bluuebunny/crossref_metadata_2025_split huggingface dataset:
Breaking the Ru−O−Ru Symmetry of a RuO2 Catalyst for Sustainable Acidic Water Oxidation
Authors: Wang Yi , Lei Xue , Zhang Bo , Bai Bing , Das Pratteek , Azam Tasmia , Xiao Jianping , Wu Zhong‐Shuai 
Published: November 2023

AbstractProton exchange membrane water electrolysis is a highly promising hydrogen production technique for sustainable energy supply, however, achieving a highly active and durable catalyst for acidic water oxidation still remains a formidable challenge. Herein, we propose a local microenvironment regulation strategy for precisely tuning In−RuO2/graphene (In−RuO2/G) catalyst with intrinsic electrochemical activity and stability to boost acidic water oxidation. The In−RuO2/G displays robust acid oxygen evolution reaction performance with a mass activity of 671 A gcat−1 at 1.5 V, an overpotential of 187 mV at 10 mA cm−2, and long‐lasting stability of 350 h at 100 mA cm−2, which arises from the asymmetric Ru−O−In local structure interactions. Further, it is unraveled theoretically that the asymmetric Ru−O−In structure breaks the thermodynamic activity limit of the traditional adsorption evolution mechanism which significantly weakens the formation energy barrier of OOH*, thus inducing a new rate‐determining step of OH* absorption. Therefore, this strategy showcases the immense potential for constructing high‐performance acidic catalysts for water electrolyzers.
Olefination of Aromatic Carbonyls via Site‐Specific Activation of Cycloalkanone Ketals**
Authors: To Tuong Anh , Nguyen Thanh Vinh 
Published: November 2023

AbstractSkeletal editing is an important strategy in organic synthesis as it modifies the carbon backbone to tailor molecular structures with precision, enabling access to compounds with specific desired properties. Skeletal editing empowers chemists to transform synthetic approaches of target compounds across diverse applications from drug discovery to materials science. Herein, we introduce a new skeletal editing method to convert readily available aromatic carbonyl compounds into valuable unsaturated carboxylic acids with extended carbon chains. Our reaction setup enables a cascade reaction of enolization‐[2+2]cycloaddition‐[2+2]cycloreversion between aromatic carbonyl compounds and ketals of cyclic ketones to generate unsaturated carboxylic acids as ring‐opening products. Through a simple design, our substrates are specifically activated to react at predetermined positions to enhance selectivity and efficiency. This practical method offers convenient access to versatile organic building blocks as well as provides fresh insights into manipulating traditional reaction pathways for new synthetic applications.
Analgesic Buxus alkaloids with Enhanced Selectivity for the Low‐Voltage‐Gated Calcium Channel Cav3.2 over Cav3.1 through a New Binding Mode
Authors: Gong Ye , Liu Rui , Zha Hongjing , Dong Ding , Lu Nihong , Yan Hui , Wan Luosheng , Nian Yin 
Published: November 2023

AbstractLow‐voltage‐gated calcium channels (LVGCCs; Cav3.1‐3.3) represent promising drug targets for epilepsy, pain, and essential tremor. At present, modulators with heightened selectivity for a subtype of LVGCCs are still highly desired. In this study we explored three classes of Buxus alkaloids and identified 9(10/19)abeo‐artanes Buxusemine H and Buxusemine L (BXSL) as an unprecedented type of Cav3.2 inhibitors. Particularly, BXSL exhibited Cav3.2 inhibition comparable to Z944, a non‐subtype‐selective LVGCCs inhibitor under clinical trial. While lacking specificity for Cav3.3, BXSL showed a 30‐fold selectivity of Cav3.2 over Cav3.1. As compared to several well‐known inhibitors, the experimental and computational studies suggested BXSL exhibits a distinct binding mode to Cav3.2, notably through the essential interaction with serine‐1543 in domain III. Furthermore, BXSL showed minimal impact on various recombinant and native nociceptive ion channels, while significantly reducing the excitability of isolated mouse dorsal root ganglion neurons. Animal studies in wild‐type and Cav3.2 knock‐out mice revealed that BXSL (5 mg/kg), by inhibiting Cav3.2, exhibits an analgesic effect equivalent to Z944 (10 mg/kg) or mibefradil (10 mg/kg). Moreover, we proposed a structural rationale for the high selectivity of 9(10/19)abeo‐artane‐type alkaloids towards Cav3.2 over Cav3.1. This study introduces a novel analgesic agent and valuable molecular insight for structure‐based innovative Cav3.2 drug development.
Multi‐Selenophene Incorporated Thiazole Imide‐Based n‐Type Polymers for High‐Performance Organic Thermoelectrics
Authors: Li Yongchun , Wu Wenchang , Wang Yimei , Huang Enmin , Jeong Sang Young , Woo Han Young , Guo Xugang , Feng Kui 
Published: November 2023

