bluuebunny/crossref_metadata_2025_split huggingface dataset:
Iridium‐Catalyzed Ligand‐Controlled Remote para‐Selective C−H Activation and Borylation of Twisted Aromatic Amides
Authors: Hoque Md Emdadul , Bisht Ranjana , Unnikrishnan Anju , Dey Sayan , Mahamudul Hassan Mirja Md , Guria Saikat , Rai Rama Nand , Sunoj Raghavan B. , Chattopadhyay Buddhadeb 
Published: April 2022

AbstractA method of para‐selective borylation of aromatic amides is described. The borylation proceeded via an unprecedented substrate–ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa) that is different from the traditionally used ligand (dtbpy) for the C−H borylation reactions. The designed ligand framework (defa) has led to the development of a new type of catalytic system that shows excellent para selectivity for a range of aromatic amides. Moreover, the designed ligand has shown excellent reactivity and selectivity for a range of heterocyclic aromatic amides. The identification of key transition states and intermediates using the DFT computations associated with the three regio‐isomeric pathways revealed that the most efficient catalytic pathway with the defa ligand leads to the para borylation while in the case of bpy the borylation at the para and meta sites compete.
Scalable Nitrate Treatment for Constructing Integrated Surface Structures to Mitigate Capacity Fading and Voltage Decay of Li‐Rich Layered Oxides
Authors: Luo Dong , Xie Huixian , Tan Fulin , Ding Xiaokai , Cui Jiaxiang , Xie Xiaoyan , Liu Chenyu , Lin Zhan 
Published: April 2022

AbstractCapacity fading and voltage decay is one of the biggest obstacles for the practical application of Li‐rich layered oxides due to the serious surface‐related detrimental reactions. Herein, we develop a versatile and scalable method to construct a robust surface‐integrated structure. All the designed samples deliver outstanding capacity and voltage stability, among which the Zn‐treated sample possesses the best electrochemical performance. Its capacity retention is larger than 90 % after 400 cycles with a voltage decay ratio as small as 0.73 mV per cycle. What is more, the rules of surface‐integrated structure with different cations in terms of capacity and voltage stability is further deciphered by combining with density function theory (DFT) calculations. It is found that to obtain advanced Li‐rich layered oxide cathodes, cations in Li‐sites should firstly ensure the binding energy of the surface‐integrated structure in a lower level and then provide Bader charge for the nearest O atoms as small as possible.
Tetracoordinate Boron‐Based Multifunctional Chiral Thermally Activated Delayed Fluorescence Emitters
Authors: Zhou Ling , Ni Fan , Li Nan , Wang Kai , Xie Guohua , Yang Chuluo 
Published: April 2022

AbstractPurely organic emitters have shown great potential but still suffer from low efficiency in near‐infrared organic light‐emitting diodes (NIR‐OLEDs) due to the intensive non‐radiative recombination. In this contribution, two pairs of thermally activated delayed fluorescence (TADF) enantiomers (R/S‐DOBP and R/S‐HDOBP) with tetracoordinate boron geometries were designed and synthesized. The TADF emitters simultaneously showed aggregation‐induced emission, circularly polarized luminescence, high‐contrast mechanochromism, and piezochromism behaviors. More importantly, R/S‐DOBP and R/S‐HDOBP revealed high photoluminescence quantum yields and efficient reverse intersystem crossing in neat films. The nondoped solution‐processed OLEDs based on these unique emitters revealed the NIR emission (peaking at 716 nm) with a maximum external quantum efficiency of 1.9 % and high exciton utilization efficiency of 86 %, which represent one of the best solution‐processed nondoped NIR‐OLEDs.
Biomacromolecule‐Fueled Transient Volume Phase Transition of a Hydrogel
Authors: Nakamoto Masahiko , Kitano Shiro , Matsusaki Michiya 
Published: April 2022

