bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ultrahigh Supramolecular Cascaded Room‐Temperature Phosphorescence Capturing System
Authors: Huo Man , Dai Xian‐Yin , Liu Yu 
Published: October 2021

AbstractAn ultrahigh supramolecular cascaded phosphorescence‐capturing aggregate was constructed by multivalent co‐assembly of cucurbit[7]uril (CB[7]) and amphipathic sulfonatocalix[4]arene (SC4AD). The initial dibromophthalimide derivative (G) generated a weak phosphorescent emission at 505 nm by host–guest interaction with CB[7], which further assembled with SC4AD to form homogeneously spherical nanoparticles with a dramatic enhancement of both phosphorescence lifetime to 1.13 ms and emission intensity by 40‐fold. Notably, this G⊂CB[7]@SC4AD aggregate exhibited efficient phosphorescence energy transfer to Rhodamine B (RhB) and benzothiadiazole (DBT) with high efficiency (ϕET) of 84.4 % and 76.3 % and an antenna effect (AE) of 289.4 and 119.5, respectively, and then each of these can function as a bridge to further transfer their energy to second near‐IR acceptors Cy5 or Nile blue (NiB) to achieve cascaded phosphorescence energy transfer. The final aggregate with long‐range effect from 425 nm to 800 nm and long‐lived photoluminescence was further employed as an imaging agent for multicolour cell labeling.
Metal‐Triazolate‐Framework‐Derived FeN4Cl1 Single‐Atom Catalysts with Hierarchical Porosity for the Oxygen Reduction Reaction
Authors: Hu Linyu , Dai Chunlong , Chen Liwei , Zhu Yuhao , Hao Yuchen , Zhang Qinghua , Gu Lin , Feng Xiao , Yuan Shuai , Wang Lu , Wang Bo 
Published: October 2021

AbstractThe construction of single‐atom catalysts (SACs) with high single atom densities, favorable electronic structures and fast mass transfer is highly desired. We have utilized metal‐triazolate (MET) frameworks, a subclass of metal–organic frameworks (MOFs) with high N content, as precursors since they can enhance the density and regulate the electronic structure of single‐atom sites, as well as generate abundant mesopores simultaneously. Fe single atoms dispersed in a hierarchically porous N‐doped carbon matrix with high metal content (2.78 wt %) and a FeN4Cl1 configuration (FeN4Cl1/NC), as well as mesopores with a pore:volume ratio of 0.92, were obtained via the pyrolysis of a Zn/Fe‐bimetallic MET modified with 4,5‐dichloroimidazole. FeN4Cl1/NC exhibits excellent oxygen reduction reaction (ORR) activity in both alkaline and acidic electrolytes. Density functional theory calculations confirm that Cl can optimize the adsorption free energy of Fe sites to *OH, thereby promoting the ORR process. The catalyst demonstrates great potential in zinc‐air batteries. This strategy selects, designs, and adjusts MOFs as precursors for high‐performance SACs.
Monometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine‐hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerization
Authors: Gois Patrik Dione de Santana , Maia Juliana Iris Pereira , Masson Gustavo Henrique Cicero , Martins Daniele Maria , Machado Antonio Eduardo da Hora , Goi Beatriz Eleutério , Maia Pedro Ivo da Silva , Carvalho‐Jr Valdemiro Pereira de 
Published: October 2021