AbstractDeveloping polymers with high electrical conductivity (σ) after n‐doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide‐based n‐type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene‐free analogue. Consequently, polymer PDTzSI−Se with the highest selenophene content achieves a champion σ of 164.0 S cm−1 and a power factor of 49.0 μW m−1 K−2 in the series when applied in OTEs after n‐doping. The σ value is the highest one for n‐type donor‐acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high‐performance n‐type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n‐type polymers with high backbone coplanarity, deep‐lying LUMO and enhanced mobility/conductivity.
Progress and Advances in Porous Silica‐based Scaffolds for Enhanced Solid‐state Hydrogen Storage: A Systematic Literature Review
Authors: Abdulkadir B. A. , Jalil A. A. , Cheng C. K. , Setiabudi H. D. 
Published: November 2023

AbstractHydrogen plays a crucial role in the future energy landscape owing to its high energy density. However, finding an ideal storage material is the key challenge to the success of the hydrogen economy. Various solid‐state hydrogen storage materials, such as metal hydrides, have been developed to realize safe, effective, and compact hydrogen storage. However, low kinetics and thermodynamic stability lead to a high working temperature and a low hydrogen sorption rate of the metal hydrides. Using scaffolds made from porous materials like silica to confine the metal hydrides is necessary for better and improved hydrogen storage. Therefore, this article reviews porous silica‐based scaffolds as an ideal material for improved hydrogen storage. The outcome showed that confining the metal hydrides using scaffolds based on porous silica significantly increases their storage capacities. It was also found that the structural modifications of the silica‐based scaffold into a hollow structure further improved the storage capacity and increased the affinity and confinement ability of the metal hydrides, which prevents the agglomeration of metal particles during the adsorption/desorption process. Hence, the structural modifications of the silica material into a fibrous and hollow material are recommended to be crucial for further enhancing the metal hydride storage capacity.
Young children's perspectives of time: New directions for co‐constructing understandings of quality in ECEC
Authors: Dýrfjörð Kristín , Hreinsdóttir Anna Magnea , Visnjic‐Jevtic Adrijana , Clark Alison 
Published: November 2023

AbstractChildren's relationship with time in preschools is an under‐researched area. Young children rarely know how to measure time using a clock, but their experiences of time may contribute to understanding children's well‐being and debates about quality in preschools. This paper brings together two empirical exploratory studies conducted in preschools in Iceland and Croatia, respectively, and is based on participatory research methods that highlight young children's perspectives on their sense of time. First, the paper provides examples of young children's understanding of the sequence of events in preschools. Most days were marked by regular routines, such as mealtimes, circle time and outdoor activities. These stepping stones were seen as providing a rhythm for the day. Children's conversations and drawings indicated an embodied sense of time that is subjective, relational and situational. Second, questions have been raised about the impact of different time practices on young children's everyday lives in preschools. In some cases, the management of time appeared to have unintended consequences for factors relating to quality in preschools. Adherence to daily visual schedules could lead to fragmented days with fewer opportunities for uninterrupted play than time management based on ‘flow’. The subjective nature of children's sense of time is complex, and shared understandings between adults and children are not guaranteed. Careful and imaginative listening is required in order to deepen understandings on this topic. This could, in turn, support teachers to further consider the impact on children's daily experiences of preschool when planning based solely on ‘clock time’.
Loss of DNA methylation disrupts syncytiotrophoblast development: Proposed consequences of aberrant germline gene activation
Authors: Lea Georgia , Hanna Courtney W. 
Published: November 2023

