bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d‐Band Center in WS2‐WO3 for Enhanced Intermediate Adsorption
Authors: Wang Xiaoxuan , Li Shuyuan , Yuan Zhi , Sun Yanfei , Tang Zheng , Gao Xueying , Zhang Huiying , Li Jingxian , Wang Shiyu , Yang Dongchun , Xie Jiangzhou , Yang Zhiyu , Yan Yi‐Ming 
Published: May 2023

AbstractElectrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate‐determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS2‐WO3 to elevate the d‐band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS2‐WO3 exhibited a high NH3 yield of 62.38 μg h−1 mgcat−1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS2‐WO3 upshifted the d‐band center of W towards the Fermi level, leading to enhanced adsorption of −NH2 and −NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d‐band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process.
Exploring the Strain Effect in Single Particle Electrochemistry using Pd Nanocrystals
Authors: Zhao Jiao , Wang Menglin , Peng Yu , Ni Jie , Hu Sunpei , Zeng Jie , Chen Qianjin 
Published: May 2023

AbstractTuning the surface strain of heterogeneous catalysts is recognized as a powerful strategy for tailoring their catalytic activity. However, a clear understanding of the strain effect in electrocatalysis at single‐particle resolution is still lacking. Here, we explore the electrochemical hydrogen evolution reaction (HER) of single Pd octahedra and icosahedra with the same surface bounded {111} crystal facet and similar sizes using scanning electrochemical cell microscopy (SECCM). It is revealed that tensilely strained Pd icosahedra display significantly superior HER electrocatalytic activity. The estimated turnover frequency at −0.87 V vs RHE on Pd icosahedra is about two times higher than that on Pd octahedra. Our single‐particle electrochemistry study using SECCM at Pd nanocrystals unambiguously highlights the importance of tensile strain on electrocatalytic activity and may offer new strategy for understanding the fundamental relationship between surface strain and reactivity.
A Cleavable Crosslinking Strategy for Commodity Polymer Functionalization and Generation of Reprocessable Thermosets
Authors: Bi Liting , Godwin Benjamin , Baran Miranda J. , Nazir Rashid , Wulff Jeremy E. 
Published: May 2023

AbstractCovalently crosslinked polymeric materials, known as thermosets, possess enhanced mechanical strength and thermal stability relative to the corresponding uncrosslinked thermoplastics. However, the presence of covalent inter‐chain crosslinks that makes thermosets so attractive is precisely what makes them so difficult to reprocess and recycle. Here, we demonstrate the introduction of chemically cleavable groups into a bis‐diazirine crosslinker. Application of this cleavable crosslinker reagent to commercial low‐functionality polyolefins (or to a small‐molecule model) results in the rapid, efficient introduction of molecular crosslinks that can be uncoupled by specific chemical inputs. These proof‐of‐concept findings provide one potential strategy for circularization of the thermoplastic/thermoset plastics economy, and may allow crosslinked polyolefins to be manufactured, used, reprocessed, and re‐used without losing value. As an added benefit, the method allows the ready introduction of functionality into non‐functionalized commodity polymers.
Feinjustierung von Substrat–Katalysator Halogen–Halogen Interaktionen zur Steigerung der Enantioselektivität in der Halogenbrückenbindungs‐Katalyse
Authors: Keuper Alica C. , Fengler Kevin , Ostler Florian , Danelzik Tobias , Piekarski Dariusz G. , García Mancheño Olga 
Published: May 2023

AbstractEin neuer Ansatz für eine hoch enantioselektive Halogenbrückenbindungs‐Katalyse wurde entwickelt. Um die intrinsischen Probleme der Halogenbrückenbindungen (XB) und die daraus resultierenden ungelösten Limitierungen in der asymmetrischen Katalyse zu umgehen, wurden fein justierte Halogen–Halogen Interaktionen zwischen dem Substrat und dem XB‐Donor designt, um das Substrat im Katalysatorhohlraum vorzuorganisieren und die Kontrolle über die Enantioselektivität zu verbessern. Bei der vorliegenden Strategie wurden sowohl die Elektronenwolke (Lewis basische Stelle) als auch die sigma (σ)‐Loch Stelle des Halogen‐substituenten der Substrate genutzt, um einen engen chiralen Katalysator–Substrat–Gegenanion Komplex zu bilden. Dies ermöglicht eine kontrollierte Einführung eines hohen Chiralitätstransfers. Bemerkenswerte Enantioselektivitäten von bis zu 95 : 5 e.r. (90 %ee) wurden erreicht in einer Modell‐Dearomatisierungsreaktion von halogensubstituierten (Iso)chinolinen mit mehrzähnigen anionen‐bindenden Tetrakis‐Iodotriazol Katalysatoren.
Managing Multiple Halide‐Related Defects for Efficient and Stable Inorganic Perovskite Solar Cells
Authors: Wang Zhiteng , Tian Qingwen , Zhang Hao , Xie Huidong , Du Yachao , Liu Lei , Feng Xiaolong , Najar Adel , Ren Xiaodong , Liu Shengzhong (Frank) 
Published: May 2023

