bluuebunny/crossref_metadata_2025_split huggingface dataset:
Improving Electroluminescence of Two‐Coordinate Au(I) Complexes: Insights into Steric and Electronic Control
Authors: Heo Seunga , Jhun Byung Hak , Woo Sihyun , Kim Hwang Suk , Kim Inkoo , Kim Joonghyuk , Son Won‐Joon , Jung Yongsik , Kim Kyungmin , Cho Jaeheung , You Youngmin 
Published: November 2023

AbstractThis research elucidates the effects of structural modulations on electroluminescent Au(I) complexes, shedding light on factors governing radiative and nonradiative processes. A series of Au(I) complexes, fortified with ortho‐substituents in carbene and amido ligands, are subjected to rigorous structural, photophysical, and quantum chemical investigations, which unveil distinct structural and electronic effects exerted by the ligands. The investigations reveal that nonradiative processes are governed primarily by the energy‐gap law. Radiative processes are observed to have a weak correlation with the mutual interactions of the molecular orbitals of carbene and amido ligands. Rather, it is discovered that an accumulation of the negative charge in the Au 5d orbital in the excited state decelerates radiative processes. The effectiveness of these findings is substantiated through the larger external quantum efficiency of electroluminescence devices employing the Au(I) complex, in comparison to those based on the archetypical Au(I) complex and the organic thermally activated delayed fluorescent molecule. These compelling revelations underscore the untapped potential of Au(I) complexes in the advancement of electroluminescence technology and advocate for continued investigations into the intriguing domain of ligand structural control.
Electrochemical Annulation of ortho‐Alkynylbiphenyls to Fused Sulfenyl Phenanthrenes and Spiro Cyclohexenone Indenes
Authors: Balajirao Dapkekar Anil , Naveen Jakkula , Satyanarayana Gedu 
Published: November 2023

AbstractHere, we present an electrochemically induced synthesis of 9‐sulfenylarylphenanthrenes and 3’‐sulfenylarylspiro‐cyclohexa[4.5]trienones starting from o‐alkynylbiphenyls and diaryl disulfides. This method was accomplished through constant current electrolysis of 10 mA in an undivided cell setup by utilizing CH3CN as a solvent and LiClO4 as an electrolyte at room temperature. Notably, the present strategy enabled the formation of sulfenylphenanthrenes and sulfenyl spiro cyclohexa[4.5]trienones in 70%–95% yield. Scale‐up synthesis, mechanistic studies, and cyclic voltammetry have also been carried out.
The Onset of Molecule‐Spanning Dynamics in Heat Shock Protein Hsp90
Authors: Sohmen Benedikt , Beck Christian , Frank Veronika , Seydel Tilo , Hoffmann Ingo , Hermann Bianca , Nüesch Mark , Grimaldo Marco , Schreiber Frank , Wolf Steffen , Roosen‐Runge Felix , Hugel Thorsten 
Published: November 2023

AbstractProtein dynamics have been investigated on a wide range of time scales. Nano‐ and picosecond dynamics have been assigned to local fluctuations, while slower dynamics have been attributed to larger conformational changes. However, it is largely unknown how fast (local) fluctuations can lead to slow global (allosteric) changes. Here, fast molecule‐spanning dynamics on the 100 to 200 ns time scale in the heat shock protein 90 (Hsp90) are shown. Global real‐space movements are assigned to dynamic modes on this time scale, which is possible by a combination of single‐molecule fluorescence, quasi‐elastic neutron scattering and all‐atom molecular dynamics (MD) simulations. The time scale of these dynamic modes depends on the conformational state of the Hsp90 dimer. In addition, the dynamic modes are affected to various degrees by Sba1, a co‐chaperone of Hsp90, depending on the location within Hsp90, which is in very good agreement with MD simulations. Altogether, this data is best described by fast molecule‐spanning dynamics, which precede larger conformational changes in Hsp90 and might be the molecular basis for allostery. This integrative approach provides comprehensive insights into molecule‐spanning dynamics on the nanosecond time scale for a multi‐domain protein.
Amino Acid‐Starved Cancer Cells Utilize Macropinocytosis and Ubiquitin‐Proteasome System for Nutrient Acquisition
Authors: Wang Tianyi , Zhang Yaming , Liu Yuwei , Huang Yi , Wang Weiping 
Published: November 2023