AbstractDNA methylation is a repressive epigenetic modification that is essential for development and its disruption is widely implicated in disease. Yet, remarkably, ablation of DNA methylation in transgenic mouse models has limited impact on transcriptional states. Across multiple tissues and developmental contexts, the predominant transcriptional signature upon loss of DNA methylation is the de‐repression of a subset of germline genes, normally expressed in gametogenesis. We recently reported loss of de novo DNA methyltransferase DNMT3B resulted in up‐regulation of germline genes and impaired syncytiotrophoblast formation in the murine placenta. This defect led to embryonic lethality. We hypothesize that de‐repression of germline genes in the Dnmt3b knockout underpins aspects of the placental phenotype by interfering with normal developmental processes. Specifically, we discuss molecular mechanisms by which aberrant expression of the piRNA pathway, meiotic proteins or germline transcriptional regulators may disrupt syncytiotrophoblast development.
Tuning mobile phase properties to improve empty and full particle separation in adeno‐associated virus productions by anion exchange chromatography
Authors: Chen Dennis P. , Wei Julie Y. , Warren James C. , Huang Chao 
Published: November 2023

AbstractIn the past decade, recombinant adeno‐associated virus (rAAV) has gained increased attention as a prominent gene therapy technology to treat monogenetic diseases. One of the challenges in rAAV production is the enrichment of full rAAV particles containing the gene of interest (GOI) payload. By adjusting the mobile phase properties of anion‐exchange chromatography (AEX), it was demonstrated that empty and full separation of rAAV was improved in monolith based preparative AEX chromatography. When compared to the baseline method using NaCl, the use of tetraethylammonium acetate (TEA‐Ac) in the AEX mobile phase resulted in enhanced resolution from 0.75 to 1.23 between “Empty” and “Full” peaks by salt linear gradient elution, as well as increased the percentage of full rAAV particles from 20% to 36% and genome recovery from 59% to 62%. Furthermore, a dual wash plus step elution AEX method was developed. Wherein, the first wash step harnesses TEA‐Ac to separate empty and full capsids, which is followed by a second wash step that ensures no TEA‐Ac salt is carried over into AEX eluate. The resulting optimized AEX purification method has the potential to be adapted for manufacturing and purification processes involving various rAAV production platforms that experience empty and full rAAV separation challenges.
Management of a supernumerary tooth fused to the labial surface of a permanent maxillary central incisor
Authors: Assadian Hadi , Bolhari Behnam , Khoshkhounejad Mehrfam , Chitsaz Nazanin , Babaahmadi Maryam 
Published: November 2023

Key Clinical MessageManagement of supernumerary teeth fused to the labial surface of permanent maxillary central incisors would require a multidisciplinary approach comprising of endodontic treatment, periodontal recontouring, and cosmetic composite restoration.AbstractThe reported cases of supernumerary teeth fused to the labial surface of maxillary central incisors are rare. Such cases need multidisciplinary approaches. Herein, management of a supernumerary tooth fused to the labial surface of a maxillary central incisor is reported. Due to the presence of a communication path between the root canal systems of the two fused teeth, root canal therapy was performed first for the maxillary left central incisor and the supernumerary tooth. The crown of the supernumerary tooth was then removed in a surgical setting while preserving the root to maintain the thin covering of alveolar bone and prevent future periodontal problems. Subsequently, an esthetic composite restoration was performed.
Treatment of recurrent pediatric myelodysplastic syndrome post hematopoietic stem cell transplantation
Authors: Wachter Franziska , Pikman Yana , Bledsoe Jacob , Kapadia Malika , Baumeister Susanne , Rowe Jared , Shimamura Akiko , Place Andrew E. , Prockop Susan , Whangbo Jennifer , Lehmann Leslie , Horan John , Pollard Jessica 
Published: November 2023

