bluuebunny/crossref_metadata_2025 huggingface dataset:
Achievements in the Photomagnetic Effect of Cobalt‐Iron Prussian Blue Analogues
Authors: Yao Kangkang , Dong Chengwei , Cao Kaiyan , Zhang Yin , Yang Sen
Published: April 2024

Harnessing light for magnetization control presents a promising approach with compelling merits such as non‐contact operation, ultrafast response, reversibility, high spatial resolution, tunability, and energy efficiency. Photoinduced metal‐to‐metal charge transfer (MMCT) is one key mechanism in achieving photo‐controlled magnetic properties, making relevant materials prime candidates for versatile switchable devices. Cobalt iron Prussian blue analogues (CoFePBA) are trailblazers in showcasing photomagnetic properties via MMCT and the numerous related studies on CoFePBA have significantly enhanced the understanding of photoinduced MMCT processes. Thus, this review embarks on a thorough examination of three decades of research on the photomagnetic of CoFePBA to deep into the art of the photocontrol of spin. In addition to an introduction to the structure and preparation of CoFePBA, the focus is on elucidating the underlying mechanisms and introducing strategies for its manipulation and control. Finally, the challenges and prospects at this moment are summarized and discussed.
Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface
Authors: Li Zhi , Mali Kunal , Hapiot Philippe , De Feyter Steven , Attias André‐Jean , Mertens Stijn F. L.
Published: April 2024

The development and integration of cyclophanes into future functional materials require a detailed understanding of the physicochemical principles that underlie their properties, phase behavior, and in particular the relationship between structure and function. Here, electrochemically switchable crystallization of a ferrocene‐bearing 3D Janus tecton (M‐Fc) at the interface between highly oriented pyrolytic graphite (HOPG) and an electrolyte solution is demonstrated. The M‐Fc adlayer is successfully visualized under both ambient and electrochemical conditions using scanning tunneling microscopy. Voltammetric measurements show a surface‐confined redox process for the M‐Fc modified surface that drives the phase transition between a visible 2D ordered linear phase (M‐Fc0, with ferrocene in the neutral state) and an invisible gas‐like adsorption layer with high mobility when ferrocene is oxidized, M‐Fc+, and a “square scheme” mechanism explains the data. Analogous experiments in a ferrocene‐free tecton adlayer show no phase transition and confirm that the dynamics in M‐Fc are redox‐driven. On‐surface 3D nanoarchitectures are also demonstrated by forming inclusion complexes between M‐Fc and β‐cyclodextrin and device behavior through electrochemical scanning tunneling spectroscopy (STS). These results showcase the functional potential of this class of cyclophanes, which can find use in actuators, optical crystals, and other smart materials.
Defining New Benchmarks of Low CTAB‐Concentration‐Based Gold Nanorod Synthesis: The Underestimated Potential of Polymer‐Directed Anisotropic Growth
Authors: Lemich Sascha Benedict , Soltau Steffen , Weißpflog Maria , Schulze Verena R. , Feliu Neus , Hankiewicz Birgit , Abetz Volker
Published: April 2024

This work presents new anisotropic growth‐directing copolymers suitable for the seed‐mediated growth of gold nanorods (GNRs). Copolymers with different architectures are studied. They all contain dimethylaminomethyl methacrylate (DMAEMA) functionalized with 1‐bromohexadecane (BHD) as the vital component. For the synthesis of the different copolymers, the photo‐iniferter reversible addition–fragmentation chain transfer (photoRAFT) polymerization is used, where DMAEMA is combined with a lower critical solution temperature (LCST) polymer block for better solubility after the functionalization. The results show that the presented copolymers can induce anisotropic growth of gold nanoparticles. Additionally, the influence of the LCST of the water‐soluble block and the temperature of the growth solution on the GNR synthesis are investigated. Furthermore, the plasmonic behavior of the resulting GNRs solution is investigated at temperatures around the LCST of the copolymer.
Modulation of Sulfur Vacancies in ZnIn2S4/MXene Schottky Heterojunction Photocatalyst Promotes Hydrogen Evolution
Authors: Xu Minghua , Ruan Xiaowen , Meng Depeng , Fang Guozhen , Jiao Dongxu , Zhao Shengli , Liu Zheyang , Jiang Zhifeng , Ba Kaikai , Xie Tengfeng , Zhang Wei , Leng Jing , Jin Shengye , Ravi Sai Kishore , Cui Xiaoqiang
Published: April 2024

The sustainable production of hydrogen utilizing solar energy is a pivotal strategy for reducing reliance on fossil fuels. ZnIn2S4 (ZIS), as a typical metal sulfide semiconductor, has received extensive attention in photocatalysis. Although the introduction of sulfur (S) vacancies in ZIS to enhance photocatalytic hydrogen production by creating defect energy levels has been explored, detailed studies on the control and modulation of S‐vacancies in ZIS are sparce. This study demonstrates that while moderate levels of S‐vacancies can enhance hydrogen evolution, excessive vacancies may hinder the process, underscoring the importance of S‐vacancy modulation. Guided by theoretical calculations, We have designed and synthesized ZIS with modulated S‐vacancies to realize favorable hydrogen adsorption‐free energy and integrated in a Schottky‐heterojunction with MXene co‐catalysts for enhanced hydrogen evolution. The optimized hydrogen evolution performance of ZnIn2S4/MXene (ZMX) reaches 14.82 mmol g−1 h−1 under visible light irradiation, surpassing many reported ZnIn2S4‐based photocatalysts. The enhanced performance is ascribed to widened light absorption and enhanced carrier transportation realized by S‐vacancy modulation and the co‐catalytic effect. Femtosecond ultrafast absorption (fs‐TA) spectra and other in‐situ/ex‐situ characterizations further prove an efficient separation and transfer in an as‐prepared ZMX catalyst. These findings open up new perspectives for designing catalysts with vacancy modulation.
In Situ Construction of a Lithiophilic and Electronically Insulating Multifunctional Hybrid Layer Based on the Principle of Hydrolysis for a Stable Garnet/Li Interface
Authors: Wang Lingchen , Lu Yan , Zheng Chujun , Cai Mingli , Xu Fangfang , Wen Zhaoyin
Published: April 2024

