bluuebunny/crossref_metadata_2025_split huggingface dataset:
Complementary Multisite Turnover Catalysis toward Superefficient Bifunctional Seawater Splitting at Ampere‐Level Current Density
Authors: Liao Liling , Li Dongyang , Zhang Yan , Zhang Yong , Yu Fang , Yang Lun , Wang Xiuzhang , Tang Dongsheng , Zhou Haiqing 
Published: July 2024

AbstractThe utilization of seawater for hydrogen production via water splitting is increasingly recognized as a promising avenue for the future. The key dilemma for seawater electrolysis is the incompatibility of superior hydrogen‐ and oxygen‐evolving activities at ampere‐scale current densities for both cathodic and anodic catalysts, thus leading to large electric power consumption of overall seawater splitting. Here, in situ construction of Fe4N/Co3N/MoO2 heterostructure arrays anchoring on metallic nickel nitride surface with multilevel collaborative catalytic interfaces and abundant multifunctional metal sites is reported, which serves as a robust bifunctional catalyst for alkaline freshwater/seawater splitting at ampere‐level current density. Operando Raman and X‐ray photoelectron spectroscopic studies combined with density functional theory calculations corroborate that Mo and Co/Fe sites situated on the Fe4N/Co3N/MoO2 multilevel interfaces optimize the reaction pathway and coordination environment to enhance water adsorption/dissociation, hydrogen adsorption, and oxygen‐containing intermediate adsorption, thus cooperatively expediting hydrogen/oxygen evolution reactions in base. Inspiringly, this electrocatalyst can substantially ameliorate overall freshwater/seawater splitting at 1000 mA cm−2 with low cell voltages of 1.65/1.69 V, along with superb long‐term stability at 500–1500 mA cm−2 for over 200 h, outperforming nearly all the ever‐reported non‐noble electrocatalysts for freshwater/seawater electrolysis. This work offers a viable approach to design high‐performance bifunctional catalysts for seawater splitting.
Reaction‐Induced Self‐Assembly of Polymyxin Mitigates Cytotoxicity and Reverses Drug Resistance
Authors: Hu Xiaowen , Li Dongdong , Li Huaping , Piao Yinzi , Wan Hongping , Zhou Tieli , Karimi Mahdi , Zhao Xinghong , Li Yuanfeng , Shi Linqi , Liu Yong 
Published: July 2024

AbstractPolymyxins have been regarded as an efficient therapeutic against many life‐threatening, multidrug resistant Gram‐negative bacterial infections; however, the cytotoxicity and emergence of drug resistance associated with polymyxins have greatly hindered their clinical potential. Herein, the reaction‐induced self‐assembly (RISA) of polymyxins and natural aldehydes in aqueous solution is presented. The resulting assemblies effectively mask the positively charged nature of polymyxins, reducing their cytotoxicity. Moreover, the representative PMBA4 (composed of polymyxin B (PMB) and (E)‐2‐heptenal (A4)) assemblies demonstrate enhanced binding to Gram‐negative bacterial outer membranes and exhibit multiple antimicrobial mechanisms, including increased membrane permeability, elevated bacterial metabolism, suppression of quorum sensing, reduced ATP synthesis, and potential reduction of bacterial drug resistance. Remarkably, PMBA4 assemblies reverse drug resistance in clinically isolated drug‐resistant strains of Gram‐negative bacteria, demonstrating exceptional efficacy in preventing and eradicating bacterial biofilms. PMBA4 assemblies efficiently eradicate Gram‐negative bacterial biofilm infections in vivo and alleviate inflammatory response. This RISA strategy offers a practical and clinically applicable approach to minimize side effects, reverse drug resistance, and prevent the emergence of resistance associated with free polymyxins.
Enhanced Performance of Self‐Powered Ge Schottky Photodetectors Enabled by 2D hBN Monolayer Passivation
Authors: Park HyunJung , Kim Munho 
Published: July 2024

AbstractEnsuring high‐quality surface passivation is the key to realizing high‐performance self‐powered optoelectronic devices, as it significantly impacts carrier transport. 2D hexagonal boron nitride (hBN) exhibits exceptional material characteristics, including a wide bandgap, high dielectric constant, minimized dangling bonds, and high chemical stability, making it one of the most promising candidates for high‐quality passivation. Nevertheless, the passivation characteristics of hBN on Ge and their influence on self‐powered photodetection remain unexplored, as well as their effects on carrier recombination lifetime, interface defect density, and Schottky barrier height. In this study, the first demonstration of enhanced Schottky junction photodiode characteristics and the impact of the surface passivation on carrier lifetime and defect density using an hBN monolayer on Ge are presented. The characteristics of hBN/Ge with Al2O3/Ge are compared to demonstrate the superior passivation quality of hBN over conventional materials. These results highlight the significant potential of hBN as an effective passivation for optoelectronic device applications.
Enzyme Cascade with Four Enzymes in One Pot for the Synthesis of L‐Phosphinothricin
Authors: Xu Jianmiao , Xi Zhijie , Zhao Keji , He Chenxiang , Cheng Feng , Xue Yaping , Zheng Yuguo 
Published: July 2024