Key Clinical MessageTreatment of recurrent myelodysplastic syndrome (MDS) after hematopoietic cell transplantation (HCT) remains challenging. We present a 4‐year‐old girl experiencing early MDS relapse post‐HCT treated with a multimodal strategy encompassing a second HCT and innovative targeted therapies. We underscore the potential of a comprehensive treatment approach in managing recurrent pediatric MDS.
Defect engineering on electrocatalysts for sustainable nitrate reduction to ammonia: Fundamentals and regulations
Authors: Fang Ling , Lu Shun , Wang Sha , Yang Xiaohui , Song Cheng , Yin Fengjun , Liu Hong 
Published: November 2023

AbstractElectrocatalytic nitrate (NO3−) reduction to ammonia (NH3) is a “two birds‐one stone” method that targets remediation of NO3−‐containing sewage and production of valuable NH3. The exploitation of advanced catalysts with high activity, selectivity, and durability is a key issue for the efficient catalytic performance. Among various strategies for catalyst design, defect engineering has gained increasing attention due to its ability to modulate the electronic properties of electrocatalysts and optimize the adsorption energy of reactive species, thereby enhancing the catalytic performance. Despite previous progress, there remains a lack of mechanistic insights into the regulation of catalyst defects for NO3− reduction. Herein, this review presents insightful understanding of defect engineering for NO3− reduction, covering its background, definition, classification, construction, and underlying mechanisms. Moreover, the relationships between regulation of catalyst defects and their catalytic activities are illustrated by investigating the properties of electrocatalysts through the analysis of electronic band structure, charge density distribution, and controllable adsorption energy. Furthermore, challenges and perspectives for future development of defects in NO3RR are also discussed, which can help researchers to better understand the defect engineering in catalysts, and also inspire scientists entering into this promising field.
Enhancing Intrinsic Magnetic Hardness by Modulating Antagonistic Interactions in the Rare‐Earth‐Free Magnetic Solid Solution Hf2Fe1−δRu5−xIrx+δB2
Authors: Luong Diana , Schumacher Lars , Kilic Sam , Haddon Elena , Pöttgen Rainer , Fokwa Boniface P. T. 
Published: November 2023

AbstractThe quinary members in the solid solution Hf2Fe1−δRu5−xIrx+δB2 (x=1–4, VE=63–66) have been investigated experimentally and computationally. They were synthesized via arc‐melting and analyzed by EDX and X‐ray diffraction. Density functional theory (DFT) calculations predicted a preference for magnetic ordering in all members, but with a strong competition between ferro‐ and antiferromagnetism arising from interchain Fe−Fe interactions. The spin exchange and magnetic anisotropy energies predicted the lowest magnetic hardness for x=1 and 3 and the highest for x=2. Magnetization measurements confirm the DFT predictions and demonstrate that the antiferromagnetic ordering (TN=55–70 K) found at low magnetic fields changed to ferromagnetic (TC=150–750 K) at higher fields, suggesting metamagnetic behavior for all samples. As predicted, Hf2FeRu3Ir2B2 has the highest intrinsic coercivity (Hc=74 kA/m) reported to date for Ti3Co5B2‐type phases. Furthermore, all coercivities outperform that of ferromagnetic Hf2FeIr5B2, indicating the importance of AFM interactions in enhancing magnetic anisotropy in these materials. Importantly, two members (x=1 and 4) maintain intrinsic coercivities in the semi‐hard range at room temperature. This study opens an avenue for controlling magnetic hardness by modulating antagonistic AFM and FM interactions in low‐dimensional rare‐earth‐free magnetic materials.
The Surface of Ionic Liquids in Water: From an Ionic Tug of War to a Quasi‐Ordered Two‐Dimensional Layer
Authors: Walz Marie‐Madeleine , Signorelli Matheus Ruas Miranda , Caleman Carl , Costa Luciano T. , Björneholm Olle 
Published: November 2023