AbstractThe monometallic complex [Pd(L)(PPh3)] (mono‐Pd) was synthesized using a potentially tridentate hydrazone (H2L) and used as precursor to prepare a heterobimetallic ruthenium (II)‐palladium (II) complex [Cl2(p‐cymene)Ru(μ‐L)Pd (PPh3)] (Ru‐Pd). Mono‐Pd and Ru‐Pd were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet‐visible spectroscopy (UV–Vis), 1H, 13C{1H} and 31P{1H} nuclear magnetic ressonance(NMR) spectroscopy, elemental analysis, cyclic voltammetry, matrix‐assisted laser desorption/ionization ‐ time of flight (MALDI‐TOF) mass spectrometry, and computational methods. The mono‐Pd was additionally studied by single‐crystal X‐ray diffraction. The complex [RuCl2(p‐cymene)(Isoniazid)] (mono‐Ru) was also obtained following literature methods aiming a comparison in the catalytic activity. The ring opening metathesis polymerization (ROMP) of norbornene (NBE) using mono‐Ru or Ru‐Pd as precatalysts in the presence of ethyl diazoacetate (EDA) was evaluated as a function of time (10–60 min) using [NBE]/[EDA]/[Ru] = 5000/28/1 at 50°C. The time increases produced good yields of polyNBE, reaching 38% and 46% for mono‐Ru and Ru‐Pd, respectively. The polyNBE produced was measured by size‐exclusion chromatography (SEC) and reached an order of magnitude of 105 g·mol−1 of Mn, with Ð values ranging from 2.51 to 1.86 for mono‐Ru and from 3.50 to 1.66 for Ru‐Pd. The catalytic activity of mono‐Pd and Ru‐Pd on ethylene polymerization was assessed with a range of [Al]/[Pd] molar ratio between 350 and 1750, 30–70°C temperature, 2 to 4 h reaction time, and total reaction volume of 25 and 50 ml. Mono‐Pd achieved an activity of 22.80 kg PE (mol Pd)−1 h−1 at 60°C after 4 h using [Al]/[Pd] = 1050, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. For Ru‐Pd, an activity of 20.35 kg PE (mol Pd)−1 h−1 at 60°C after 4 h was obtained using [Al]/[Pd] = 1750, 7 μmol of catalyst in 25 ml of toluene, and 116 psi ethylene. Overall, Ru‐Pd showed to be active in both ROMP and ethylene polymerization reactions, being categorized as a bifunctional catalyst.
Mixed Alkyl/Aryl Diphos Ligands for Iron‐Catalyzed Negishi and Kumada Cross Coupling Towards the Synthesis of Diarylmethane
Authors: Ma Xufeng , Wang Han , Liu Yao , Zhao Xing , Zhang Jun 
Published: October 2021

AbstractMixed alkyl/aryl diphos ligands have been prepared and their application in iron‐catalyzed cross coupling of benzylic chlorides with diaryl zinc (Negishi) or aryl Grignard reagents (Kumada) towards the synthesis of diarylmethane has been evaluated. The iron−diphos catalytic system exhibited the enhanced activity and selectivity in the two coupling reactions. The electron‐rich mixed PPh2/PCy2ligands outperformed their symmetrical PPh2congeners, and led to decreased homocoupling byproduct formation. It indicates that the electronic effect of the ligands plays an important role in the catalytic performance. The Fe catalyst supported byL8bearing an electron‐rich PCy2substituent and a sterically demanding tert‐butyl on ethene backbone exhibited the best catalytic performance and good functional group tolerance in the two cross coupling reactions.
Progress of Solid‐state Electrolytes Used in Organic Secondary Batteries
Authors: Wang Shaolong , Lv Jing , Wang Xuehan , Cui Haixia , Huang Weiwei , Wang Yanzhi 
Published: October 2021

AbstractOrganic electrode materials (OEMs) have attracted intensive attention owing to their high energy density, diverse structures and environmental friendliness. Unfortunately, the easy dissolution of OEMs in the organic liquid electrolytes (OLEs) severely damages the cycle stability of batteries. There is a hidden danger of catching fire due to a lot of heat generated from overcharge of the batteries. Moreover, OLEs are liable to leak and unstable at high voltage. Using solid‐state electrolytes (SSEs) could effectively alleviate the above‐mentioned problems at some extent. However, SSEs still show some weaknesses, including the large impedance of electrolyte‐electrode interface (EEI) and low ion conductivity. In this review, the latest progress in the research of SSEs used in organic secondary batteries (OSBs) are summarized, with particularly focus on the ionic conductivity of SSEs, the combination of organic electrodes/solid‐state electrolytes, the optimization of EEI and the batteries cycle stability. Future directions for the development of OSBs are given from viewpoints of solid batteries.
Immobilized Poly(anthraquinones) for Electrochemical Energy Storage Applications: Structure‐Property Relations
Authors: Wielend Dominik , Salinas Yolanda , Mayr Felix , Bechmann Matthias , Yumusak Cigdem , Neugebauer Helmut , Brüggemann Oliver , Sariciftci Niyazi Serdar 
Published: October 2021