Adapting solid‐state Li‐metal batteries is an attractive way to pursue higher energy density and safety compared to liquid‐based ones. With high ionic conductivity and excellent stability with Li, Ta‐doped Li7La3Zr2O12 (LLZTO) is an effective option. However, the poor solid–solid interface contact induced by the lithiophobic Li2CO3 layer hinder its practical application. Herein, a versatile strategy is proposed based on the hydrolysis of sodium tetrafluoroborate (NaBF4), aiming to convert the Li2CO3 into multifunctional hybrid layer containing LiF, LiBO2, and NaF. Among them, LiF and LiBO2 serve as the primary Li ion conductors, the introduction of NaF with high surface energy not only enhances the interface wettability, but also further elevates the critical dendrite strength against Li dendrites. All three components serve as excellent electronic insulators, suppressing electron invasion at the interface and preventing Li dendrite growth in the solid electrolyte. As expected, the interfacial impedance of the NaBF4 treated symmetric cell is reduced to 6.0 Ω cm2, the critical current density (CCD) comes to 2.0 mA cm−2, and cycles over 3000 h at 0.3 mA cm−2 and 1500 h at 0.5 mA cm−2 respectively. Besides, the modified SSBs matched with LiFePO4 or LiNi0.6Co0.2Mn0.2O2 cathode show great long‐term cycling and rate performance.
Ultrahigh X‐Ray Imaging Spatial Resolution Enabled by an 0D Mn(II) Hybrid Scintillator
Authors: Xiao Shang‐Biao , Zhang Xiangzhou , Mao Xingchu , Yang Han‐Jiang , Chen Zhong‐Ning , Xu Liang‐Jin
Published: April 2024

Spatial resolution of scintillator is crucial for high‐quality X‐ray imaging, especially in tiny and complicated electronic component. In this work, PrPP2MnBr4 single crystal is obtained by dual‐solvent evaporation method, which gives an unprecedented high spatial resolution of 104.3 lp/mm, representingstate of the art among non‐lead metal halides. The study also conducts the preparation of large area scintillation screen (10 cm × 10 cm) by solidifying melted salt PrPP2MnBr4, thus giving an excellent X‐ray imaging with spatial resolution of 53.5 lp mm−1, which demonstrates its application on large area detection.
Large‐Area Knittable, Wash‐Durable, and Healable Smart Fibers for Dual‐Modal Sensing Applications
Authors: Zhou Bo , Yuan Man , Lu Hao , Qiu Xiaoyan , Liu Jize , Zhao Zhong , Zhang Xinxing , Cai Guangming
Published: April 2024

Fiber‐based multimodal sensors with electrical/optical signals are highly desired for next‐generation wearable electronics. Despite the remarkable progress in this area, achieving large‐scale knittable, washable, and self‐healing performance in fiber‐based multimodal sensors simultaneously remains a great challenge. Here, a smart fiber capable of exhibiting piezoresistive/luminescent properties based on an H‐bonding connected multilayered core–shell nanostructure is developed. The core principle of this design involves constructing strong interfacial interactions between the fiber layers, which results in a sensor with high sensitivity (gauge factor = 12383500), exceptional water resistance, and robust self‐healing properties (tensile strength 30.9 MPa, healing efficiency 72.9%). Unlike traditional fiber‐based sensors where elaborate nanostructures are prone to shedding during knitting, this strategy enables the fiber sensors with excellent knittability to be patterned in the fabric, improving both optical and electrical sensitivities. This work is anticipated to make a significant contribution to the further development of wearable electronic products and visual human–computer interaction electronic devices.
Liquid‐Metal‐Based Soft Pressure Sensor and Multidirectional Detection by Machine Learning
Authors: Gul Osman , Kim Jeongnam , Kim Kyuyoung , Kim Hye Jin , Park Inkyu
Published: April 2024

Electronic skin (e‐skin) is an emerging technology with promising applications in various fields, including human–machine interfaces, prosthetics, and robotics. Soft and flexible sensors are vital components for the e‐skin that can mimic human skin's sensing capabilities. Among soft sensors, liquid‐metal‐based sensors have gained attention owing to their unique properties, such as high electrical conductivity, stretchability, and elasticity. Herein, a novel approach is presented that enables multidirectional pressure sensing with a machine‐learning approach from the transient response of the liquid‐metal‐based soft pressure sensor for the e‐skins. In this study, a soft sensor is developed that utilizes liquid metal and has an array of microchannels on a dome‐shaped structure to detect pressures from multiple directions. The transient response from six microchannels of the sensor is used as the input for a convolutional neural network (CNN) to predict the direction (classification accuracy of 99.1%) and magnitude (regression error of 20.13%) of the applied pressures in real time. Finally, a potential application of the developed liquid‐metal‐based soft sensor as a human–machine interface device is demonstrated by using it to control an RC model car through multidirectional predictions (pressure direction and magnitude) through machine learning in real time.
Highly Efficient Pure‐Red Quasi‐2D Perovskite Light‐Emitting Diodes Enabled by Propylammonium Chloride Passivator
Authors: Shen Piaoyang , Tang Zhaobing , Fan Junpeng , Zhang Ting , Qian Lei , Zhao Dewei , Xiang Chaoyu
Published: April 2024

