bluuebunny/crossref_metadata_2025_split huggingface dataset:
Real‐Time Cellular Cytochrome C Monitoring through an Optical Microfiber: Enabled by a Silver‐Decorated Graphene Nanointerface
Authors: Li Hongtao , Huang Yunyun , Chen Chaoyan , Xiao Aoxiang , Hou Guanhua , Huang Yugang , Feng Xinhuan , Guan Bai‐Ou 
Published: June 2018

AbstractThe translocation of cytochrome c (cyt c) from mitochondria and out of cell is an important signal of cell apoptosis. Monitoring this process extracellularly without invasion and cytotoxicity to cells is of great importance to understand certain diseases at the cellular level; however, it requires sensors with ultrahigh sensitivity and miniature size. This study reports an optical microfiber aptasensor with a silver‐decorated graphene (Ag@RGO) nanointerface for real‐time cellular cyt c monitoring. Owing to an interfacial sensitization effect coupled with the plasmonic electromagnetic enhancement of silver nanoparticles and chemical enhancement of graphene platforms, which enhances the energy density on microfiber surface obviously, the lowest limit of detection achieved is 6.82 × 10−17m, which is approximately five orders of magnitude lower than those of existing methods. This microfiber successfully detects the ultralow concentrations of cyt c present during the initial stage of apoptosis in situ. As the microfiber functionalized by Ag@RGO nanointerface can be varied to meet any specific detection objective, this work opens up new opportunities to quantitatively monitor biological functions occurring at the cellular level.
Nahinfrarotaktive Bleichalkogenid‐Quantenpunkte: Herstellung, postsynthetischer Ligandenaustausch und Anwendungen in Solarzellen
Authors: Shrestha Aabhash , Batmunkh Munkhbayar , Tricoli Antonio , Qiao Shi Zhang , Dai Sheng 
Published: June 2018

AbstractQuantenpunkte (QDs) von Bleichalkogeniden (z. B. PbS, PbSe und PbTe) sind nahinfrarotaktive Materialien, die großes Potenzial für einen breiten Bereich von Anwendungen wie Photovoltaik, Optoelektronik, Sensorik und Bioelektronik zeigen. Oberflächenliganden spielen eine wesentliche Rolle bei der Herstellung und postsynthetischen Modifizierung von QDs sowie bei deren Einsatz in Anwendungen. Daher ist ein gutes Verständnis des Einflusses von Oberflächenliganden auf die Synthese und Eigenschaften von QDs für deren Anwendungen in verschiedenen Bauelementen unerlässlich. Der vorliegende Aufsatz beschäftigt sich mit der Anwendung kolloidaler Synthesetechniken zur Herstellung von bleichalkogenidbasierten QDs. Der Schwerpunkt liegt auf dem Einfluss von Oberflächenliganden auf die QD‐Synthese sowie dem Ligandenaustausch in Lösung. Angesichts der Bedeutung von Bleichalkogenid‐QDs als möglichen Lichtsammlern richten wir unsere Aufmerksamkeit besonders auf die aktuellen Fortschritte von PV‐Anwendungen mit diesen QDs.
Organic‐Free Synthesis of Silicoaluminophosphate Molecular Sieves
Authors: Park Sung Hwan , Choi Wanuk , Choi Hyun June , Hong Suk Bong 
Published: June 2018

AbstractSilicoaluminophosphate (SAPO) molecular sieves are an important class of microporous materials and are useful for industrial catalysis and separations. They have been synthesized exclusively by the use of expensive and environmentally unfriendly organic structure‐directing agents. Now the synthesis of SAPO molecular sieves is reported with MER, EDI, GIS, and ANA topologies under wholly inorganic conditions. Multinuclear MAS NMR analyses demonstrate the presence of Si, Al, and P atoms in their frameworks. These SAPO materials all have unusually high framework charge densities (0.25–0.46), owing to the small size of alkali metal cations used as an inorganic structure‐directing agent. A continuous Si increase in the synthesis gel for MER‐type SAPO molecular sieves led to the formation of framework Si(0Al) units, decreasing the number of extra‐framework cations per unit cell and thus making the resulting solid useful for CO2 adsorption.
Charge Separation in a Multifunctionalized Framework of Hydrogen‐Bonded Periodic Mesoporous Organosilica
Authors: Mizoshita Norihiro , Inagaki Shinji 
Published: June 2018