AbstractThe majority of energy storage devices like batteries, fuel cells or electrolyzers require heterogeneous electrodes. Immobilization of redox‐active organic molecules by a polymeric approach seems to be a promising route towards organic electrodes for electrocatalytic energy storage or in batteries. Although numerous reports on synthesis and application of new poly‐anthraquinones exist, a universal guideline or tool for selection of the best polymer, concerning several energy storage applications, is still underdeveloped. Moving into the direction of developing such a tool, we have selected and synthesized three poly(anthraquinones). NMR, FTIR, UV‐Vis, TGA, contact angle measurement and SEM revealed certain structure‐property trends, which can be correlated with the performance in the electrochemical investigation. The insights gained within this work demonstrate correlations between the FTIR frequencies and the electrochemical reduction potential, as well as between the polymer hydrophobicity and the electrochemical performance.
Highly Efficient Thermally Activated Delayed Fluorescence from Pyrazine‐Fused Carbene Au(I) Emitters
Authors: Yang Jian‐Gong , Song Xiu‐Fang , Wang Jian , Li Kai , Chang Xiaoyong , Tan Li‐Ying , Liu Chu‐Xuan , Yu Fei‐Hu , Cui Ganglong , Cheng Gang , To Wai‐Pong , Yang Chuluo , Che Chi‐Ming , Chen Yong 
Published: October 2021

AbstractMetal‐based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high‐performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine‐fused nitrogen‐heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single‐crystal X‐ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge‐transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short‐lived (<1 μs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔEST), the spin‐orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application.
Versatile Para‐Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function
Authors: Starck Matthieu , Fradgley Jack D. , De Rosa Davide F. , Batsanov Andrei S. , Papa Maria , Taylor Michael J. , Lovett Janet E. , Lutter Jacob C. , Allen Matthew J. , Parker David 
Published: October 2021

AbstractA series of cationic and neutral p−Br and p−NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C−N and C−C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transition accompanied by a reduction in the Eu−Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p‐substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions.
Real‐time Voltammetric Anion Sensing Under Flow**
Authors: Patrick Sophie C. , Hein Robert , Sharafeldin Mohamed , Li Xiaoxiong , Beer Paul D. , Davis Jason J. 
Published: October 2021

AbstractThe development of real‐life applicable ion sensors, in particular those capable of repeat use and long‐term monitoring, remains a formidable challenge. Herein, we demonstrate, in a proof‐of‐concept, the real‐time voltammetric sensing of anions under continuous flow in a 3D‐printed microfluidic system. Electro‐active anion receptive halogen bonding (XB) and hydrogen bonding (HB) ferrocene‐isophthalamide‐(iodo)triazole films were employed as exemplary sensory interfaces. Upon exposure to anions, the cathodic perturbations of the ferrocene redox‐transducer are monitored by repeat square‐wave voltammetry (SWV) cycling and peak fitting of the voltammograms by a custom‐written MATLAB script. This enables the facile and automated data processing of thousands of SW scans and is associated with an over one order‐of‐magnitude improvement in limits of detection. In addition, this improved analysis enables tuning of the measurement parameters such that high temporal resolution can be achieved. More generally, this new flow methodology is extendable to a variety of other analytes, including cations, and presents an important step towards translation of voltammetric ion sensors from laboratory to real‐world applications.
Electrospun Tungsten‐Polyurethane Composite Nanofiber Mats for Medical Radiation‐Shielding Applications
Authors: Yun Jaehan , Hou Jian , Jang Wongi , Kim Sung‐Yul , Byun Hongsik 
Published: October 2021

