bluuebunny/crossref_metadata_2025 huggingface dataset:
Phenology, gas exchange, biomass accumulation, and irrigated rice yield under alternative irrigation managements
Authors: dos Santos Marcos Paulo , Heinemann Alexandre Bryan , Stone Luís Fernando , da Silva Mellissa Ananias Soler , Lanna Anna Cristina , dos Santos Alberto Baêta
Published: December 2023

In Brazil, rice production is predominantly concentrated in the South region, employing a continuous flood irrigation system throughout the crop cycle. However, this irrigation management strategy in the tropical region contributes to low water‐use efficiency owing to adverse climatic conditions. Furthermore, with climate change projections indicating reduced water availability, the study aims to investigate the impact of alternative irrigation management strategies on the phenological development, gas exchange, biomass accumulation, and productivity of tropical irrigated rice. Three alternative irrigation management approaches—intermittent flood irrigation with aeration (IFA), intermittent flood irrigation throughout the growth cycle (IFC), and intermittent flooding up to the flowering stage (IFF)—were compared with the traditional continuous flood irrigation throughout the growth cycle. Phenological data, gas exchange, growth, and productivity dynamics were subject to analysis, providing overarching insights into management practices. Notably, irrigation management exhibited no influence on the vegetative phase of the crop. The implementation of intermittent flood irrigation facilitated a reduction in water supply without compromising the physiological performance of tropical irrigated rice. Strategies promoting judicious water utilization, such as IFA and IFC, can be readily integrated into the cultivation of tropical irrigated rice without detriment to grain yield or harvest index.
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

Avatrombopag 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

Ableist 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.
RNA Foci in Two bi‐Allelic RFC1 Expansion Carriers
Authors: Wada Taishi , Doi Hiroshi , Okubo Masaki , Tada Mikiko , Ueda Naohisa , Suzuki Hidefumi , Tominaga Wakana , Koike Haruki , Komiya Hiroyasu , Kubota Shun , Hashiguchi Shunta , Nakamura Haruko , Takahashi Keita , Kunii Misako , Tanaka Kenichi , Miyaji Yosuke , Higashiyama Yuichi , Koshimizu Eriko , Miyatake Satoko , Katsuno Masahisa , Fujii Satoshi , Takahashi Hidehisa , Matsumoto Naomichi , Takeuchi Hideyuki , Tanaka Fumiaki
Published: December 2023

Cerebellar ataxia, neuropathy, vestibular areflexia syndrome (CANVAS) is a late‐onset, autosomal recessive neurodegenerative disorder caused by biallelic AAGGG/ACAGG repeat expansion (AAGGG‐exp/ACAGG‐exp) in RFC1. The recent identification of patients with CANVAS exhibiting compound heterozygosity for AAGGG‐exp and truncating variants supports the loss‐of‐function of RFC1 in CANVAS patients. We investigated the pathological changes in 2 autopsied patients with CANVAS harboring biallelic ACAGG‐exp and AAGGG‐exp. RNA fluorescence in situ hybridization of the 2 patients revealed CCTGT‐ and CCCTT‐containing RNA foci, respectively, in neuronal nuclei of tissues with neuronal loss. Our findings suggest that RNA toxicity may be involved in the pathogenesis of CANVAS. ANN NEUROL 2024;95:607–613
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

Ion 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

Osmotic 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

Electrocatalysts 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

Two‐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

Photoactivated 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

Aryl‐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

Multi‐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

Aqueous 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

Nitrous 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

The 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

Inspired 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

Molecular 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

Important 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

Controlled 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.
Metal Ion‐Induced Large Fragment Deactivation: A Different Strategy for Site‐Selectivity in a Complex Molecule
Authors: Ruskin Jonah , Sachs Roseann K. , Wang Muyuan , Dekeyser Roxanne , Lew Zachary , Williams Phoebe , Hwang Habin , Majumdar Ananya , Dudding Travis , Lectka Thomas
Published: December 2023