Perovskite light‐emitting diodes (PeLEDs) based on quasi‐2D perovskites have attracted great attention in the past few years. Although significant achievements are made in device performance, fabrication of high‐efficiency PeLEDs with pure‐red (620–635 nm) light emission remains a significant challenge, which inhibits their practical application for full‐color displays. Herein, a series of efficient red PeLEDs at 625 nm are realized by employing volatile alkylammonium chlorides (propylammonium chloride) passivators. The interaction of PbI2 with propylamine (PA)…H+Cl− in the precursor solution effectively passivates the defects, leading to reduced non‐radiative recombination and enhanced device performance. By optimizing the amount of PACl, an external quantum efficiency (EQE) of 16.1% and a maximum brightness of 1701 cd m−2 are achieved, among the best‐performing quasi‐2D I‐based PeLEDs with emissions ranging from 620 to 635 nm. This work provides a new route to improve the stability and efficiency of pure‐red PeLEDs.
Fabrication of MnO2@Porous Carbons with High Energy and Power Density and Their Application in Supercapacitors
Authors: Cao Yuan‐Jia , Lu Cui‐Ying , Wang Zhen , Bai Rui , Liu Guanghui
Published: April 2024

MnO2@PCs (porous carbons) exhibiting high energy and power density are utilized as supercapacitor electrodes and prepared by impregnating porous carbons (PCs) derived from coal tar pitch (CTP) with KMnO4 as the manganese source. This study systematically investigates the impact of MnO2 loading on the microstructure and electrochemical performance in sample. It is found that the specific surface areas (SSA) of all MnO2@PCs significantly reduced compared to that of the PCs 2789 m2 g−1. The suggested mechanism might be a combination of the energy storage mechanism of dual layer capacitors with pseudo‐capacitance due to redox reactions of MnO2. Notably, MnO2@PCs‐0.0075 exhibits a maximum SSA of 1454.62 m2 g−1. Its specific capacitance reached 561 F g−1 at 0.5 A g−1, while the capacitance of the PCs increased by 81.5% to 309 F g−1. Remarkably, the Coulombic efficiency remained at 100%. The power density and energy density are determined in a two‐electrode test system to be 0.5 kW kg−1 and 58.01 Wh kg−1, respectively, at 0.5 A g−1. Concluding from these results and related literature, the MnO2 content significantly influences the electrochemical performance, suggesting that MnO2@PCs‐0.0075 could be a promising supercapacitor (SC) electrode material, provided its capacitance retention is enhanced.
Defect Engineering Boosting High‐Performance Graphite Anode for Sodium‐Ion Batteries in Ether‐Based Electrolytes
Authors: Yao Luobin , Zhang Kaicheng , Tian Yu , Zhang Shuyan , Zeng Yujie , Hu Shan , Jian Zelang
Published: April 2024

Sodium‐ion batteries (NIBs) as one of the next‐generation energy storage devices are gradually used in energy field and entering lithium‐ion batteries (LIBs) market. Graphite with low price exhibits excellent Li+ reversible intercalation properties, which has been widely applied in anodes of LIBs. But it has low capacity for sodium because of its weak chemical bonding with sodium. Here, a defect engineered graphite with low graphitization structure is reported. This graphite demonstrates a defect adsorption and solvated ion intercalation of sodium ions by introducing more active sites and ether electrolytes, effectively improving the storage capacity of sodium. Further experiments and characterization show defects increased after ball milling with surface area increased, and the favorable defects on the interface of graphite are significantly increased. The defect engineered graphite absorbs more sodium‐ions and exhibits capacitive characteristics with fast sodiation/desodiation process, leading to an improved capacity storage than the defect‐free graphite. Meanwhile, the defect engineered graphite can deliver a capacity of 175 mAh g−1, and maintain a good capacity retention of 84% at 5 A g−1 after 6000 cycles. This work discovers a general methodology to obtain defect engineered graphite, which will provide an experimental strategy to achieve large‐scale industrialization for low‐cost NIBs.
Beef cattle feedlot runoff impacts on soil antimicrobial resistance
Authors: Speicher Scott , Miller Daniel N. , Durso Lisa M. , Li Xu , Woodbury Bryan. L. , Eskridge Kent M. , Schmidt Amy Millmier
Published: April 2024