AbstractTo grow in nutrient‐deprived tumor microenvironment, cancer cells often internalize and degrade extracellular proteins to refuel intracellular amino acids. However, the nutrient acquisition routes reported by previous studies are mainly restricted in autophagy‐lysosomal pathway. It remains largely unknown if other protein degradation systems also contribute to the utilization of extracellular nutrients. Herein, it is demonstrated that under amino acid starvation, extracellular protein internalization through macropinocytosis and protein degradation through ubiquitin‐proteasome system are activated as a nutrient supply route, sensitizing cancer cells to proteasome inhibition. By inhibiting both macropinocytosis and ubiquitin‐proteasome system, an innovative approach to intensify amino acid starvation for cancer therapy is presented. To maximize therapeutic efficacy and minimize systemic side effects, a pH‐responsive polymersome nanocarrier is developed to deliver therapeutic agents specifically to tumor tissues. This nanoparticle system provides an approach to exacerbate amino acid starvation for cancer therapy, which represents a promising strategy for cancer treatment.
Kirigami‐Structured, Low‐Impedance, and Skin‐Conformal Electronics for Long‐Term Biopotential Monitoring and Human–Machine Interfaces
Authors: Xia Meili , Liu Jianwen , Kim Beom Jin , Gao Yongju , Zhou Yunlong , Zhang Yongjing , Cao Duxia , Zhao Songfang , Li Yang , Ahn Jong‐Hyun 
Published: November 2023

AbstractEpidermal dry electrodes with high skin‐compliant stretchability, low bioelectric interfacial impedance, and long‐term reliability are crucial for biopotential signal recording and human–machine interaction. However, incorporating these essential characteristics into dry electrodes remains a challenge. Here, a skin‐conformal dry electrode is developed by encapsulating kirigami‐structured poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/polyvinyl alcohol (PVA)/silver nanowires (Ag NWs) film with ultrathin polyurethane (PU) tape. This Kirigami‐structured PEDOT:PSS/PVA/Ag NWs/PU epidermal electrode exhibits a low sheet resistance (≈3.9 Ω sq−1), large skin‐compliant stretchability (>100%), low interfacial impedance (≈27.41 kΩ at 100 Hz and ≈59.76 kΩ at 10 Hz), and sufficient mechanoelectrical stability. This enhanced performance is attributed to the synergistic effects of ionic/electronic current from PEDOT:PSS/Ag NWs dual conductive network, Kirigami structure, and unique encapsulation. Compared with the existing dry electrodes or standard gel electrodes, the as‐prepared electrodes possess lower interfacial impedance and noise in various conditions (e.g., sweat, wet, and movement), indicating superior water/motion‐interference resistance. Moreover, they can acquire high‐quality biopotential signals even after water rinsing and ultrasonic cleaning. These outstanding advantages enable the Kirigami‐structured PEDOT:PSS/PVA/Ag NWs/PU electrodes to effectively monitor human motions in real‐time and record epidermal biopotential signals, such as electrocardiogram, electromyogram, and electrooculogram under various conditions, and control external electronics, thereby facilitating human–machine interactions.
Soft Self‐Healing Robot Driven by New Micro Two‐Way Shape Memory Alloy Spring
Authors: Liang Xianrong , Yuan Chenggang , Wan Chaoying , Gao Xiaolong , Bowen Chris , Pan Min 
Published: November 2023

AbstractSoft robotic bodies are susceptible to mechanical fatigue, punctures, electrical breakdown, and aging, which can result in the degradation of performance or unexpected failure. To overcome these challenges, a soft self‐healing robot is created using a thermoplastic methyl thioglycolate–modified styrene–butadiene–styrene (MG‐SBS) elastomer tube fabricated by melt‐extrusion, to allow the robot to self‐heal autonomously at room temperature. After repeated damage and being separated into several parts, the robot is able to heal its stiffness and elongation to break to enable almost complete recovery of robot performance after being allowed to heal at room temperature for 24 h. The self‐healing capability of the robot is examined across the material scale to robot scale by detailed investigations of the healing process, healing efficiency, mechanical characterization of the robot, and assessment of dynamic performance before and after healing. The self‐healing robot is driven by a new micro two‐way shape‐memory alloy (TWSMA) spring actuator which achieved a crawling speed of 21.6 cm/min, equivalent to 1.57 body length per minute. An analytical model of the robot is created to understand the robot dynamics and to act as an efficient tool for self‐healing robot design and optimization. This work therefore provides a new methodology to create efficient, robust, and damage‐tolerant soft robots.
Stimulus‐Responsive Hydrogels as Drug Delivery Systems for Inflammation Targeted Therapy
Authors: Yu Haoyu , Gao Rongyao , Liu Yuxin , Fu Limin , Zhou Jing , Li Luoyuan 
Published: November 2023