Complex natural product functionalizations generally involve the use of highly engineered reagents, catalysts, or enzymes to react exclusively at a desired site through lowering of a select transition state energy. In this communication, we report a new, complementary strategy in which all transition states representing undesirable sites in a complex ionophore substrate are simultaneously energetically increased through the chelation of a metal ion to the large fragment we wish to neutralize. In the case of an electrophilic, radical based fluorination reaction, charge repulsion (electric field effects), induced steric effects, and electron withdrawal provide the necessary deactivation and proof of principle to afford a highly desirable natural product derivative. We envisage that many other electrophilic or charge based synthetic methods may be amenable to this approach as well.
Origin of an intermediate peak in DMTA analysis of multilayer ABS/PC samples
Authors: Alkhuder Aboubaker , Caro Anne‐Sophie , Gervais Matthieu , Guinault Alain , Ienny Patrick , Perrin Didier , Sollogoub Cyrille
Published: December 2023

Three layers film shaped by thermocompression of acrylonitrile butadiene styrene copolymer and polycarbonate have been analyzed in dynamic mechanical thermal analysis in tensile mode. They present two peaks as the film is loaded perpendicularly to the layers and three peaks as the film is loaded in parallel to the layers. Numerical computations confirm that the origin of this peak is not related to a mechanical issue such as the transmission of the imposed deformation from one layer to the other. Using this method, it is demonstrated that this third peak can only be obtained assuming a material transition with its own behavior between layers. Tan δ measurements provide a simple and useful experimental tool to understand more about the interfacial zone in polymer blends.
Preparation and application of high sound insulation polyurethane composite film through glass fiber reinforcement
Authors: Liu Hongyan , Zhan Siqi , Bo Yanyan , Ding Wenhe , Yuan Ruize , Yu Zaiqian , Zhang Yuting , Sun Yuetong , Yu Longjiao , Wang Shiwei , Zhang Mingyao
Published: December 2023

Laminated glasses have been widely used in buildings, physical protections, and vehicles because of their safety, sound insulation, thermal insulation, and other performance. In recent years, the high sound insulation performance of laminated glass intermediate films in the frequency range of low or high frequencies has attracted more and more attentions. In this work, a glass fiber/polyurethane elastomer composite (PU‐MGF) film with high transparency and impact resistance has been successfully synthesized, 5 dB of the transmission loss increased at 1600–6000 Hz, and 3.6 dB increased at 63–1600 Hz compared with the control polyurethane film. This is a significant progress in the laminated glass industry. In addition, the transmittance of the composite reaches over 75%. The excellent impact resistance of the laminated glass, based on PU‐MGF film, has been confirmed through falling ball impact test, demonstrating its ability to withstand multiple impacts without spattering. The PU‐MGF film prepared in this work exhibits great potential for applications in building windows, transportation, and soundproof devices.
Poly‐Refractory Rheumatoid Arthritis: An Uncommon Subset of Difficult to Treat Disease With Distinct Inflammatory and Noninflammatory Phenotypes
Authors: David Paula , Di Matteo Andrea , Hen Or , Dass Shouvik , Marzo‐Ortega Helena , Wakefield Richard J. , Bissell Leslie‐Anne , Nam Jacqueline , Mankia Kulveer , Emery Paul , Saleem Benazir , McGonagle Dennis
Published: December 2023

Objective

To investigate the prevalence of poly‐refractory rheumatoid arthritis (RA) defined as failure of all biological (b)/targeted synthetic (ts)‐disease‐modifying drugs (DMARDs). To further investigate whether patients with persistent inflammatory refractory RA (PIRRA) and noninflammatory refractory RA (NIRRA), determined by objective ultrasound (US) synovitis, have distinct clinical phenotypes in both EULAR difficult‐to‐treat RA (D2T‐RA) and poly‐refractory RA groups.

Methods

A cross‐sectional study of 1,591 patients with RA on b/tsDMARDs that evaluated D2T‐RA criteria and subclassified as poly‐refractory if inefficacy/toxicity to at least one drug of all classes. PIRRA was defined if US synovitis in one or more swollen joint and NIRRA if absent. Univariate tests and multivariate logistic regression were conducted to investigate factors associated with poly‐refractory, PIRRA, and NIRRA phenotypes.

