bluuebunny/crossref_metadata_2025_split huggingface dataset:
Avatrombopag for adults with early versus chronic immune thrombocytopenia
Authors: Virk Zain M. , Leaf Rebecca K. , Kuter David J. , Goodarzi Katayoon , Connell Nathan T. , Connors Jean M. , Al‐Samkari Hanny 
Published: December 2023

AbstractAvatrombopag is a newer thrombopoietin receptor agonist (TPO‐RA) currently approved to treat chronic ITP (duration >12 months). No studies have yet evaluated the safety and effectiveness of avatrombopag in newly diagnosed ITP (duration <3 months) or persistent ITP (duration 3–12 months), and so its use in these populations is presently off‐label worldwide. We hypothesize that avatrombopag has similar safety and effectiveness irrespective of ITP disease phase. To evaluate this, we performed a multicenter observational cohort study of adults with ITP treated with avatrombopag, comparing patient outcomes by disease phase (newly diagnosed/persistent versus chronic). Seventy‐five patients were included, 23 with newly diagnosed/persistent ITP (17.7 patient‐years of avatrombopag treatment) and 52 with chronic ITP (65.3 patient‐years of avatrombopag treatment). On avatrombopag, 91% of newly diagnosed/persistent patients versus 96% of chronic patients (p = .58) achieved a platelet response (≥50 × 109/L) and 86% versus 81% of patients (p = .78) achieved a complete response (≥100 × 109/L). Median platelet counts on avatrombopag were similar between the two groups (165 × 109/L vs. 129 × 109/L, p = .57). Response durability was high and similar in both groups. No patients in the newly diagnosed/persistent group had a major bleeding event, thromboembolic event or avatrombopag discontinuation for adverse events, compared with 4, 1, and 2, respectively, in the chronic group. Thrombocytosis (platelets ≥400 × 109/L) incidence was similar in the two groups. No other drug‐related adverse events occurred in either group. Avatrombopag was safe and effective in patients with newly diagnosed and persistent ITP, with outcomes numerically, statistically, and clinically similar to patients receiving avatrombopag for chronic ITP.
“I hope you aren't becoming woke”: New politicised contours of online ableism in response to disability advocacy by 2022 Australian of the Year Dylan Alcott
Authors: West Raelene , Johnson Belinda 
Published: December 2023

AbstractAbleist hate speech regularly appears in online comment‐enabled articles on social media, whenever disability‐related topics enter public discourse. In 2022, Dylan Alcott's appointment as Australian of the Year as a person with disability was widely celebrated. Despite this progress, we identified new forms of politicised ableism in online responses to his disability advocacy in this role. This research considers readership responses to an April 2022 Facebook post by an Australian tabloid publication. The post editorialised Alcott's Twitter response to the then Australian Prime Minister's comments on feeling “blessed” to have children without disability. Enmeshed within the usual ableist imaginary—“why would any parent want to have a child with disability?”—were new justifications for ableism associated with political “wokeness.” We analyse this emerging contour of politicised ableism in contemporary Australia to consider the complex patterns of progress toward social justice for people with disability.
Stabilizing Sulfur Sites in Tetraoxygen Tetrahedral Coordination Structure for Efficient Electrochemical Water Oxidation
Authors: Jin Jing , Yin Jie , Hu Yang , Zheng Yao , Liu Hongbo , Wang Xinyao , Xi Pinxian , Yan Chun‐Hua 
Published: December 2023

AbstractIon regulation strategy is regarded as a promising pathway for designing transition metal oxide‐based electrocatalysts for oxygen evolution reaction (OER) with improved activity and stability. Precise anion conditioning can accurately change the anionic environment so that the acid radical ions (SO42−, PO32−, SeO42−, etc.), regardless of their state (inside the catalyst, on the catalyst surface, or in the electrolyte), can optimize the electronic structure of the cationic active site and further increase the catalytic activity. Herein, we report a new approach to encapsulate S atoms at the tetrahedral sites of the NaCl‐type oxide NiO to form a tetraoxo‐tetrahedral coordination structure (S‐O4) inside the NiO (S‐NiO ‐I). Density functional theory (DFT) calculations and operando vibrational spectroscopy proves that this kind of unique structure could achieve the S‐O4 and Ni‐S stable structure in S‐NiO‐I. Combining mass spectroscopy characterization, it could be confirmed that the S‐O4 structure is the key factor for triggering the lattice oxygen exchange to participate in the OER process. This work demonstrates that the formation of tetraoxygen tetrahedral structure is a generalized key for boosting the OER performances of transition metal oxides.
Bio‐inspired Double Angstrom‐Scale Confinement in Ti‐deficient Ti0.87O2 Nanosheet Membranes for Ultrahigh‐performance Osmotic Power Generation
Authors: Liu Chao , Ye Caichao , Zhang Tianning , Tang Jiheng , Mao Kunpeng , Chen Long , Xue Liang , Sun Jingwen , Zhang Wenqing , Wang Xin , Xiong Pan , Wang Guoxiu , Zhu Junwu 
Published: December 2023