AbstractThe biocatalytic oxidative deamination‐ reductive amination process for the production of L‐phosphinothricin (L‐PPT) from D,L‐phosphinothricin (D,L‐PPT) is a green and environmentally friendly approach with significant development potential. In this study, the adopted technological route involves the oxidative deamination of the D‐PPT component in D,L‐PPT to 2‐oxo‐4‐(hydroxymethylphosphinyl)butanoic acid (PPO) by utilizing D‐amino acid oxidase (DAAO), followed by the catalytic reductive amination of PPO to L‐PPT using phosphinothricin dehydrogenase (PpDH). In order to enhance the catalytic rate and reduce the inhibitory effect of the intermediate product PPO on the catalytic process, optimization of both oxidative deamination and reductive amination phases was conducted through separate strategies of constant‐pressure oxygen supply and substrate feeding, respectively. A “two‐step one‐pot” method was employed to link the optimized reactions, significantly shortening the production time. Furthermore, the “two‐step one‐pot” catalytic strategy was optimized, ultimately achieving a high 97.7% yield of L‐PPT with ee of L‐PPT>99.9% after 5.5 h of reaction under 800 mM D,L‐PPT catalytic conditions, D‐PPT and PPO could not bedetected in the reaction system, further enchanced the catalytic efficiency, production efficiency and product quality. The aforementioned results demonstrate that this proposed approach has great potential for industrial‐scale production of L‐PPT as well as significant competitive advantages in terms of economic feasibility.
Efficacy Evaluation of Adjuvant Therapeutic Drugs Against Early and Middle Stage Non‐Small Cell Lung Cancer Organoids
Authors: Liu Lin‐Jie , Li Hong , Chen Chun‐Yuan , Li Ting‐Ting , Deng Biao , Liang Zhu , Liu Jia 
Published: July 2024

Abstract30–55% post‐surgical recurrent rate of early and middle stage non‐small cell lung cancer (e/mNSCLC) suggests the need of adjuvant therapy. The e/mNSCLC derived organoids (e/mNSCLCOs)‐based efficacy evaluation of the proposed regimens may improve clinical benefits for e/mNSCLC patients. The e/mNSCLCOs are established from 33 IA‐IIIB resectable non‐small cell lung cancer (NSCLC) patients without systemic antitumor therapy via optimized 3D culture, of which six with epidermal growth factor receptor (EGFR) mutation. Immunohistochemical staining is employed to ascertain the maintenance of biomarker expression patterns of e/mNSCLCOs with that of their parental tumors. The e/mNSCLCOs are treated with six conventional anti‐NSCLC chemotherapeutic regimens, respectively. Calcein‐AM/PI cell viability/cytotoxicity assay and EdU cell proliferation test reveal that the platinum‐based chemotherapeutic or mono‐chemotherapeutic regimens are generally ineffective to e/mNSCLCOs because of their high IC50 values. Non‐platinum gemcitabine combined with vinorelbine achieve better anti‐e/mNSCLCOs outcome in terms of suppressed cell proliferation and 51.6–65.8% of intra‐organoid cell death. The 6 e/mNSCLCOs with EGFR mutations are sensitive to EGFR‐tyrosine kinase inhibitors (EGFR‐TKIs) in drug selective patterns. The low efficacy of conventional anti‐NSCLC drugs to e/mNSCLCOs suggests the necessity to explore alternative approaches for better adjuvant management of e/mNSCLC patients.
DDR1 Drives Malignant Progression of Gastric Cancer by Suppressing HIF‐1α Ubiquitination and Degradation
Authors: Wei Zhewei , Li Jin , Zhong Li , Yang Dongjie , Li Wuguo , Chen Wei , Zhou Hao , He Yulong , Song Wu , Wang Boyan , Zeng Leli 
Published: July 2024

