bluuebunny/crossref_metadata_2025_split huggingface dataset:
Folding 2D Structures into 3D Configurations at the Micro/Nanoscale: Principles, Techniques, and Applications
Authors: Liu Zhe , Cui Ajuan , Li Junjie , Gu Changzhi 
Published: October 2018

AbstractCompared to their 2D counterparts, 3D micro/nanostructures show larger degrees of freedom and richer functionalities; thus, they have attracted increasing attention in the past decades. Moreover, extensive applications of 3D micro/nanostructures are demonstrated in the fields of mechanics, biomedicine, optics, etc., with great advantages. However, the mainstream micro/nanofabrication technologies are planar ones; therefore, they cannot be used directly for the construction of 3D micro/nanostructures, making 3D fabrication at the micro/nanoscale a great challenge. A promising strategy to overcome this is to combine the state‐of‐the‐art planar fabrication techniques with the folding method to produce 3D structures. In this strategy, 2D components can be easily produced by traditional planar techniques, and then, 3D structures are constructed by folding each 2D component to specific orientations. In this way, not only will the advantages of existing planar techniques, such as high precision, programmable patterning, and mass production, be preserved, but the fabrication capability will also be greatly expanded without complex and expensive equipment modification/development. The goal here is to highlight the recent progress of the folding method from the perspective of principles, techniques, and applications, as well as to discuss the existing challenges and future prospectives.
Programming Niche Accessibility and In Vitro Stemness with Intercellular DNA Reactions
Authors: Li Xiaojiao , Xie Xiaodong , Ma Zhiwei , Li Qian , Liu Lin , Hu Xingjie , Liu Chang , Li Bin , Wang Hui , Chen Nan , Fan Chunhai , Song Haiyun 
Published: October 2018

AbstractStem cells generally exist in low abundance and tend to lose stemness in the absence of self‐renewal signals. While extracellular‐matrix‐mimicking techniques have been developed to support stem cell proliferation, the lack of niche cells in these synthetic systems often hampers continuous stem cell expansion and maintenance of pluripotency, which are indispensable for regenerative medicine. Here, an intercellular DNA‐reaction‐programmed ESPN (expansion of stem cells with pairing niches) strategy is developed for 3D culture of mammary stem cells (MaSCs). Boolean logic operations are implemented to confer DNA‐programmed mechanical signaling and genetically engineered morphogen signaling by niche cells, resulting in sustained expansion of MaSCs in vitro. The creation of stem cell niches improves the proliferation of pluripotent cells by four times during one‐week culture. This method thus provides a novel approach for logical regulation of stemness and proliferation of stem cells for biomedicine.
Enantioseletive Fluorination of 3‐Functionalized Oxindoles Using Electron‐rich Amino Urea Catalyst
Authors: Jiang Xiaojian , Wang Haitao , He Haoquan , Wang Wei , Wang Yuqiang , Ke Zhihai , Yeung Ying‐Yeung 
Published: October 2018

AbstractAn enantioselective fluorination of 3‐functionalized oxindoles using electron‐rich amino urea catalyst is described. Various 3‐functionalized 3‐fluoro‐2‐oxindoles were obtained in good yields and enantio‐selectivity. The resulting enantioenriched 3‐methylene nitrile 3‐fluoro‐2‐oxindole product was found to inhibit indoleamine 2,3‐dioxygenase considerably.magnified image
The “In Situ Electrolyte” Concept: Using Activation Chemicals as Electrolytes for Carbon‐Based Supercapacitors
Authors: Leistenschneider Desirée , Schneidermann Christina , Hippauf Felix , Grätz Sven , Borchardt Lars 
Published: October 2018

AbstractThe “in situ electrolyte” concept displays a novel method for the fabrication of carbon‐based supercapacitors. The synthesis is designed in such way that by‐products formed during the carbon synthesis directly act as an electrolyte salt and contribute to the supercapacitor's functionality. The presented method produces materials competitive with conventional approaches but simplifies and economizes their whole synthesis and application. The concept shows how process steps can be rendered obsolete by taking a holistic view on the material synthesis and its respective application, by not treating by‐products as waste, but rather as integral part of the desired application.
Enhanced Cycling Stability of Macroporous Bulk Antimony‐Based Sodium‐Ion Battery Anodes Enabled through Active/Inactive Composites
Authors: Ruiz Olivia , Cochrane Mark , Li Manni , Yan Yan , Ma Ke , Fu Jintao , Wang Zeyu , Tolbert Sarah H. , Shenoy Vivek B. , Detsi Eric 
Published: October 2018

