Zn deposition by controlling the spatial deposition rate of the rearranged crystal planes, thereby promoting bottom‐up “superfilling” of the 3D Zn skeletons. Meanwhile, our designed anode also induces the epitaxial Zn deposition, alleviating the parasitic reactions owing to the lowest surface energy of the (002) plane. Attributed to these superiorities, uniform and oriented Zn deposition can be obtained, exhibiting an ultra‐long lifespan over 479 hrs at an ultrahigh depth of discharge (DOD) of 82.12 %. The Zn|Na2V6O16 ⋅ 3H2O battery delivers an improved cycling performance, even at a high area capacity of 5.15 mAh/cm2 with a low negative/positive (N/P) capacity ratio of 1.63. The superconformal deposition approach for Zn anodes paves the way for the practical application of high‐performance zinc‐ion batteries.
Chemo‐Enzymatic Depolymerization of Functionalized Low‐Molecular‐Weight Polyethylene
Authors: Oiffer Thomas , Leipold Friedemann , Süss Philipp , Breite Daniel , Griebel Jan , Khurram Muhammad , Branson Yannick , de Vries Erik , Schulze Agnes , Helm Christiane A. , Wei Ren , Bornscheuer Uwe T. 
Published: September 2024

AbstractPolyethylene (PE) is the most commonly used plastic type in the world, contributing significantly to the plastic waste crisis. Microbial degradation of PE in natural environments is unlikely due to its inert saturated carbon‐carbon backbones, which are difficult to break down by enzymes, challenging the development of a biocatalytic recycling method for PE waste. Here, we demonstrated the depolymerization of low‐molecular‐weight (LMW) PE using an enzyme cascade that included a catalase‐peroxidase, an alcohol dehydrogenase, a Baeyer Villiger monooxygenase, and a lipase after the polymer was chemically pretreated with m‐chloroperoxybenzoic acid (mCPBA) and ultrasonication. In a preparative experiment with gram‐scale pretreated polymers, GC‐MS and weight loss determinations confirmed ~27 % polymer conversion including the formation of medium‐size functionalized molecules such as ω‐hydroxycarboxylic acids and α,ω‐carboxylic acids. Additional analyses of LMWPE‐nanoparticles using AFM showed that enzymatic depolymerization reduced the sizes of these mCPBA‐ and enzyme‐treated LMWPE‐nanoparticles. This multi‐enzyme catalytic concept with distinct chemical steps represents a unique starting point for future development of bio‐based recycling methods for polyolefin waste.
Visible‐Light‐Driven Solid‐State Fluorescent Photoswitches for High‐Level Information Encryption
Authors: Han Zhiyuan , He Meixia , Wang Gang , Lehn Jean‐Marie , Li Quan 
Published: September 2024

AbstractDeveloping visible‐light‐driven fluorescent photoswitches in the solid state remains an enormous challenge in smart materials. Such photoswitches are obtained from salicylaldimines through excited‐state intramolecular proton transfer (ESIPT) and subsequent cis‐trans isomerization strategies. By incorporating a bulky naphthalimide fluorophore into a Schiff base, three photoswitches achieve dual‐mode changes (both in color and fluorescence) in the solid state. In particular, the optimal one generates triple fluorescence changing from green, to yellow and finally to orange upon visible‐light irradiation. This switching process is fully reversible and can be repeated at least 10 times without obvious attenuation, suggesting its good photo‐fatigue resistance. Mechanism studies reveal that the naphthalimide group not only enables the tuning of multicolor with an additional emission, but also induces a folded structure, reducing molecular stacking and facilitating ESIPT and cis‐trans isomerization. As such, photopatterning, ternary encoding and transient information recording and erasing are successfully developed. The present study provides a reliable strategy for visible‐light‐driven fluorescent photoswitches, showing implications for advanced information encryption materials.
Stabilizing Hydrogen Radicals in Two‐Dimensional Cobalt‐Copper Mesoporous Nanoplates for Complete Nitrate Reduction Electrocatalysis to Ammonia
Authors: Han Chenyu , Sun Lizhi , Han Shu , Liu Ben 
Published: September 2024

AbstractAmbient electrochemical reduction of waste nitrate (NO3−) represents an alternative green route for sustainable ammonia (NH3) electrosynthesis in water. Despites some encouraged achievements, sluggish eight electron and nine proton reduction routes that involve multi‐step hydrogenation pathways have severely hindered their NH3 Faradaic efficiency (FENH3) and yield rate. Herein, we develop a robust two‐dimensional mesoporous cobalt‐copper (meso‐CoCu) nanoplate electrocatalyst that delivers excellent performance of complete NO3− reduction reaction (NO3RR), including superior FENH3 of 98.8 %, high NH3 yield rate of 3.39 mol h−1 g−1 and energy efficiency of 49.8 %, and good cycling stability. Mechanism investigations unveil that active hydrogen (*H) radicals produced from water splitting on Co sites spillover to adjacent Cu sites and further stabilize within confined mesopores, which kinetically promote its coupling hydrogenation reactions of nitrogen intermediates and thus facilitate complete NO3RR for favorable NH3 electrosynthesis. Moreover, meso‐CoCu nanoplates perform well as a bifunctional electrocatalyst in the two‐electrode coupling system that concurrently synthesizes NH3 from NO3− at cathode and 2,5‐furanedicarboxylic acid from 5‐hydroxymethylfurfural at anode. This work in stabilizing *H radicals in mesoporous microenvironment provides some insights applied to various hydrogenation reactions for selective electrosynthesis of high value‐added chemicals in water.
Electrochemically Driven Asymmetric Hydrogenation of Aromatic Ketones by Noyori–Ikariya Catalyst
Authors: Zhu Jing‐Wei , Wang Le‐Ting , Wang Ya‐Li , Chen Lei‐Bing , Lu Jia‐Xing , Wang Huan 
Published: September 2024

