bluuebunny/crossref_metadata_2025_split huggingface dataset:
Complex Growth Behavior of Li Dendrites in Al2O3 Nanoparticles‐Driven Viscoelastic Electrolytes for Lithium Metal Batteries: Dynamic versus Quasistatic Rheology
Authors: Park Kyobin , Lee Myungjae , Kim Dong‐Min , Kwon Bomee , Lee Jeonghyeop , Jo Seunghyeon , Nam Jaewook , Lee Kyu Tae 
Published: July 2021

AbstractViscoelastic electrolytes have been focused as innovative electrolytes for Li metal batteries because of their unique mechanical and electrochemical properties compared to conventional Newtonian liquid electrolytes. However, the role of the mechanochemical properties of viscoelastic electrolytes in the electrochemical performance of Li metal has not been fully understood yet. In particular, dynamic rheology of viscoelastic electrolytes has not been considered one of significant factors accelerating Li dendrites growth. Herein, Al2O3 nanoparticles‐driven viscoelastic electrolytes are introduced to improve the electrochemical performance of Li metal. In contrast to conventional Newtonian liquid electrolytes, viscoelastic electrolytes significantly suppress Li dendrites growth during cycling, resulting in excellent electrochemical performance, such as stable capacity retention over 400 cycles. Moreover, the complex growth mechanism of Li dendrites in viscoelastic electrolytes is demonstrated in terms of dynamic versus quasistatic rheology. Dynamic rheology prevails over quasistatic rheology as Al2O3 weight fraction and current density is increased in viscoelastic electrolytes. Dynamic rheology gives rise to spatial non‐uniformity in the mechanical and rheological properties of viscoelastic electrolytes, leading to promoting Li dendrites growth due to the uneven distribution of local current density on the Li metal surface. These findings provide fundamental insights into strategies to design advanced electrolytes for Li metal batteries.
Copper‐Catalyzed Chemo‐ and Diastereoselective 1,3‐Dipolar Cycloaddition of Carbonyl Ylide and Aldehyde‐Tethered‐Cyclohexadienone to Access Polycyclic Systems
Authors: Peng Shiyong , Zhang Hong , Zhu Yuqi , Zhou Ting , He Jieyin , Chen Nuan , Lang Ming , Li Hongguang , Wang Jian 
Published: July 2021

AbstractA copper‐catalyzed tandem intermolecular ylide formation/intramolecular cycloaddition of diazo compounds and aldehyde‐tethered‐cyclohexadienones was reported, chemo‐ and diastereoselectively providing oxapolycyclic frameworks in moderate to excellent yields under mild conditions. This reaction creates two C−C bonds and one C−O bond with five stereocentres including two all‐carbon quaternary centres. Moreover, the late‐stage diversification of products can be realized via chemoselective substitutions.magnified image
Multicomponent Catalytic Enantioselective Synthesis of Isoxazolidin‐5‐Ones
Authors: Annibaletto Julien , Martzel Thomas , Levacher Vincent , Oudeyer Sylvain , Brière Jean‐François 
Published: July 2021

AbstractWe report herein a strategy to afford a multicomponent catalytic enantioselective synthesis of β‐substituted isoxazolidin‐5‐ones via a KMC process promoted by a suited cupreine used as bifunctional organocatalyst. The hydroxamic acid component, with a sterically hindered amide moiety, proved to be key for the successful formation and transformation of the obtained original N‐amide isoxazolidin‐5‐ones.magnified image
Mentoring Children in Foster Care: Examining Relationship Histories as Moderators of Intervention Impact on Children’s Mental Health and Trauma Symptoms
Authors: Weiler Lindsey M. , Lee Sun‐Kyung , Zhang Jingchen , Ausherbauer Kadie , Schwartz Sarah E. O. , Kanchewa Stella S. , Taussig Heather N. 
Published: July 2021