AbstractThe extracellular matrix (ECM) has been demonstrated to be dysregulated and crucial for malignant progression in gastric cancer (GC), but the mechanism is not well understood. Here, that discoidin domain receptor 1 (DDR1), a principal ECM receptor, is recognized as a key driver of GC progression is reported. Mechanistically, DDR1 directly interacts with the PAS domain of hypoxia‐inducible factor‐1α (HIF‐1α), suppresses its ubiquitination and subsequently strengthens its transcriptional regulation of angiogenesis. Additionally, DDR1 upregulation in GC cells promotes actin cytoskeleton reorganization by activating HIF‐1α/ Ras Homolog Family Member A (RhoA)/Rho‐associated protein kinase 1 (ROCK1) signaling, which in turn enhances the metastatic capacity. Pharmacological inhibition of DDR1 suppresses GC progression and angiogenesis in patient‐derived xenograft (PDX) and organoid models. Taken together, this work first indicates the effects of the DDR1‐HIF‐1α axis on GC progression and reveals the related mechanisms, providing experimental evidence for DDR1 as a therapeutic target for GC.
Inactivated cGAS‐STING Signaling Facilitates Endocrine Resistance by Forming a Positive Feedback Loop with AKT Kinase in ER+HER2– Breast Cancer
Authors: Zhang Kai‐Ming , Zhao De‐Chang , Li Ze‐Yu , Wang Yan , Liu Jian‐Nan , Du Tian , Zhou Ling , Chen Yu‐Hong , Yu Qi‐Chao , Chen Qing‐Shan , Cai Rui‐Zhao , Zhao Zi‐Xuan , Shan Jia‐Lu , Hu Bing‐Xin , Zhang Hai‐Liang , Feng Gong‐Kan , Zhu Xiao‐Feng , Tang Jun , Deng Rong 
Published: July 2024

AbstractEndocrine‐resistant ER+HER2– breast cancer (BC) is particularly aggressive and leads to poor clinical outcomes. Effective therapeutic strategies against endocrine‐resistant BC remain elusive. Here, analysis of the RNA‐sequencing data from ER+HER2– BC patients receiving neoadjuvant endocrine therapy and spatial transcriptomics analysis both show the downregulation of innate immune signaling sensing cytosolic DNA, which primarily occurs in endocrine‐resistant BC cells, not immune cells. Indeed, compared with endocrine‐sensitive BC cells, the activity of sensing cytosolic DNA through the cGAS‐STING pathway is attenuated in endocrine‐resistant BC cells. Screening of kinase inhibitor library show that this effect is mainly mediated by hyperactivation of AKT1 kinase, which binds to kinase domain of TBK1, preventing the formation of a trimeric complex TBK1/STING/IRF3. Notably, inactivation of cGAS–STING signaling forms a positive feedback loop with hyperactivated AKT1 to promote endocrine resistance, which is physiologically important and clinically relevant in patients with ER+HER2– BC. Blocking the positive feedback loop using the combination of an AKT1 inhibitor with a STING agonist results in the engagement of innate and adaptive immune signaling and impairs the growth of endocrine‐resistant tumors in humanized mice models, providing a potential strategy for treating patients with endocrine‐resistant BC.
Tracing the Cross‐Talk Phenomenon of Vinylethylene Carbonate to Unveil its Counterintuitive Influence as an Electrolyte Additive on High‐Voltage Lithium‐Ion Batteries
Authors: Pfeiffer Felix , Griggio Angela , Weiling Matthias , Wang Jian‐Fen , Reißig Friederike , Peschel Christoph , Pillatsch Lex , Warrington Stefan , Nowak Sascha , Grimaudo Valentine , Wright Iain , Baghernejad Masoud 
Published: July 2024

AbstractThe formation of effective interphases is crucial to enable high‐performance lithium‐ion batteries. This can be facilitated by the introduction of electrolyte additives, ensuring improved stability and transport properties. The identification of proper additives requires a comprehensive understanding of the fundamental mechanisms of interfacial reactions governing interphase formation. This study presents a detailed investigation of widely known and less conventional interphase‐forming additives in high‐voltage LiNi0.6Mn0.2Co0.2O2, NMC622||artificial graphite cells. The electrochemical characterization shows that cells containing vinylethylene carbonate (VEC) significantly outperform all other investigated electrolyte formulations. Surprisingly, gas chromatography‐mass spectroscopy measurements of the electrolyte composition after cycling indicate the formation of an ineffective solid‐electrolyte interphase (SEI) in the presence of VEC. A thorough analysis of the interfacial composition via operando shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) and surface‐enhanced Raman spectroscopy elucidates rather the formation of an effective cathode‐electrolyte interphase (CEI). This phenomenon results from the reductive reaction of VEC on the anode, followed by the product transfer and electro‐polymerization of reaction products on the cathode. Additionally, focused ion beam secondary ion mass spectrometry (FIB‐SIMS) with a time of flight (ToF)‐detector is used to analyze the elemental spatial distribution of Li‐species and Mn in the respective SEIs.
Empowering a person‐centered long‐term care workforce
Authors: Pace Doug , Betts Shadoworee , Reda Lillian , Griff Merle , Stratton Lauren , Shubeck Emily , Eichenberger Lakelyn , Holles Nikki , Holloway Lisa , Little Rachel , Maguire Sharon , Mahoney Joyce , Smith Cole , Fazio Sam 
Published: July 2024