AbstractIntegration of functional molecular parts into nanoporous materials in a state that allows intermolecular charge or energy transfer is one of the key approaches to the development of photofunctional and electroactive materials. Herein, we report charge separation in a functionalized framework of a periodic mesoporous organosilica (PMO) self‐assembled by hydrogen bonds. Electroactive π‐conjugated organic species with different electron‐donating and electron‐accepting properties were selectively fixed onto the external surface of a nanoparticulate PMO, within the pore wall, and onto the surface of the internal mesopore. UV irradiation of the modified PMO resulted in photoinduced electron transfer and charge separation from the external surface to the pore wall and from the pore wall to the surface of the internal mesopores. These results suggest the high potential of multifunctionalized PMOs in the construction of photocatalytic reaction fields.
Much ado about nothing: The zero effect in life‐saving decisions
Authors: Zhang Yufeng , Slovic Paul 
Published: June 2018

AbstractZero is a special value in our daily lives, and previous research on how zero values affect decision making leaves many questions to be explored. The present research examined the zero effect in life‐saving decisions and found that people expressed strong preferences for options offering a possibility that no one will die, even when the expected loss was relatively high. The prominence effect (the notion that the option with possibly zero deaths is easy to defend and justify) was proposed as one possible explanation. Furthermore, we also found that the zero effect in these life‐saving decisions occurs only in loss framing rather than gain framing. We discuss the relationships between the zero effect, framing, and evaluation mode in life saving and other domains.
Improved two‐stage group sequential procedures for testing a secondary endpoint after the primary endpoint achieves significance
Authors: Li Huiling , Wang Jianming , Luo Xiaolong , Grechko Janis , Jennison Christopher 
Published: June 2018

AbstractIn two‐stage group sequential trials with a primary and a secondary endpoint, the overall type I error rate for the primary endpoint is often controlled by an α‐level boundary, such as an O'Brien‐Fleming or Pocock boundary. Following a hierarchical testing sequence, the secondary endpoint is tested only if the primary endpoint achieves statistical significance either at an interim analysis or at the final analysis. To control the type I error rate for the secondary endpoint, this is tested using a Bonferroni procedure or any α‐level group sequential method. In comparison with marginal testing, there is an overall power loss for the test of the secondary endpoint since a claim of a positive result depends on the significance of the primary endpoint in the hierarchical testing sequence. We propose two group sequential testing procedures with improved secondary power: the improved Bonferroni procedure and the improved Pocock procedure. The proposed procedures use the correlation between the interim and final statistics for the secondary endpoint while applying graphical approaches to transfer the significance level from the primary endpoint to the secondary endpoint. The procedures control the familywise error rate (FWER) strongly by construction and this is confirmed via simulation. We also compare the proposed procedures with other commonly used group sequential procedures in terms of control of the FWER and the power of rejecting the secondary hypothesis. An example is provided to illustrate the procedures.
Rational design of thiolase substrate specificity for metabolic engineering applications
Authors: Bonk Brian M. , Tarasova Yekaterina , Hicks Michael A. , Tidor Bruce , Prather Kristala L. J. 
Published: June 2018

