bluuebunny/crossref_metadata_2025_split huggingface dataset:
Boosting CO2 Electroreduction over a Covalent Organic Framework in the Presence of Oxygen
Authors: Guo Hui , Si Duan‐Hui , Zhu Hong‐Jing , Chen Zi‐Ao , Cao Rong , Huang Yuan‐Biao 
Published: February 2024

AbstractHerein, we propose an oxygen‐containing species coordination strategy to boost CO2 electroreduction in the presence of O2. A two‐dimensional (2D) conjugated metal‐covalent organic framework (MCOF), denoted as NiPc‐Salen(Co)2‐COF that is composed of the Ni‐phthalocyanine (NiPc) unit with well‐defined Ni−N4−O sites and the salen(Co)2 moiety with binuclear Co−N2O2 sites, is developed and synthesized for enhancing the CO2RR under aerobic condition. In the presence of O2, one of the Co sites in the NiPc‐Salen(Co)2‐COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO2 molecules and stabilize the key intermediate *COOH of the CO2RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni−N4−O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO2RR. Thus, NiPc‐Salen(Co)2‐COF exhibits high oxygen‐tolerant CO2RR performance and achieves outstanding CO Faradaic efficiency (FECO) of 97.2 % at −1.0 V vs. the reversible hydrogen electrode (RHE) and a high CO partial current density of 40.3 mA cm−2 at −1.1 V in the presence of 0.5 % O2, which is superior to that in pure CO2 feed gas (FECO=94.8 %, jCO=19.9 mA cm−2). Notably, the NiPc‐Salen(Co)2‐COF achieves an industrial‐level current density of 128.3 mA cm−2 in the flow‐cell reactor with 0.5 % O2 at −0.8 V, which is higher than that in pure CO2 atmosphere (jCO=104.8 mA cm−2). It is worth noting that an excellent FECO of 86.8 % is still achieved in the presence of 5 % O2 at −1.0 V. This work provides an effective strategy to enable the CO2RR under O2 atmosphere by utilizing the *OOH intermediates of ORR to boost CO2 electroreduction.
Breaking Iron Homeostasis: Iron Capturing Nanocomposites for Combating Bacterial Biofilm
Authors: Sun Wenyue , Sun Jiao , Ding Qihang , Qi Manlin , Zhou Jing , Shi Yujia , Liu Jia , Won Miae , Sun Xiaolin , Bai Xue , Dong Biao , Kim Jong Seung , Wang Lin 
Published: February 2024

AbstractGiven the scarcity of novel antibiotics, the eradication of bacterial biofilm infections poses formidable challenges. Upon bacterial infection, the host restricts Fe ions, which are crucial for bacterial growth and maintenance. Having coevolved with the host, bacteria developed adaptive pathways like the hemin‐uptake system to avoid iron deficiency. Inspired by this, we propose a novel strategy, termed iron nutritional immunity therapy (INIT), utilizing Ga‐CT@P nanocomposites constructed with gallium, copper‐doped tetrakis (4‐carboxyphenyl) porphyrin (TCPP) metal–organic framework, and polyamine‐amine polymer dots, to target bacterial iron intakes and starve them. Owing to the similarity between iron/hemin and gallium/TCPP, gallium‐incorporated porphyrin potentially deceives bacteria into uptaking gallium ions and concurrently extracts iron ions from the surrounding bacteria milieu through the porphyrin ring. This strategy orchestrates a “give and take” approach for Ga3+/Fe3+ exchange. Simultaneously, polymer dots can impede bacterial iron metabolism and serve as real‐time fluorescent iron‐sensing probes to continuously monitor dynamic iron restriction status. INIT based on Ga‐CT@P nanocomposites induced long‐term iron starvation, which affected iron‐sulfur cluster biogenesis and carbohydrate metabolism, ultimately facilitating biofilm eradication and tissue regeneration. Therefore, this study presents an innovative antibacterial strategy from a nutritional perspective that sheds light on refractory bacterial infection treatment and its future clinical application.
Anion‐Involved Solvation Structure of Lithium Polysulfides in Lithium–Sulfur Batteries
Authors: Song Yun‐Wei , Shen Liang , Yao Nan , Feng Shuai , Cheng Qian , Ma Jin , Chen Xiang , Li Bo‐Quan , Zhang Qiang 
Published: February 2024

AbstractLithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium–sulfur (Li−S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li−S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion‐involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li−S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li−S batteries.
Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover
Authors: Tan Qiang , Li Linsen , Li Yuefei , Jiang Zhao , Ma Yuanyuan , Qu Yongquan , Li Jiayuan 
Published: February 2024

AbstractElectrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low production efficiency or high energy consumption. Here, we describe a tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, is partnered with component (ii), which can readily release hydrogen for hydrogenation, to enable efficient generation of active hydrogen on component (i) at low overpotentials and timely (i)‐to‐(ii) hydrogen spillover and facile desorptive hydrogenation on component (ii). We examine this concept over bicomponent palladium‐copper catalysts for the production of representative 2‐methyl‐3‐butene‐2‐ol (MBE) from 2‐methyl‐3‐butyne‐2‐ol (MBY) and achieve a record high MBE production rate of 1.44 mmol h−1 cm−2 and a Faraday efficiency of ~88.8 % at a low energy consumption of 1.26 kWh kgMBE−1. With these catalysts, we further achieve 60 h continuous production of MBE with record high profit space.
Spidroin‐mimetic Engineered Protein Fibers with High Toughness and Minimized Batch‐to‐batch Variations through β‐sheets Co‐assembly
Authors: Qin Dawen , Wang Mengyao , Cheng Wenhao , Chen Jing , Wang Fan , Sun Jing , Ma Chao , Zhang Yingying , Zhang Hongjie , Li Huanrong , Liu Kai , Li Jingjing 
Published: February 2024

AbstractSynthetic spidroin fibers have not yet attained the same level of toughness and stability as natural spider silks due to the complexity of composition and hierarchical structure. Particularly, understanding the intricate interactions between spidroin components in spider fiber is still elusive. Herein, we report modular design and preparation of spidroin‐mimetic fibers composed of a conservative C‐terminus spidroin module, two different natural β‐sheets modules, and a non‐spidroin random‐coil module. The resulting fibers exhibit a toughness of ~200 MJ/m3, reaching the highest value among the reported artificial spider silks. The interactions between two components of recombinant spidroins facilitate the intermolecular co‐assembly of β‐sheets, thereby enhancing the mechanical strength and reducing batch‐to‐batch variability in the dual‐component spidroin fibers. Additionally, the dual‐component spidroin fibers offer potential applications in implantable or even edible devices. Therefore, our work presents a generic strategy to develop high‐performance protein fibers for diverse translations in different scenarios.
Anionic Hydrogen‐Bonded Frameworks Showing Tautomerism and Colorful Luminescence for the Ultrasensitive Detection of Acetone
Authors: Wang Shuaiqi , Liu Jun , Feng Shangwei , Wu Junyan , Yuan Zhen , Chen Banglin , Ling Qidan , Lin Zhenghuan 
Published: February 2024

AbstractTautomers coexisting in an equilibrium system have significant potential for regulating luminescent properties because of their structural differences. However, separating and stabilizing tautomers at room temperature is a considerable challenge. In this study, it is found that hydrogen‐bonded organic frameworks (HOFs) composed of Br‐ anions can effectively separate and stabilize two proton‐transfer tautomers of triarylformamidinium bromide: namely, the nitrogen cation (BA‐N) and carbon cation (BA‐C). The BA‐N crystal consisting of a dense anionic HOF and parallelly aligned organic cations exhibits green thermally activated delayed fluorescence and red room‐temperature phosphorescence (RTP). The BA‐C crystal contains acetone molecules that induce an antiparallel arrangement of the organic cations to form a loose HOF, producing blue prompt fluorescence and green RTP. Interestingly, switching of the HOFs between BA‐N and BA‐C can be achieved through the uptake and release of acetone, thereby dynamically adjusting multiple luminescent properties. Consequently, the HOF crystals can be used for the highly sensitive and specific sensing of acetone with a detection limit of 66.74 ppm. This study not only stabilizes tautomeric luminescent materials at room temperature, but also provides a new method for constructing smart HOFs with a sensitive response to a stimulus.
Nanoscale Visualization of Lithium Plating/Stripping Tuned by On‐site Formed Solid Electrolyte Interphase in All‐Solid‐State Lithium‐Metal Batteries
Authors: Shen Zhen‐Zhen , Zhang Xu‐Sheng , Wan Jing , Liu Gui‐Xian , Tian Jian‐Xin , Liu Bing , Guo Yu‐Guo , Wen Rui 
Published: February 2024