AbstractMentoring‐based interventions show promise among children in foster care, but previous research suggests that some benefit more than others. Because children in foster care experience relationship disruptions that could affect mentoring effectiveness, we examined whether children’s relational histories at baseline (i.e., relationship quality with birth parents, relationship quality with foster parents, caregiver instability, and previous mentoring experience) moderated the impact of a mentoring intervention on children’s mental health, trauma symptoms, and quality of life. Participants included 426 racially and ethnically diverse children (age: 9–11; 52% male) who participated in a randomized controlled trial of the Fostering Healthy Futures program (FHF), a 9‐month one‐to‐one mentoring and skills group intervention. Results showed that relationship quality with foster parents and prior mentoring experience did not moderate intervention impact. Relationship quality with birth parents and caregiver instability pre‐program, however, moderated the effect on some outcomes. The impact on quality of life was stronger for children with weaker birth parent relationships and fewer caregiver changes. Likewise, the impact on trauma symptoms was stronger for those with fewer caregiver changes. Overall, FHF seems to positively impact children with varied relational histories, yet some may derive more benefits – particularly those with fewer caregiver changes pre‐program.
Mortality in the Western Pyrenees during the 18th century. Data from the parish register of the village of Arudy (1741–1800), Bearn, France
Authors: Dugène Jean‐Pierre , Bauduer Frédéric 
Published: July 2021

AbstractObjectivesWe aimed to determine the public health status of an 18th century mountain locality.MethodsWe collected data registered in parish death certificates from Arudy, a small village in the French Pyrenees during the period 1741–1800.ResultsTwo thousand and six hundred and sixty‐three cases were studied. About 50% of deaths occurred during the first 10 years of life. There were some particularities in deaths pattern with regards to age categories between males and females and seasonality. A fraction of individuals died at advanced ages (24.1% ≥60 years and of note three cases ≥100 years). The cause of death was reported in only 2.2% of cases (nearly always sudden fatalities). Maternal mortality could not be precisely determined. Throughout this period we identified a series of mortality crises which targeted mostly children and were probably in relation with undocumented epidemics.ConclusionsThese data offer some clues about the sanitary situation of an European mountain community during the 18th century.
Cobalt‐Catalysed, Ligand‐Controlled Regiodivergent Alkene Hydrosilylation
Authors: Docherty Jamie H. , Dominey Andrew P. , Thomas Stephen P. 
Published: July 2021

AbstractAlkene hydrosilylation is amongst the largest industrial homogenous catalysis processes. Cobalt catalysis offers a sustainable alternative to commonly used platinum catalysts to achieve this transformation. Using two bisiminopyridine cobalt(II) catalysts the regiodivergent hydrosilylation of alkenes has been developed. Variation of pre‐catalyst activator and ligand substituents were investigated to enable the controlled, regiodivergent hydrosilylation of both aryl‐ and alkyl‐substituted alkenes with phenylsilane. In contrast to other regiodivergence strategies, excellent regioselectivity for either isomer was achieved using the same ligand class but differing by a single methyl group (ethylvs isopropyl).
Designable Assembly of Aluminum Molecular Rings for Sequential Confinement of Iodine Molecules
Authors: Liu Chen‐Hui , Fang Wei‐Hui , Sun Yayong , Yao Shuyang , Wang San‐Tai , Lu Dongfei , Zhang Jian 
Published: July 2021

AbstractAlthough numerous adsorbent materials have been reported for the capture of radioactive iodine, there is still demand for new absorbents that are economically viable and can be prepared by reliable synthetic protocols. Herein, we report a coordination‐driven self‐assembly strategy towards adsorbents for the sequential confinement of iodine molecules. These adsorbents are versatile heterometallic frameworks constructed from aluminum molecular rings of varying size, flexible copper ions, and conjugated carboxylate ligands. Additionally, these materials can quickly remove iodine from cyclohexane solutions with a high removal rate (98.8 %) and considerable loading capacity (555.06 mg g−1). These heterometallic frameworks provided distinct pore sizes and binding sites for iodine molecules, and the sequential confinement of iodine molecules was supported by crystallographic data. This work not only sets up a bridge between molecular rings and infinite porous networks but also reveals molecular details for the underlying host–guest binding interactions at crystallographic resolution.
Asymmetric Enamide–Imine Tautomerism in the Kinetic Resolution of Tertiary Alcohols
Authors: Tang Mengyao , Gu Huanchao , He Shunlong , Rajkumar Subramani , Yang Xiaoyu 
Published: July 2021