AbstractDeregulated inflammations induced by various factors are one of the most common diseases in people's daily life, while severe inflammation can even lead to death. Thus, the efficient treatment of inflammation has always been the hot topic in the research of medicine. In the past decades, as a potential biomaterial, stimuli‐responsive hydrogels have been a focus of attention for the inflammation treatment due to their excellent biocompatibility and design flexibility. Recently, thanks to the rapid development of nanotechnology and material science, more and more efforts have been made to develop safer, more personal and more effective hydrogels for the therapy of some frequent but tough inflammations such as sepsis, rheumatoid arthritis, osteoarthritis, periodontitis, and ulcerative colitis. Herein, from recent studies and articles, the conventional and emerging hydrogels in the delivery of anti‐inflammatory drugs and the therapy for various inflammations are summarized. And their prospects of clinical translation and future development are also discussed in further detail.
SINE‐Associated LncRNA SAWPA Regulates Porcine Zygotic Genome Activation
Authors: He Tianyao , Peng Jinyu , Yang Shu , Liu Dongsong , Gao Shuang , Zhu Yanlong , Chai Zhuang , Lee Byeong Chun , Wei Renyue , Wang Jiaqiang , Liu Zhonghua , Jin Jun‐Xue 
Published: November 2023

AbstractIn mice, retrotransposon‐associated long noncoding RNAs (lncRNA) play important regulatory roles in pre‐implantation development; however, it is largely unknown whether they function in the pre‐implantation development in pigs. The current study aims to screen for retrotransposon‐associated lncRNA in porcine early embryos and identifies a porcine 8‐cell embryo‐specific SINE‐associated nuclear long noncoding RNA named SAWPA. SAWPA is essential for porcine embryonic development as depletion of SAWPA results in a developmental arrest at the 8‐cell stage, accompanied by the inhibition of the JNK‐MAPK signaling pathway. Mechanistically, SAWPA works in trans as a transcription factor for JNK through the formation of an RNA‐protein complex with HNRNPA1 and MED8 binding the SINE elements upstream of JNK. Therefore, as the first functional SINE‐associated long noncoding RNAs in pigs, SAWPA provides novel insights for the mechanism research on retrotransposons in mammalian pre‐implantation development.
Handgrip strength of young athletes differs based on the type of sport played and age
Authors: Abe Takashi , Abe Akemi , Loenneke Jeremy P. 
Published: November 2023

AbstractObjectiveHandgrip strength may differ depending on the type of sport played during the developmental period. Youth sports in which athletes hold equipment in their hands may be the most effective for improving handgrip strength. This study aimed to examine the age at which differences in handgrip strength appear by comparing sports that involve gripping (kendo) with those that do not involve gripping (soccer) in young athletes.MethodsTwo hundred and twenty‐two male athletes (115 kendo and 107 soccer) between 6 and 15 years old participated in this study. Handgrip strength was measured using a dynamometer, and the average value of both hands was used for analysis. Sports experience was determined when they started practicing each sport. Handgrip strength was compared between sports. Statistical moderation was used to determine if the relationship between sport and handgrip strength depended upon the age of the athlete.ResultsKendo athletes had significantly higher handgrip strength than soccer athletes (4.77 kg [95% CI: 2.34, 7.19]) in the overall sample. We found that the relationship between sport and handgrip strength depended upon the age of the child (sport*age t = −3.6, p = .004). Using the Johnson‐Neyman procedure, we found statistically significant differences between sports from 8.48 years and older.ConclusionsOur results suggest that the type of sport played, that is, whether or not an athlete plays with sports equipment in their hands, may influence the development of handgrip strength during the period of growth, and these sports may contribute to a higher level of handgrip strength in adulthood.
Synthesis of a Pinacol Boronate Precursor for [18F]Rucaparib Radiosynthesis
Authors: Seo Ju‐Ahn , Park Jinjae , Cheon Cheol‐Hong 
Published: November 2023