AbstractHalide‐related surface defects on inorganic halide perovskite not only induce charge recombination but also severely limit the long‐term stability of perovskite solar cells. Herein, adopting density functional theory calculation, we verify that iodine interstitials (Ii) has a low formation energy similar to that of the iodine vacancy (VI) and is also readily formed on the surface of all‐inorganic perovskite, and it is regarded to function as an electron trap. We screen a specific 2,6‐diaminopyridine (2,6‐DAPy) passivator, which, with the aid of the combined effects from halogen‐Npyridine and coordination bonds, not only successfully eliminates the Ii and dissociative I2 but also passivates the abundant VI. Furthermore, the two symmetric neighboring ‐NH2 groups interact with adjacent halides of the octahedral cluster by forming hydrogen bonds, which further promotes the adsorption of 2,6‐DAPy molecules onto the perovskite surface. Such synergetic effects can significantly passivate harmful iodine‐related defects and undercoordinated Pb2+, prolong carrier lifetimes and facilitate the interfacial hole transfer. Consequently, these merits enhance the power‐conversion efficiency (PCE) from 19.6 % to 21.8 %, the highest value for this type of solar cells, just as importantly, the 2,6‐DAPy‐treated CsPbI3−xBrx films show better environmental stability.
Bi‐affinity Electrolyte Optimizing High‐Voltage Lithium‐Rich Manganese Oxide Battery via Interface Modulation Strategy
Authors: Yuan Xuedi , Dong Tao , Liu Jiaxin , Cui Yingyue , Dong Haotian , Yuan Du , Zhang Haitao 
Published: May 2023

AbstractThe practical implementation of high‐voltage lithium‐rich manganese oxide (LRMO) cathode is limited by the unanticipated electrolyte decomposition and dissolution of transition metal ions. The present study proposes a bi‐affinity electrolyte formulation, wherein the sulfonyl group of ethyl vinyl sulfone (EVS) imparts a highly adsorptive nature to LRMO, while fluoroethylene carbonate (FEC) exhibits a reductive nature towards Li metal. This interface modulation strategy involves the synergistic use of EVS and FEC as additives to form robust interphase layers on the electrode. As‐formed S‐endorsed but LiF‐assisted configuration cathode electrolyte interphase with a more dominant −SO2− component may promote the interface transport kinetics and prevent the dissolution of transition metal ions. Furthermore, the incorporation of S component into the solid electrolyte interphase and the reduction of its poorly conducting component can effectively inhibit the growth of lithium dendrites. Therefore, a 4.8 V LRMO/Li cell with optimized electrolyte may demonstrate a remarkable retention capacity of 97 % even after undergoing 300 cycles at 1 C.
Interface modified Si@SiO2/PVDF composite dielectrics with synchronously ameliorative dielectric and mechanical properties
Authors: Kong Fanrong , Zhou Wenying , Peng Weiwei , Liang Chen , Wu Hongju , Lin Na , Wang Guangheng , Liu Dengfeng , Feng Aihong , Liu Xiangrong 
Published: May 2023

