bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lithium All‐Solid‐State Batteries Fabricated at Room Temperature by the Powder Aerosol Deposition Method with Garnet‐Type Electrolyte and Graded Composite Cathode
Authors: Hennerici Lukas , Ficht Paula , Schamel Maximilian , Mansfeld Ulrich , Linz Mario , Paulus Daniel , Kita Jaroslaw , Danzer Michael A. , Moos Ralf 
Published: August 2024

AbstractLithium‐based all‐solid‐state batteries (ASSBs) are attracting worldwide attention as the next step in the evolution of Li‐ion batteries (LIBs). They have the potential to address safety concerns and limited energy densities, which are key challenges for LIBs. The current focus is on enhancing the electrochemical properties of ASSBs. However, a suitable economic method for fabricating them remains to be established, especially when ceramic materials are used as solid electrolytes. The powder aerosol deposition method (PAD or ADM) is a ceramic processing method that uses raw ceramic powders to fabricate dense, several micrometer thick ceramic films. The entire process takes place at room temperature and in the absence of additional binders. Therefore, PAD is used in this study to fabricate ASSBs with LiNi0.83Mn0.11Co0.06O2 (NMC) as the cathode active material and Al0.2Li6.025La3Zr1.625Ta0.375O12 (LLZO) as the solid electrolyte. The cathode is fabricated as a composite with a gradient in the electrolyte concentration. The successful fabrication is confirmed through scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis. Electrochemical characterization shows that a PAD‐ASSB can be cycled. Furthermore, it can be shown that 145 µm thick NMC films can be fabricated by PAD. The electrochemical results are compared with the theoretical potential of PAD‐ASSBs, and methods to further improve the achieved state are discussed.
Boron and Nitrogen Co‐Doped Porous Carbon with Ultrahigh Volumetric Performance for Zinc‐Ion Hybrid Supercapacitors
Authors: Song Tingting , Chen Jiayi , Chen Weijian , Zhang Xinyang , Wu Xiaoliang , Wang Xin 
Published: August 2024

AbstractIt is a huge challenge for carbon materials to obtain high volumetric capacitance without sacrificing gravimetric capacitance for supercapacitors with limited space. Herein, B/N/O co‐doped porous carbon materials are prepared by one‐step carbonization method using boric acid as the template and boron source, polyacrylamide as the carbon and nitrogen sources. Boric acid and polyacrylamide can be closely combined by hydrogen bond, so as to not only give full play to the role of boric acid template, but also to achieve high content of nitrogen and boron functional groups. Benefiting from the high bulk density (1.51 g cm−3), suitable specific surface area (243.2 m2 g−1) and numerous B (7.55 at.%), N (14.38 at.%), O (8.89 at.%) functional groups, the prepared BNPC‐700 electrode shows an ultrahigh volumetric specific capacitance of 545.6 F cm−3 at 0.5 A g−1, excellent rate characteristic and superior electrochemical performance. Furthermore, the assembled BNPC‐700 symmetric supercapacitor achieves a high volumetric energy density of 31.1 Wh L−1 (20.6 Wh kg−1) in ZnSO4 aqueous electrolyte. More importantly, the assembled Zn//ZnSO4//BNPC‐700 hybrid supercapacitor delivers a high volumetric capacity of 210.8 mAh cm−3 and a high volumetric energy density of 147.7 Wh L−1(97.8 Wh kg−1).
Facile Generation of Trideuteromethyl Radical from Alkylsilyl Peroxide and Subsequent Functionalization
Authors: Liu Jiahao , Nie Jiachun , Wang Zhe , Kato Terumasa , Liu Yan , Maruoka Keiji 
Published: August 2024