AbstractOsmotic power, a clean energy source, can be harvested from the salinity difference between seawater and river water. However, the output power densities are hampered by the trade‐off between ion selectivity and ion permeability. Here we propose an effective strategy of double angstrom‐scale confinement (DAC) to design ion‐permselective channels with enhanced ion selectivity and permeability simultaneously. The fabricated DAC‐Ti0.87O2 membranes possess both Ti atomic vacancies and an interlayer free spacing of ≈2.2 Å, which not only generates a profitable confinement effect for Na+ ions to enable high ion selectivity but also induces a strong interaction with Na+ ions to benefit high ion permeability. Consequently, when applied to osmotic power generation, the DAC‐Ti0.87O2 membranes achieved an ultrahigh power density of 17.8 W m−2 by mixing 0.5/0.01 M NaCl solution and up to 114.2 W m−2 with a 500‐fold salinity gradient, far exceeding all the reported macroscopic‐scale membranes. This work highlights the potential of the construction of DAC ion‐permselective channels for two‐dimensional materials in high‐performance nanofluidic energy systems.
Bimetal‐bridging Nitrogen Coordination in Carbon‐based Electrocatalysts for pH‐universal Oxygen Reduction
Authors: Shu Xinxin , Tan Dongxing , Wang Yueqing , Ma Jizhen , Zhang Jintao 
Published: December 2023

AbstractElectrocatalysts with atomically dispersed metal sites (e.g., metal‐nitrogen‐carbon) have been deemed as promising alternatives for noble‐metal catalysts in couples of electrocatalytic reactions. However, the modulation of such atomic sites and the understanding of their interactions are still highly challenging. Herein, we propose a unique supermolecule assembly‐profile coating strategy to prepare a series of diatomic electrocatalysts by profile coating of eight Prussian blue analogues (PBAs) on supramolecular supports respectively as bimetallic sources. The detailed microstructure analysis revealed that the metal‐nitrogen‐carbon sites with four‐ (Zn−N4) and five‐coordination (Fe−N5) via the nitrogen coordination are similar to the cytochrome c oxidases. For promising electrocatalysis, such unique microstructure is able to activate oxygen molecules due to nitrogen‐bonding coordination with bimetal sites, thus leading to efficient four‐electron oxygen reduction in alkaline, neutral, and acid electrolytes. Especially, zinc group elements (e.g., Zn and Cd) with d10 electron configuration would significantly boost the nitrogen‐bonding coordination with bimetal sites to enhance electrocatalytic activity. The proof‐of‐concept for the general synthesis of advanced electrocatalysts with controllable bimetal active sites and the mechanistic understanding will promote the promising electrocatalysis by applying the similar principles.
Tetra‐Coordinated W2S3 for Efficient Dual‐pH Hydrogen Production
Authors: Xie Lingbin , Wang Longlu , Liu Xia , Zhao Weiwei , Liu Shujuan , Huang Xiao , Zhao Qiang 
Published: December 2023

AbstractTwo‐dimensional (2D) transition‐metal dichalcogenides (TMDs) have emerged as promising catalysts for the hydrogen evolution reaction (HER) that play a crucial role in renewable energy technologies. Breaking the inherent structural paradigm limitations of 2D TMDs is the key to exploring their fascinating physical and chemical properties, which is expected to develop a revolutionary HER catalyst. Herein, we unambiguously present metallic W2S3 instead of energetically favorable WS2 via a unique stoichiometric growth strategy. Benefiting from the excellent conductivity and hydrophilicity of the tetra‐coordinated structure, as well as an appropriate Gibbs free energy value and an enough low energy barrier for water dissociation, the W2S3 as catalyst achieves Pt‐like HER activity and high long‐term stability in both acidic and alkaline electrolytes. For application in proton exchange membrane (PEM) and anion exchange membrane (AEM) electrolysers, W2S3 as the cathode catalyst yields excellent bifunctionality index (ɳ
=1.73 V, ɳ
=1.77 V) and long‐term stability (471 h@PEM with a decay rate of 85.7 μV h−1, 360 h@AEM with a decay rate of 27.1 μV h−1). Our work provides significant insight into the tetra‐coordinated W2S3 and facilitates the development of advanced electrocatalysts for sustainable hydrogen production.
Red‐Light Activation of a Microtubule Polymerization Inhibitor via Amide Functionalization of the Ruthenium Photocage
Authors: Bretin Ludovic , Husiev Yurii , Ramu Vadde , Zhang Liyan , Hakkennes Matthijs , Abyar Selda , Johns Andrew C. , Le Dévédec Sylvia E. , Betancourt Tania , Kornienko Alexander , Bonnet Sylvestre 
Published: December 2023