AbstractCurrently there is a crisis in the long‐term care workforce, as many workers experience poor pay, a lack of training, burnout, low quality working conditions, and physical strain, which is leading to a workforce shortage. To address this, the Alzheimer's Association Dementia Care Provider Roundtable (AADCPR) convened a panel of direct care workers to discuss and provide direction on their view of the current state of the workforce. From this panel, five touchpoints for hiring and retaining direct care workers were highlighted: high quality jobs; recruitment and reputation management; onboarding; retention; and training and career advancement. In addition, the DCPR put together a set of standards to follow to meet these needs, which includes promoting staff dementia education opportunities, creating recommendations around peer mentoring programs specific to dementia care, and increasing inclusion of direct care workers in decision‐making and plans of care.Highlights
Presents the current state of workforce in long‐term care.
Provides five touchpoints that long‐term and home and community‐based services should implement for hiring and retaining direct care workers.
Recommends a set of standards to follow to meet the needs of the workforce within long‐term care.
Cotunneling Effects in the Geometric Statistics of a Nonequilibrium Spin‐Resolved Junction
Authors: Sandilya Mriganka , Akhtar Javed , Sarmah Manash Jyoti , Goswami Himangshu Prabal 
Published: July 2024

AbstractIn the nonequilibrium steady state of electronic transport across a spin‐resolved quantronic junction, the role of cotunneling on the emergent statistics under phase‐different adiabatic modulation of the reservoirs' chemical potentials is investigated. By explicitly identifying the sequential and inelastic cotunneling rates, the geometric or Pancharatnam–Berry contribution to the spin exchange flux between the spin system and the right reservoir is numerically evaluated. The relevant conditions wherein the sequential and cotunneling processes compete and selectively influence the total geometric flux upshot are identified. The Fock space coherences are found to suppress the cotunneling effects when the system reservoir couplings are comparable. The cotunneling contribution to the total geometric flux can be made comparable to the sequential contribution by creating a right‐sided asymmetrically stronger system‐reservoir coupling strength. Using a recently proposed geometric thermodynamic uncertainty relationship, the total rate of minimal entropy production is estimated. The geometric flux and the minimum entropy is found to be nonlinear as a function of the interaction energy of the junctions' spin orbitals.
“Anions‐in‐Colloid” Hydrated Deep Eutectic Electrolyte for High Reversible Zinc Metal Anodes
Authors: Cheng Min , Li Diantao , Cao Junlun , Sun Tianjiang , Sun Qiong , Zhang Weijia , Zha Zhengtai , Shi Mengyao , Zhang Kai , Tao Zhanliang 
Published: July 2024

AbstractZn metal as a promising anode for aqueous batteries suffers from severe zinc dendrites, anion‐related side reactions, hydrogen evolution reaction (HER) and narrow electrochemical stable window (ESW). Herein, an “anions‐in‐colloid” hydrated deep eutectic electrolyte consisting of Zn(ClO4)2 ⋅ 6H2O, β‐cyclodextrin (β‐CD), and H2O with mass ratio of 7 : 4.5 : 3 (ACDE‐3) is designed to improve the stability of zinc anode. The ACDE‐3 reconfigures the hydrogen‐bond (HB) network and regulates the solvation shell. More importantly, the hydroxyl‐rich β‐cyclodextrins (β‐CDs) in ACDE‐3 self‐assemble into micelles, in which the steric effect between adjacent β‐CDs in micelles restricts the movement of anions. This unique “anions‐in‐colloid” structure enables the eutectic system with a high Zn2+ transference number (tZn2+) of 0.84. Thus, ACDE‐3 inhibits the formation of dendrite, prevents the anion‐involved side reactions, suppresses the HER, and enlarges the ESW to 2.32 V. The Zn//Zn symmetric cell delivers a long lifespan of 900 hours at 0.5 mA cm−2, and the Zn//Cu half cells have a high average columbic efficiency (ACE) of 97.9 % at 0.5 mA cm−2 from cycle 15 to 200 with a uniform and compact zinc deposition. When matched with a poly(1,5‐naphthalenediamine) (poly(1, 5‐NAPD)) cathode, the full battery with a low negative/positive capacity (N/P) ratio of 2 can still cycle steadily for 200 cycles at a current density of 1.0 A g−1. Additionally, this electrolyte has been proven to be operative over a wide temperature range from −40 °C to 40 °C.
Dual Channel Emissions of Kasha and Anti‐Kasha from a Single Radical Molecule
Authors: Zhu Zihao , Kuang Zhiyuan , Shen Li , Wang Shengjie , Ai Xin , Abdurahman Alim , Peng Qiming 
Published: July 2024