AbstractCu‐ and Fe‐ catalyzed trideuteromethylation reactions using alkylsilyl peroxide as trideuteromethyl radical precursor are reported. The alkylsilyl peroxide was synthesized from acetone‐d6 in a three‐step sequence, and the reactions with various coupling partners afforded efficiently the corresponding N−CD3, O−CD3 and C−CD3 bond formation products. The radical heptadeuteriopropylation using alkylsilyl peroxide prepared from butyric acid‐d7 is also described.
The β‐Ketoacyl‐ACP Synthase FabF Catalyzes Carbon‐Carbon Bond Formation in a Bimodal Pattern for Fatty Acid Biosynthesis
Authors: Huang Yuzhou , Wang Yiran , Cai Chang , Zhang Lin , Ye Fei , Zhang Liang 
Published: August 2024

AbstractFatty acids produced by the type‐II fatty acid biosynthetic pathway (FAS‐II) are essential biomaterials for bacterial membrane construction and numerous metabolic routes. The β‐ketoacyl‐ACP synthase FabF catalyzes the key C−C bond formation step for fatty acid elongation in FAS‐II. Here, we revealed the substrate recognition and catalytic mechanisms of FabF by determining FabF‐ACP complexes. FabF displays a distinctive bimodal catalytic pattern specifically on C6 and C10 acyl‐ACP substrates. It utilizes positively charged residues located on the η3‐helix and loop1 regions near the catalytic tunnel entrance to bind ACP, and two hydrophobic cavities as well as “front”, “middle”, and “back” door residues to specifically stabilize C6 and C10 acyl substrates for preferential catalysis. Further quantum chemistry calculations suggest that the FabF catalytic residues Lys336 and His304 facilitate proton transfer during condensation catalysis and C−C bond formation. Our results provide key mechanistic insights into the biosynthesis of molecular carbon skeletons based on ketosynthases that are highly conserved through the FAS and polyketide synthase (PKS) analogous biosynthetic routes, broaden the understanding of the tricarboxylic acid cycle that utilizes lipoic acid derived from C8‐ACP accumulated due to the FabF distinctive catalytic pattern for oxidative decarboxylations, and may facilitate the development of narrow‐spectrum antibacterial drugs.
Unlocking of Hidden Mesopores for Enzyme Encapsulation by Dynamic Linkers in Stable Metal‐Organic Frameworks
Authors: Qiao Meng , Li Youcong , Li Yanqi , Chang Mengting , Zhang Xing , Yuan Shuai 
Published: August 2024

AbstractMesoporous metal‐organic frameworks (MOFs) are promising supports for the immobilization of enzymes, yet their applications are often limited by small pore apertures that constrain the size of encapsulated enzymes to below 5 nm. In this study, we introduced labile linkers (4,4′,4′′‐(2,4,6‐boroxintriyl)‐tribenzoate, TBTB) with dynamic boroxine bonds into mesoporous PCN‐333, resulting in PCN‐333‐TBTB with enhanced enzyme loading and protection capabilities. The selective breaking of B−O bonds creates defects in PCN‐333, which effectively expands both window and cavity sizes, thereby unlocking hidden mesopores for enzyme encapsulation. Consequently, this strategy not only increases the adsorption kinetics of small enzymes (<5 nm) such as cytochrome c (Cyt C) and horseradish peroxidase (HRP), but also enables the immobilization of various large‐sized enzymes (>5 nm), such as glycoenzymes. The glycoenzymes@PCN‐333‐TBTB platform was successfully applied to synthesize thirteen complex oligosaccharides and polysaccharides, demonstrating high activity and enhanced enzyme stability. The dynamic linker‐mediated enzyme encapsulation strategy enables the immobilization of enzymes exceeding the inherent pore size of MOFs, thus broadening the scope of enzymatic catalytic reactions achievable with MOF materials.
Hyperconjugation‐Driven Isodesmic Reaction of Indoles and Anilines: Reaction Discovery, Mechanism Study, and Antitumor Application
Authors: Xiao Yu‐Qing , Fang Kai‐Xin , Zhang Zhihan , Zhang Chen , Li Yu‐Jie , Wang Bao‐Cheng , Zhang Bin‐Jun , Jiang Yu‐Qing , Zhang Miao , Tan Ying , Xiao Wen‐Jing , Lu Liang‐Qiu 
Published: August 2024

AbstractIsodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general and powerful strategy for both biological and chemical synthesis. However, most isodesmic reactions involve either metathesis or functional‐group transfer. Here, we serendipitously discovered a novel isodesmic reaction of indoles and anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five‐membered ring of the indole motif is broken and a new indole motif is constructed on the aniline side, accompanied by the formation of a new aniline motif. Mechanistic studies revealed the pivotal role of σ→π* hyperconjugation on the nitrogen atom of the indole motif in driving this unusual isodesmic reaction. Furthermore, we successfully synthesized a diverse series of polycyclic indole derivatives; among quinolines, potential antitumor agents were identified using cellular and in vivo experiments, thereby demonstrating the synthetic utility of the developed methodology.
Precise Preparation of Supramolecular Spherical Nucleic Acids for Nucleolin‐Targeted Gene Delivery
Authors: Chen Ming , Miao Siyuan , Zhang Yaqi , Chang Xueman , Dai Jun , Chen Chuxin , Li Shaoguang , Li Hui , Xia Fan 
Published: August 2024

AbstractMolecular spherical nucleic acids (m‐SNAs) are a second generation of spherical nucleic acids (SNAs), which are of significance in potential application of targeted delivery of nucleic acids or gene regulation due to their defined molecular structures. Nevertheless, m‐SNAs typically involve a single DNA sequence which greatly limits its functions as either targeting purpose or gene regulation. In response, we proposed here a third generation, supramolecular spherical nucleic acids (Supra‐SNAs) with two different sequences to achieve both above‐mentioned functions. Specifically, we constructed a series of supramolecular self‐assembly structures by coupling a cell membrane receptor (i.e., nucleolin)‐recognizing aptamer (AS1411)‐modified adamantine as targeting probe and human epithelial growth factor receptor 2 (HER2) antisense‐functionalized β‐cyclodextrin to specifically inhibit the overexpression of HER2 proteins for gene regulations. In comparison to the m‐SNA precursors, such Supra‐SNA structures exhibited enhanced levels of resistance to nuclease degradation, cellular uptake, gene regulation capabilities and tumor retention capacity. We demonstrated that Supra‐SNAs exhibited optimal cell suppression rates and cell apoptosis via a phosphatidylinositol 3‐kinase/protein kinase B signaling pathway. The well‐defined molecular structures provide an attractive platform for investigating interrelationship between structure and property at the molecular level.
In‐Situ Construction of Functional Multi‐Dimensional MXene‐based Composites Directly from MAX Phases through Gas‐Solid Reactions
Authors: Liu Yang , Gao Xinyue , Shen Maoqiang , Zhao Yanhao , Zhang Xu , Liu Sen , Liu Xuesen , Hou Linrui , Yuan Changzhou 
Published: August 2024

AbstractThe weak bonding of A atoms with MX layers in MAX phases not only enables the selective etching of A layers for MXene preparation but brings about the chance to construct A derivatives/MXene composites via in situ conversion. Here, a facile and general gas‐solid reaction systems are elegantly devised to construct multi‐dimensional MXene based composites including AlF3 nanorods/MXene, AlF3 nanocrystals/MXene, amorphous AlF3/MXene, A filled carbon nanotubes/MXene, layered metal chalcogenides/MXene, MOF/MXene, and so on. The intrinsic effect mechanism of interlayer confinement towards crystal growth, catalytic behavior, van der Waals‐heterostructure construction and coordination reaction are rationally put forward. The tight interface combination and synergistic effect from distinct components make them promising active materials for electrochemical applications. More particularly, the AlF3 nanorods/Nb2C MXene demonstrate bi‐directional catalytic activity toward the conversion between Li2S and lithium polysulfides, which alleviates the shuttle effect in lithium‐sulfur batteries.
Self‐Assembly of Thienopyrrole‐Fused Thiadiazoles Containing an Amide Linker: Control of Supramolecular Polymerization Mechanism and Chiroptical Properties by Trialkoxy Side Chains
Authors: Yamaguchi Taiki , Naito Yukako , Kitamura Chitoshi , Takeshita Hiroki , Ida Shohei , Ishi‐i Tsutomu , Suzuki Kazumasa , Matsumoto Taisuke , Shiota Yoshihito , Suzuki Daiya , Imai Yoshitane , Ikeda Toshiaki , Kato Shin‐ichiro 
Published: August 2024