Field application of beef cattle feedlot runoff may transport manure‐borne microbes and antibiotic resistant bacteria to agricultural soils eventually impacting deeper soils and groundwater. To evaluate this potential, total soil, antibiotic resistance (AR), and fecal indicator bacteria (Escherichia coli and Enterococcus) and the presence/abundance of AR genes were examined to a depth of 1.8 m in an agricultural field receiving long‐term application of feedlot runoff and compared to a nearby pasture receiving no runoff. While plate counts of total soil bacteria and cefotaxime‐resistant, erythromycin‐resistant, and tetracycline‐resistant bacteria decreased with depth on both fields (p < 0.001) by an average 2‐log10 colony forming unit g−1 to 1.8‐m depth, field differences were only observed with greater abundances of total soil and erythromycin‐resistant bacteria (p ≤ 0.026) in the runoff‐amended versus control field soils. Soil bacterial and fecal indicator bacterial isolates evaluated phenotypically for resistance to 12 antibiotics varied in range and sensitivity. Using a culture‐independent approach, erm(C) and tet(Q) were detected using polymerase chain reaction in 31% and 58% of runoff‐field samples throughout the soil profile. Detection of erm(C) and tet(Q) in the control field soil profile was less frequent (0% and 11%, respectively). Two other genes, erm(A) and tet(X) were not detected in any soil samples. Based upon these results, long‐term applications of beef cattle feedlot runoff may increase the total abundance of microorganisms in the surface and shallow soil, but the relative enrichment of AR was dependent upon the type of resistance evaluated and, more specifically, the genes targeted for analysis.
“Bio‐based Plastic? Hm, I've Never Seen It!”—A mixed‐methods investigation into consumer preferences for different packaging material of fresh apples and tomatoes
Authors: Lehberger Mira , Kleih Anne‐Katrin , Sparke Kai
Published: April 2024

Packaging of fresh fruits and vegetables is standard in many grocery stores. This mixed methods study aims to identify the role packaging plays in consumer choice and what packaging material consumers prefer. We analyzed data from quantitative stated preference experiments with a quota sample of 485 consumers living in Germany. In addition to the experiments, we conducted a qualitative study and analyzed data from 13 consumers who participated in think aloud protocols and responded to open‐ended questions. We analyzed the data from the quantitative and qualitative studies separately and then systematically compared their key findings. Choice‐based conjoint analyses showed that packaging was less important than price and origin in consumers' decisions, but that consumers clearly preferred unpackaged to packaged produce. This is true for both apples, a relatively robust produce, and tomatoes, which are more susceptible to damage. The qualitative research indicated that consumers appreciate the ability to see and choose an unpackaged product, but also see some benefits of packaging, such as the protection of the produce. Overall, we found that by combining qualitative and quantitative insights, we were able to identify overlapping but also distinct facets of consumer preference for fresh produce packaging. Regarding the use of bio‐based plastics for fresh produce, our results indicate that German consumers were not currently inclined to choose this type of packaging, and evidence suggests that they have little knowledge and/or awareness about it. Our findings have implications for researchers, marketing practitioners, packaging manufacturers, and policy makers. [EconLit Citations: D12, Q50].
Exploring Kinematic Bifurcations and Hinge Compliance for In‐Hand Manipulation: How Could Thick‐Panel Origami Contribute?
Authors: Liu Chenying , He Liang , Wang Sihan , Williams Albert , You Zhong , Maiolino Perla
Published: April 2024

Origami‐inspired mechanisms have found significant applications in end effector design. So far, the exploration of thick‐panel origami has been relatively limited, but it is worth noting that the incorporation of rigid thick panels can introduce unique mechanical properties, showcasing great potential in addressing manipulation challenges. Our previous work has developed a gripper from thick‐panel waterbomb origami, which can pick up a variety of daily objects. Based on the same prototype, this article extends the gripper's function from grasping to in‐hand manipulation, which is attributed to the kinematic bifurcations and compliance of thick‐panel origami. A kinematic study is carried out to investigate the gripper's bifurcated motion modes. The hinge compliance is also taken into account to enhance the gripper's motion dexterity. Theoretical analysis and experiments are conducted to demonstrate both features, thereby paving the foundation for achieving dexterous motions with a simplified control strategy. Aided by a differential mechanism, the gripper can effectively interact with objects with the actuation inputs from only two motors. Objects including balls, cuboids, and cones are explored for in‐hand manipulation under different motion modes, showing varied trajectories. With the integration of tactile sensors at the fingertips, we have also revealed the gripper's potential for classification tasks.
Parents of children with Down syndrome reflect on their postnatal diagnoses, 2003–2022
Authors: Artal Jonathan M. , Randall Lindsey , Rubeck Sabina , Allyse Megan , Michie Marsha , Riggan Kirsten A. , Meredith Stephanie , Skotko Brian G.
Published: April 2024

A 2003 survey revealed the scope of mothers' dissatisfaction with their postnatal support following a diagnosis of Down syndrome (DS). Substantial proportions of mothers reported that providers conveyed diagnoses with pity, emphasized negative aspects of DS, and neglected to provide adequate materials explaining DS. This study follows up on the 2003 survey by assessing whether parents' experiences have improved. Four DS nonprofit organizations, which participated in the original study, distributed a mixed‐methods survey to families who have had children with DS between 2003 and 2022. Quantitative analysis assessed correlations among responses and differences between the 2003 and 2022 survey groups. Open‐ended responses were qualitatively analyzed. Compared to the 2003 findings, parents' perceptions of their postnatal care have not improved (N = 89). Parents are increasingly likely to report that their providers pitied them, omitted positive aspects of DS, and provided insufficient materials describing DS. Substantial proportions of parents reported fear (77%) and anxiety (79%), only 24% described receiving adequate explanatory materials, and parents were 45% likelier to report that physicians discussed negative aspects of DS than positive aspects. Qualitatively, substantial numbers of parents recounted insensitive conduct by providers. These results suggest that despite interventions, parents' experiences of postnatal diagnoses of DS have not improved over time. Certain provider behaviors—such as describing positive aspects of DS and providing comprehensive explanatory materials—can reduce fear and anxiety, pointing to directions for reform.
Evaluating olfactory function and quality of life in patients with traumatic brain injury
Authors: Lawrence Amelia S. , Alapati Rahul , Wagoner Sarah F. , Nieves Antonio Bon , Bird Cole , Wright Robert , Jafri Shah , Rippee Michael , Villwock Jennifer A.
Published: April 2024