AbstractEngineering strategies based on “nanostructuring” and “active/inactive composites” are commonly used separately to improve the performance of alkali‐ion battery electrodes. Here, these two strategies are merged to further enhance the performance of alloy‐type alkali‐ion battery anodes. Specifically, macroporous antimony (Sb)/magnesium fluoride (MgF2) active/inactive composite material is used as a high‐performance Na‐ion battery anode. The porous Sb phase with pore size in the sub‐micrometer range acts as the electrochemically active component and the electrochemically inactive dense MgF2 phase acts as a mechanical buffer. Na‐ion battery anodes made of porous Sb/MgF2 active/inactive composites are reversibly sodiated for over 300 cycles, delivering a capacity of ≈551 mAh g−1 after 300 cycles at a C‐rate of C/2. This performance is remarkable because the porous Sb/MgF2 composite is not made of mesoporous structures. Furthermore, the cycling longevity of this porous Sb/MgF2 composite outperforms the common nanostructured Sb‐based Na‐ion battery anode materials. This good performance is attributed to the “porous active/inactive” configuration, where the dense inactive mechanical buffer phase absorbs part of the phase transformation‐induced stresses, while porosity in the active phase helps to accommodate the phase transformation induced volume expansions and electrolyte transfer into the bulk of this composite.
Congenital lumbar hernia–A feature of diabetic embryopathy?
Authors: Stevens Cathy A. , Hogue Jacob S. , Hopkin Robert J. , Lombardo Rachel C. , Schrier Vergano Samantha A. 
Published: October 2018

AbstractCongenital lumbar hernia is a rare anomaly consisting of protrusion of abdominal organs or extraperitoneal tissue through a defect in the lateral abdominal wall. The majority of affected patients have additional anomalies in a pattern described as the lumbocostovertebral syndrome. We report four patients born to mothers with poorly controlled diabetes with congenital lumbar hernia. All patients exhibited features of lumbocostovertebral syndrome with lumbar hernia, multiple vertebral segmentation anomalies in the lower thoracic and/or upper lumbar spine, rib anomalies, and unilateral renal agenesis. Additional anomalies present in the patients included preaxial hallucal polydactyly, abnormal situs, and sacral dysgenesis, anomalies known to be associated with diabetic embryopathy. At least 11 other patients have been previously reported with the lumbocostovertebral syndrome in the setting of maternal diabetes. We suggest that congenital lumbar hernia and the lumbocostovertebral syndrome are related to diabetic embryopathy.
Ranging behavior and potential for territoriality in equatorial sakis (Pithecia aequatorialis) in Amazonian Ecuador
Authors: Van Belle Sarie , Porter Amy , Fernandez‐Duque Eduardo , Di Fiore Anthony 
Published: October 2018

AbstractObjectivesTerritoriality refers to the consistent defense of an area within the home range (HR) against intrusions of conspecifics. It implies exclusive space use with low degree of overlap among neighboring groups, high site fidelity, specific ranging behavior such as high mobility relative to HR size and frequent visits of territory borders, and monitoring behavior. We examined ranging behavior and use of space to evaluate territoriality in Pithecia aequatorialis in Ecuador.Materials and methodsBetween 2005 and 2015, we monitored one main study group continuously and five additional groups for shorter periods (5 months to 2.5 years) at the Tiputini Biodiversity Station, in eastern Ecuador. We scored the location of the study groups at 20 min intervals during, on average, 5 days per month. We estimated saki HRs and core areas (CAs) using the fixed kernel density method (95 and 50%, respectively).ResultsThe average HR size was 57 ha and the average CA 14 ha. The degree of overlap between HRs of neighboring groups was low (2–9%). For the main study group, the average overlap between annual HRs was 82%. Mean daily path length across groups was 1,151 m; the defensibility index varied between 1.1 and 2.3 (values >1 are suggestive of territoriality), and the fractional monitoring rate varied between 0.06 and 0.15 (values >0.08 are suggestive of territoriality). Groups did not visit their HR borders (100 m inner buffer) more often than would be expected by chance. Travel speed and directness were comparable between the borders and the centers of groups' HRs.DiscussionOur multiyear study suggests that equatorial sakis show low degree of range overlap and high site fidelity and have the potential to be territorial, given their high mobility relative to HR size that allows for frequent border monitoring. Nevertheless, their movement patterns in border areas did not reveal evidence for monitoring behavior.
Palladium‐Catalyzed Divergent Cyclopropanation by Regioselective Solvent‐Driven C(sp3)−H Bond Activation
Authors: Chung Da Sol , Lee Jae Sung , Ryu Ho , Park Jiyong , Kim Hyunjoong , Lee Joo Hyun , Kim U Bin , Lee Won Koo , Baik Mu‐Hyun , Lee Sang‐gi 
Published: October 2018