AbstractA metabolic cycle‐inspired hydrogel which exhibits the biomacromolecule‐fueled transient volume phase transition is reported. This hydrogel has the affinity and digestive capacity for a fuel α‐poly‐L‐lysine by incorporating acrylic acid and trypsin. The hydrogel captured fuel and transiently shrank owing to the construction of electrostatic cross‐linkages. This process was inherently connected with the digestion of these cross‐linkages and the release of oligo‐lysine as waste, which induced the reswelling of the hydrogel at equilibrium. The transient volume change of the hydrogel realized the fuel‐stimulated transient release of a payload. This study provides a strategy for engineering materials with biomacromolecule‐fueled dynamic functions under the out‐of‐equilibrium condition.
Beyond Bioisosteres: Divergent Synthesis of Azabicyclohexanes and Cyclobutenyl Amines from Bicyclobutanes**
Authors: Dhake Kushal , Woelk Kyla J. , Becica Joseph , Un Andy , Jenny Sarah E. , Leitch David C. 
Published: April 2022

AbstractThe development of two divergent and complementary Lewis acid catalyzed additions of bicyclobutanes to imines is described. Microscale high‐throughput experimentation was integral to the discovery and optimization of both reactions. N‐arylimines undergo formal (3+2) cycloaddition with bicyclobutanes to yield azabicyclo[2.1.1]hexanes in a single step; in contrast, N‐alkylimines undergo an addition/elimination sequence to generate cyclobutenyl methanamine products with high diastereoselectivity. These new products contain a variety of synthetic handles for further elaboration, including many functional groups relevant to pharmaceutical synthesis. The divergent reactivity observed is attributed to differences in basicity and nucleophilicity of the nitrogen atom in a common carbocation intermediate, leading to either nucleophilic attack (N‐aryl) or E1 elimination (N‐alkyl).
Fixed‐time backstepping distributed cooperative control for multiple unmanned aerial vehicles
Authors: Cui Lei , Zhou Qi , Jin Nan 
Published: April 2022

AbstractThis paper proposes a fixed‐time backstepping distributed cooperative control scheme based on fixed‐time extended state observer (FxTESO) for multiple unmanned aerial vehicles (UAVs). A fixed‐time ESO, which is convergent independently of initial conditions, is designed to estimate and compensate the external disturbances in tracking process. Moreover, to eliminate the “explosion of complexity” in the traditional backstepping architecture, a nonlinear first‐order filter is adopted to construct the distributed fixed‐time control scheme. Based on the local information of neighboring UAVs, a fixed‐time backstepping cooperative controller is designed. The proposed formation algorithm can be shown practicable for the UAV control system by using of Lyapunov stability theory and graph theory. Simulation results are given to demonstrate the effectiveness of the proposed control scheme.
Genauigkeitsgrenzen modularer Betontragwerke – Teil 2: Probabilistische Bewertung der Montage mit Schraubenverbindung
Authors: Stindt Jan , Frey Alex Maximilian , Forman Patrick , Lanza Gisela , Mark Peter 
Published: April 2022

AbstractDer Beitrag behandelt die Montage von modulartigen Betonfertigteilen mit Fachwerkknoten aus Stahl. Dazu werden Wabenstrukturen betrachtet, die aus vielen Fertigteilen mit Y‐Form bestehen. Der Beitrag baut auf der für die Wabenstrukturen im Teil 1 abgeleiteten Bewegungskinematik zwischen den einzelnen Modulen auf, wobei Schwinddehnungen Verformungen in den Modularmen erzeugen. Für die Montage werden Schraubenverbindungen betrachtet, die entweder klassisches Lochspiel besitzen oder gleitfest fixiert werden. Bei Letzterem kompensiert ein Ausrichten vor dem Fixieren einen Teil von Abweichungen. Die Zuverlässigkeit der Montage wird mit probabilistischen Methoden auf Grundlage von Monte‐Carlo‐Simulationen überprüft. Es zeigt sich, dass reine Lochleibungsverbindungen nur für sehr wenige zu kombinierende Module geeignet sind. Gleitfeste Verbindungen mit kompensatorischem Ausrichten sind mit einem Konfidenzintervall vierfacher Standardabweichung geeignet, Wabenstrukturen bis ca. 60 m Höhe und Breite zuverlässig zusammenzusetzen.
Preparation and application of taste bud organoids in biomedicine towards chemical sensation mechanisms
Authors: Liu Shuge , Zhu Ping , Tian Yulan , Chen Yating , Liu Yage , Chen Wei , Du Liping , Wu Chunsheng 
Published: April 2022