Results

122 of 1,591 were excluded due to missing data. 247 of 1,469 (16.8%) had D2T‐RA and only 40 of 1,469 (2.7%) poly‐refractory RA. This latter group had higher disease activity score 28 C‐reactive protein (CRP) (median 5.4 vs 5.02, P < 0.05), CRP levels (median 13 vs 5 mg/l, P < 0.01), and smoking (ever) rates (20% vs 4%, P < 0.01) compared with other D2T patients. Smoking was associated with poly‐refractory RA (odds ratio 5.067, 95% CI 1.774–14.472, P = 0.002). Of 107 patients with D2T‐RA with recent US, 61 (57%) were PIRRA and 46 (43%), NIRRA. Patients with NIRRA had elevated body mass index (median 30 vs 26, P < 0.001) and higher fibromyalgia prevalence (15% vs 3%, P < 0.05), lower swollen joint count (median: 2 vs 5, P < 0.001), and lower CRP levels (5 vs 10, P < 0.01).

Conclusion

Only 2.7% of D2T‐RA failed all classes of b/tsDMARDs. Among D2T‐RA, less than 60% had objective signs of inflammation, representing a target for innovative strategies.

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Inhibition of biofilm, quorum‐sensing, and swarming motility in pathogenic bacteria by magnetite, manganese ferrite, and nickel ferrite nanoparticles
Authors: Doğaç Yasemin İspirli , Tamfu Alfred Ngenge , Bozkurt Selahattin , Kayhan Mehmet , Teke Mustafa , Ceylan Ozgur
Published: December 2023

Resistance to antibiotics by pathogenic bacteria constitutes a health burden and nanoparticles (NPs) are being developed as alternative and multipurpose antimicrobial substances. Magnetite (Fe3O4 np), manganese ferrite (MnFe2O4 np) and nickel ferrite (NiFe3O4 np) NPs were synthesized and characterized using thermogravimetric analysis, transmission electron microscopy, Fourier transformed infra‐red, and X‐ray diffraction. The minimal inhibitory concentrations (MIC) ranged from 0.625 to 10 mg/mL against gram‐positive (Staphylococcus aureus ATCC 25923 and Enterococcus faecalis ATCC 29212), gram‐negative (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853) and candida (Candida albicans ATCC 10239 and Candida tropicalis ATCC 13803) species. The NPs exhibited violacein inhibition against Chromobacterium violaceum CV12472 of 100% at MIC and reduced to 27.2% ± 0.8% for magnetite NPs, 12.7% ± 0.3% for manganese ferrite NPs and 43.1% ± 0.2% for nickel ferrite NPs at MIC/4. Quorum‐sensing (QS) inhibition zones against C. violaceum CV026 were 12.5 ±0.6 mm for Fe3O4 np, 09.1 ± 0.5 mm for MnFe3O4 NP and 17.0 ± 1.2 mm for NiFe3O4 np. The NPs inhibited swarming motility against P. aeruginosa PA01 and biofilm against six pathogens and the gram‐positive biofilms were more susceptible than the gram‐negative ones. The NiFe2O4 np had highest antibiofilm activity against gram‐positive and gram‐negative bacteria as well as highest QS inhibition while Fe3O4 NP had highest biofilm inhibition against candida species. The synthesized magnetic NPs can be used in developing anti‐virulence drugs which reduce pathogenicity of bacteria as well as resistance.
Towards understanding how bisphosphonate‐dependent alterations to nutrient canal integrity can contribute to risk for atypical femoral fractures: Biomechanical considerations and potential relationship to a real‐world analogy
Authors: Hart David A.
Published: December 2023