AbstractReported is a tandem palladium‐catalyzed Heck/regioselective C(sp3)−H activation reaction for the divergent synthesis of spiro‐ and fused‐cyclopropanated indolines from N‐methallylated 2‐bromoarylamides. The regioselectivity of the C−H bond activation in the σ‐alkylPdII intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition‐state energy, leading to a bifurcation of the C−H bond activation in the σ‐alkylPdII intermediate.
Solid‐Phase Conversion of Four Stereoisomers into a Single Enantiomer
Authors: Engwerda Anthonius H. J. , Mertens Johannes C. J. , Tinnemans Paul , Meekes Hugo , Rutjes Floris P. J. T. , Vlieg Elias 
Published: October 2018

AbstractViedma ripening is an emerging method for the solid‐phase deracemization of mixtures of enantiomers. Up to now, the scope of the method has remained limited to molecules with a single stereocenter. We show here that this method can be extended to obtain a single enantiomer from a mixture of stereoisomers with two different stereocenters. In addition, we show that by using tailor‐made chiral additives, the conversion time can be reduced by a factor of 100.
Activated carbon‐supported cobalt molybdate as a heterogeneous catalyst to activate peroxymonosulfate for removal of organic dyes
Authors: Tao Xiaoming , Wu Yunhai , Wu Yunying , Zhang Bing , Sha Haitao , Cha Ligen , Liu Ningning 
Published: October 2018

Activated carbon‐supported cobalt molybdate (CoMoO4/AC) composite was conveniently fabricated using a simple hydrothermal route and high‐temperature calcination, aiming to create a novel heterogeneous catalyst for activation of peroxymonosulfate (PMS) to degrade organic dyes. The CoMoO4/AC catalyst was characterized using scanning electron microscopy, powder X‐ray diffraction, energy‐dispersive spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, elemental mapping analysis and X‐ray photoelectron spectroscopy. Efficient catalytic activity, high stability and superior reusability were observed. Additionally, the catalytic performance of CoMoO4/AC was systematically assessed through numerous controlled experiments and several operational factors, such as catalyst dosage, oxidant dosage, reaction temperature, initial pH and catalyst stability. Under the condition of CoMoO4/AC = 0.1 g l−1, oxidant = 2.0 mM, dye = 100 mg l−1, T = 25°C, the removal of methylene blue reached 90% within 60 min without pH adjustment. Batch experiment results showed that the degradation of organic dye relied upon the dosage of catalyst and oxidant and reaction temperature. Further, high catalyst and oxidant dosage, as well as high reaction temperature, were favorable for dye removal. Moreover, quenching experiments suggested that the CoMoO4/AC catalyst successfully activated PMS to generate sulfate and hydroxyl radicals. A rational mechanism is proposed based on a non‐radical process and a free radical process. The result revealed that the enhanced active sites were mainly ascribed to the synergistic effects between Co species and oxygen‐containing functional groups (especially ketone groups) on the catalyst surface. The findings of this study demonstrated the as‐prepared CoMoO4/AC composite has potential superiority for refractory organic contaminant removal from water.
Half‐sandwich Iridium(III) Benzimidazole‐Appended Imidazolium‐Based N‐heterocyclic Carbene Complexes and Antitumor Application
Authors: Han Yali , Liu Xicheng , Tian Zhenzhen , Ge Xingxing , Li Juanjuan , Gao Min , Li Yanru , Liu Yi , Liu Zhe 
Published: October 2018

AbstractA series of half‐sandwich iridium(III) benzimidazole‐appended imidazolium‐based N‐heterocyclic carbene (NHC) antitumor complexes [(η5‐Cpx)Ir(C^N)Cl]Cl, where Cpx is pentamethylcyclopentadienyl (Cp*) or its biphenyl derivative (Cpxbiph) and C^N is a NHC chelating ligand, were successfully synthesized and characterized. The IrIII complexes showed potential antitumor activity against A549 cells, at most three times more potent than cis‐platin under the same conditions. Complexes could bind to BSA by a static quenching mode, catalyzing the change of NADH to NAD+ and inducing the production of reactive oxygen species (maximum turnover number, 9.8), which play an important role in regulating cell apoptosis. Confocal microscopy showed that the complexes could specifically target lysosomes in cells with a Pearson's co‐localization coefficient 0.76 and 0.72 after 1 h and 6 h, respectively, followed an energy‐dependent cellular uptake mechanism and damaged the integrity of lysosomes. At the same time, complexes caused a marked loss of mitochondrial membrane potential.
Effect of Reynolds Number on Laminar Mixing in an Annular Tube Combining Two Crossed Secondary Flows
Authors: Bouvier Pascale , André Christophe , Russeil Serge 
Published: October 2018