AbstractTaste is one of the most basic and important sensations that is able to monitor the food quality and avoid intake of potential danger materials. Whether as an inevitable symptom of aging or a complication of cancer treatment, taste loss very seriously affects the patient's life quality. Taste bud organoids provide an alternative and convenient approach for the research of taste functions and the underlying mechanisms due to their characteristics of availability, strong maneuverability, and high similarity to the in‐vivo taste buds. This review gives a systemic and comprehensive introduction to the preparation and application of taste bud organoids towards chemical sensing mechanisms. First, the basic structures and functions of taste buds will be briefly introduced. Then, the currently available approaches for the preparation of taste bud organoids are summarized and discussed, which are mainly divided into two categories, that is, the stem/progenitor cell‐derived approach and the tissue‐derived approach. Next, different applications of taste bud organoids in biomedicine are outlined based on their central roles such as disease modeling, biological sensing, gene regulation, and signal transduction. Finally, the current challenges, future development trends, and prospects of research in taste bud organoids are proposed and discussed.
Biosynthesis of 1,3‐propanodiol and 2,3‐butanodiol from residual glycerol in continuous cell‐immobilized Klebsiella pneumoniae bioreactors
Authors: Damasceno Ana Paula Klaus , Rossi Daniele Misturini , Ayub Marco Antônio Záchia 
Published: April 2022

AbstractIn recent years, residual glycerol from biodiesel synthesis made this chemical a cheap, readily available carbon source to bioprocess, which is also a form to reduce costs in the fuel industry. We propose and describe a bioprocess using fluidized and packed‐bed continuous bioreactors to convert this residual glycerol into value‐added products such as 1,3‐propanediol (1,3‐PD) and 2,3‐butanediol (2,3‐BD), largely used in the chemical industry. The bacterium Klebsiella pneumoniae BLh‐1, strain isolated by us, was immobilized in the permeable support of polyvinyl alcohol (LentiKats®). After testing different dilution rates (D) for all bioreactor configurations, the best obtained productivities of 1,3‐PD was 8.69 g L−1 h−1 at a D = 0.45 h−1, and 2.99 g L−1 h−1 at a D = 0.30 h−1 for 2,3‐BD, both in the packed‐bed configuration. In the fluidized‐bed reactor, the highest productivity values achieved were 4.48 and 1.16 g L−1 h−1 for 1,3‐PD and 2,3‐BD, respectively, both at D = 0.33 h−1. These results show the potential of setting up a bioprocess based on continuous cultures using immobilized K. pneumoniae BLh‐1 in PVA matrices in order to efficiently convert the abundant surplus of glycerol into commercially important chemicals such as 1,3‐PD and 2,3‐BD.
Clipping costs
Authors: Drosou Maria E. , Gray William A. 
Published: April 2022

Key Points
Early data on mitral TEER indicate that decrease in cost trends is primarily attributed to decrease in length of index hospitalization and relatively stable 30‐day readmission rates.
The addition of functional MR in the population set and a more stable, less expansive operator pool will affect outcomes over the following years and should be included in cost analyses.
Additional baseline patient characteristics, optimal medical therapy and longer follow up will provide more information regarding mitral TEER outcomes and costs.
Step back to see the complete picture: Complete versus incomplete revascularization of multivessel coronary disease
Authors: Grines Cindy L. , Marshall J. Jeffrey 
Published: April 2022

Key Points
Multivessel disease patients who are incompletely revascularized with PCI have have worse clinical outcomes including death and need for subsequent revascularization
The mechanism of increased mortality with incomplete revascularization is uncertain, and is confounded by higher atherosclerotic burden and more comorbidities
Although we recommend complete revascularization, there are no randomized trials except in the STEMI population.
Ileal gastrointestinal stromal tumor causing mesenteric gangrene
Authors: Beji Hazem , Bouassida Mahdi , Zribi Slim , Touinsi Hassen 
Published: April 2022

AbstractTo our knowledge, this is one of the rare literature reports of an ileal GIST complicated with mesenteric gangrene. We reported successful surgical treatment. Infection of GIST is an extremely rare complication that should be treated with no delays to avoid rupture and peritonitis.
Photoactivatable V‐Shaped Bifunctional Quinone Methide Precursors as a New Class of Selective G‐quadruplex Alkylating Agents
Authors: Lena Alberto , Benassi Alessandra , Stasi Michele , Saint‐Pierre Christine , Freccero Mauro , Gasparutto Didier , Bombard Sophie , Doria Filippo , Verga Daniela 
Published: April 2022