AbstractA novel synthetic approach toward pinacol boronate used as a precursor in the recent radiosynthesis of [18F]rucaparib is described in this study. The Heck reaction of an ortho‐iodoaniline derivative bearing a chloride group at the meta‐position with acrylonitrile produced the desired (E)‐2‐aminocinnamonitrile derivative. The subsequent cyanide‐catalyzed imino‐Stetter reaction of aldimine derived from the obtained 2‐aminocinnamonitrile and aldehyde afforded the required trisubstituted indole‐3‐acetonitrile. The reduction of the nitrile group with cobalt boride followed by the construction of an azepinone scaffold generated indoloazepinone bearing a chloride substituent at the C6‐position of the indole scaffold. The Suzuki–Miyaura borylation of the chloride substituent produced pinacol boronate previously used in the synthesis of [18F]rucaparib. Detailed outcomes of different approaches using different 2‐aminocinnamonitriles were discussed as well.
Consensus definition of advance care planning in dementia: A 33‐country Delphi study
Authors: van der Steen Jenny T. , Nakanishi Miharu , Van den Block Lieve , Di Giulio Paola , Gonella Silvia , in der Schmitten Jürgen , Sudore Rebecca L. , Harrison Dening Karen , Parker Deborah , Mimica Ninoslav , Holmerova Iva , Larkin Philip , Martins Pereira Sandra , Rietjens Judith A. C. , Korfage Ida J. ,   European Association for Palliative Care (EAPC)
Published: November 2023

AbstractINTRODUCTIONExisting advance care planning (ACP) definitional frameworks apply to individuals with decision‐making capacity. We aimed to conceptualize ACP for dementia in terms of its definition and issues that deserve particular attention.METHODSDelphi study with phases: (A) adaptation of a generic ACP framework by a task force of the European Association for Palliative Care (EAPC); (B) four online surveys by 107 experts from 33 countries, September 2021 to June 2022; (C) approval by the EAPC board.RESULTSACP in dementia was defined as a communication process adapted to the person's capacity, which includes, and is continued with, family if available. We identified pragmatic boundaries regarding participation and time (i.e., current or end‐of‐life care). Three interrelated issues that deserve particular attention were capacity, family, and engagement and communication.DISCUSSIONA communication and relationship‐centered definitional framework of ACP in dementia evolved through international consensus supporting inclusiveness of persons with dementia and their family.Highlights
This article offers a consensus definitional framework of advance care planning in dementia.
The definition covers all stages of capacity and includes family caregivers.
Particularly important are (1) capacity, (2) family, (3) engagement, and communication.
Fluctuating capacity was visualized in relation to roles and engaging stakeholders.
Boosted Mg−CO2 Batteries by Amine‐Mediated CO2 Capture Chemistry and Mg2+‐Conducting Solid‐electrolyte Interphases
Authors: Peng Chengxin , Xue Linlin , Zhao Zhengfei , Guo Longyuan , Zhang Chenyue , Wang Aoxuan , Mao Jianfeng , Dou Shixue , Guo Zaiping 
Published: November 2023

AbstractMg−CO2 battery has been considered as an ideal system for energy conversion and CO2 fixation. However, its practical application is significantly limited by the poor reversibility and sluggish kinetics of CO2 cathode and Mg anode. Here, a new amine mediated chemistry strategy is proposed to realize a highly reversible and high‐rate Mg−CO2 battery in conventional electrolyte. Judiciously combined experimental characterization and theoretical computation unveiled that the introduced amine could simultaneously modify the reactant state of CO2 and Mg2+ to accelerate CO2 cathodic reactions on the thermodynamic‐kinetic levels and facilitate the formation of Mg2+‐conductive solid‐electrolyte interphase (SEI) to enable highly reversible Mg anode. As a result, the Mg−CO2 battery exhibits boosted stable cyclability (70 cycles, more than 400 h at 200 mA g−1) and high‐rate capability (from 100 to 2000 mA g−1 with 1.5 V overpotential) even at −15 °C. This work opens a newly promising avenue for advanced metal‐CO2 batteries.
Metavalent Bonding in 2D Chalcogenides: Structural Origin and Chemical Mechanisms
Authors: Arora Raagya , Waghmare Umesh , Rao C. N. R. 
Published: November 2023