AbstractAn efficient protocol for kinetic resolution of tertiary alcohols has been developed through an unprecedented asymmetric enamide‐imine tautomerism process enabled by chiral phosphoric acid catalysis. A broad range of racemic 2‐arylsulfonamido tertiary allyl alcohols could be kinetically resolved with excellent kinetic resolution performances (with s‐factor up to >200). This method is particularly effective for a series of 1,1‐dialkyl substituted allyl alcohols, which produced chiral tertiary alcohols that would be difficult to access via other asymmetric methods. Facile and versatile transformations of the chiral α‐hydroxy imine and enamide products, especially the efficient stereodivergent synthesis of all four stereoisomers of β‐amino tertiary alcohols using one enantiomer of the catalyst, demonstrated the value of this kinetic resolution method.
Aggregation‐Induced Emissive Carbon Dots Gels for Octopus‐Inspired Shape/Color Synergistically Adjustable Actuators
Authors: Wu Shuangshuang , Shi Huihui , Lu Wei , Wei Shuxin , Shang Hui , Liu Hao , Si Muqing , Le Xiaoxia , Yin Guangqiang , Theato Patrick , Chen Tao 
Published: July 2021

AbstractSome living organisms such as the octopus have fantastic abilities to simultaneously swim away and alter body color/morphology for disguise and self‐protection, especially when there is a threat perception. However, it is still quite challenging to construct artificial soft actuators with octopus‐like synergistic shape/color change and directional locomotion behaviors, but such systems could enhance the functions of soft robotics dramatically. Herein, we proposed to utilize unique hydrophobic carbon dots (CDs) with rotatable surficial groups to construct the aggregation‐induced emission (AIE) active glycol CDs polymer gel, which could be further employed to be interfacially bonded to an elastomer to produce anisotropic bilayer soft actuator. When putting the actuator on a water surface, glycol spontaneously diffused out from the gel layer to allow water intake, resulting in a color change from a blue dispersion fluorescence to red AIE and a shape deformation, as well as a large surface tension gradient that can promote its autonomous locomotion. Based on these findings, artificial soft swimming robots with octopus‐like synergistic shape/color change and directional swimming motion were demonstrated. This study provides an elegant strategy to develop advanced multi‐functional bio‐inspired intelligent soft robotics.
Schottky Barrier‐Induced Surface Electric Field Boosts Universal Reduction of NOx− in Water to Ammonia
Authors: Gao Peng , Xue Zhong‐Hua , Zhang Shi‐Nan , Xu Dong , Zhai Guang‐Yao , Li Qi‐Yuan , Chen Jie‐Sheng , Li Xin‐Hao 
Published: July 2021

AbstractNOx− reduction acts a pivotal part in sustaining globally balanced nitrogen cycle and restoring ecological environment, ammonia (NH3) is an excellent energy carrier and the most valuable product among all the products of NOx− reduction reaction, the selectivity of which is far from satisfaction due to the intrinsic complexity of multiple‐electron NOx−‐to‐NH3 process. Here, we utilize the Schottky barrier‐induced surface electric field, by the construction of high density of electron‐deficient Ni nanoparticles inside nitrogen‐rich carbons, to facilitate the enrichment and fixation of all NOx− anions on the electrode surface, including NO3− and NO2−, and thus ensure the final selectivity to NH3. Both theoretical and experimental results demonstrate that NOx− anions were continuously captured by the electrode with largely enhanced surface electric field, providing excellent Faradaic efficiency of 99 % from both electrocatalytic NO3− and NO2− reduction. Remarkably, the NH3 yield rate could reach the maximum of 25.1 mg h−1 cm−2 in electrocatalytic NO2− reduction reaction, outperforming the maximum in the literature by a factor of 6.3 in neutral solution. With the universality of our electrocatalyst, all sorts of available electrolytes containing NOx− pollutants, including seawater or wastewater, could be directly used for ammonia production in potential through sustainable electrochemical technology.
Laparoscopic‐Assisted Ventriculoperitoneal Shunt Placement: A Less Invasive Approach to Treating Hydrocephalus
Authors: Karasin Beth , Eskuchen Lauren , Hardinge Tara , Watkinson Johanna , Grzelak Monica , Boyce Marissa 
Published: July 2021