AbstractPhotoactivated chemotherapy (PACT) is a promising cancer treatment modality that kills cancer cells via photochemical uncaging of a cytotoxic drug. Most ruthenium‐based photocages used for PACT are activated with blue or green light, which penetrates sub‐optimally into tumor tissues. Here, we report amide functionalization as a tool to fine‐tune the toxicity and excited states of a terpyridine‐based ruthenium photocage. Due to conjugation of the amide group with the terpyridine π system in the excited state, the absorption of red light (630 nm) increased 8‐fold, and the photosubstitution rate rose 5‐fold. In vitro, red light activation triggered inhibition of tubulin polymerization, which led to apoptotic cell death both in normoxic (21 % O2) and hypoxic (1 % O2) cancer cells. In vivo, red light irradiation of tumor‐bearing mice demonstrated significant tumor volume reduction (45 %) with improved biosafety, thereby demonstrating the clinical potential of this compound.
Photochemical [2+4]‐Dimerization Reaction from the Excited State
Authors: Ahuja Sapna , Baburaj Sruthy , Valloli Lakshmy Kannadi , Rakhimov Sarvar Aminovich , Manal Kavyasree , Kushwaha Aakrati , Jockusch Steffen , Forbes Malcolm D. E. , Sivaguru Jayaraman 
Published: December 2023

AbstractAryl‐maleimides undergo a novel [2+4]‐photodimerization instead of the expected [2+2]‐photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl‐maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non‐bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions.
Carbonyl‐ and Nitrogen‐Embedded Multi‐Resonance Emitter with Ultra‐Pure Green Emission and High Electroluminescence Efficiencies
Authors: Liang Lu , Qu Cheng , Fan Xiangyu , Ye Kaiqi , Zhang Yuewei , Zhang Zuolun , Duan Lian , Wang Yue 
Published: December 2023

AbstractMulti‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters with narrow emission spectra have garnered significant attention in future organic light‐emitting diode (OLED) displays. However, current C=O/N‐embedded MR‐TADF systems still lack satisfactory performance in terms of electroluminescence bandwidths and external quantum efficiencies (EQEs). In this study, a C=O/N‐embedded green MR‐TADF emitter, featuring two acridone units incorporated in a sterically protected 11‐ring fused core skeleton, is successfully synthesized through finely controlling the reaction selectivity. The superior combination of multiple intramolecular fusion and steric wrapping strategies in the design of the emitter not only imparts an extremely narrow emission spectrum and a high fluorescence quantum yield to the emitter but also mitigates aggregation‐induced spectral broadening and fluorescence quenching. Therefore, the emitter exhibits leading green OLED performance among C=O/N‐based MR‐TADF systems, achieving an EQE of up to 37.2 %, a full width at half maximum of merely 0.11 eV (24 nm), and a Commission Internationale de l′Éclairage coordinate of (0.20, 0.73). This study marks a significant advance in the realization of ideal C=O/N‐based MR‐TADF emitters and holds profound implications for the design and synthesis of other MR‐TADF systems.
A Fluorinated Solid‐state‐electrolyte Interface Layer Guiding Fast Zinc‐ion Oriented Deposition in Aqueous Zinc‐ion Batteries
Authors: Zhu Mengyu , Wang Huicai , Wang Huibo , Li Chunxin , Chen Danling , Wang Kexuan , Bai Zhengshuai , Chen Shi , Zhang Yanyan , Tang Yuxin 
Published: December 2023