Key points

Patients with traumatic brain injury (TBI) had worse olfactory quality of life (QoL) and Sino‐Nasal Outcome Test‐22 scores compared to a normal cohort.

A worse olfactory QoL correlated with concussion symptom burden.

Olfactory dysfunction among TBI patients should be addressed to improve overall outcomes.
Ein‐Topf‐Synthese von Schwefelkathoden mit hoher Kapazität durch In situ‐Polymerisation eines porösen Polymers auf Iminbasis
Authors: Li Guiping , Liu Ye , Schultz Thorsten , Exner Moritz , Muydinov Ruslan , Wang Hui , Scheurell Kerstin , Huang Jieyang , Szymoniak Paulina , Pinna Nicola , Koch Norbert , Adelhelm Philipp , Bojdys Michael J.
Published: April 2024

Lithium‐Ionen‐Batterien, die für elektronische Geräte und Elektrofahrzeuge unerlässlich sind, verwenden hauptsächlich Kathoden aus kritischen Materialien wie Kobalt. Eine nachhaltigere Alternative sind Kathoden auf Schwefelbasis, die eine hohe theoretische Kapazität von 1675 mAh g−1 und Umweltvorteile bieten, da Schwefel reichlich vorhanden und weniger toxisch ist. Moderne Elektroden auf Schwefelbasis erreichen die theoretische Kapazität jedoch nicht, vor allem weil die herkömmliche Elektrodenherstellung auf dem Mischen der Komponenten zu schwach koordinierten Aufschlämmungen beruht. Infolgedessen führt die Mobilität des Schwefels zu einer Degradation der Batterie – ein Effekt, der als „Schwefel‐Shuttle“ bekannt ist. Diese Studie stellt eine Lösung vor, indem ein mikroporöses, kovalent gebundenes, iminbasiertes Polymernetzwerk entwickelt wird, das in situ um die Schwefelpartikel auf dem Stromkollektor wächst. Das Polymernetzwerk (i) ermöglicht den selektiven Transport von Elektrolyt und Li‐Ionen durch Poren definierter Größe und (ii) fungiert als robuster Wirt, um die aktive Komponente der Elektrode (Schwefelspezies) zurückzuhalten. Die resultierende Kathode hat eine überlegene Leistung von 0,1 C (1360 mAh g−1) bis 3 C (807 mAh g−1). Mit der Demonstration einer leistungsstarken, langlebigen Schwefelkathode, die in einem einfachen Eintopfverfahren hergestellt wurde, unterstreicht unsere Forschung das Potenzial mikroporöser Polymere bei der Lösung von Schwefeldiffusionsproblemen und ebnet den Weg für Schwefelelektroden als praktikable Alternative zu herkömmlichen Kathoden auf Metallbasis.
An n‐Type Open‐Shell Conjugated Polymer with High‐Spin Ground‐State and High Intrinsic Electrical Conductivity
Authors: Cai Houji , Tang Haoran , Wang Tianzuo , Xu Chenhui , Xie Juxuan , Fu Muyi , Luo Xi , Hu Zhengwei , Zhang Yi , Deng Yunfeng , Li Guangwu , Liu Chunchen , Huang Fei , Cao Yong
Published: April 2024

Open‐shell conjugated polymers with a high intrinsic conductivity and high‐spin ground state hold considerable promise for applications in organic electronics and spintronics. Herein, two novel acceptor‐acceptor (A–A) conjugated polymers based on a highly electron‐deficient quinoidal benzodifurandione unit have been developed, namely DPP‐BFDO‐Th and DPP‐BFDO. The incorporation of the quinoidal moiety into the polymers backbones enables deeply aligned lower‐lying lowest unoccupied molecular orbital (LUMO) levels of below −4.0 eV. Notably, DPP‐BFDO exhibits an exceptionally low LUMO (−4.63 eV) and a high‐spin ground state characterized by strong diradical characters. Moreover, a self‐doping through intermolecular charge‐transfer is observed for DPP‐BFDO, as evidenced by X‐ray photoelectron spectroscopy (XPS) studies. The high carrier concentration in combination with a planar and linear conjugated backbone yields a remarkable electrical conductivity (σ) of 1.04 S cm−1 in the “undoped” native form, ranking among the highest values reported for n‐type radical‐based conjugated polymers. When employed as an n‐type thermoelectric material, DPP‐BFDO achieves a power factor of 12.59 μW m−1 K−2. Furthermore, upon n‐doping, the σ could be improved to 65.68 S cm−1. This study underscores the great potential of electron‐deficient quinoidal units in constructing dopant‐free n‐type conductive polymers with a high‐spin ground state and exceptional intrinsic conductivity.
Molecular Symmetry and Art: Visualizing the Near‐Symmetry of Molecules in Piet Mondrian's De Stijl
Authors: Kingsbury Christopher J. , Senge Mathias O.
Published: April 2024

Symmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost—investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors or coordinates, is informative, though far from engaging. Often relationships between chemical structure and derived values are obscured. Taking our inspiration from Piet Mondrian's Compositions, we have depicted the symmetry information encoded within 3D data as blocks of color, to show clearly how chemical arguments and resultant molecular distortion may contribute to symmetry. Great art gives us a new perspective on the world; as a pastiche, this art may allow us to look at familiar molecules, such as porphyrins, in a new light, understanding how their shape and properties are intertwined.
Divalent Titanium via Reductive N−C Coupling of a TiIV Nitrido with π‐Acids
Authors: Bhunia Mrinal , Sandoval‐Pauker Christian , Fehn Dominik , Grant Lauren N. , Senthil Shuruthi , Gau Michael R. , Ozarowski Andrew , Krzystek J. , Telser Joshua , Pinter Balazs , Meyer Karsten , Mindiola Daniel J.
Published: April 2024

The nitrido‐ate complex [(PN)2Ti(N){μ2‐K(OEt2)}]2 (1) (PN−=(N‐(2‐PiPr2‐4‐methylphenyl)‐2,4,6‐Me3C6H2) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five‐coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=NtBu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2–5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene, [(PN)2Ti(NCE)] (E=O, (6); E=NAd (7), NtBu (8)) and characterization by CW X‐band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e− reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high‐frequency and ‐field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C6F5)4] resulted in a ligand disproportionated TiIV complex having transoid carbodiimides, [(PN)2Ti(NCNAd)2] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as TiII→TiIII→TiIV and increasing order of π‐donation as TiII→TiIII→TiIV, thus displaying more covalency in TiIII species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N‐atom to CO and CNAd.
One‐Pot Synthesis of High‐Capacity Sulfur Cathodes via In‐Situ Polymerization of a Porous Imine‐Based Polymer
Authors: Li Guiping , Liu Ye , Schultz Thorsten , Exner Moritz , Muydinov Ruslan , Wang Hui , Scheurell Kerstin , Huang Jieyang , Szymoniak Paulina , Pinna Nicola , Koch Norbert , Adelhelm Philipp , Bojdys Michael J.
Published: April 2024

Lithium‐ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur‐based cathodes, offering a high theoretical capacity of 1675 mAh g−1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state‐of‐the‐art sulfur‐based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur‘s mobility leads to battery degradation—an effect known as the “sulfur‐shuttle”. This study introduces a solution by developing a microporous, covalently‐bonded, imine‐based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li‐ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g−1) to 3 C (807 mAh g−1). Demonstrating a high‐performance, sustainable sulfur cathode produced via a simple one‐pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal‐based cathodes.
Tuning Electron Delocalization of Redox‐Active Porous Aromatic Framework for Low‐Temperature Aqueous Zn−K Hybrid Batteries with Air Self‐Chargeability
Authors: Wang Junhao , Zhang Xupeng , Liu Zhaoli , Yu Jie , Wang Heng‐Guo , Wu Xing‐Long , Cui Fengchao , Zhu Guangshan
Published: April 2024

Air self‐charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self‐charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low‐temperature self‐charging aqueous Zn−K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)‐based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn‐ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all‐climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self‐charging process in the absence of an external power source. Impressively, the air self‐charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g−1), and exceptional self‐charging performance even at −40 °C. Therefore, the development of self‐charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.
Achieving Near‐Unity Red Light Photoluminescence in Antimony Halide Crystals via Polyhedron Regulation
Authors: Liao Jin‐Feng , Zhang Zhipeng , Zhou Lei , Tang Zikang , Xing Guichuan
Published: April 2024

Exploration of efficient red emitting antimony hybrid halide with large Stokes shift and zero self‐absorption is highly desirable due to its enormous potential for applications in solid light emitting, and active optical waveguides. However, it is still challenging and rarely reported. Herein, a series of (TMS)2SbCl5 (TMS=triphenylsulfonium cation) crystals have been prepared with diverse [SbCl5]2− configurations and distinctive emission color. Among them, cubic‐phase (TMS)2SbCl5 shows bright red emission with a large Stokes shift of 312 nm. In contrast, monoclinic and orthorhombic (TMS)2SbCl5 crystals deliver efficient yellow and orange emission, respectively. Comprehensive structural investigations reveal that larger Stokes shift and longer‐wavelength emission of cubic (TMS)2SbCl5 can be attributed to the larger lattice volume and longer Sb⋅⋅⋅Sb distance, which favor sufficient structural aberration freedom at excited states. Together with robust stability, (TMS)2SbCl5 crystal family has been applied as optical waveguide with ultralow loss coefficient of 3.67 ⋅ 10−4 dB μm−1, and shows superior performance in white‐light emission and anti‐counterfeiting. In short, our study provides a novel and fundamental perspective to structure‐property‐application relationship of antimony hybrid halides, which will contribute to future rational design of high‐performance emissive metal halides.
3D Printing of Aqueous Two‐Phase Systems with Linear and Bottlebrush Polyelectrolytes
Authors: Jin Zichen , Seong Hong‐Gyu , Srivastava Satyam , McGlasson Alex , Emrick Todd , Muthukumar Murugappan , Russell Thomas P.
Published: April 2024