AbstractThe sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water‐vacuum interface is representative for their water interfacial properties. Using X‐ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion‐pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface‐enriched due to cooperative surface propensity between the cations and anions, forming a two‐dimensional ionic liquid on the water surface at low concentrations.
Combination of three‐coil and LCC‐S structures for misalignment tolerance in wireless charging system with load‐independent output
Authors: Zhang Yiming , Wu Yuanchao , Liu Chao , Zhou Mingzhu , Zhuang Yizhan 
Published: November 2023

SummaryMisalignment tolerance is an important issue for the electric vehicle wireless charging system. This letter proposes a hybrid topology of the inductor–capacitor–capacitor‐series (LCC‐S) and three‐coil structures with load‐independent output to achieve misalignment tolerance, which is suitable for anti‐offset in the door‐to‐door direction of electric vehicles. The unipolar coil is divided into two windings to form the two coils in the three‐coil structure. The bipolar coil is employed as the transmitting coil of the LCC‐S topology, realizing decoupling from the two unipolar windings of three‐coil structure. The receiving coil only consists of a unipolar coil. From the central to the boundary positions, the output power of the three‐coil structure decreases while that of the LCC‐S topology increases. In this way, the output power can be stabilized against misalignment. Compared with existing hybrid topologies with two sets of coils, the receiver side adopts only one receiving coil and one compensation, which is compact, low‐profile, and cost effective. Besides, the output voltage is independent of the load, and the system can achieve constant voltage output characteristic. The experimental results validate the proposed system.
Investigation and Characterization of Nitrazapropane‐, Oxapropane‐ and Trinitrazaheptane‐Bridged Nitro Esters
Authors: Lechner Jasmin T. , Riedelsheimer Christian , Gerold Nina M. , Heidrich Jennifer , Krumm Burkhard , Stierstorfer Jörg , Klapötke Thomas M. 
Published: November 2023

AbstractIn this work, 1,3‐dinitroxy‐2‐nitrazapropane and 1,7‐dinitroxy‐2,4,6‐trinitrazaheptane were synthesized and investigated. Starting from hexamine, the open‐chain compounds were prepared by a modified Bachmann procedure which is commonly used for the synthesis of hexogen (RDX) and octogen (HMX). All new compounds were characterized by NMR spectroscopy, X‐ray diffraction, vibrational analysis and elemental analysis. Their thermal behavior was studied by differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The sensitivities towards impact (IS) and friction (FS) were determined according to the BAM (Bundesanstalt für Materialforschung und ‐prüfung) standard method. Their energetic properties, which were determined from the energies of formation at the CBS‐4 M level, were calculated using the EXPLO5 computer code. Moreover, 1,3‐dinitroxy‐2‐oxapropane was synthesized and investigated. The various compounds were compared with each other and with the commonly used explosives in terms of their physicochemical properties and detonation behavior.
The effect of in vitro digestion on the interaction between polysaccharides derived from Pleurotus eryngii and intestinal mucus
Authors: Ma Sai , Li Xinyi , Tao Qi , Hu Qiuhui , Yang Wenjian , Kimatu Benard Muinde , Ma Gaoxing 
Published: November 2023

AbstractPleurotus eryngii polysaccharides (PEPs) have been proven to display multiple activities through digestive system action, from which the digestion products should first interact with intestinal mucus (MUC), followed by the function of intestinal cells. Hence, possible interacting characterizations between MUC and in vitro simulated digestion products of P. eryngii polysaccharides (DPEPs) and PEP were carried out in the present study. Results showed that both PEP and DPEP could significantly interact with MUC. Moreover, digestion can modify the interaction between polysaccharides and MUC; the degree of interaction also changes with time incrementing. Viscosity could be decreased after digesting. According to the zeta potential and stability analysis result, the digestive behavior could be regular and stable between polysaccharides and MUC interactions. Following fluorescence and infrared spectra, the structure of polysaccharides and mucin might be changed by digestion between polysaccharides and MUC. The study indicates that the interaction formed between DPEP and MUC might indirectly impact the exercise and immune activities of polysaccharides and influence the transportation of other nutrients. Overall, our results, the absorption and transport pathways of PEP, can be initially revealed and may provide a novel research viewpoint on the active mechanism of PEP in the intestinal tract.