AbstractMetabolic engineering efforts require enzymes that are both highly active and specific toward the synthesis of a desired output product to be commercially feasible. The 3‐hydroxyacid (3HA) pathway, also known as the reverse β‐oxidation or coenzyme‐A‐dependent chain‐elongation pathway, can allow for the synthesis of dozens of useful compounds of various chain lengths and functionalities. However, this pathway suffers from byproduct formation, which lowers the yields of the desired longer chain products, as well as increases downstream separation costs. The thiolase enzyme catalyzes the first reaction in this pathway, and its substrate specificity at each of its two catalytic steps sets the chain length and composition of the chemical scaffold upon which the other downstream enzymes act. However, there have been few attempts reported in the literature to rationally engineer thiolase substrate specificity. In this study, we present a model‐guided, rational design study of ordered substrate binding applied to two biosynthetic thiolases, with the goal of increasing the ratio of C6/C4 products formed by the 3HA pathway, 3‐hydroxy‐hexanoic acid and 3‐hydroxybutyric acid. We identify thiolase mutants that result in nearly 10‐fold increases in C6/C4 selectivity. Our findings can extend to other pathways that employ the thiolase for chain elongation, as well as expand our knowledge of sequence–structure–function relationship for this important class of enzymes.
Exposure to attachment narratives dynamically modulates cortical arousal during the resting state in the listener
Authors: Borchardt Viola , Surova Galina , van der Meer Johan , Bola Michał , Frommer Jörg , Leutritz Anna Linda , Sweeney‐Reed Catherine M. , Buchheim Anna , Strauß Bernhard , Nolte Tobias , Olbrich Sebastian , Walter Martin 
Published: June 2018

AbstractBackgroundAffective stimulation entails changes in brain network patterns at rest, but it is unknown whether exogenous emotional stimulation has a prolonged effect on the temporal dynamics of endogenous cortical arousal. We therefore investigated differences in cortical arousal in the listener following stimulation with different attachment‐related narratives.MethodsResting‐state EEG was recorded from sixteen healthy subjects for ten minutes each with eyes closed: first at baseline and then after passively listening to three affective narratives from strangers about their early childhood experiences (prototypical for insecure‐dismissing, insecure‐preoccupied, and secure attachment). Using the VIGALL 2.1 algorithm, low or high vigilance stages in consecutive EEG segments were classified, and their dynamic profile was analyzed. Questionnaires assessed the listeners’ emotional response to the content of the narrative.ResultsAs a general effect of preceding affective stimulation, vigilance following the stimulation was significantly elevated compared to baseline rest, and carryover effects in dynamic vigilance profiles were observed. A difference between narrative conditions was revealed for the insecure‐dismissing condition, in which the decrease in duration of high vigilance stages was fastest compared to the other two conditions. The behavioral data supported the observation that especially the insecure narratives induced a tendency in the listener to affectively disengage from the narrative content.DiscussionThis study revealed carryover effects in endogenous cortical arousal evoked by preceding affective stimulation and provides evidence for attachment‐specific dynamic alterations of brain states and individual differences in emotional reactivity.
Peptides Derived from Histone 3 and Modified at Position 18 Inhibit Histone Demethylase KDM6 Enzymes
Authors: Jones Sarah E. , Olsen Lars , Dorosz Jerzy , Seger Signe T. , Andersson Jan L. , Kristensen Line H. , Gajhede Michael 
Published: June 2018

AbstractThe KDM6 subfamily of histone lysine demethylases has recently been implicated as a putative target in the treatment of a number of diseases; this makes the availability of potent and selective inhibitors important. Due to high sequence similarity of the catalytic domain of Jumonji C histone demethylases, the development of small‐molecule, family‐specific inhibitors has, however, proven challenging. One approach to achieve the selective inhibition of these enzymes is the use of peptides derived from the substrate, the histone 3 C terminus. Here we used computational methods to optimize such inhibitors of the KDM6 family. Through natural amino acid substitution, it is shown that a K18I variant of a histone H3 derived peptide significantly increases affinity towards the KDM6 enzymes. The crystal structure of KDM6B in complex with a histone 3 derived K18I peptide reveals a tighter fit of the isoleucine side chain, compared with that of the arginine. As a consequence, the peptide R17 residue also has increased hydrophilic interactions. These interactions of the optimized peptide are likely to be responsible for the increased affinity to the KDM6 enzymes.
Granulomatous fasciitis followed by morphea profunda: Is granulomatous fasciitis part of a spectrum of deep morphea? A case report and review of the literature
Authors: Christensen Angie , Di Loreto Christina , Smitaman Edward , Paravar Taraneh , Jones Karra A. , Guma Monica 
Published: June 2018