AbstractAqueous zinc ion batteries are gaining popularity due to their high energy density and environmental friendliness. However, random deposition of zinc ions on the anode and sluggish migration of zinc ions on the interface would lead to the growth of zinc dendrites and poor cycling performance. To address these challenges, we developed a fluorinated solid‐state‐electrolyte interface layer composed of Ca5(PO4)3F/Zn3(PO4)2 via an in situ ion exchange strategy to guide zinc‐ion oriented deposition and fast zinc ion migration on the anode during cycling. The introduction of Ca5(PO4)3F (FAP) can increase the nucleation sites of zinc ions and guide the oriented deposition of zinc ions along the (002) crystal plane, while the in situ formation of Zn3(PO4)2 during cycling can accelerate the migration of zinc ions. Benefited from our design, the assembled Zn//V2O5 ⋅ H2O batteries based on FAP‐protected Zn anode (FAP‐Zn) achieve a higher capacity retention of 84 % (220 mAh g−1) than that of bare‐Zn based batteries, which have a capacity retention of 23 % (97 mAh g−1) at 3.0 A g−1 after 800 cycles. This work provides a new solution for the rational design and development of the solid‐state electrolyte interface layer to achieve high‐performance zinc‐ion batteries.
Inverse Adsorption Separation of N2O/CO2 in AgZK‐5 Zeolite
Authors: Wang Li , Lin Caihong , Boldog István , Yang Jiangfeng , Janiak Christoph , Li Jinping 
Published: December 2023

AbstractNitrous oxide (N2O), as the third largest greenhouse gas in the world, also has great applications in daily life and industrial production, like anesthetic, foaming agent, combustion supporting agent, N or O atomic donor. The capture of N2O in adipic acid tail gas is of great significance but remains challenging due to the similarity with CO2 in molecular size and physical properties. Herein, the influence of cation types on CO2−N2O separation in zeolite was studied comprehensively. In particular, the inverse adsorption of CO2−N2O was achieved by AgZK‐5, which preferentially adsorbs N2O over CO2, making it capable of trapping N2O from an N2O/CO2 mixture. AgZK‐5 shows a recorded N2O/CO2 selectivity of 2.2, and the breakthrough experiment indicates excellent performance for N2O/CO2 separation. The density functional theory (DFT) calculation shows that Ag+ has stronger adsorption energy with N2O, and the kinetics of N2O is slightly faster than that of CO2 on AgZK‐5.
A Breast Cancer Stem Active Cobalt(III)‐Cyclam Complex Containing Flufenamic Acid with Immunogenic Potential
Authors: Fang Jiaxin , Orobator Owamagbe N. , Olelewe Chibuzor , Passeri Ginevra , Singh Kuldip , Awuah Samuel G. , Suntharalingam Kogularamanan 
Published: December 2023

AbstractThe cytotoxic and immunogenic‐activating properties of a cobalt(III)‐cyclam complex bearing the non‐steroidal anti‐inflammatory drug, flufenamic acid is reported within the context of anti‐cancer stem cell (CSC) drug discovery. The cobalt(III)‐cyclam complex 1 displays sub‐micromolar potency towards breast CSCs grown in monolayers, 24‐fold and 31‐fold greater than salinomycin (an established anti‐breast CSC agent) and cisplatin (an anticancer metallopharmaceutical), respectively. Strikingly, the cobalt(III)‐cyclam complex 1 is 69‐fold and 50‐fold more potent than salinomycin and cisplatin towards three‐dimensionally cultured breast CSC mammospheres. Mechanistic studies reveal that 1 induces DNA damage, inhibits cyclooxygenase‐2 expression, and prompts caspase‐dependent apoptosis. Breast CSCs treated with 1 exhibit damage‐associated molecular patterns characteristic of immunogenic cell death and are phagocytosed by macrophages. As far as we are aware, 1 is the first cobalt complex of any oxidation state or geometry to display both cytotoxic and immunogenic‐activating effects on breast CSCs.
Tuning CH Hydrogen Bond‐Based Receptors toward Picomolar Anion Affinity via the Inductive Effect of Distant Substituents
Authors: Chvojka Matúš , Madea Dominik , Valkenier Hennie , Šindelář Vladimír 
Published: December 2023