AbstractTo improve static and continuous mixers, several methods have been proposed in the literature. Herein, two well‐known passive intensification configurations were applied to an annular laminar flow and numerically studied. Residence time distributions (RTDs) and Poincaré sections were examined to investigate the dispersion of the particles. These two approaches show that geometric perturbations of the walls improve the mixing level for all Reynolds numbers investigated. Above Re = 300, the increase in mixing can be attributed to chaotic advection within the flow. Finally, a general reactor model that allows the RTD in the annular tube to be predicted with high confidence is proposed.
Electrochemical and Operando Spectroscopic Studies of Sr2Fe1.5Mo0.5O6‐δ Anode Catalysts in Solid Oxide Fuel Cells Operating with Direct Alcohol Fuels
Authors: Bode Gregory L. , McIntyre Melissa D. , Neuberger Daniel M. , Walker Robert A. , Thorstensen Brad P. , Eigenbrodt Bryan C. 
Published: October 2018

AbstractThe front cover artwork is provided by the Eigenbrodt (Villanova University, USA) and Walker (Montana State University, USA) research groups. The cover picture shows a background image of the operando spectroscopy apparatus focusing the Raman laser onto the solid oxide fuel cell's Sr2Fe1.5Mo0.5O6‐δ anode catalyst at 800 °C. The forefront of this cover photo showcases Raman spectra that reveal that the anode catalyst has the ability to resists detrimental graphite deposits during fuel cell operation with direct alcohol fuels. Read the full text of the Article at 10.1002/celc.201800827.
Fluorinated Carbohydrates as Lectin Ligands: Synthesis of OH/F‐SubstitutedN‐Glycan Core Trimannoside and Epitope Mapping by 2D STD‐TOCSYreF NMR spectroscopy
Authors: Diercks Tammo , Infantino Angela Simona , Unione Luca , Jiménez‐Barbero Jesús , Oscarson Stefan , Gabius Hans‐Joachim 
Published: October 2018

AbstractGlycan‐protein interactions play an important role in a broad range of physiological processes, raising interest to elucidate the structural interplay. Yet, their dynamic nature limits the analysis by crystallography, whereas NMR spectroscopy suffers from the low1H dispersion of glycans. Therefore, their sparse fluorination and NMR screening by 1D Saturation Transfer Difference with relay to19F (STDreF) was previously proposed to exploit the superior dispersion in19F NMR spectroscopy. A new 2D STD‐TOCSYreF experiment is presented here that enables comprehensive epitope mapping of fluorinated glycans by combining the spectral resolution of19F with the spatial resolution and coverage of1H. For an illustration, the 2‐deoxy‐2‐fluoro derivative of theN‐glycan core trimannoside was synthesised and its recognition ofPisum sativumagglutinin by either of the two terminal mannose residues was confirmed. Going beyond the crystallographic information, the 2D STD‐TOCSYreF spectrum moreover visualised collateral contacts from the branching mannose and allowed to assess the ratio of both co‐existing binding modes through the α1,3‐ (67 %) and α1,6‐linked (33 %) terminal mannose moieties.
Multivalent Fucosides with Nanomolar Affinity for the Aspergillus fumigatus Lectin FleA Prevent Spore Adhesion to Pneumocytes
Authors: Lehot Victor , Brissonnet Yoan , Dussouy Christophe , Brument Sami , Cabanettes Aurore , Gillon Emilie , Deniaud David , Varrot Annabelle , Le Pape Patrice , Gouin Sébastien G. 
Published: October 2018

AbstractFleA (or AFL), a fucose lectin, was recently identified in the opportunistic mold Aspergillus fumigatus, which causes fatal lung infections in immunocompromised patients. We designed di‐, hexa‐ and octavalent fucosides with various spacer arm lengths to block the hexameric FleA through chelation. Microcalorimetry measurements showed that the ethylene glycol (EG) spacer arm length has a strong influence on the binding affinity of the divalent fucosides. The relationship between the EG length and chelate binding efficiency to FleA was explored according to polymer theory. Hexa‐ and octavalent compounds based on cyclodextrin and octameric silsesquioxane scaffolds were nanomolar FleA inhibitors, surpassing their monovalent fucose analogue by more than three orders of magnitude. Importantly, some of the fucosides were highly efficient in preventing fungal spore adhesion to bronchoepithelial cells, with half maximal inhibitory concentration values in the micromolar range. We propose that the synergistic antiadhesive effect observed can be ascribed to chelate binding to FleA and to the formation of conidium aggregates, as observed by optical microscopy. These fucosides are promising tools that can be used to better understand the role of FleA in conidia pathogenicity and host defenses against invasive aspergillosis.
Planar‐Chiral Ferrocene‐Based N‐Heterocyclic Carbene Ligands
Authors: Yoshida Kazuhiro , Yasue Risa 
Published: October 2018