AbstractAn unusual set of anomalous functional properties of rocksalt crystals of Group IV chalcogenides were recently linked to a kind of bonding termed as metavalent bonding (MVB) which involves violation of the 8‐N rule. Precise mechanisms of MVB and the relevance of lone pair of Group IV cations are still debated. With restrictions of low dimensionality on the possible atomic coordination, 2D materials provide a rich platform for exploration of MVB. Here, we present first‐principles theoretical analysis of the nature of bonding in five distinct 2D lattices of Group IV chalcogenides MX (M: Sn, Pb, Ge and X: S, Se, Te), in which the natural out‐of‐plane expression of the lone pair versus in‐plane bonding can be systematically explored. While their honeycomb lattices respecting the 8‐N rule are shown to exhibit covalent bonding, their square and orthorhombic structures exhibit MVB only in‐plane, with cationic lone pair activating the out‐of‐plane structural puckering that controls their relative stability. Anomalies in Born‐effective charges, dielectric constants, Grüneisen parameters occur only in their in‐plane behaviour, confirming MVB is confined strictly to 2D and originates from p‐p orbital interactions. Our work opens up directions for chemical design of MVB based 2D materials and their heterostructures.
Regiodivergent Arylation of Pyridines via Zincke Intermediates
Authors: Wang Haiwen , Greaney Michael F. 
Published: November 2023

AbstractAn arylation protocol for pyridines is described, via the ring‐opened Zincke intermediate. Treatment of pyridines with triflic anhydride and a secondary amine produces an azahexatriene species, which undergoes regioselective Pd‐catalyzed arylation at the putative C4 position. Recyclization then provides the pyridine products. Alternatively, metal‐free arylation with a diaryliodonium salt is selective for the pyridine meta‐position, affording a regiodivergent approach to pyridine biaryls from a common intermediate.
Palladium‐Based Dyotropic Rearrangement Enables A Triple Functionalization of Gem‐Disubstituted Alkenes: An Unusual Fluorolactonization Reaction
Authors: Feng Qiang , Liu Chen‐Xu , Wang Qian , Zhu Jieping 
Published: November 2023

AbstractWe report in this paper a Pd(II)‐catalyzed migratory gem‐fluorolactonization of ene‐carboxylic acids. Reaction of 4‐methylenealkanoic acid derivatives with Selectfluor in the presence of Pd(OAc)2 (1.0 mol %) at room temperature affords fluorolactones in good to excellent yields. 2‐(2‐Methylenecycloalkanyl)acetic acids are transformed to bridged fluorolactones under identical conditions. One C−C, one C−O and one tertiary C−F bond were generated along the gem‐disubstituted carbon‐carbon double bond in this operationally simple transformation. Trapping experiments indicates that the reaction is initiated by a 5‐exo‐trig oxypalladation followed by Pd oxidation, regioselective ring‐enlarging 1,2‐alkyl/Pd(IV) dyotropic rearrangement and C−F bond forming reductive elimination cascade. Post‐transformations of these fluorolactones taking advantage of the electrophilicity of the 1‐fluoroalkylcarboxylate function are also documented.
Corrosion protection effect of rust and scales: A “metal protects metal” perception by considering the examples of hematite and magnetite
Authors: Ratnani Sonia , Kumari Anita , Verma Chandrabhan 
Published: November 2023

AbstractThe present report proposes a contradictory remark on the idiom “Iron cuts Iron” that could be synonymized as “Metal cuts Metal” using the example of hematite and magnetite. Most metals and alloys are highly reactive, forming rusts and scales primarily consisting of metal oxides. The formation of metal oxide layers is known as passivation. Generally, passivated metallic surfaces provide anticorrosive protection by avoiding the attacks of corrosive species on the fresh metal surface; therefore, “Corrosion is a Necessary Evil (CNE).” Most passive films are protective, but not all, and their actual nature can be determined using the Pilling–Bedworth ratio (PBR). In dry conditions, passivation occurs spontaneously by the oxidation of metal atoms, but in aqueous media, some external additives, called passivators, are added to build the passive films. Herein, by considering examples of hematite and magnetite, the anticorrosive properties of rusts and scales are described in dry and wet (solution and coating) environments.