bluuebunny/crossref_metadata_2025_split huggingface dataset:
Exploring Ferrocenyl Imine‐Phosphane Complexes in Gold(I) Redox Switchable Catalysis and the Role of the “Magic Blue” Oxidant
Authors: Pérez‐Sánchez Juan Carlos , Herrera Raquel P. , Gimeno M. Concepción 
Published: July 2024

AbstractAnother class of gold(I) redox‐switchable catalysts, incorporating ferrocenyl phosphane‐imines, enriches the existing library of gold(I) complexes. Our catalyst proves efficacy in gold(I)‐catalyzed cyclizations of furans and benzamides, exhibiting reversible “on‐off” switching. Furthermore, we explored the unconventional role of “Magic Blue”, commonly used as an oxidizing agent in various organic transformations, as a potential activator of the Au−Cl bond, initiating conventional gold(I) catalysis.
Electric‐Field Manipulation of Magnetic Chirality in a Homo‐Ferro‐Rotational Helimagnet
Authors: Yang Junjie , Matsuda Masaaki , Tyson Trevor , Young Joshua , Ratcliff William , Gao Yunpeng , Obeysekera Dimuthu , Guo Xiaoyu , Owen Rachel , Zhao Liuyan , Cheong Sang‐wook 
Published: July 2024

AbstractFerro‐rotational (FR) materials, renowned for their distinctive material functionalities, present challenges in the growth of homo‐FR crystals (i.e., single FR domain). This study explores a cost‐effective approach to growing homo‐FR helimagnetic RbFe(SO4)2 (RFSO) crystals by lowering the crystal growth temperature below the TFR threshold using the high‐pressure hydrothermal method. Through polarized neutron diffraction experiments, it is observed that nearly 86% of RFSO crystals consist of a homo‐FR domain. Notably, RFSO displays remarkable stability in the FR phase, with an exceptionally high TFR of ≈573 K. Furthermore, RFSO exhibits a chiral helical magnetic structure with switchable ferroelectric polarization below 4 K. Importantly, external electric fields can induce a single magnetic domain state and manipulate its magnetic chirality. The findings suggest that the search for new FR magnets with outstanding material properties should consider magnetic sulfates as promising candidates.
Interfacial Crosslinking for Efficient and Stable Planar TiO2 Perovskite Solar Cells
Authors: Duan Linrui , Liu Siyu , Wang Xiaobing , Zhang Zhuang , Luo Jingshan 
Published: July 2024

AbstractThe buried interface between the electron transport layer (ETL) and the perovskite layer plays a crucial role in enhancing the power conversion efficiency (PCE) and stability of n–i–p type perovskite solar cells (PSCs). In this study, the interface between the chemical bath deposited (CBD) titanium oxide (TiO2) ETL and the perovskite layer using multi‐functional potassium trifluoromethyl sulfonate (SK) is modified. Structural and elemental analyses reveal that the trifluoromethyl sulfonate serves as a crosslinker between the TiO2 and the perovskite layer, thus improving the adhesion of the perovskite to the TiO2 ETL through strong bonding of the ─CF3 and ─SO3− terminal groups. Furthermore, the multi‐functional modifiers reduced interface defects and suppressed carrier recombination in the PSCs. Consequently, devices with a champion PCE of 25.22% and a fill factor (FF) close to 85% is achieved, marking the highest PCE and FF observed for PSCs based on CBD TiO2. The unencapsulated device maintained 81.3% of its initial PCE after operating for 1000 h.
Observation of Ultra‐High‐Q Resonators in the Ultrasound via Bound States in the Continuum
Authors: Farhat Mohamed , Achaoui Younes , Martínez Julio Andrés Iglesias , Addouche Mahmoud , Wu Ying , Khelif Abdelkrim 
Published: July 2024

AbstractThe confinement of waves in open systems represents a fundamental phenomenon extensively explored across various branches of wave physics. Recently, significant attention is directed toward bound states in the continuum (BIC), a class of modes that are trapped but do not decay in an otherwise unbounded continuum. Here, the theoretical investigation and experimental demonstration of the existence of quasi‐bound states in the continuum (QBIC) for ultrasonic waves are achieved by leveraging an elastic Fabry–Pérot metasurface resonator. Several intriguing properties of the ultrasound quasi‐bound states in the continuum that are robust to parameter scanning are unveiled, and experimental evidence of a remarkable Q‐factor of 350 at ≈1 MHz frequency, far exceeding the state‐of‐the‐art using a fully acoustic underwater system is presented. The findings contribute novel insights into the understanding of BIC for acoustic waves, offering a new paradigm for the design of efficient, ultra‐high Q‐factor ultrasound devices.
Ultrathin, High‐Aspect‐Ratio Bismuth Sulfohalide Nanowire Bundles for Solution‐Processed Flexible Photodetectors
Authors: Lee Da Won , Oh Seongkeun , Lee Dong Hyun David , Woo Ho Young , Ahn Junhyuk , Kim Seung Hyeon , Jung Byung Ku , Choi Yoonjoo , Kim Dagam , Yu Mi Yeon , Park Chun Gwon , Yun Hongseok , Kim Tae‐Hyung , Han Myung Joon , Oh Soong Ju , Paik Taejong 
Published: July 2024