ABSTRACTHydrocephalus is caused by the disruption of the normal flow of cerebrospinal fluid (CSF), which results in a buildup of CSF. Hydrocephalus comprises two key categories: communicating and noncommunicating. Normal‐pressure hydrocephalus, a type of communicating hydrocephalus, currently has no cure; the main treatment option is ventriculoperitoneal shunt (VPS) placement surgery. This procedure is performed to reestablish the balance between CSF production, flow, and absorption. Recently, general surgeons have begun assisting the neurosurgeon by placing the distal or abdominal end of the shunt using a laparoscopic technique. This article briefly reviews the pathophysiology and treatment options for hydrocephalus; presents a thorough review of the laparoscopic‐assisted VPS placement procedure, as well as the expected perioperative course and care considerations; and concludes with a case study of a 68‐year‐old patient who undergoes a laparoscopic‐assisted VPS placement.
Nanomolar potency of imidazo[2,1‐b]thiazole analogs as indoleamine 2,3‐dioxygenase inhibitors
Authors: Ewida Menna A. , Ewida Heba A. , Ahmed Mahmoud S. , Allam Heba Abdelrasheed , ElBagary Ramzia I. , George Riham F. , Georgey Hanan H. , El‐Subbagh Hussein I. 
Published: July 2021

AbstractNovel series of imidazo[2,1‐b]thiazole analogs were designed, synthesized, and biologically evaluated as indoleamine 2,3‐dioxygenase (IDO1) inhibitors. Imidazo[2,1‐b]thiazoles 6, 7, and 8 showed inhibitory profiles against IDO1 at IC50 values of 68.48, 82.39, and 48.48 nM, respectively, compared with IDO5L at IC50 67.40 nM. Benzo[d]imidazo[2,1‐b]thiazoles 17, 20, and 22 showed promising IDO1 inhibition at IC50 values of 53.58, 53.16, and 57.95 nM, respectively. Compound 7 showed a growth‐inhibitory profile at GI of 39.33% against the MCF7 breast cancer cell line, while 8 proved lethal to ACHN renal cancer cells. Cells treated with compounds 17 and 22 showed a typical apoptosis pattern of DNA fragments that reflected the G0/G1, S, and G2/M phases of the cell cycle, together with a pre‐G1 phase corresponding to apoptotic cells, which indicates that cell growth arrest occurred at the S phase. Molecular modeling simulations validated the potential of benzo[d]imidazo[2,1‐b]thiazole analogs to chelate iron(III) within the IDO1 binding pocket and, hence, to have a better binding affinity via hydrophobic–hydrophobic interactions.
A Photoluminescent Ag10Cu6 Cluster Stablized by a PNNP Ligand and Phenylacetylides Selectively and Reversibly Senses Ammonia in Air and Water
Authors: Wang Yuwei , Yan Jia‐Jun , Hu Shengnan , James Young David , Li Hong‐Xi , Ren Zhi‐Gang 
Published: July 2021

AbstractA photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 (1, bdppthi=N,N’‐bis(diphenylphosphanylmethyl)‐tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in‐situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste‐gas and waste‐water.
NO Electroreduction by Transition Metal Dichalcogenides with Chalcogen Vacancies
Authors: Tursun Mamutjan , Wu Chao 
Published: July 2021

AbstractNitric oxide electroreduction reaction (NOER) is one of the most attractive routes for ammonia synthesis and NOx‐related pollutant treatment. However, current research on NOER catalysts mainly focus on noble metals and single atom catalysts, while low‐cost transition metal dichalcogenides (TMDs) are rarely considered, let alone their product selectivity. Herein, using first‐principles calculations, we systematically investigate the performance of a series of single‐layer TMDs (MoS2, MoSe2, MoTe2, TaTe2 and WTe2) in the 1T’ phase as electrocatalysts for NOER. Our results reveal that defective 1T’‐MoS2 and 1T’‐MoSe2 monolayers (with the most common sulphur and selenium vacancies, respectively) exhibit excellent activity for NOER as well as high selectivity for ammonia, which can be correspondingly yielded at 0 and −0.06 V potentials, comparable to the best Pt‐based and single atom catalysts. Furthermore, these two catalysts efficiently suppress the competing hydrogen evolution reaction (HER). Thus, single‐layer TMDs synthesized with chalcogen vacancies may serve as efficient catalysts for electrochemical ammonia synthesis from pollutants and electrocatalytic denitrification.
Ternary Conductance Switching Realized by a Pillar[5]arene‐Functionalized Two‐Dimensional Imine Polymer Film
Authors: Song Yaru , Feng Guangyuan , Sun Chenfang , Liang Qiu , Wu Lingli , Yu Xi , Lei Shengbin , Hu Wenping 
Published: July 2021