AbstractCombining the selectivity of G‐quadruplex (G4) ligands with the spatial and temporal control of photochemistry is an emerging strategy to elucidate the biological relevance of these structures. In this work, we developed six novel V‐shaped G4 ligands that can, upon irradiation, form stable covalent adducts with G4 structures via the reactive intermediate, quinone methide (QM). We thoroughly investigated the photochemical properties of the ligands and their ability to generate QMs. Subsequently, we analyzed their specificity for various topologies of G4 and discovered a preferential binding towards the human telomeric sequence. Finally, we tested the ligand ability to act as photochemical alkylating agents, identifying the covalent adducts with G4 structures. This work introduces a novel molecular tool in the chemical biology toolkit for G4s.
BRGraph: An efficient graph neural network training system by reusing batch data on GPU
Authors: Ge Keshi , Ran Zhejiang , Lai Zhiquan , Zhang Lizhi , Li Dongsheng 
Published: April 2022

SummaryWith the increasing adoption of graph neural networks (GNNs) in the community, various GPU‐based graph programming systems have been developed to improve the productivity of GNNs. However, sampling‐based GNN training is still inefficient, and we observe that the main bottleneck comes from the data transferring, where vertex features are transferred from host memory to GPU through limited bandwidth. In this article, we propose BRGraph, a sampling‐based GNN training system that supports efficient data transferring. BRGraph leverages the duplicate vertices between mini‐batches by batch reusing (BR) strategy to avoid duplicate data transmission. Furthermore, to reduce the overhead of detecting duplicate vertices, we design an efficient parallel batch reusing algorithm based on GPU. BRGraph also exploits the data reusing potential of the non‐duplicate vertex features by the two‐level batch reusing (two‐level BR) strategy. Comprehensive evaluations on three representative GNN models show that BRGraph reduces data transferring time by up to 60% and delivers up to 1.79

GNN training speedup over the state‐of‐the‐art baselines. Besides, it can save GPU memory by up to 40% while reaching the same training time compared with the static cache strategy. When applying the two‐level BR, BRGraph further reduces 20% of the data transferring time compared with the BR.
GPU‐accelerated and mixed norm regularized online extreme learning machine
Authors: Polat Önder , Kayhan Sema Koç 
Published: April 2022

SummaryExtreme learning machine (ELM) is a prominent example of neural network with its fast training speed, and good prediction performance. An online version of ELM called online sequential extreme learning machine (OS‐ELM) has also been proposed for the sequential training. Combined with the need for regularization to prevent over‐fitting in addition to the large number of neurons required in the hidden layer, OS‐ELM demands huge amount of computation power for the large‐scale data. In this article, a mixed norm () regularized online machine learning algorithm (MRO‐ELM) that is based on alternating direction method of multipliers (ADMM) is proposed. A linear combination of the mixed norm and the Frobenius norm regularization is applied using the ADMM framework and update formulas are derived. Graphics processing unit (GPU) accelerated version of MRO‐ELM (GPU‐MRO‐ELM) is also proposed to reduce the training time by processing appropriate parts in parallel using the implemented custom kernels. In addition, a novel automatic hyper‐parameter tuning method is incorporated to GPU‐MRO‐ELM using progressive validation with GPU acceleration. The experimental results show that the MRO‐ELM algorithm and its GPU version outperform OS‐ELM in terms of training speed, and testing accuracy. Also, compared to the cross validation, the proposed automatic hyper‐parameter tuning demonstrates dramatical reduction in the tuning time.
A Magnetocaloric Glass from an Ionic‐Liquid Gadolinium Complex
Authors: Kartal Seda , Rogez Guillaume , Robert Jérôme , Heinrich Benoît , Boudalis Athanassios K. 
Published: April 2022

Abstract[Gd5(L)16(H2O)8](Tf2N)15 was obtained from reaction of Gd2O3 with 1‐carboxymethyl‐3‐ethylimidazolium chloride (LHCl). The material was found to be an ionic liquid that freezes to glassy state on cooling to −30 °C. Variable‐temperature magnetic studies reveal the presence of weak magnetic intramolecular interactions in the glass. Isothermal variable‐field magnetization demonstrates a magnetocaloric effect (MCE), which is the first finding of such an effect in a molecular glass. This MCE is explainable by an uncoupled representation, with a magnetic entropy change of −11.36 J K−1 kg−1 at 1.8 K for a 0–7 T magnetic field change, and with a refrigerant capacity of 125.9 J kg−1, in the 1.8‐50 K interval.
Boosting the Photovoltaic Performance and Thermal Stability of Organic Solar Cells via an Insulating Fluoropolymer Additive
Authors: Zeng Hang , Hu Cetao , Wu Di , Xia Jianlong 
Published: April 2022