AbstractIn this study, a novel synthesis of ultrathin, highly uniform colloidal bismuth sulfohalide (BiSX where X = Cl, Br, I) nanowires (NWs) and NW bundles (NBs) for room‐temperature and solution‐processed flexible photodetectors are presented. High‐aspect‐ratio bismuth sulfobromide (BiSBr) NWs are synthesized via a heat‐up method using bismuth bromide and elemental S as precursors and 1‐dodecanethiol as a solvent. Bundling of the BiSBr NWs occurs upon the addition of 1‐octadecene as a co‐solvent. The morphologies of the BiSBr NBs are easily tailored from sheaf‐like structures to spherulite nanostructures by changing the solvent ratio. The optical bandgaps are modulated from 1.91 (BiSCl) and 1.88 eV (BiSBr) to 1.53 eV (BiSI) by changing the halide compositions. The optical bandgap of the ultrathin BiSBr NWs and NBs exhibits blueshift, whose origin is investigated through density functional theory‐based first‐principles calculations. Visible‐light photodetectors are fabricated using BiSBr NWs and NBs via solution‐based deposition followed by solid‐state ligand exchanges. High photo‐responsivities and external quantum efficiencies (EQE) are obtained for BiSBr NW and NB films even under strain, which offer a unique opportunity for the application of the novel BiSX NWs and NBs in flexible and environmentally friendly optoelectronic devices.
Advancements in 3D In Vitro Models for Colorectal Cancer
Authors: Vitale Sara , Calapà Federica , Colonna Francesca , Luongo Francesca , Biffoni Mauro , De Maria Ruggero , Fiori Micol E. 
Published: July 2024

AbstractThe process of drug discovery and pre‐clinical testing is currently inefficient, expensive, and time‐consuming. Most importantly, the success rate is unsatisfactory, as only a small percentage of tested drugs are made available to oncological patients. This is largely due to the lack of reliable models that accurately predict drug efficacy and safety. Even animal models often fail to replicate human‐specific pathologies and human body's complexity. These factors, along with ethical concerns regarding animal use, urge the development of suitable human‐relevant, translational in vitro models.
Variation in grandmaternal investment in Ukraine
Authors: Shreyer Sofiya 
Published: July 2024

AbstractBackgroundGrandmothers vary in their contributions to grandchildren based on their relatedness and the sex of the child. Maternal grandmothers decrease grandchildren's risk of mortality and increase grandchildren's health more significantly than paternal grandmothers, but limited evidence suggests that paternal grandmothers may invest more in female than male grandchildren.AimsIn this study, I test whether contact frequency between grandmothers and grandchildren is influenced by their relatedness (maternal vs paternal) or the sex of the child. This research was carried out in Ukraine because it is neither matrilocal nor patrilocal, and Ukrainian grandmothers are known to provide a high rate of childcare.MethodsThis study included interviews with 60 grandmothers that asked about contact frequency with grandchildren, relatedness (maternal or paternal), and contact frequency between the grandchild and the other grandmother. A dataset generated for each grandchild (n = 128) included sex, age, and contact frequency with both maternal and paternal grandmothers. Linear mixed models were fit to the data to explore the relationship between grandmother relatedness and contact frequency.ResultsOn average, maternal grandmothers saw their grandchildren 173.8 days/year, while paternal grandmothers saw their grandchildren 87.5 days/year (p < 0.001). The sex of the child was not a significant factor in determining contact frequency.ConclusionIn Ukraine, maternal grandmothers have more frequent contact with their grandchildren. This finding supports the idea that grandmaternal investment is an evolutionarily adaptive strategy. However, the bias towards maternal grandmothers may also be explained by a post‐socialist cultural context, which necessitates grandmaternal care.
Novel measures of cognition and function for the AD spectrum in the Novel Measures for Alzheimer's Disease Prevention Trials (NoMAD) project: Psychometric properties, convergent validation, and contrasts with established measures
Authors: Kim Hyun , Lee Seonjoo , Levine Alina , Huber Benjamin , Andrews Howard , Kerner Nancy A. , Cohen Daniel , Carlson Scott , Bell Sophie A. , Rivera Andres M. , Gordon Marc L. , Simoes Sabrina , Devanand Davangere. P. , Brickman Adam M. , Schneider Lon S. , Harvey Philip D. , Goldberg Terry E. 
Published: July 2024