AbstractNowadays, most manufacturing memory devices are based on materials with electrical bistability (i. e., “0” and “1”) in response to an applied electric field. Memory devices with multilevel states are highly desired so as to produce high‐density and efficient memory devices. Herein, we report the first multichannel strategy to realize a ternary‐state memristor. We make use of the intrinsic sub‐nanometer channel of pillar[5]arene and nanometer channel of a two‐dimensional imine polymer to construct an active layer with multilevel channels for ternary memory devices. Low threshold voltage, long retention time, clearly distinguishable resistance states, high ON/OFF ratio (OFF/ON1/ON2=1 : 10 : 103), and high ternary yield (75 %) were obtained. In addition, the flexible memory device based on 2DPTPAZ+TAPB can maintain its stable ternary memory performance after being bent 500 times. The device also exhibits excellent thermal stability and can tolerate a temperature as high as 300 °C. It is envisioned that the results of this work will open up possibilities for multistate, flexible resistive memories with good thermal stability and low energy consumption, and broaden the application of pillar[n]arene.
Facile Synthesis of Platinum Right Bipyramids by Separating and Controlling the Nucleation Step in a Continuous Flow System
Authors: Chen Ruhui , Shi Yifeng , Xie Minghao , Xia Younan 
Published: July 2021

AbstractColloidal synthesis of metal nanocrystals with controlled shapes and internal structures calls for a tight control over both the nucleation and growth processes. Here we report a method for the facile synthesis of Pt right bipyramids (RBPs) by separating nucleation from growth and controlling the nucleation step in a continuous flow reactor. Specifically, homogeneous nucleation was thermally triggered by introducing the reaction solution into a tubular flow reactor held at an elevated temperature to generate singly‐twinned seeds. At a lower temperature, the singly‐twinned seeds were protected from oxidative etching to allow their slow growth and evolution into RBPs while additional nucleation of undesired seeds could be largely suppressed to ensure RBPs as the main product. Further investigation indicated that the internal structure and growth pattern of the seeds were determined by the temperatures used for the nucleation and growth steps, respectively. The Br− ions involved in the synthesis also played a critical role in the generation of RBPs by serving as a capping agent for the Pt{100} facets while regulating the reduction kinetics through coordination with the Pt(IV) ions.
Efficient Entropy‐Driven Inhibition of Dipeptidyl Peptidase III by Hydroxyethylene Transition‐State Peptidomimetics
Authors: Ivkovic Jakov , Jha Shalinee , Lembacher‐Fadum Christian , Puschnig Johannes , Kumar Prashant , Reithofer Viktoria , Gruber Karl , Macheroux Peter , Breinbauer Rolf 
Published: July 2021

AbstractDipeptidyl peptidase III (DPP3) is a ubiquitously expressed Zn‐dependent protease, which plays an important role in regulating endogenous peptide hormones, such as enkephalins or angiotensins. In previous biophysical studies, it could be shown that substrate binding is driven by a large entropic contribution due to the release of water molecules from the closing binding cleft. Here, the design, synthesis and biophysical characterization of peptidomimetic inhibitors is reported, using for the first time an hydroxyethylene transition‐state mimetic for a metalloprotease. Efficient routes for the synthesis of both stereoisomers of the pseudopeptide core were developed, which allowed the synthesis of peptidomimetic inhibitors mimicking the VVYPW‐motif of tynorphin. The best inhibitors inhibit DPP3 in the low μM range. Biophysical characterization by means of ITC measurement and X‐ray crystallography confirm the unusual entropy‐driven mode of binding. Stability assays demonstrated the desired stability of these inhibitors, which efficiently inhibited DPP3 in mouse brain homogenate.
Aminotroponiminates: Impact of the NO2 Functional Group on Coordination, Isomerisation, and Backbone Substitution
Authors: Hanft Anna , Rottschäfer Dennis , Wieprecht Nele , Geist Felix , Radacki Krzysztof , Lichtenberg Crispin 
Published: July 2021

AbstractAminotroponiminate (ATI) ligands are a versatile class of redox‐active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron‐withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro‐substituent in the backbone. It is demonstrated that the NO2 group actively contributes to the coordination chemistry of these complexes, effectively competing with the N,N‐binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first “naked” (i. e., without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N‐coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT‐)NMR spectroscopy, single‐crystal X‐ray diffraction analysis, and DFT calculations.