AbstractElectrospun composite nanofiber mats consisting of polyurethane (PU) and nontoxic tungsten powder are manufactured via electrospinning for use as X‐ray shielding materials. Upon systematical formation of tungsten‐PU composite nanofiber layers, heat and pressure are simultaneously treated to design light‐weight mats containing various amount of tungsten metals. After examining their structural and physical properties, the X‐ray mass attenuation coefficient, nitrogen permeability, and flexibility of the resulting mats are compared to conventional film‐type shielding mats. While the nanofiber‐based composite mats still exhibit a comparable X‐ray mass attenuation coefficient (9.64 cm2/g), their gas permeability (8.56 L/min) and flexibility (bending angle of 28.8°) are almost two and five times higher than those of conventional mats, respectively. This work clearly demonstrates the preparation of effective composite mats with controlled properties for the development of nontoxic shielding suits that can replace conventional lead‐based materials possessing environmental and health concerns.
MrFbP: Markov random field‐driven spatial entropy‐based routing protocol in opportunistic networks
Authors: Kumar Arun , Dutta Aniruddha A. , Jain Nayan , Dhurandher Sanjay K. 
Published: October 2021

SummaryRecently, research towards technologies associated with the 5G communication is in full operation. Amongst these enabling technologies, device‐to‐device(D2D) communication is one of the critical factors for scaling up the network efficiency in 5G communication. Intermittent connections due to higher mobility lead to frequent path breaks, and hence a mobility‐based opportunistic routing is suitable enough to control the forwarding process. Opportunistic networks (OppNet) use the pairwise opportunistic contacts and higher mobility to rely on the store‐carry and forward mechanism for routing purpose. In this work, a novel mobility‐induced context‐based routing process has been designed to support D2D communication. The designed Markov random field‐induced protocol (MrFbP) is based on spatial entropy for capturing the coverage span of the forwarding node in the network. The work relies on the monitored historic mobility of a node and is then used to capture the utility metric for taking forwarding decision. MrFbP is compared against the established Direct Delivery (DD), Epidemic (EP), Spray & Wait (SW), and PropHet (PR) on parameters like throughput, delay, hops, overheads, and energy consumption. Simulation has been carried out using ONE simulator to validate an improvement in the design of a designed protocol against the baseline protocols.
Applying deep neural networks to predict incidence and phenology of plant pests and diseases
Authors: Grünig Marc , Razavi Elisabeth , Calanca Pierluigi , Mazzi Dominique , Wegner Jan Dirk , Pellissier Loïc 
Published: October 2021

AbstractA major challenge of agriculture is to improve the sustainability of food production systems in order to provide enough food for a growing human population. Pests and pathogens cause vast yield losses, while crop protection practices raise environmental and human health concerns. Decision support systems provide detailed information on optimal timing and necessity of crop protection interventions, but are often based on phenology models that are time‐, cost‐, and labor‐intensive in development. Here, we aim to develop a data‐driven approach for pest damage forecasting, relying on big data and deep learning algorithms. We present a framework for the development of deep neural networks for pest and pathogen damage classification and show their potential for predicting the phenology of damages. As a case study, we investigate the phenology of the pear leaf blister moth (Leucoptera malifoliella, Costa). We employ a set of 52,322 pictures taken during a period of 19 weeks and establish deep neural networks to categorize the images into six main damage classes. Classification tools achieved good performance scores overall, with differences between the classes indicating that the performance of deep neural networks depends on the similarity to other damages and the number of training images. The reconstructed damage phenology of the pear leaf blister moth matches mine counts in the field. We further develop statistical models to reconstruct the phenology of damages with meteorological data and find good agreement with degree‐day models. Hence, our study indicates a yet underexploited potential for data‐driven approaches to enhance the versatility and cost efficiency of plant pest and disease forecasting.
Mutual cheating strengthens a tropical seed dispersal mutualism
Authors: Cao Lin , Jansen Patrick A. , Wang Bo , Yan Chuan , Wang Zhenyu , Chen Jin 
Published: October 2021