AbstractINTRODUCTIONThis study derived composite scores for two novel cognitive measures, the No Practice Effect (NPE) battery and the Miami Computerized Functional Skills Assessment and Training system for use in early‐stage Alzheimer's disease (AD) clinical trials. Their psychometric properties and associations with AD risk markers were compared to those of well‐established measures.METHODSFor 291 older adults with healthy cognition or early mild cognitive impairment, Exploratory factor analyses were used to identify the factor structure of the NPE. Factor and total scores were examined for their psychometric properties and associations with AD risk biomarkers.RESULTSComposite scores from the novel cognitive and functional measures demonstrated better psychometric properties (distribution and test‐retest reliability) and stronger associations with AD‐related demographic, genetic, and brain risk markers than well‐established measures,DISCUSSIONThese novel measures have potential for use as primary cognitive and functional outcomes in early‐stage AD clinical trials.Highlights
Well‐established cognitive tests may not accurately detect subtle cognitive changes.
No Practice Effect (NPE) and Computerized Functional Skills Assessment and Training are novel measures designed to have improved psychometric properties.
NPE had Executive Function, Cognitive Control/Speed, and Episodic Memory domains.
Novel measures had better psychometric properties compared to established measures.
Significant associations with Alzheimer's disease biomarkers were found with novel measures.
Green Syngas Production from Natural Lignin, Sunlight, and Water over Pt‐Decorated InGaN Nanowires
Authors: Yu Tianqi , Li Jingling , Li Yixin , Qiu Liang , Pan Hu , Zhu Lei , Huang Zheng , Zhou Baowen 
Published: July 2024

AbstractTransformation of lignin to syngas can turn waste into treasure yet remains a tremendous challenge because of its naturally evolved stubborn structure. In this work, light‐driven reforming of natural lignin in water for green syngas production is explored using Pt‐decorated InGaN nanowires. The spectroscopic characterizations, isotope, and model compound experiments, as well as density function theory calculation, disclose that among a variety of groups including aromatic ring, −OH, −OCH3, −C3H7 with complex chemical bonds of O−H, C−H, C−C, C−O, etc., InGaN nanowires are cooperative with Pt for preferably breaking the C−O bond of the rich O−CH3 group in lignin to liberating ⋅CH3 by photogenerated holes with a minimum dissociation energy of 2.33 eV. Syngas are subsequently yielded from the continuous evolution of ⋅CH3 and ⋅OH from photocatalytic reforming of lignin in water. Together with the superior optoelectronic attributes of Pt‐decorated InGaN nanowires, the evolution rate of syngas approaches 43.4 mol ⋅ g−1 ⋅ h−1 with tunable H2/CO ratios and a remarkable turnover number (TON) of 150, 543 mol syngas per mol Pt. Notably, the architecture demonstrates a high light efficiency of 12.1 % for syngas generation under focused light without any extra thermal input. Outdoor test ascertains the viability of producing syngas with the only inputs of natural lignin, water, and sunlight, thus presenting a low‐carbon route for synthesizing transportation fuels and value‐added chemicals.
Red‐Light Triggered H‐Abstraction Photoinitiators for the Efficient Oxygen‐Independent Therapy of Hypoxic Tumors
Authors: Han Fuping , Zhou Xiao , Wang Zhaolong , Cai Lihan , Zhang Han , Shi Tiancong , Zhang Zhenyu , Lu Yang , Wu Kaifeng , Long Saran , Sun Wen , Du Jianjun , Fan Jiangli , Peng Xiaojun 
Published: July 2024