Bisphosphonates are a class of drugs which have shown good efficacy in the treatment of post‐menopausal osteoporosis, as well as a good safety profile. However, side‐effects such as risk for atypical femoral fractures (AFF) have appeared, leading to a decline in use of the drugs by many patients who would benefit from the treatment. While patient characteristics have contributed to improved understanding of risk factors, the mechanisms involved that explain AFF risk have not appeared. Recently, the possibility that the mechanism(s) involved drug‐induced modification of cells of the nutrient canals of the femur and subsequent compromise in the bone matrix has been published. The present Hypothesis article builds on the concept presented earlier and expands into biomechanical considerations. An analogy of the mechanisms involved to a real‐life scenario is also presented. While this analogy has limitations, consideration of the biomechanical implications of progressive alterations to defects presented by compromised nutrient canal‐bone matrix also presents potential relationships with AFF risk.
Effects of home‐cage elevation on behavioral tests in mice
Authors: Ueno Hiroshi , Takahashi Yu , Murakami Shinji , Wani Kenta , Matsumoto Yosuke , Okamoto Motoi , Ishihara Takeshi
Published: December 2023

Background

Research reproducibility is a common problem in preclinical behavioral science. Mice are an important animal model for studying human behavioral disorders. Experimenters, processing methods, and rearing environments are the main causes of data variability in behavioral neuroscience. It is likely that mice adapt their behavior according to the environment outside the breeding cage. We speculated that mice housed on elevated shelves and mice housed on low shelves might have differently altered anxiety‐like behavior toward heights.

Purpose

The purpose of this study was to investigate potential behavioral changes in mice raised at different heights for 3 weeks. Changes in behavior were examined using various experimental tests.

Results

Mice housed on elevated shelves showed reduced anxiety‐like behavior in a light/dark traffic test compared with mice housed on low shelves. There were no significant differences between the two groups in terms of activity, exploratory behavior, muscle strength, or depression‐like behavior.

Conclusions

Our results indicate that different cage heights and corresponding light exposure may alter the anxiety‐like behavior of mice in response to brightness. Researchers need to carefully control the cage height and light intensity experienced by the mice to produce reproducible test results.
Board competence and green innovation—Does external governance matter?
Authors: Yousaf Umair Bin , Tauni Muhammad Zubair , Yousaf Imran , Su Nancy Lixin
Published: December 2023

Previous research examining the link between board attributes and ecological strategies such as green innovation has primarily focused on structural board attributes, yielding mixed findings. Moreover, the critical contextual grounds that shape the relationship between board attributes and green innovation have often been overlooked, leading to potential biases in empirical investigations. Considering that competence drives outstanding performance, we developed a unique measure of board competence that represents the board's intrinsic ability to perform in corporate strategies. Drawing on a holistic perspective of agency, resource dependence, and stakeholder theories, we posit a strong relationship between board competence and green innovation. Furthermore, we contend that this association is moderated by external governance mechanisms, namely audit quality, media coverage, and imitative pressure. Through our analysis of publicly traded Chinese companies, we found compelling evidence to support our assertions. These findings have important implications for policymakers, practitioners, and managers.
Efficacy of catheter‐based drug delivery in a hybrid in vitro model of cardiac microvascular obstruction with porcine microthrombi
Authors: Rösch Yannick , Stolte Thorald , Weisskopf Miriam , Frey Sabrina , Schwartz Rob , Cesarovic Nikola , Obrist Dominik
Published: December 2023

Microvascular obstruction (MVO) often occurs in ST‐elevation myocardial infarction (STEMI) patients after percutaneous coronary intervention (PCI). Diagnosis and treatment of MVO lack appropriate and established procedures. This study focused on two major points by using an in vitro multiscale flow model, which comprised an aortic root model with physiological blood flow and a microfluidic model of the microcirculation with vessel diameters down to 50 μm. First, the influence of porcine microthrombi (MT), injected into the fluidic microchip, on perfusion was investigated. We found that only of all injected MT were fully occlusive. Second, it could also be shown that the maximal concentration of a dye (representing therapeutic agent) during intracoronary infusion could be increased on average by , when proximally occluding the coronary artery by a balloon during drug infusion. The obtained results and insights enhance the understanding of perfusion in MVO‐affected microcirculation and could lead to improved treatment methods for MVO patients.
Retrospective longitudinal assessment of optic nerve sheath diameter in patients with malignant glioma
Authors: Feucht Daniel , Kerscher Susanne R. , Ruff Christer , Schuhmann Martin U. , Roder Constantin , Zipfel Julian
Published: December 2023