AbstractIn the last few decades, N‐heterocyclic carbene (NHC) ligands, characterized by attractive features, have increased their presence in transition‐metal catalysis. However, chiral NHC ligands still require further design enhancement to realize far more exciting synthetic applications. This review documents advances in chiral NHC ligands, focusing on planar‐chiral ferrocene‐based NHCs. As the basic shape of most classes of NHC rings is planar, it seems rational to employ a planar‐chiral element in the design of chiral NHC ligands.
Molecular Basis for the Mechanical Response of Sulfa Drug Crystals
Authors: SeethaLekshmi Sunil , Kiran Mangalampalli S. R. N. , Ramamurty Upadrasta , Varughese Sunil 
Published: October 2018

AbstractComprehension of the nanomechanical response of crystalline materials requires the understanding of the elastic and plastic deformation mechanisms in terms of the underlying crystal structures. Nanoindentation data were combined with structural and computational inputs to derive a molecular‐level understanding of the nanomechanical response in eight prototypical sulfa drug molecular crystals. The magnitude of the modulus, E, was strongly connected to the non‐covalent bond features, that is, the bond strength, the relative orientation with the measured crystal facet and their disposition in the crystal lattice. Additional features derived from the current study are the following. Firstly, robust synthons well isolated by weak and dispersive interactions reduce the material stiffness; in contrast, the interweaving of interactions with diverse energetics fortifies the crystal packing. Secondly, mere observation of layered structures with orthogonal distribution of strong and weak interactions is a prerequisite, but inadequate, to attain higher plasticity. Thirdly, interlocked molecular arrangements prevent long‐range sliding of molecular planes and, hence, lead to enhanced E values. In a broader perspective, the observations are remarkable in deriving a molecular basis of the mechanical properties of crystalline solids, which can be exploited through crystal engineering for the purposeful design of materials with specific properties.
Diphenylamine‐Substituted Osmanaphthalyne Complexes: Structural, Bonding, and Redox Properties of Unusual Donor–Bridge–Acceptor Systems
Authors: Zhang Ming‐Xing , Zhang Jing , Jin Xuyang , Sun Xiaona , Yin Jun , Hartl František , Liu Sheng Hua 
Published: October 2018

AbstractDiarylamine‐substituted osmanaphthalyne complexes that feature two redox centers linked by the rigid skeleton of the metallacycle (C^C+), specifically, [OsCl2(PPh3)2{(C^C+)NAr2}][BF4−] (Ar=Ph (1 a), p‐MeOPh (1 b)) and their open‐ring precursors [OsHCl2(PPh3)2{(≡C−C(PPh3+)=CHPh)NR2}][BF4−] (Ar=Ph (2 a), p‐MeOPh (2 b)), were successfully synthesized and characterized by 1H, 13C, and 31P NMR spectroscopy, ESI‐MS, and elemental analysis. The solid‐state molecular structures of complexes 1 a and 2 a were ascertained by single‐crystal X‐ray diffraction. The Os≡C bond length in both complexes 1 a and 2 a fell within the range reported for similar osmanaphthalynes and osmium carbyne complexes, respectively. The structural parameters determined for complex 1 a, which were successfully reproduced by theoretical calculations, point to a π‐delocalized metallacycle structure. The purple color of compounds 1 a and b was explained by the diarylamine→Os(metallacycle) charge‐transfer absorption in the visible region. The neutral, one‐electron‐oxidized and one‐electron‐reduced states of compounds 1 a, b, and a reference complex that lacked the diarylamine substituent, [OsCl2(PPh3)2{(C^C+)}][BF4−] (1′), were investigated by cyclic and square‐wave voltammetry, UV/Vis/NIR spectroelectrochemistry, and DFT calculations. The spin density in singly oxidized complexes [1 a]+ and [1 b]+ predominantly resided on the aminyl segment, with osmium involvement controlled by the diphenylamine substitution. Spin density in stable, singly‐reduced [1′]− was distributed mainly over the osmanaphthalyne metallacycle.