AbstractThe clinical application of photodynamic therapy (PDT) is limited by oxygen‐dependence and side effects caused by photosensitizer residues. Photoinitiators based on the H‐abstraction reaction can address these challenges because they can generate alkyl radical‐killing cells independently of oxygen and undergo rapid bleaching following H‐abstraction. Nonetheless, the development of photoinitiators for PDT has been impeded by the absence of effective design strategies. Herein, we have developed aryl‐ketone substituted cyanine (ACy−R), the first red‐light triggered H‐abstraction photoinitiators for hypoxic cancer therapy. These ACy−R molecules inherited the near‐infrared absorption of cyanine dye, and aryl‐ketone modification imparted H‐abstraction capability. Experimental and quantum calculations revealed that modifying the electron‐withdrawing groups of the aryl (e.g., ACy‐5F) improved the contribution of the O atom to the photon excitation process promoting intersystem crossing and H‐abstraction ability. Particularly, ACy‐5F rapidly penetrated cells and enriched in the endoplasmic reticulum. Even under severe hypoxia, ACy‐5F initiated red‐light induced H‐abstraction with intracellular biomolecules, inducing necroptosis and ferroptosis. Moreover, ACy‐5F was degraded after H‐abstraction, thus avoiding the side effects of long‐term phototoxicity after therapy. This study not only provides a crucial molecular tool for hypoxic tumors therapy, but also presents a promising strategy for the development of multifunctional photosensitizers and photoinitiators.
Highly Stable Carboranyl Ligated Gold Nano‐Catalysts for Regioselective Aromatic Bromination
Authors: Wang Mengyue , Zhang Shengye , Gong Yue , Zhang Wangyang , Wang Yu , Chen Yupeng , Zheng Qiang , Liu Zhipan , Tang Cen 
Published: July 2024

AbstractAchieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal‐ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carboranyls (CBs) as unprecedented carbon‐bonded functional ligands (Eads.CB‐Au(111)=−2.90 eV) for gold nanoparticles (AuNPs), showcasing their exceptional stabilization capability that is attributed by strong Au−C bonds combined with B−H⋅⋅⋅Au interactions. The synthesized CB@AuNPs exhibit core(Aun)‐satellite(CB2Au−) structure, showing high stability towards multiple stimuli (110 °C, pH=1–12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh3) stabilized AuNPs, dissolution of catalytically active gold species was suppressed in CB@AuNPs under the reaction conditions. Leveraging these distinct features, CB@AuNPs realized outstanding p : o selectivities in aromatic bromination. Unbiased arenes including chlorobenzene (up to >30 : 1), bromobenzene (15 : 1) and phenyl acrylate were examined using CB@AuNPs as catalysts to afford highly‐selective p‐products. Both carboranyl ligands and carboranyl derived counterions are crucial for such regioselective transformation. This work has provided valuable insights for AuNPs in realizing diverse regioselective transformations.
A Photocaged Microtubule‐Stabilising Epothilone Allows Spatiotemporal Control of Cytoskeletal Dynamics
Authors: Schmitt Carina , Mauker Philipp , Vepřek Nynke A. , Gierse Carolin , Meiring Joyce C. M. , Kuch Jürgen , Akhmanova Anna , Dehmelt Leif , Thorn‐Seshold Oliver 
Published: July 2024

AbstractThe cytoskeleton is essential for spatial and temporal organisation of a wide range of cellular and tissue‐level processes, such as proliferation, signalling, cargo transport, migration, morphogenesis, and neuronal development. Cytoskeleton research aims to study these processes by imaging, or by locally manipulating, the dynamics and organisation of cytoskeletal proteins with high spatiotemporal resolution: which matches the capabilities of optical methods. To date, no photoresponsive microtubule‐stabilising tool has united all the features needed for a practical high‐precision reagent: a low potency and biochemically stable non‐illuminated state; then an efficient, rapid, and clean photoresponse that generates a high potency illuminated state; plus good solubility at suitable working concentrations; and efficient synthetic access. We now present CouEpo, a photocaged epothilone microtubule‐stabilising reagent that combines these needs. Its potency increases approximately 100‐fold upon irradiation by violet/blue light to reach low‐nanomolar values, allowing efficient photocontrol of microtubule dynamics in live cells, and even the generation of cellular asymmetries in microtubule architecture and cell dynamics. CouEpo is thus a high‐performance tool compound that can support high‐precision research into many microtubule‐associated processes, from biophysics to transport, cell motility, and neuronal physiology.
Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical–Radical Cross–Coupling Reaction
Authors: Bajaj Neha , Kitos Alexandros A. , Mavragani Niki , Loutsch Nathan R. , Vlaisavljevich Bess , Murugesu Muralee 
Published: July 2024