AbstractWhile cheating can cause the degradation or collapse of mutualisms, mutualisms may theoretically stabilize or strengthen if the cheating is mutual. Here, we present an asymmetric two‐player game model to explore the evolutionary dynamics of mutual cheating in a mutualistic interaction. We found that the interaction evolved toward mutual cheating if cheating can help both partners obtain higher benefits or if counter‐cheating yields more benefits to victims than simply tolerating exploitation by partners. Then, we present empirical evidence for such mutual cheating strengthening a seed dispersal mutualism in which rodents disperse seeds by scatter hoarding, rodents sabotage seed germination by pruning radicles, and seeds escape rodents by resprouting. By tracking >8,000 Pittosporopsis kerrii seeds throughout the dispersal process in a tropical forest in southwest China, we found that rodents provided better dispersal to seeds that they pruned, i.e., pruned seeds were dispersed farther and were more likely to establish seedlings than unpruned seeds. Compared with unpruned seeds, pruned seeds retained more of their nutrients, i.e., dry mass of pruned seeds was greater than that of unpruned seeds, and were stored for longer by rodents. These findings indicate that mutual cheating benefited both partners. Payoffs estimated from the field experiments indicated that mutual cheating was indeed favored in rodents and plants P. kerrii, and that neither partner was enslaved by the other under mutual cheating. Rather, the mutualism remained stable because the partners were able to exploit each other, and each partner attempted to gain the maximum benefits from the interaction. Our findings indicate that mutual cheating between two mutualists can enhance and stabilize mutualisms.
Ring‐Closing Metathesis of Aliphatic Ethers and Esterification of Terpene Alcohols Catalyzed by Functionalized Biochar
Authors: Vidal Juliana L. , Wyper Olivia M. , MacQuarrie Stephanie L. , Kerton Francesca M. 
Published: October 2021

AbstractFunctionalized biochars, renewable carbon materials prepared from waste biomass, can catalyze transformations of a range of oxygen‐containing substrates via hydrogen‐bonding interactions. Good conversions (up to 75.2 %) to different O‐heterocycles are obtained from ring‐closing C−O/C−O metathesis reactions of different aliphatic ethers under optimized conditions using this heterogeneous, metal‐free, and easy separable catalyst. The diversity in the sorts of O‐containing feedstocks is further demonstrated by the utilization of functionalized biochar to promote the esterification of terpene alcohols, an important reaction in food and flavor industries. Under the optimized conditions, full conversions to various terpene esters are obtained. Moreover, both of the reactions studied herein are performed under neat conditions, thus increasing the overall sustainability of the process described.
White matter hyperintensities segmentation using an ensemble of neural networks
Authors: Li Xinxin , Zhao Yu , Jiang Jiyang , Cheng Jian , Zhu Wanlin , Wu Zhenzhou , Jing Jing , Zhang Zhe , Wen Wei , Sachdev Perminder S. , Wang Yongjun , Liu Tao , Li Zixiao 
Published: October 2021

AbstractWhite matter hyperintensities (WMHs) represent the most common neuroimaging marker of cerebral small vessel disease (CSVD). The volume and location of WMHs are important clinical measures. We present a pipeline using deep fully convolutional network and ensemble models, combining U‐Net, SE‐Net, and multi‐scale features, to automatically segment WMHs and estimate their volumes and locations. We evaluated our method in two datasets: a clinical routine dataset comprising 60 patients (selected from Chinese National Stroke Registry, CNSR) and a research dataset composed of 60 patients (selected from MICCAI WMH Challenge, MWC). The performance of our pipeline was compared with four freely available methods: LGA, LPA, UBO detector, and U‐Net, in terms of a variety of metrics. Additionally, to access the model generalization ability, another research dataset comprising 40 patients (from Older Australian Twins Study and Sydney Memory and Aging Study, OSM), was selected and tested. The pipeline achieved the best performance in both research dataset and the clinical routine dataset with DSC being significantly higher than other methods (p < .001), reaching .833 and .783, respectively. The results of model generalization ability showed that the model trained on the research dataset (DSC = 0.736) performed higher than that trained on the clinical dataset (DSC = 0.622). Our method outperformed widely used pipelines in WMHs segmentation. This system could generate both image and text outputs for whole brain, lobar and anatomical automatic labeling WMHs. Additionally, software and models of our method are made publicly available at https://www.nitrc.org/projects/what_v1.