ABSTRACTThe electrochemically driven asymmetric hydrogenation of 2,2,2‐trifluoroacetophenone was performed using a Noyori–Ikariya catalyst, yielding a 97% product yield and a 47% enantiomeric excess (ee) with a charge input of only 0.5 F/mol. In comparison, the ethoxylate anion generated by the electroreduction of the solvent, EtOH, can efficiently drive the transfer hydrogenation of Ru catalysts more effectively than organic bases. After optimizing the electrolysis conditions, this method has been successfully extended to other aromatic ketones, including heterocyclic aromatic ketones and the base‐sensitive substrate ethyl benzoylformate, with yields ranging from 71% to 97% and ee values ranging from 55% to 82%. A possible reaction mechanism was proposed.
Aggregation‐Enhanced Photodynamic Activity of Organometallic Ru(II)–Arene Complexes
Authors: Bu Jingjing , Xu Zhiwei , Sun Yanyan , Gao Ya , Zhao Jian , Xu Gang 
Published: September 2024

ABSTRACTOrganometallic Ru(II)–arene complexes have emerged as potential chemotherapeutic agents for improved cancer treatment. However, the application of Ru(II)–arene complexes as photosensitizers has been rarely explored. In consideration of their excellent biological performance, herein, three Ru(II)–arene complexes 1–3 bearing 2,3,8,9,14,15‐hexamethyl‐5,6,11,12,17,18‐hexaazatrinapthalene (HATN‐Me6) as acceptor ligand have been designed and investigated as potential photosensitizers. Distinctively, complexes 1–3 produced negligible singlet oxygen (1O2) generation in DMF. The mechanism investigations indicated that the large change in equilibrium displacement between the excited and ground states rather than narrow energy gap results in the increased vibrational wave function overlap and non‐radiative decay rate. Remarkably, complexes 1–3 induced greatly enhanced 1O2 generation efficiency in an aggregated state due to the suppression of the non‐radiative decay process, implying that the electronic structures of excited states play an essential role in the photochemical properties and functions of the organometallic Ru(II)–arene complexes. The biological evaluation showed that complexes 1–3 exhibited potent photocytotoxicity against cancer cells, highlighting that organometallic Ru(II)–arene scaffolds are potential platforms for the fabrication of efficient photosensitizers.
Development of morphine analgesia using biocompatible synthesized molecular imprinted hydrogel based on tragacanth gum
Authors: Hassanzadeh Marjan , Ghaemy Mousa , Ahmadi Shamseddin , Amininasab S. Mojtaba , Miraki Fatemeh 
Published: September 2024

AbstractA novel molecular imprinted hydrogel using tragacanth gum (MITMIH) was synthesized for extending morphine analgesic efficacy by controlled release. The characterized MITMIH was used as a new morphine carrier that can increase analgesic time window after its single injection in mice. During in vitro optimization, the MITMIH showed maximum adsorption capacity (~113 mg g−1) at pH = 6.5 after 20 min immersion (400 μM initial morphine concentration, 10 mg MITMIH). During in vivo test, we examined the analgesic effect in mice by dissolving morphine in physiologic saline or by loading on MITMIH. The results of a single injection revealed that morphine‐loaded MITMIH shifted the time profile of morphine analgesia from 123.4 to 257.6 min. This indicates almost 100% efficacy in the controlled release of the drug during 5 h after the injection. Furthermore, cytotoxicity and mitochondrial membrane potential test was evaluated against normal rat kidney epithelial (NRK) and Rat Dermal Fibroblasts (RDF). The results confirmed that the MITMIH could be considered as a potential carrier increasing length of morphine analgesia after the first single injection without any cytotoxicity and negative effect on cell tissues. This may in turn reduce repeated use of the drug to achieve satisfactory analgesia in patients with chronic pain.
PVA‐based Hydrogel Materials for Underwater Energy Storage and Underwater Sensing
Authors: Zhou Peidi , Xu Bingjie , Feng Haihang , Luo Zhiling , Weng Mingcen 
Published: September 2024

AbstractAs human exploration of marine continues to expand, the demand for underwater devices is also increasing. The unique properties of hydrogel materials make them well‐suited for underwater applications. We propose a multi‐functional polyvinyl alcohol (PVA) – NaCl @ Polyaniline (PANI) (PNP) hydrogel, which is characterized by easy fabrication, integrated structure, and flexibility, and can be directly applied in the fields of underwater energy storage and underwater sensing. Solid‐state supercapacitors fabricated by the PNP hydrogel, due to integrated and all‐solid‐state design, can be charged and discharged underwater without encapsulation. What's more, the PNP supercapacitor can maintain a capacitance retention rate of over 90 % after 5,000 cycles in simulated seawater, eliminating concerns about the hydrogel's dehydration when used underwater. The PNP hydrogel with an integrated three‐layer structure can also be applied to the capacitive pressure sensors, which can also be directly used in underwater environments without the need for encapsulation, significantly reducing the structural complexity and preparation steps of the device. Finally, we demonstrate a “supercapacitor module” with a voltage window greater than 1.6 V created by directly connecting multiple PNP supercapacitors in series, as well as an underwater intelligent glove, providing new solutions for underwater energy storage and underwater wearable sensing applications.