Introduction

Glioblastoma (GBM) is a tumor with rapid growth and a possible relationship to elevated intracranial pressure (ICP). High ICP may not always be associated with clinical signs. A non‐invasive technique for assessment of ICP is measuring the optic nerve sheath diameter (ONSD). Identifying patients who need immediate intervention is of importance in neuro‐oncological care. The goal of this study is to assess the available magnetic resonance imaging (MRI) of patients with GBM with respect to pre‐ and postoperative ONSD.

Methods and Materials

Retrospective data analysis was performed on all patients operated for GBM at a tertiary care center between 2010 and 2020. Two pre and one postoperative MRI had to be available. Clinical data and ONSD at multiple time points were analyzed and correlated, as well as preoperative volumetrics.

Results

Sixty‐seven patients met the inclusion criteria. Clinical signs of elevated ICP were seen in 25.4% (n = 17), while significant perifocal edema was present in 67.2% (n = 45) of patients. Clinical signs of preoperatively elevated ICP were associated with significantly elevated ONSD at diagnosis (p < 0.001) as well as preoperative tumor volume (p < 0.001). Significant perifocal edema at the time of diagnosis was associated with elevated ONSD (p = 0.029) and higher tumor volume (p = 0.003). In patients with significant edema, ONSD increased significantly between preoperative MRIs (p = 0.003/005). In patients with clinical signs of raised ICP, ONSD also increased, whereas it was stable in asymptomatic patients (yes: 5.01+/−4.17 to 5.83+/−0.55 mm, p = 0.010, no: 5.17+/−0.46 mm to 5.38+/−0.41 mm, p = 0.81). A significant increase of ONSD from diagnosis to preoperative MRI and a significant decrease until 3 months postoperatively were observed (p < 0.001).

Conclusions

ONSD might help identify high ICP in patients with GBM. In this first‐of‐its kind study, we observed a significant increase of ONSD preoperatively, likely associated with edema. Postoperatively, ONSD decreased significantly until 3 months after surgery and increased again at 12 months. Further prospective data collection is warranted.
Hydrogels Loaded with Atorvastatin‐Metal Organic Framework Have a Preventive Effect on Coronary Heart Disease
Authors: Bai Xinghua , Jiang Jun , Tu Sijia , Zhang Weizong
Published: December 2023

In the research, a new three‐dimensional coordination polymer was synthesized by solvothermal method based on the metal ligand LCu=[Cu(2,4‐pydca)2]2− (2,4‐pydca=pyridine‐2,4‐dicarboxylate) and alkaline‐earth ion CaII with chemical composition {[Ca(H2O)2][LCu]⋅DMSO ⋅ 2H2O}n (1) (DMSO=dimethyl sulfoxide). The complex 1 was characterized soundly by Fourier transform infrared (FT‐IR) spectroscopy, elemental analysis (EA), single‐crystal X‐ray diffraction (SCXRD) and thermogravimetric analysis (TGA). Using atorvastatin as drug model, carboxymethyl chitosan and calcium alginate as raw materials, a new type of metal gel particles was prepared. The microstructure of the gel was observed by scanning Electron Microscope (SEM) and its modulation effect on the activity of human cardiomyocytes was evaluated. The results show that the gel particles presented a three‐dimensional porous structure and were able to significantly up‐regulate the cell activity of human cardiomyocytes, which is expected to develop the metal gel particles into drugs for the treatment of coronary heart disease.
Cnidium officinale Makino: Phytology, Phytochemistry, Toxicology, Pharmacology and Prescriptions (1967–2023)
Authors: Ma Jiahui , Liu Wei , Wang Xueyu , Lu Chang , Hao Zezhuang , Wang Ye , Ding Yuling , Li Yong
Published: December 2023