AbstractThree thienopyrrole‐fused thiadiazole (TPT) fluorescent dyes featuring a common amide linker and different alkoxy substituents on peripheral trialkoxybenzene moieties were synthesized, and their self‐assembly behavior in solution was investigated. The obtained results revealed a substantial steric effect of the alkoxy substituents on the supramolecular polymerization mechanism, which results from a combination of π‐stacking and hydrogen (H)‐bonding interactions. Detailed spectroscopic measurements revealed that with increasing steric demand of the substituents, the supramolecular polymerization processes in pure methylcyclohexane (MCH) or a mixture of MCH and toluene become temperature‐sensitive and enthalpically favorable, resulting in a change from the isodesmic assembly mechanism to the cooperative mechanism. Theoretical calculations suggested that in TPTs with bulky substituents, steric hindrance causes the H‐bonding array of the amide moieties to be aligned along the stacking axis of the π‐systems; thus, the H‐bonding interactions are strengthened compared to those in TPTs with less bulky substituents, compensating for the weakened π‐stacking interactions. A chiral TPT derivative with (S) stereogenic centers was found to form homochiral helical supramolecular assemblies that generate discernible circularly polarized luminescence. Achiral TPTs also generate helical assemblies to which preferential helicity can be imparted through the external chiral bias of the solvents (R)‐ and (S)‐limonene.
Dual Sulfone‐Bridged Triphenylamine Heteroaromatics for High‐Performance Blue Organic Electroluminescence
Authors: Ma Zetong , Deng Lisong , Xu Pei , Zhou Jiadong , Chen Liangjian , Qiao Xianfeng , Ma Dongge , Hu Dehua 
Published: August 2024

AbstractPolycyclic heteroaromatics (PHAs) are a highly versatile class of functional materials, especially applicable as efficient luminophores in organic light‐emitting diodes (OLEDs). Those constructed by tethered phenyl surrounding the main group center attract extensive attention due to their excellent OLED device performance. However, the development of such a class of emitters is often limited to boron, nitrogen‐doped π‐conjugated heterocycles. Herein, we proposed a novel kind of blue emitter by constructing a donor‐acceptor molecular configuration, utilizing a dual sulfone‐bridged triphenylamine (BTPO) core and mono/di‐diphenylamine (DPA) substituents. The twisted D−A molecular structures and appropriate donor strength facilitate the effective separation of natural transition orbitals, endowing the emitters with charge‐transfer dominant hybridized local and charge‐transfer characteristics for the excited states. Both BTPO‐DPA and BTPO‐2DPA own small S1–T1 splitting energy, thus demonstrating blue thermally activated delayed fluorescence. The more symmetrical structure and enhanced CT features brought by additional DPA moiety confer BTPO‐2DPA with a shorter delayed fluorescence lifetime, a higher fluorescence quantum yield and narrower emission. Therefore, BTPO‐2DPA based OLED devices exhibit superior blue electroluminescence performance, with external quantum efficiencies reaching 12.31 %.
Association of race/ethnicity and insurance with survival in patients with diffuse large B‐cell lymphoma in a large real‐world cohort
Authors: Jin Yanling , Li Jia , Mun Yong , Masaquel Anthony , Hu Sylvia , Biondo Juliana M. L. 
Published: August 2024