Key Clinical MessageAlthough eosinophilic fasciitis is known to be part of the deep morphea spectrum, this first report of the coexistence of granulomatous fasciitis and morphea profunda suggests that granulomatous fasciitis may also be a part of the spectrum of deep morphea.
Visceral leishmaniasis in acute myeloid leukemia revealed on peripheral blood smear
Authors: Moniot Maxime , Loyens Maxime , Mary Charles , L’Ollivier Coralie 
Published: June 2018

Key Clinical MessageImages of parasitic forms of Leishmania infantum are typical in the hands of a skilled expert but should be known by biologists of Hematology Department. In an endemic region, the diagnosis of visceral leishmaniasis (VL) must be considered because of its potential role in accelerating hematological malignancy.
Materials Based on Antimony and Bismuth for Sodium Storage
Authors: Li Xinyan , Ni Jiangfeng , Savilov S. V. , Li Liang 
Published: June 2018

AbstractSodium‐ion batteries (SIBs) that efficiently store electricity into chemical energy have been extensively pursued because of their great potential for low‐cost and large‐scale stationary application such as smart grid and renewable energy. Successful deployment of SIBs requires efficient anode materials that could store Na+ ions via a reversible way at reasonable rates. Materials based on antimony and bismuth are capable of storing a high‐concentration of Na+ ions via a reversible alloying reaction at suitable redox potentials, and thus have drawn substantial attention. However, these electrode materials are facing significant technical challenges, such as poor conductivity, multiple phase transformation, and severe volume swelling and shrinking, which make efficient materials design a necessity. In this review, we will give a latest overview of research progress in the design and application of electrode materials based on antimony and bismuth, and offer some value insights into their future development in sodium storage.
Topology‐Selective, Fluorescent “Light‐Up” Probes for G‐Quadruplex DNA Based on Photoinduced Electron Transfer
Authors: Xie Xiao , Reznichenko Oksana , Chaput Ludovic , Martin Pascal , Teulade‐Fichou Marie‐Paule , Granzhan Anton 
Published: June 2018

AbstractSix novel probes were prepared by covalent attachment of a G4‐DNA ligand (bis(quinolinium) pyridodicarboxamide; PDC) to various coumarin or pyrene fluorophores. In the absence of DNA, the fluorescence of all probes is quenched due to intramolecular photoinduced electron transfer (PET), as evidenced by photophysical and electrochemical studies, molecular modeling, and DFT calculations. All probes demonstrate similarly high thermal stabilization of various G4‐DNA substrates belonging to different folding topologies, as assessed by fluorescence melting experiments; however, their fluorimetric response is strongly heterogeneous with respect to the structures of the probes and G4‐DNA targets. Thus, the probes containing the 7‐diethylaminocoumarin fluorophore demonstrate significant fluorescence enhancement in the presence of G4‐DNA, with the strongest “light‐up” response (20‐ to 180‐fold) observed for antiparallel G4 structures as well as for hybrid G4 structures, formed by the variants of human telomeric sequence and capable of a conformation change to the antiparallel isoform. These results shed light on the influence of the linker and electronic properties of fluorophores on the efficiency of G4‐DNA “light‐up” probes operating via PET.
Making a Splash in Homogeneous CO2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms
Authors: Wiedner Eric S. , Linehan John C. 
Published: June 2018

AbstractMolecular catalysts for hydrogenation of CO2 are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO2 hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO2. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO2. Additionally, the solvent can impact catalysis by converting CO2 into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems.
Au@TiO2 Core–Shell Composites for the Photocatalytic Reduction of CO2
Authors: Pougin Anna , Dodekatos Georgios , Dilla Martin , Tüysüz Harun , Strunk Jennifer 
Published: June 2018

AbstractAu/TiO2 catalysts in different geometrical arrangements were designed to explore the role of morphology and structural properties for the photocatalytic reduction of CO2 with H2O in the gas‐phase. The most active sample was a Au@TiO2 core–shell catalyst with additional Au nanoparticles (NPs) deposited on the outer surface of the TiO2 shell. CH4 and CO are the primary carbon‐containing products. Large amounts of H2 are additionally formed by photocatalytic H2O splitting. Shell thickness plays a critical role. The highest yields were observed with the thickest layer of TiO2, stressing the importance of the semiconductor for the reaction. Commercial TiO2 with and without Au NPs was less active in the production of CH4 and CO. The enhanced activation of CO2 on the core–shell system is concluded to result from electronic interaction between the gold core, the titania shell, and the Au NPs on the outer surface. The improved exposure of Au−TiO2 interface contributes to the beneficial effect.
Atom‐ and Mass‐economical Continuous Flow Production of 3‐Chloropropionyl Chloride and its Subsequent Amidation
Authors: Movsisyan Marine , Heugebaert Thomas S. A. , Roman Bart I. , Dams Rudolf , Van Campenhout Rudy , Conradi Matthias , Stevens Christian V. 
Published: June 2018