We formed core–shell‐like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes could be tuned by the conformation of the BBs. By combining the linear/bottlebrush polyelectrolyte complexation with all‐liquid 3D printing, flow‐through tubular constructs were produced that showed selective transport across the PEC membrane comprising the walls of the tubules. These tubular constructs afford a new platform for flow‐through delivery systems.
Unveiling the Pivotal Role of dx2−y2 Electronic States in Nickel‐Based Hydroxide Electrocatalysts for Methanol Oxidation
Authors: Li Junhua , Wu Chao , Wang Zhen , Meng Haoyan , Zhang Qi , Tang Ying , Zou Anqi , Zhang Yiming , Zhong Haoyin , Xi Shibo , Xue Junmin , Wang Xiaopeng , Wu Jiagang
Published: April 2024

The anodic methanol oxidation reaction (MOR) plays a crucial role in coupling with the cathodic hydrogen evolution reaction (HER) and enables the sustainable production of the high‐valued formate. Nickel‐based hydroxide (Ni(OH)2) as MOR electrocatalyst has attracted enormous attention. However, the key factor determining the intrinsic catalytic activity remains unknown, which significantly hinders the further development of Ni(OH)2 electrocatalyst. Here, we found that the
electronic state within antibonding bands plays a decisive role in the whole MOR process. The onset potential depends on the deprotonation ability (Ni2+ to Ni3+), which was closely related to the band center of
orbital. The closer of
orbital to the Fermi level showed the stronger the deprotonation ability. Meanwhile, in the high potential region, the broadening of
orbital would facilitate the electron transfer from methanol to catalysts (Ni3+ to Ni2+), further enhancing the catalytic properties. Our work for the first time clarifies the intrinsic relationship between
electronic state and the MOR activities, which adds a new layer of understanding to the methanol electrooxidation research scene.
The vascular footprint in cardiac homeostasis and hypertensive heart disease—A link between apelin receptor, vascular endothelial growth factor, and neuronal nitric oxide synthase
Authors: Iliev Alexandar , Gaydarski Lyubomir , Kotov Georgi , Landzhov Boycho , Kirkov Vidin , Stanchev Stancho
Published: April 2024

Recent studies have suggested a connection between disturbances of the apelin system and various cardiac pathologies, including hypertension, heart failure, and atherosclerosis. Vascular endothelial growth factor is crucial for cardiac homeostasis as a critical molecule in cardiac angiogenesis. Neuronal nitric oxide synthase is an essential enzyme producing nitric oxide, a key regulator of vascular tone. The present study aims to shed light upon the complex interactions between these three vital signaling molecules and examine their changes with the progression of hypertensive heart disease. We used two groups of spontaneously hypertensive rats and age‐matched Wistar rats as controls. The expression of the apelin receptor, vascular endothelial growth factor, and neuronal nitric oxide synthase were assessed immunohistochemically. We used capillary density and cross‐sectional area of the cardiomyocytes as quantitative parameters of cardiac hypertrophy. Immunoreactivity of the molecules was more potent in both ventricles of spontaneously hypertensive rats compared with age‐matched controls. However, capillary density was lower in both ventricles of the two age groups of spontaneously hypertensive rats compared with controls, and the difference was statistically significant. In addition, the cross‐sectional area of the cardiomyocytes was higher in both ventricles of the two age groups of spontaneously hypertensive rats compared with controls, and the difference was statistically significant. Our study suggests a potential link between the apelin receptor, vascular endothelial growth factor, and neuronal nitric oxide synthase in cardiac homeostasis and the hypertensive myocardium. Nevertheless, further research is required to better comprehend these interactions and their potential therapeutic implications.
Assess the Effectiveness of Multichannel Analysis of Surface Waves Method in Mapping Ancient Structures in Ultrashallow Aquatic Environments: The Case of Agioi Theodoroi, Greece
Authors: Kritikakis George , Papadopoulos Nikos , Andronikidis Nikos , Simyrdanis Kleanthis , Theodoulou Theotokis
Published: April 2024

The present geophysical research aims to evaluate the applicability of multichannel analysis of surface waves (MASW) on mapping ultrashallow underwater ancient masonry remnants. The work presents the analysis from a single seismic line using MASW and seismic refraction tomography (SRT) methods and its corresponding electrical resistivity tomography (ERT) section surveyed at the submerged prehistoric site of Agioi Theodoroi area located 10 km eastern of Heraklion, Crete, Greece. The 2D MASW velocity model exhibits significant correspondence with the resistivity structure extracted from the ERT data, showing lateral S‐wave velocity (Vs) variations at the positions where the high resistivity anomalies exist. The analysis of synthetic seismic data calculated from a respective model reproduced a comparable S‐wave velocity pseudo‐section with the real data. However, the investigated targets (submerged buried masonry) appear shallower and wider in MASW sections than in the real world and the corresponding synthetic models, due to insufficient vertical and horizontal resolution of this method. Surface waves travelling through the seafloor sediments (Scholte‐waves) demonstrate very low velocity values. This makes them suitable for the detection of shallow and relatively large (> 0.5 m) underwater manmade structures, providing the enhancement of MASW method resolution, by utilizing a high frequency (> 100 Hz) seismic source, recording short Scholte wavelengths (≤ 1 m) and using shorter (≤ 0.5 m) receiver spacing and array length. Consequently, the results of this work demonstrate the potential in employing conventional seismic techniques in the delineation of underwater antiquities and the revealing of the cultural dynamics in very shallow off‐shore archaeological sites.
Re‐imagining a decolonised, anti‐racist curriculum within initial teacher education in a Welsh university
Authors: Davis Susan , Watkins Sharne , Haughton Chantelle , Oliver Eve , Farag Josephine , Webber Paula , Goold Samuel
Published: April 2024