AbstractObjectiveFew studies have evaluated disparities in race, ethnicity, and health insurance in real‐world health outcomes for patients with diffuse large B‐cell lymphoma (DLBCL). This study aimed to evaluate association between racial disparities and health insurance with real‐world health outcomes.MethodsPatients with DLBCL (January 2011–July 2021) treated with first‐line therapy were selected from a real‐world database. Variables of interest included race/ethnicity, health insurance type (Medicaid, Commercial) by patient age (<65, ≥65 years), stage at diagnosis, overall survival (OS), and time to second‐line therapy or death due to any cause (TTNTD).ResultsAmong 5362 patients with DLBCL (82% White, 7% Black, 8% Hispanic/Latino, 3% Asian), White patients were older (mean age, 66.7 vs. 59.3–62.5 years) and less likely to have Medicaid insurance (1.7% vs. 3.4%–5.9%). Adjusted hazard ratios (aHR) for OS (Black, 0.88 [95% confidence interval, 0.72–1.07]; Hispanic/Latino, 0.84 [0.70–1.03]; Asian, 0.82 [0.59–1.16]) and TTNTD (Black, 0.89 [0.75–1.05]; Hispanic/Latino, 0.85 [0.73–1.00]; Asian, 1.11 [0.86–1.43]) were similar to those of White patients. Among patients aged <65 years, Medicaid‐insured versus Commercially insured patients had more advanced disease (stage III–IV, 66% vs. 48%), worse OS (aHR, 0.52 [0.34–0.80]; p = 0.003), and shorter TTNTD (aHR, 0.70 [0.49–0.99]; p = 0.044).ConclusionsThere was no statistically significant difference in these variables/outcomes between Medicaid‐insured and commercially insured patients aged ≥65 years. Medicaid‐insured status was significantly associated with poorer OS and TTNTD in patients with DLBCL aged <65 years but not in those aged ≥65 years, with or without adjusting for other baseline characteristics. Race was not significantly associated with these outcomes.
A qualitative exploration of the pathway to diagnosis and treatment of cutaneous squamous cell carcinoma of the head and neck with perineural spread
Authors: Pradhan Poorva , Wan Ke (Zoe) , Chan Li , Low Tsu‐Hui (Hubert) , Wu Raymond , Lee Jenny H. , Palme Carsten E. , Clark Jonathan R. , Venchiarutti Rebecca L. 
Published: August 2024

AbstractBackgroundPerineural spread (PNS) is associated with a poor prognosis in cutaneous squamous cell carcinoma of the head and neck (cSCCHN). Hence, investigating facilitators and barriers of early diagnosis and treatment of PNS in cSCCHN may improve outcomes.MethodsPatients were recruited from an institutional database. Semi‐structured interviews were conducted according to the Model of Pathways to Treatment. Thematic analysis was based on the four main intervals in the framework using a data‐driven analytical method.ResultsSeventeen participants were interviewed. Facilitators included patients' past experiences, symptom progression, trust in healthcare professionals (HCPs), and capacity to leverage relationships. Barriers included difficult diagnoses, limited access to cancer services, lack of care coordination, and lack of awareness of PNS among primary health care providers.ConclusionThese findings emphasise the complexity early diagnosis and treatment of PNS. Interventions like clinical practice guidelines, education for HCPs, and telehealth could facilitate timely detection and management.
Cytotoxic Effects of Oleanane‐type Saponins from Lysimachia laxa
Authors: Huyen Le Thi , Bao Dang Gia , Son Nguyen Thi , Anh Nguyen Thi Van , Tai Bui Huu , Huong Phan Thi Thanh , Kiem Phan Van , Thuy Nguyen Thi Kim , Hanh Nguyen Thi , Park SeonJu , Nhiem Nguyen Xuan 
Published: August 2024