AbstractTo efficaciously decrease dielectric loss while still synchronously harvesting a high dielectric constant (ε′) and breakdown strength (Eb), as well as good mechanical properties in silicon (Si)/poly(vinylidene fluoride) (PVDF), in this work, the core@shell structured Si@silicon dioxide (SiO2) particles were first prepared via a high temperature oxidation, and subsequently incorporated into the PVDF to generate morphology‐dependent composites with a high‐ε′ and Eb but low loss. The SiO2 shell effects on the morphology, dielectric, and mechanical properties of PVDF composites were explored. In comparison to pristine Si/PVDF, the Si@SiO2/PVDF presents significantly suppressed loss and boosted Eb because the SiO2 interlayer not only efficiently blocks the connection between the raw Si and greatly impedes the long‐range charges migration even at high filler loadings, but also obviously improves the compatibility between Si and PVDF at the interfaces which promotes fillers' uniform dispersion in host matrix, thus leading to enhanced dielectric and mechanical properties. The fitting result by the Havriliak–Negami equation theoretically elucidates the SiO2 interlayer's suppression effect on charge migration behavior in the composites. More importantly, dielectric properties can be efficiently turned via tailoring the SiO2 shell thickness. The Si@SiO2/PVDF with simultaneously enhanced dielectric and mechanical performances shows promising uses in the electrical and microelectronics industries.
Effect of electron beam irradiation on thermal stability and crystallization behavior of flexible copolyester/multiwalled carbon nanotubes nanocomposites
Authors: Dhakal Kedar Nath , Lach Ralf , Grellmann Wolfgang , Müller Michael Thomas , Krause Beate , Pionteck Jürgen , Adhikari Rameshwar 
Published: May 2023

AbstractPoly(butylene adipate‐co‐terephthalate) (PBAT), a biodegradable copolyester, was used as the polymer matrix to prepare nanocomposites with multiwalled carbon nanotubes (MWCNT) by melt‐mixing followed by hot‐pressing. The PBAT/MWCNT nanocomposites were exposed to electron beam (EB) irradiation, and thermal stability, melting and crystallization behavior of irradiated and unirradiated nanocomposites were comparatively investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. TGA results reveal increased thermal stability (up to 17°C) and maximum degradation temperature (Tmax) (up to 15°C) of PBAT/MWCNT nanocomposites, attributed to the high thermal stability of MWCNT and good MWCNT–PBAT interfacial interactions. However, the activation energy for thermal degradation (Ea) decreased with the presence of MWCNT in comparison to neat PBAT regardless of the MWCNT concentration. Both the thermal stability and Tmax of irradiated nanocomposites decreased by 3°C despite the crosslinking which can be attributed to successive minor irradiation‐induced polymer degradation, while Ea remained unchanged. Declined melting temperature (Tm), enthalpy of crystallization, enthalpy of melting and crystallinity of nanocomposites with the presence of MWCNT suggest the formation of less perfect crystals. Meanwhile, their increased glass transition temperature (Tg) and crystallization temperature (Tc) are due to the increased rigidity of PBAT chains and a reduced crystallization process in the presence of MWCNT, respectively. Similarly, reduced crystallinity and values of Tm and Tc of EB‐irradiated nanocomposites by 4.1%, 9.6%, and 7.5%, respectively, signifying the presence of PBAT‐crosslinks resulting in crystal defects.
Near‐Field Nano‐Optical Imaging of van der Waals Materials
Authors: Kwon Soyeong , Kim Jin Myung , Ma Peiwen J. , Guan Weilin , Nam SungWoo 
Published: May 2023

Abstract2D van der Waals (vdW) materials are emerging as the next generation platform for optical and electronic devices with their wide coverage of the energy bandgaps. The strong light–matter interactions in 2D vdW layers allow for exploring novel optical and electronic phenomena such as 2D polaritons exhibiting ultrahigh field confinement, defects‐induced new quantum states, and strain‐modulated quantum confinement of 2D excitons. Far‐field optical imaging techniques are extensively used to characterize the 2D vdW materials so far, however, subdiffraction spatial resolution is required for comprehensive investigations of 2D vdW materials of which physical properties are greatly influenced by local defects and strain. This article aims to cover historical advances, fundamental principles, and distinct features of emerging near‐field optical imaging techniques: scattering‐type scanning near‐field optical microscopy, tip‐enhanced Raman spectroscopy, tip‐enhanced photoluminescence techniques, and photo‐induced force microscopy. The recent developments toward spectroscopic analysis of near‐field imaging and applications for unveiling unique properties of 2D polaritons, nanoscale defects, and mechanical strains in 2D vdW materials, are also discussed. This review article provides an understanding of emerging near‐field imaging techniques and suggests prospective applications for exploring 2D vdW materials.
Thinking inside the box: An evaluation of a novel search‐assisting tool for supporting (meta)cognition during exploratory search
Authors: Li Yuan , Crescenzi Anita , Ward Austin R. , Capra Rob 
Published: May 2023