AbstractStable open‐shell luminescent radicals have recently attracted much attention due to their unique luminescence properties. However, a radical molecule with both Kasha and anti‐Kasha doublet emission properties has not been reported. Herein, we have successfully synthesized a stable chlorine‐substituted Chichibabin's hydrocarbon, TTM‐TTM, along with its mono‐radical counterpart, TTM‐HTTM. The emission of TTM‐TTM follows Kasha's rule in the near infrared region. However, TTM‐HTTM shows dual channel doublet emissions of Kasha and anti‐Kasha. Remarkably, these two types of emission compete dynamically in both solution and condensed states. Our findings provide valuable insights into the rational design and discovery of stable radicals that possess distinctive luminescent properties, thus broadening the horizons of luminescent materials research.
Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character
Authors: Saddington Artemis , Dong Shicheng , Yao Shenglai , Zhu Jun , Driess Matthias 
Published: July 2024

AbstractThe suitability of electron‐rich bis‐silylenes, specifically the neutral chelating [SiII(Xant)SiII] ligand (SiII=PhC(NtBu)2Si, Xant=9,9‐dimethylxanthene) and the anionic [SiII(NAcrid)SiII)]− pincer ligand (NAcrid=2,7,9,9‐tetramethylacridane), has been successfully probed to stabilize monovalent bis‐silylene‐supported aluminium complexes (aluminylenes). At first, the unprecedented aluminium(III) iodide precursors [SiII(Xant)SiII]AlI2+ I− 1 and [SiII(NAcrid)SiII)]AlI2 2 were synthesized using AlI3 and [SiII(Xant)SiII] or [SiII(NAcrid)SiII)]Li(OEt2)], respectively, and structurally characterized. While reduction of 1 with KC8 led merely to unidentified products, the dehalogenation of 2 afforded the dimer of the desired {[SiII(NAcrid)SiII)]Al:} aluminylene with a four‐membered SiIV2AlIII2 ring. Remarkably, the proposed aluminylene intermediates [SiII(Xant)SiII]AlII and {[SiII(NAcrid)SiII)]Al:} could be produced through reaction of 1 and 2 with Collman's reagent, K2Fe(CO)4, and trapped as AlI:→Fe(CO)4 complexes 5 and 6, respectively. While 6 is stable in solution, 5 loses one CO ligand in solution to afford the silylene‐ and aluminylene‐coordinated iron(0) complex 7 from an intramolecular substitution reaction. The electronic structures of the novel compounds were investigated by Density Functional Theory calculations.
Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two‐Dimensional Hybrid Perovskite Photocatalysts
Authors: Fang Zhaohui , Wang Guohong , Guan Chen , Zhang Jianjun , Xiang Quanjun 
Published: July 2024

AbstractTwo‐dimensional organic–inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron‐hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4− octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non‐overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.
Enantioselective Copper‐Catalyzed Sequential Hydrosilylation of Arylmethylenecyclopropanes
Authors: Fu Bin , Wang Lianghua , Chen Kexin , Yuan Xiuping , Yin Jianjun , Wang Simin , Shi Dazhen , Zhu Bo , Guan Wei , Zhang Qian , Xiong Tao 
Published: July 2024

AbstractDespite impressive advances in the construction of enantioenriched silacarbocycles featuring silicon‐stereogenic centers via a selection of well‐defined sila‐synthons, the development of a more convenient and economic method with readily available starting materials is significantly less explored and remains a considerable challenge. Herein, we report the first example of copper‐catalyzed sequential hydrosilylation of readily accessible methylenecyclopropanes (MCPs) and primary silanes, affording an efficient and convenient route to a wide range of chiral silacyclopentanes bearing consecutive silicon‐ and carbon‐stereogenic centers with excellent enantio‐ and diastereoselectivities (generally ≥98 % ee, >25 : 1 dr). Mechanistic studies reveal that these reactions combine copper‐catalyzed intermolecular ring‐opening hydrosilylation of aryl MCPs and intramolecular asymmetric hydrosilylation of the resultant Z/E mixture of homoallylic silanes.