AbstractPhytochemical investigation of the methanol extract of the aerial parts of Lysimachia laxa led to the isolation of four new oleanane‐type saponins, lysimosides A–D (1–4) and one known compound, lysimachigenoside B (5). Their structures were elucidated using a combination of HR‐ESI‐MS, 1D and 2D‐NMR spectral data, chemical methods, and comparison with previous literature. The cytotoxic activity of these compounds was evaluated against human lung cancer (A‐549) and human breast cancer (MCF‐7) cell lines. All compounds exhibited cytotoxic activity against A‐549 and MCF‐7 cell lines with IC50 values ranging from 6.1–16.0 μM, comparable to the positive control, mitoxantrone. Interestingly, oleanane‐type saponins with an acetyl group (2–4) exhibited increased cytotoxic activities compared to those without an acetyl group (1).
Baclofen‐induced excessive perspiration: A case report and review of literature
Authors: Farahneh Othman , Akpati Lois , Alvarez silva Miguel , Damlakhy Ahmad , Ross Emily 
Published: August 2024

Key Clinical MessageThis report highlights an unexpected baclofen side effect, a medication known for its safety profile. The rarity of excessive perspiration as a side effect distinguishes this case from typical baclofen adverse reactions. Documenting uncommon reactions is vital for physicians to broaden their awareness of baclofen's side effects and improve care.
Oxidative [4+2] Annulation of Pyrrole‐2‐carbaldehyde Derivatives with o‐Hydroxyphenyl Propargylamines: Syntheses of 5,6,7‐Trisubstituted Indolizines
Authors: Wang Yu‐Qing , Chen Li‐Jia , Yang Rui‐Lin , Lang Ming , Peng Jin‐Bao 
Published: August 2024

AbstractA base promoted oxidative [4+2] annulation of pyrrole‐2‐carbaldehyde derivatives with o‐hydroxyphenyl propargylamines for the synthesis of highly substituted indolizines has been developed. Using DBN as base, a broad range of 5,6,7‐trisubstituted indolizines have been prepared in good to excellent yields under mild conditions, and many useful functional groups can be tolerated.
Glucoconjugated Dinuclear Copper(II) Complex: An Efficient Catalyst for Stereoselective Synthesis of Trisubstituted Propargylamines via Solvent‐free A3 Coupling Reaction
Authors: Kumar Mishra Santosh , Parikh Parmeshthi , Parikh Anuvasita , Rangan Krishnan , Kumar Sah Ajay 
Published: August 2024

AbstractDevelopment of catalytic systems using nontoxic natural precursors is the need of the era, and along this line, we have synthesized a new D‐glucose derived ligand (4,6‐O‐ethylidene‐N‐(2‐hydroxy‐4‐(octyloxy)benzylidene)‐β‐D‐glucopyranosylamine) and its dinuclear copper(II) complex. The molecular structure of the complex has been established by single‐crystal X‐ray diffraction studies and detailed noncovalent intermolecular interactions present in it have been explored by Hirshfeld surface analysis. Further, the complex has been used as a catalyst in the enantioselective (87–99 % ee) synthesis of propargylamines in good to excellent yield (82–95 %) via aldehyde‐amines‐alkynes (A3) coupling reaction under solvent‐free condition. The formation of aminal intermediate during the reaction has been confirmed by 1H‐NMR and single‐crystal X‐ray diffraction studies. The catalytic system is reusable without any appreciable loss in the enantioselectivity or product yield.
Pnictogen Chemistry: From Light to Heavy Compounds
Authors: Müller Christian , Hey‐Hawkins Evamarie , Lichtenberg Crispin 
Published: August 2024

AbstractPnictogen compounds offer a broad and highly tunable set of characteristics, including pronounced Lewis acidity and basicity, privileged ligand behavior, the reversible switching between different oxidation states, the accessibility of low‐valent species, and intriguing photophysical properties. In the recent renaissance of p‐block chemistry, researchers are focusing their efforts to investigate and exploit these properties, to reveal unprecedented reactivity patterns and to design fascinating applications based on modern and innovative pnictogen chemistry. This special issue presents current trends in the field of pnictogen chemistry.