AbstractThe interfacial processes, mainly the lithium (Li) plating/stripping and the evolution of the solid electrolyte interphase (SEI), are directly related to the performance of all‐solid‐state Li‐metal batteries (ASSLBs). However, the complex processes at solid‐solid interfaces are embedded under the solid‐state electrolyte, making it challenging to analyze the dynamic processes in real time. Here, using in situ electrochemical atomic force microscopy and optical microscopy, we directly visualized the Li plating/stripping/replating behavior, and measured the morphological and mechanical properties of the on‐site formed SEI at nanoscale. Li spheres plating/stripping/replating at the argyrodite solid electrolyte (Li6PS5Cl)/Li electrode interface is coupled with the formation/wrinkling/inflating of the SEI on its surface. Combined with in situ X‐ray photoelectron spectroscopy, details of the stepwise formation and physicochemical properties of SEI on the Li spheres are obtained. It is shown that higher operation rates can decrease the uniformity of the Li+‐conducting networks in the SEI and worsen Li plating/stripping reversibility. By regulating the applied current rates, uniform nucleation and reversible plating/stripping processes can be achieved, leading to the extension of the cycling life. The in situ analysis of the on‐site formed SEI at solid‐solid interfaces provides the correlation between the interfacial evolution and the electrochemical performance in ASSLBs.
Enhancing the Crystallinity of Keto‐enamine‐Linked Covalent Organic Frameworks through an in situ Protection‐Deprotection Strategy
Authors: Koner Kalipada , Mohata Shibani , Ogaeri Yutaro , Nishiyama Yusuke , Addicoat Matthew A. , Banerjee Rahul 
Published: February 2024

Abstractβ‐Keto‐enamine‐linked 2D covalent organic frameworks (COFs) have emerged as highly robust materials, showing significant potential for practical applications. However, the exclusive reliance on 1,3,5‐triformylphloroglucinol (Tp aldehyde) in the design of such COFs often results in the production of non‐porous amorphous polymers when combined with certain amine building blocks. Attempts to adjust the crystallinity and porosity by a modulator approach are inefficient because Tp aldehyde readily forms stable β‐keto‐enamine‐linked monomers/oligomers with various aromatic amines through an irreversible keto‐enol tautomerization process. Our research employed a unique protection‐deprotection strategy to enhance the crystallinity and porosity of β‐keto‐enamine‐linked squaramide‐based 2D COFs. Advanced solid‐state NMR studies, including 1D 13C CPMAS, 1H fast MAS, 15N CPMAS, 2D 13C−1H correlation, 1H−1H DQ‐SQ, and 14N−1H HMQC NMR were used to establish the atomic‐level connectivity within the resultant COFs. The TpOMe‐Sqm COFs synthesized utilizing this strategy have a surface area of 487 m2 g−1, significantly higher than similar COFs synthesized using Tp aldehyde. Furthermore, detailed time‐dependent PXRD, solid‐state 13C CPMAS NMR, and theoretical DFT studies shed more light on the crystallization and linkage conversion processes in these 2D COFs. Ultimately, we applied this protection‐deprotection method to construct novel keto‐enamine‐linked highly porous organic polymers with a surface area of 1018 m2 g−1.
Gain of Function Recyclable Photoswitches: Reversible Simultaneous Substitution and Photochromism Generation
Authors: Zitzmann Max , Fröhling Matthias , Dube Henry 
Published: February 2024