AbstractInspired by nature, artificial hydrogen bond‐based anion receptors have been developed to achieve high anion selectivity; however, their binding affinity is usually low. The potency of these receptors is usually increased by the introduction of aryl substituents, which withdraw electrons from their binding site through the resonance effect. Here, we show that the polarization of the C(sp3)‐H binding site of bambusuril receptors, and thus their potency to bind anions, can be modulated by the inductive effect. The presence of electron‐withdrawing groups on benzyl substituents of bambusurils significantly increases their binding affinities to halides, resulting in the strongest iodide receptor reported to date with an association constant greater than 1013 M−1 in acetonitrile. A Hammett plot showed that while the bambusuril affinity toward halides linearly increases with the electron‐withdrawing power of their substituents, their binding selectivity remains essentially unchanged.
Topological Single‐stranded DNA Encoding and Programmable Assembly of Molecular Nanostructures for NIR‐II Cancer Theranostics
Authors: Wang Zhiqiang , Wang Linlin , Chen Hong , Li Ting , Li Jili , Zhang Lili , Zhong Minjuan , Liu Yanlan , Tan Weihong 
Published: December 2023

AbstractMolecular nanotechnology promises to offer privileged access to developing NIR‐II materials with precise structural and functional manipulation for transformable theranostic applications. However, the lack of an affordable, yet general, method makes this goal currently inaccessible. By virtue of the intriguing nucleic acid chemistry, here we present an artificial base‐directed topological single‐strand DNA encoding design that enables one‐step synthesis of valence‐controlled NIR‐II molecular nanostructures and spatial assembly of these nanostructures to modulate their behaviors in living systems. As proof‐of‐concept studies, we construct ultrasmall Ag2S quantum dots and pH‐responsive, size‐tunable CuS assemblies for in vivo NIR‐II fluorescence imaging and deep tumor photothermal therapy. This work paves a new way for creating functionally diversified architectures and broadens the scope of DNA‐encoded material engineering.
A Photoswitchable Macrocycle Controls Anion‐Templated Pseudorotaxane Formation and Axle Relocalization
Authors: de Jong Jorn , Siegler Maxime A. , Wezenberg Sander J. 
Published: December 2023

AbstractImportant biological processes, such as signaling and transport, are regulated by dynamic binding events. The development of artificial supramolecular systems in which binding between different components is controlled could help emulate such processes. Herein, we describe stiff‐stilbene‐containing macrocycles that can be switched between (Z)‐ and (E)‐isomers by light, as demonstrated by UV/Vis and 1H NMR spectroscopy. The (Z)‐isomers can be effectively threaded by pyridinium halide axles to give pseudorotaxane complexes, as confirmed by 1H NMR titration studies and single‐crystal X‐ray crystallography. The overall stability of these complexes can be tuned by varying the templating counteranion. However, upon light‐induced isomerization to the (E)‐isomer, the threading capability is drastically reduced. The axle component, in addition, can form a heterodimeric complex with a secondary isophthalamide host. Therefore, when all components are combined, light irradiation triggers axle exchange between the macrocycle and this secondary host, which has been monitored by 1H NMR spectroscopy and simulated computationally.
Soccer Ball‐like Assembly of Edge‐to‐edge Oriented 2D‐silica Nanosheets: A Promising Catalyst Support for High‐Temperature Reforming
Authors: Jang Sun Woo , Kumari Nitee , Nam Eonu , Lee Yun Kyung , Cha Yunmi , An Kwangjin , Lee In Su 
Published: December 2023

AbstractControlled assembly of nanoparticles into well‐defined assembled architectures through precise manipulation of spatial arrangement and interactions allows the development of advanced mesoscale materials with tailored structures, hierarchical functionalities, and enhanced properties. Despite remarkable advancements, the controlled assembly of highly anisotropic 2Dnanosheets is significantly challenging, primarily due to the limited availability of selective edge‐to‐edge connectivity compared to the abundant large faces. Innovative strategies are needed to unlock the full potential of 2D‐nanomaterialsin self‐assembled structures with distinct and desirable properties. This research unveils the discovery of controlled self‐assembly of 2D‐silica nanosheets (2D‐SiNSs) into hollow micron‐sized soccer ball‐like shells (SA‐SiMS). The assembly is driven by the physical flexibility of the 2D‐SiNSs and the differential electricdouble‐layer charge gradient creating electrostatic bias on the edge and face regions. The resulting SA‐SiMS structures exhibit high mechanical stability, even at high‐temperatures, and exhibit excellent performance as catalyst support in the dry reforming of methane. The SA‐SiMS structures facilitate improved mass transport, leading to enhanced reaction rates, while the thin silica shell prevents sintering of small catalyst nanocrystals, thereby preventing coke formation. This discovery sheds light on the controllable self‐assembly of 2D nanomaterials and provides insights into the design and synthesis of advanced mesoscale materials with tailored properties.