AbstractExploratory searches involve significant cognitively demanding aiming at learning and investigation. However, users gain little support from search engines for their cognitive and metacognitive activities (e.g., discovery, synthesis, planning, transformation, monitoring, and reflection) during exploratory searches. To better support the exploratory search process, we designed a new search assistance tool called OrgBox. OrgBox allows users to drag‐and‐drop information they find during searches into “boxes” and “items” that can be created, labeled, and rearranged on a canvas. We conducted a controlled, within‐subjects user study with 24 participants to evaluate the OrgBox versus a baseline tool called the OrgDoc that supported rich‐text features. Our findings show that participants perceived the OrgBox tool to provide more support for grouping and reorganizing information, tracking thought processes, planning and monitoring search and task processes, and gaining a visual overview of the collected information. The usability test reveals users' preferences for simplicity, familiarity, and flexibility of the design of OrgBox, along with technical problems such as delay of response and restrictions of use. Our results have implications for the design of search‐assisting systems that encourage cognitive and metacognitive activities during exploratory search processes.
Distributed dynamic matrix control with constrained optimization for collision and obstacle avoidance of simulated multiple quadcopters
Authors: Dubay Shaundell , Pan Ya‐Jun 
Published: May 2023

AbstractA system of fast moving quadcopters has a high risk of collisions with neighboring quadcopters or obstacles. The objective of this work is to develop a control strategy for collision and obstacle avoidance of multiple quadcopters. In this paper, the problem of distributed dynamic matrix control (DMC) for collision avoidance among a team of multiple quadcopters attempting to reach consensus in the horizontal plane and yaw direction ( , and ) is investigated. Violations of a predetermined safety radius generates output constraints on the DMC optimization function, which has not been dealt with in the literature. Different from past works, the proposed strategy can perform collision avoidance in the , , and ‐directions. In addition, logarithmic barrier functions are implemented as input rate constraints on the control actions. Extensive simulation studies for a team of quadcopters illustrate promising results of the proposed control strategy and case variations. In addition, DMC parameter effects on the system performance are studied, and a successful study for obstacle avoidance is presented.
Stachydrine, N‐acetylornithine and trimethylamine N‐oxide levels as candidate milk biomarkers of maternal consumption of an obesogenic diet during lactation
Authors: Castillo Pedro , Kuda Ondrej , Kopecky Jan , Pomar Catalina Amadora , Palou Andreu , Palou Mariona , Picó Catalina 
Published: May 2023

AbstractWe aimed to evaluate whether improving maternal diet during lactation in diet‐induced obese rats reverts the impact of western diet (WD) consumption on the metabolome of milk and offspring plasma, as well as to identify potential biomarkers of these conditions. Three groups of dams were followed: control‐dams (CON‐dams), fed with standard diet (SD); WD‐dams, fed with WD prior and during gestation and lactation; and reversion‐dams (REV‐dams), fed as WD‐dams but moved to SD during lactation. Metabolomic analysis was performed in milk at lactation days 5, 10, and 15, and in plasma from their male and female offspring at postnatal day 15. Milk of WD‐dams presented, throughout lactation and compared to CON‐dams, altered profiles of amino acids and of the carnitine pool, accompanied by changes in other polar metabolites, being stachydrine, N‐acetylornithine, and trimethylamine N‐oxide the most relevant and discriminatory metabolites between groups. The plasma metabolome profile was also altered in the offspring of WD‐dams in a sex‐dependent manner, and stachydrine, ergothioneine and the acylcarnitine C12:1 appeared as the top three most discriminating metabolites in both sexes. Metabolomic changes were largely normalized to control levels both in the milk of REV‐dams and in the plasma of their offspring. We have identified a set of polar metabolites in maternal milk and in the plasma of the offspring whose alterations may indicate maternal intake of an unbalanced diet during gestation and lactation. Levels of these metabolites may also reflect the beneficial effects of implementing a healthier diet during lactation.
Development of an aminotransferase‐driven biocatalytic cascade for deracemization of d,l‐phosphinothricin
Authors: Liu Han‐Lin , Wu Jia‐Min , Deng Xin‐Tong , Yu Lan , Yi Pu‐Hong , Liu Zhi‐Qiang , Xue Ya‐Ping , Jin Li‐Qun , Zheng Yu‐Guo 
Published: May 2023