AbstractThe use of molecular photoswitches has spread to virtually every field of pure and applied chemistry because of the extraordinary level of control they provide over the behavior of matter at the smallest scales. Photoswitches possess at least two different states with distinct structures and/or electronics and further functionalization of their core chromophore structures is needed to tailor them for a specific application. In this work we present a different concept for the generation and use of molecular photoswitches. It allows not only simultaneous establishment of photochromism and functionalization, but also full recyclability of a non‐photochromic precursor material. Using a high‐yielding and reversible ammonium salt formation, a functional group is introduced into a symmetric precursor while at the same time a strong electronic push‐pull character is established in the structure. The resulting desymmetrization leads to efficient photoswitching capacity and the functional group can be fully removed subsequently by a simple heating step recovering the precursor for another functionalization round. We finally demonstrate feasibility of this concept over two consecutive closed loop functionalization/photoswitching/recovery steps. This concept offers great potential in any chemical research and application driven area but especially for the creation of responsive reprogrammable materials, no‐background photoswitch labeling, and sustainable chemistry.
Role of Surface Terminations for Charge Storage of Ti3C2Tx MXene Electrodes in Aqueous Acidic Electrolyte
Authors: Liu Liyuan , Raymundo‐Piñero Encarnacion , Sunny Sanjay , Taberna Pierre‐Louis , Simon Patrice 
Published: February 2024

AbstractIn this study, we used 2‐Dimmensionnal Ti3C2 MXene as model materials to understand how the surface groups affect their electrochemical performance. By adjusting the nature of the surface terminations (Cl‐, N/O‐, and O‐) of Ti3C2 MXene through a molten salt approach, we could change the spacing between MXene layers and the level of water confinement, resulting in significant modifications of the electrochemical performance in acidic electrolyte. Using a combination of techniques including in‐operando X‐ray diffraction and electrochemical quartz crystal microbalance (EQCM) techniques, we found that the presence of confined water results in a drastic transition from an almost electrochemically inactive behavior for Cl‐terminated Ti3C2 to an ideally fast pseudocapacitive signature for N,O‐terminated Ti3C2 MXene. This experimental work not only demonstrates the strong connection between surface terminations and confined water but also reveals the importance of confined water on the charge storage mechanism and the reaction kinetics in MXene.
Coherent Modulation of the Aggregation Behavior and Intramolecular Charge Transfer in Small Molecule Probes for Sensitive and Long‐term Nerve Agent Monitoring
Authors: Xiao Fangfang , Lei Da , Liu Chaogan , Li Yushu , Ren Wenfei , Li Jiguang , Li Dezhong , Zu Baiyi , Dou Xincun 
Published: February 2024

AbstractAggregation‐induced emission (AIE) shows promising performance in chemical sensing relying on the change of the emission behavior of the probe molecule monomers to the aggregated product. However, whether the response contrast could be further boosted by utilizing the emission property of the aggregated probe and the aggregated product remains a big challenge. Here, an exciting AIE probe regulation strategy was proposed by coherently modulating the aggregation behavior and the intramolecular charge transfer (ICT) property of the probes and thus an aggregated‐to‐aggregated colorimetric‐fluorescent dual‐mode detection was achieved. The blue emissive film obtained with the optimal AIE probe has been proven to be effective to recognize the vapor of nerve agent analog DCP in air by emitting a sharp green fluorescence. In addition, a porous polymer‐based wet sensing chip loaded with the probe enables the immediate response to DCP vapor with a limit of detection (LOD) of 1.7 ppb, and it was further integrated into a wearable watch device for long‐term monitoring of DCP vapor up to two weeks. We expect the present probe design strategy would greatly deepen the AIE‐based science and provide new insights for long‐term monitoring sensors toward trace hazardous substances.
Electrophilic Activation of S−Si Reagents by Silylium Ions for Their Regio‐ and Diastereoselective Addition Across C−C Multiple Bonds
Authors: Zuo Honghua , Irran Elisabeth , Klare Hendrik F. T. , Oestreich Martin 
Published: February 2024

AbstractA regioselective silylium‐ion‐promoted thiosilylation of internal C−C triple bonds with control over the double bond geometry is described. Both a C(sp2)−S and a C(sp2)−Si bond are formed with a trans relationship in this two‐component reaction of an alkyne and a thiosilane. The resulting orthogonally functionalized C−C double bond can be chemoselectively defunctionalized or further processed by cross‐coupling reactions with the alkene configuration retained. The procedure is also applicable to the regio‐ and diastereoselective thiosilylation of terminal allenes to arrive at allylic thioethers containing a vinylsilane unit. These reactions involve the electrophilic activation of the S−Si reagent, both a silylated thiophenol and even alkylthiol derivative, by an in situ‐generated carbocation intermediate. The catalytic cycle is maintained by a bissilylated aryl‐ or alkylsulfonium ion as a shuttle for the cationic silicon electrophile. Its independent preparation and structural characterization by X‐ray diffraction are also reported.
Catalytic combustion of toluene performance over MnOx catalysts: Effect of KMnO4 content
Authors: Li Haiyang , Song Zhongxian , Zhang Zhuofu , Zhang Xuejun , Mao Yanli , Liu Wei , Huang Zhenzhen , Zhang Jinhui , Dong Danyan , Luo Yulong 
Published: February 2024