Abstract3‐Chloropropionyl chloride is a chemically versatile building block with applications in the field of adhesives, pharmaceuticals, herbicides and fungicides. Its current production entails problems concerning safety, prolonged reaction times and the use of excessive amounts of chlorinating reagents. We developed a continuous flow procedure for acid chloride formation from acrylic acid and a consecutive 1,4‐addition of hydrogen chloride generating 3‐chloropropionyl chloride, as presented in this paper. Up to 94 % conversion was reached in 25 minutes at mild temperatures and pressures. This continuous flow method offers a safer alternative and is highly efficient in terms of consumption of starting product and shorter residence time. Valorization of this building block is exemplified by the synthesis of beclamide, a compound with sedative and anticonvulsant properties. Over 80 % conversion towards this drug was achieved in 1 minute in a continuous flow setup. Further research is needed to telescope the synthesis of 3‐chloropropionyl chloride and subsequent beclamide formation without intermediate purification.
Slow Magnetic Relaxation in a Palladium–Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion
Authors: Izuogu David C. , Yoshida Takefumi , Zhang Haitao , Cosquer Goulven , Katoh Keiichi , Ogata Shuhei , Hasegawa Miki , Nojiri Hiroyuki , Damjanović Marko , Wernsdorfer Wolfgang , Uruga Tomoya , Ina Toshiaki , Breedlove Brian K. , Yamashita Masahiro 
Published: June 2018

AbstractInvited for the cover of this issue are David C. Izuogu and Takefumi Yoshida with the group of Masahiro Yamashita and co‐workers at Tohoku University, Karlsruhe Institute of Technology, Aoyama Gakuin University, Japan Synchrotron Radiation Research Institute, Tohoku University Institute for Materials Research, University of Cambridge, University of Nigeria, Nsukka and National Institute for Materials Science. Read the full text of the article at 10.1002/chem.201800699.
Linear CuI2Pd0, CuIPd02, and AgI2Pd0 Metal Chains Supported by Rigid N,N′‐Diphosphanyl N‐Heterocyclic Carbene Ligands and Metallophilic Interactions
Authors: Ai Pengfei , Monakhov Kirill Yu. , van Leusen Jan , Kögerler Paul , Gourlaouen Christophe , Tromp Moniek , Welter Richard , Danopoulos Andreas A. , Braunstein Pierre 
Published: June 2018

AbstractInvited for the cover of this issue is the group of Pierre Braunstein and Andreas Danopoulos at the University of Strasbourg. The image depicts the double short‐bite character of the two PCNHCP ligands. Read the full text of the article at 10.1002/chem.201801170.
The Direct and Indirect Effects of Self‐Efficacy on Salespeople's Emotional Exhaustion and Work‐Family Conflict: A Study Using the Job Demands‐Resources Model
Authors: Carballo‐Penela Adolfo , Varela José , Bande Belén 
Published: June 2018

AbstractThis study integrates Social Cognitive Theory with the Job Demands‐Resources Model to examine self‐efficacy in relation to emotional exhaustion and work‐family conflict (WFC) in a sample of 192 employees. The results obtained through structural equation analysis show: a negative association between self‐efficacy and both work overload and emotional exhaustion; a positive relationship between work overload and both emotional exhaustion and WFC; that work overload mediates the relation between self‐efficacy and both emotional exhaustion and WFC; that role ambiguity moderates the relation of self‐efficacy with work overload; and that tenure in the sales territory moderates the relation of work overload with WFC. Copyright © 2018 ASAC. Published by John Wiley & Sons, Ltd.