Changes to the Welsh curriculum are becoming apparent. The Williams Report culminated in recommendations for schools and initial teacher education (ITE) on the inclusion and teaching of Black Asian and Minority Ethnic histories in Wales. The subsequent Welsh Government ITE action plan was designed to ensure the pro‐active recruitment of trainee teachers from Black and racially minoritised backgrounds in Wales. As a result of this legislation, a team of ITE lecturers in a school of education in a Welsh university formed a research triad and larger research collective, the idea being that we needed to decolonise our own pedagogy and curriculum delivery and re‐imagine ITE within an anti‐racist paradigm. It was key to reflect on our ITE provision, ensuring that our curriculum delivery reflected the ambition of the new Curriculum for Wales,* which encourages practitioners to think differently on what they teach, how they teach and what they want young people to learn. Using a patchwork methodology—which included ‘deep thinking and deep listening’—we examined our current ITE delivery and work that has been done thus far and looked at the gains and areas for development. It became clear that staff within our ‘ITE research collective’ were becoming more knowledgeable and confident in working within a racial dynamic, and consequently felt more able to impart knowledge when engaging with other ITE colleagues and students. This paper charts our ongoing journey and makes recommendations gained from our experiences.
Investigation of the mechanism of nephrotoxicity of nux‐vomica by PTGS2/CYP2C9‐mediated arachidonic acid pathway and Jian Pi Tong Luo compound's protective effect
Authors: Zhang Na , An Baisong , Zhao Liangyou , Zhao Dapeng , Lv Bochuan , Liu Shumin
Published: April 2024

The clinical effectiveness of nux‐vomica in treating rheumatism and arthralgia is noteworthy; however, its nephrotoxicity has sparked global concerns. Hence, there is value in conducting studies on detoxification methods based on traditional Chinese medicine compatibility theory. Blood biochemistry, enzyme‐linked immunosorbent assay, and pathological sections were used to evaluate both the nephrotoxicity of nux‐vomica and the efficacy of the Jian Pi Tong Luo (JPTL) compound in mitigating this toxicity. Kidney metabolomics, using ultra‐high‐performance liquid chromatography–quadrupole‐time‐of‐flight–MS (UPLC–Q‐TOF–MS), was applied to elucidate the alterations in small‐molecule metabolites in vivo. In addition, network pharmacology analysis was used to verify the mechanism and pathways underlying the nephrotoxicity associated with nux‐vomica. Finally, essential targets were validated through molecular docking and western blotting. The findings indicated significant nephrotoxicity associated with nux‐vomica, while the JPTL compound demonstrated the ability to alleviate this toxicity. The mechanism potentially involves nux‐vomica activating the “PTGS2/CYP2C9–phosphatidylcholine–arachidonic acid metabolic pathway.” This study establishes a scientific foundation for the clinical use of nux‐vomica and lays groundwork for further research and safety assessment of toxic Chinese herbal medicines.
Foreign ownership and product market competition's influence on firm performance: Mediating role of the corporate governance index
Authors: Tran Thu Thi , Ha Thach Xuan , Vo Nhan Kim
Published: April 2024

This study examines the influence of foreign ownership and product market competition on firm performance in Vietnam's listed companies through the mediating role of the corporate governance index. Moreover, the study explores the moderating role of business strategy in the relationships between foreign ownership, product market competition, and firm performance. We use maximum likelihood structural equation modeling in Stata 14 software to analyze the data collected from 180 Vietnamese listed companies from 2015 to 2019. The results indicate that foreign ownership and product market competition positively influence firm performance by mediating the corporate governance index. Business strategy negatively moderates the relationship between product market competition and firm performance. This study has implications for managers focusing on foreign ownership and product market competition to improve corporate governance systems, enhancing firm performance. Additionally, managers may build business strategies when product market competition increases to avoid negative effects on firm performance.
Digital data‐driven technologies and the environmental sustainability of micro, small, and medium enterprises: Does size matter?
Authors: Hernández Virginia , Revilla Antonio , Rodríguez Alicia
Published: April 2024

Despite the increasing interest in understanding the relations between firms' digitalization and their environmental sustainability, they are still poorly understood as research on this hot topic is nascent and empirical evidence is sparse and fragmented. In this study, we delve into the relations between different digital data‐driven technologies (DTs) used for gathering and storing (smart devices and cloud computing), analyzing (Big Data and Artificial Intelligence), and sharing data (Blockchain) and environmental sustainability in micro, small, and medium enterprises (MSMEs). These firms, despite their relevance in the business landscape and their heterogeneity, are understudied in this area. Thus, we also examine the moderating role of firm size to understand the inherent diversity of MSMEs in the use of DTs and the development of the sustainability oriented practices. Empirical results from a large‐scale representative sample of European enterprises show that the adoption of DTs for data gathering and analysis is positively associated with sustainability‐oriented actions in MSMEs. The findings also reveal the positive moderating role of size: relations between data analysis and sharing technologies and sustainability are stronger for larger MSMEs, with the latter being significant only for medium‐sized enterprises.