MnOx samples were prepared and applied to the catalytic combustion of toluene. The results indicated that the KMnO4 content was important to the catalytic performance. Cat‐0.2 (0.2 g KMnO4) possessed the best catalytic performance, and more than 90% of toluene conversion was 255°C. Moderate amounts of KMnO4 facilitated the generation of mixed crystalline phases and structural defects, which led to the generation of more oxygen vacancies. In addition, the Cat‐0.2 possessed high contents of Oads/(Oads + Olatt) and Mn3+/(Mn3+ + Mn4+), which promoted the emergence‐annihilation cycle of oxygen vacancies and facilitated the reaction process of toluene. The reaction pathway of toluene was investigated via in situ DRIFTS, in which the by‐products included benzyl alcohol, benzaldehyde, benzoate, maleic anhydride, and short‐chain carbonate. Among them, benzoate was the main intermediate in the catalytic oxidation process of toluene.
Facial fabrication of self‐healing natural rubber foam based on zinc thiolate ionic networks
Authors: Majid Noor Aishatun , Rehman Abdul , Mohd Sani Noor Faezah , Hayeemasae Nabil , Ismail Hanafi , Masraff Mimi Syahira , Shuib Raa Khimi 
Published: February 2024

AbstractIn this work, self‐healing natural rubber (SHNR) foam incorporating an intrinsic zinc thiolate ionic network was successfully prepared. The materials exhibited the ability to autonomously repair damage at room temperature without the need for external triggers. The investigation focused on the effect of sodium bicarbonate, employed as a blowing agent, on the self‐healing performance, as well as the physical and mechanical properties of the foam. Various concentrations of sodium bicarbonate (0, 1, 4, 8, and 10 phr) were employed. The conventional two‐roller mill was used for mixing and compounding, while compression molding was utilized for the vulcanization process. With increasing sodium bicarbonate concentration, the density, tensile strength, elongation at break, and compression set of the self‐healing NR foam were found to decreased. Conversely, the porosity, shrinkage, compressive strength, and water uptake of the SHNR foam increased as the concentration of sodium bicarbonate increased. Scanning electron microscopy analysis revealed that the optimal concentration of sodium bicarbonate (8 phr) resulted in smaller, finer, and more uniform porous structures. The self‐healing rubber foam incorporating 8 phr sodium bicarbonate exhibited improved properties in terms of tensile modulus, elongation at break, and tear strength, with healing efficiencies of 91.27%, 69.39%, and 83.99%, respectively.
On the spinal venous sinus of Alligator mississippiensis
Authors: Parker Seth , Cramberg Michael , Scott Anchal , Sopko Stephanie , Swords Annelise , Taylor Ethan , Young Bruce A. 
Published: February 2024

AbstractThe epidural space of the American alligator (Alligator mississippiensis) is largely filled by a continuous venous sinus. This venous sinus extends throughout the trunk and tail of the alligator, and is continuous with the dural sinuses surrounding the brain. Segmental spinal veins (sl) link the spinal venous sinus (vs) to the somatic and visceral venous drainage. Some of these sl, like the caudal head vein along the occipital plate of the skull, are enlarged, suggesting more functional linkage. No evidence of venous valves or external venous sphincters was found associated with the vs; the relative scarcity of smooth muscle in the venous wall of the sinus suggests limited physiological regulation. The proatlas (pr), which develops between the occipital plate and C1 in crocodylians, is shaped like a neural arch and is fused to the dorsal surface of the vs. The present study suggests that the pr may function to propel venous blood around the brain and spinal cord. The vs effectively encloses the spinal dura, creating a tube‐within‐a‐tube system with the (smaller volume) spinal cerebrospinal fluid (CSF). Changes in venous blood pressure, as are likely during locomotion, would impact dural compliance and CSF pressure waves propagating along the spinal cord.