AbstractOver the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal‐carbon bonds. In this study, the pyrazine ligand undergoes a radical‐radical cross‐coupling reaction leading to the formation of a decanuclear [(Cp*)20Dy10(L1)10] ⋅ 12(C7H8) (1; where L1 = anion of 2‐prop‐2‐enyl‐2H‐pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all DyIII metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units (CpR = substituted cyclopentadienyl), 1 features the highest nuclearity obtained to date. In‐depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field.
Preparation and properties of bio‐based flame‐retardant rigid polyurethane foams with soybean oil polyols containing phosphorus
Authors: Xu Mingyang , Wang Shuai , Liu Ningning , Xu Xinyu 
Published: July 2024

AbstractTwo types of bio‐based RPUFs (RPUF‐P and RPUF‐PPOA) were prepared that contained ethanol‐modified polyols (Polyol‐E) and one contained an epoxidized polyol modified with phosphoric acid (Polyol‐P), and the other contained epoxidized polyol modified with phenylphosphonic acid (Polyol‐PPOA). The cell morphologies, thermal and mechanical properties, and flame retardancy characteristics of the RPUF, RPUF‐P, and RPUF‐PPOA were studied by scanning electron microscopy (SEM), thermogravimetric analysis(TGA), compression tests, limiting oxygen index (LOI), and cone calorimetry test (CCT). The porous structures revealed that the cell sizes of both RPUF‐P and RPUF‐PPOA increased first and then decreased, and the number of pores decreased first and then increased. Furthermore, the apparent density showed a similar trend of increasing before decreasing. The compressive strengths of the RPUF‐P and RPUF‐PPOA were higher than that of the RPUF, and the compressive strength of the RPUF‐P was better than that of the RPUF‐PPOA, because the hydroxyl value of the Polyol‐P was much higher than that of the Polyol‐PPOA. The crosslinking density of the RPUF‐P prepared by the PM‐200 reaction was much higher than that of the RPUF‐PPOA. The LOI values of the RPUF‐P4 and RPUF‐PPOA4 were 21.68 and 23.10, respectively. Furthermore, the value of the peak of the heat release rate (HRR) was reduced by 40.3% compared with that of pure RPUF. The total heat release (THR), smoke produce rate (SPR), and total smoke release (TSR) decreased with increased Polyol‐P and Polyol‐PPOA addition. The flame‐retardancy residues micrographs showed that the carbon layers generated from the combustion of the RPUF‐P4 and the RPUF‐PPOA4 lacked perforated structures and exhibited better densification than the pure RPUF. Based on the analysis and discussion, the flame retardancy of RPUF‐P and RPUF‐PPOA were improved mainly through a condensed and gas phases mechanism.
Discovery of 4‐(isopentyloxy)‐3‐nitrobenzamide derivatives as xanthine oxidase inhibitors through a non‐anthraquinone exploration
Authors: Guo Shuai , Sun Qi , Zhang Xu , Li Song‐ye , Liu Hong‐ye , Ge Gong‐hui , Wang Jing , Liu Xing‐yang , Xu Ben , Li Ting‐ting , Zhou Xian‐feng , Wang Yan‐ping , Meng Fan‐hao , Zhang Ting‐jian 
Published: July 2024

AbstractIn our previous study, we reported a series of N‐(9,10‐anthraquinone‐2‐carbonyl) amino acid derivatives as novel inhibitors of xanthine oxidase (XO). Recognizing the suboptimal drug‐like properties associated with the anthraquinone moiety, we embarked on a nonanthraquinone medicinal chemistry exploration in the current investigation. Through systematic structure–activity relationship (SAR) studies, we identified a series of 4‐(isopentyloxy)‐3‐nitrobenzamide derivatives exhibiting excellent in vitro potency against XO. The optimized compound, 4‐isopentyloxy‐N‐(1H‐pyrazol‐3‐yl)‐3‐nitrobenzamide (6k), demonstrated exceptional in vitro potency with an IC50 value of 0.13 μM. Compound 6k showed favorable drug‐like characteristics with ligand efficiency (LE) and lipophilic ligand efficiency (LLE) values of 0.41 and 3.73, respectively. In comparison to the initial compound 1d, 6k exhibited a substantial 24‐fold improvement in IC50, along with a 1.6‐fold enhancement in LE and a 3.7‐fold increase in LLE. Molecular modeling studies provided insights into the strong interactions of 6k with critical amino acid residues within the active site. Furthermore, in vivo hypouricemic investigations convincingly demonstrated that 6k significantly reduced serum uric acid levels in rats. The MTT results revealed that compound 6k is nontoxic to healthy cells. The gastric and intestinal stability assay demonstrated that compound 6k exhibits good stability in the gastric and intestinal environments. In conclusion, compound 6k emerges as a promising lead compound, showcasing both exceptional in vitro potency and favorable drug‐like characteristics, thereby warranting further exploration.