AbstractThe use of processing additives is one of the most widely used approaches to optimizing the bulk heterojunction (BHJ) morphology for boosting the photovoltaic performance of organic solar cells (OSCs). Recently, insulating polymer‐based additives have drawn great attention owing to the merits of good morphology‐directing abilities, simple post treatments, rich functionality and enhanced device stabilities. In this contribution, a known fluoropolymer poly‐p‐trifluoromethylstyrene (PTFS) is selected as a solid additive. Employing PTB7‐Th:PDI2 (ethylene‐annulated perylene diimide dimer) as the prototype active layer, the devices processed with PTFS shows a best power conversion efficiency (PCE) of 6.64 %, which is the highest efficiency for nude PDI2‐based OSCs. For comparison, the photovoltaic performance OSCs processed with polystyrene (PS) or without additive were investigated, PCEs of 5.29 % and 5.76 % were obtained, respectively. It is worth noting that the utilization of PTFS can also improve the thermal stability of the devices pronouncedly. Moreover, PTFS based additive also displays enhanced performance in other devices with different active layers, illustrating a good universality in OSCs. The enhancement of the PCE and thermal stability may result from the relatively lower surface energy of PTFS, which can boost the light absorbance capability as well as promote a favorable phase separation of the active layer.
Metal Oxide Based Photoelectrodes in Photoelectrocatalysis: Advances and Challenges
Authors: Wu Heng , Zhang Ding , Lei Bing‐Xin , Liu Zhao‐Qing 
Published: April 2022

AbstractMetal oxide materials show promise for application in photoelectrocatalytic conversion due to their inherent advantages involving positive reactive surface, improved light absorption capability, efficient charge separation yield, and fast charge transport channels. The unique electrical and optical properties of metal oxide based photoelectrodes have a great effect on their performance in solar cells, photoelectrocatalysis, and photocatalysis. It has been reported that the presence of defects on grain boundaries, oxygen vacancy, doping strategy, and heterojunction play a vital role in both the efficiency and durability of their photoelectric application. However, the intrinsic mechanisms at the atomic level remained unclear, which require more in‐depth understanding in terms of theoretical analysis. In this Review, we emphatically introduce the recent advances and current challenges of metal oxide‐based photoelectrodes for photoelectrocatalytic application, beneath the structure‐activity relationship of metal oxide catalysts. Then, we give a summary of the state‐of‐the‐art research in the preparation and application for the metal oxide based composite materials. Finally, we discuss key aspects, which should be addressed for design and construction.
Deep‐Red Luminescent Molybdenum(0) Complexes with Bi‐ and Tridentate Isocyanide Chelate Ligands
Authors: Herr Patrick , Schwab Alexander , Kupfer Stephan , Wenger Oliver S. 
Published: April 2022

AbstractIn octahedral complexes, molybdenum(0) has the same 4d6 valence electron configuration as ruthenium(II), which is beneficial for establishing energetically low‐lying metal‐to‐ligand charge transfer (MLCT) excited states. Those MLCT states often show luminescence, and they can furthermore undergo photoinduced electron and energy transfer reactions that are of interest in the context of solar energy conversion, sensing, or photocatalysis. Molybdenum is roughly 100 times more abundant than ruthenium, and it seems desirable to increase our fundamental understanding of the photophysical properties of complexes made from non‐precious metals. We report here on the luminescence behavior of two new homoleptic molybdenum(0) isocyanide complexes, one with three bidentate, the other with two tridentate chelate ligands. The key novelty is the incorporation of thiophene units into the ligand backbones, causing strongly red‐shifted photoluminescence with respect to comparable molybdenum(0) isocyanides with phenylene units in the ligand backbones. Combined experimental and computational studies provide detailed insight into the photophysical properties of this compound class. This work is relevant for the development of new luminescent compounds with possible applications in lighting and sensing, and it complements current research efforts on photoactive complexes with other abundant transition metal and main group elements.