Abstract2‐oxo‐4‐[(hydroxy)(methyl)phosphinoyl]butyric acid (PPO) is the essential precursor keto acid for the asymmetric biosynthesis of herbicide l‐phosphinothricin (l‐PPT). Developing a biocatalytic cascade for PPO production with high efficiency and low cost is highly desired. Herein, a d‐amino acid aminotransferase from Bacillus sp. YM‐1 (Ym DAAT) with high activity (48.95 U/mg) and affinity (Km = 27.49 mM) toward d‐PPT was evaluated. To circumvent the inhibition of by‐product d‐glutamate (d‐Glu), an amino acceptor (α‐ketoglutarate) regeneration cascade was constructed as a recombinant Escherichia coli (E. coli D), by coupling Ym d‐AAT, d‐aspartate oxidase from Thermomyces dupontii (TdDDO) and catalase from Geobacillus sp. CHB1. Moreover, the regulation of the ribosome binding site was employed to overcome the limiting step of expression toxic protein TdDDO in E. coli BL21(DE3). The aminotransferase‐driven whole‐cell biocatalytic cascade (E. coli D) showed superior catalytic efficiency for the synthesis of PPO from d,l‐phosphinothricin (d,l‐PPT). It revealed the production of PPO exhibited high space–time yield (2.59 g L−1 h−1) with complete conversion of d‐PPT to PPO at high substrate concentration (600 mM d,l‐PPT) in 1.5 L reaction system. This study first provides the synthesis of PPO from d,l‐PPT employing an aminotransferase‐driven biocatalytic cascade.
Photochemical Synthesis of Covalent Organic Frameworks
Authors: Wu Cheng‐Juan , Shao Ming‐Zhen , Geng Yan , Dong Yu‐Bin 
Published: May 2023

AbstractAs a booming class of crystalline porous materials, covalent organic frameworks (COFs) have attracted increasing attention and various methods to construct COFs have been investigated including solvothermal synthesis, ionothermal synthesis, microwave synthesis, mechanical synthesis, sonochemical synthesis, interfacial synthesis, and electrochemical synthesis. Recently, photochemical reaction has emerged as a powerful approach for COF synthesis, which utilizing the non‐toxic, abundant and renewable light as the energy source. Benefitting from its outstanding properties of low‐cost, safety, and environmental friendliness, the photochemical reaction was considered as a promising alternative to the conventional thermal reaction for COF synthesis. In this concept article, we summarized the up‐to‐date reports about the photochemical synthesis of COFs and provided a future perspective in this field. It is anticipated that this concept could be beneficial for the further development of photochemical synthesis of COFs.
A Predictive Model for the Pd‐Catalyzed Site‐Selective Oxidation of Diols
Authors: Marinus Nittert , Eisink Niek N. H. M. , Reintjens Niels R. M. , Dijkstra Renger S. , Havenith Remco W. A. , Minnaard Adriaan J. , Witte Martin D. 
Published: May 2023

AbstractA predictive model, shaped as a set of rules, is presented that predicts site‐selectivity in the mono‐oxidation of diols by palladium‐neocuproine catalysis. For this, the factors that govern this site‐selectivity within diols and between different diols have been studied both experimentally and with computation. It is shown that an electronegative substituent antiperiplanar to the C−H bond retards hydride abstraction, resulting in a lower reactivity. This explains the selective oxidation of axial hydroxy groups in vicinal cis‐diols. Furthermore, DFT calculations and competition experiments show how the reaction rate of different diols is determined by their configuration and conformational freedom. The model has been validated by the oxidation of several complex natural products, including two steroids. From a synthesis perspective, the model predicts whether a natural product comprising multiple hydroxy groups is a suitable substrate for site‐selective palladium‐catalyzed oxidation.
Design of molecularly imprinted resin material with sulfonic acid functionalization for enantioseparation of (±)‐cathine
Authors: Alhawiti Aliyah S. 
Published: May 2023

AbstractIn the current work, an enantioselective imprinting technique was used to develop a very selective adsorbent for the (+)‐cathine ((+)‐Cat) enantiomer. The phenolic sulfonamide produced from 2,4‐dihydroxybenzenesulfonic acid (HBS) and (+)‐Cat ((+)‐Cat‐HBS) was initially synthesized by triphenylphosphene activation and subsequently involved in condensation polymerization with resorcinol in the presence of formaldehyde under acidic conditions. Alkaline sulfonamide bond‐breaking was subsequently employed to separate the (+)‐Cat template from the polymer, and the resulting imprinted resin ((+)‐CIP) displayed high selectivity for the (+)‐Cat, with a capacity of 225 ± 2 mg/g. Studies of selectivity also showed that the (+)‐Cat enantiomer was preferred over its counterpart because of the development of configurationally matching receptors. In addition, the produced resin was used for the enantioresolution of (±)‐Cat racemate by column method, yielding a loading supernatant solution with an enantiomeric excess of (+)‐Cat 50% and a recovery eluant solution with an excess of (−)‐Cat 85%.