Cnidium officinale Makino (COM), a perennial herbaceous plant in the Apiaceous family, widely distribute in Eastern Asia and Asia‐Temperate. It has a long history application as a traditional medicine for invigorating the blood and removing blood stasis, and also has been employed to diet, pesticide, herbal bathing materials, the cosmetic and skin care industry. However, there has been no associated review of literature in the past half a century (1967–2023). By searching the international authoritative databases and collecting 229 literatures closely related to COM, herewith a comprehensive and systematic review was conducted. The phytology includes plant distribution and botanical characteristics. The phytochemistry covers 8 major categories, 208 compounds in total, and the quantitative determination of 14 monomer compounds, total polyphenols and total flavonoids. The clinical trial in pregnant women and toxic experiments in mice, the pharmacology of 7 aspects and 82 frequently used prescriptions are summarized. It is expected that this paper will provide forward‐looking scientific thinking and literature support for the further modern research, development and utilization of COM.
Promiscuity of Omphalotin A Biosynthetic Enzymes Allows de novo Production of Non‐Natural Multiply Backbone N‐Methylated Peptide Macrocycles in Yeast
Authors: Matabaro Emmanuel , Witte Luca , Gherlone Fabio , Vogt Eva , Kaspar Hannelore , Künzler Markus
Published: December 2023

Multiple backbone N‐methylation and macrocyclization improve the proteolytic stability and oral availability of therapeutic peptides. Chemical synthesis of such peptides is challenging, in particular for the generation of peptide libraries for screening purposes. Enzymatic backbone N‐methylation and macrocyclization occur as part of both non‐ribosomal and ribosomal peptide biosynthesis, exemplified by the fungal natural products cyclosporin A and omphalotin A, respectively. Omphalotin A, a 9fold backbone N‐methylated dodecamer isolated from the agaricomycete Omphalotus olearius, can be produced in Pichia pastoris by coexpression of the ophMA and ophP genes coding for the peptide precursor protein harbouring an autocatalytic peptide α‐N‐methyltransferase domain, and a peptide macrocyclase, respectively. Since both OphMA and OphP were previously shown to be relatively promiscuous in terms of peptide substrates, we expressed mutant versions of ophMA, encoding OphMA variants with altered core peptide sequences, along with wildtype ophP and assessed the production of the respective peptide macrocycles by the platform by high‐performance liquid chromatography, coupled with tandem mass spectrometry (HPLC–MS/MS). Our results demonstrate the successful production of fifteen non‐natural omphalotin‐derived macrocycles, containing polar, aromatic and charged residues, and, thus, suggest that the system may be used as biotechnological platform to generate libraries of non‐natural multiply backbone N‐methylated peptide macrocycles.
The Influence of Melting on Catalysis in Propane Oxidation
Authors: Erdem Ezgi , Tarasov Andrey V. , Kube Pierre , Koch Gregor , Plodinec Milivoj , Lunkenbein Thomas , Carey Spencer , Wang Yuanqing , Hävecker Michael , Rosowski Frank , Schlögl Robert , Trunschke Annette
Published: December 2023

A model catalyst composed of crystalline potassium pentavanadate (K3V5O14) supported on silica was studied to elucidate the effect of phase transitions on the performance of potassium‐promoted vanadia catalysts in propane oxidation. Operando calorimetry shows a clear correlation between a drop in activity and an increase in selectivity to propylene upon melting of the crystalline K3V5O14 phase under reaction conditions. The pentavanadate phase itself is not active in propane oxidation, neither in the solid nor in the molten state. The activity of the catalyst mainly originates from highly‐active, i. e., unselective VxOy surface species anchored to silica and formed during synthesis in addition to the supported pentavanadate phase. Melting of K3V5O14 leads to the coverage of these VxOy species preventing the overoxidation of propylene and leading to an increase in propylene selectivity. The change in catalyst properties is therefore due to a physical effect and not to a change in the chemical properties of the predominant crystalline phase.