bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hot Electrons at Solid–Liquid Interfaces: A Large Chemoelectric Effect during the Catalytic Decomposition of Hydrogen Peroxide
Authors: Nedrygailov Ievgen I. , Lee Changhwan , Moon Song Yi , Lee Hyosun , Park Jeong Young 
Published: July 2016

AbstractThe study of energy and charge transfer during chemical reactions on metals is of great importance for understanding the phenomena involved in heterogeneous catalysis. Despite extensive studies, very little is known about the nature of hot electrons generated at solid–liquid interfaces. Herein, we report remarkable results showing the detection of hot electrons as a chemicurrent generated at the solid–liquid interface during decomposition of hydrogen peroxide (H2O2) catalyzed on Schottky nanodiodes. The chemicurrent reflects the activity of the catalytic reaction and the state of the catalyst in real time. We show that the chemicurrent yield can reach values up to 10−1 electrons/O2 molecule, which is notably higher than that for solid–gas reactions on similar nanodiodes.
Enantioselective Allylic C−H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis
Authors: Ammann Stephen E. , Liu Wei , White M. Christina 
Published: July 2016

AbstractThe enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)‐catalyzed allylic C−H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide‐oxazoline (ArSOX) ligand. The allylic C−H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee).
Formamide als Lewis‐Basen‐Katalysatoren in SN‐Reaktionen: Effiziente Transformationen von Alkoholen zu Chloriden, Aminen und Ethern
Authors: Huy Peter H. , Motsch Sebastian , Kappler Sarah M. 
Published: July 2016

AbstractEin einfacher Formamidkatalysator ermöglicht effiziente Transformationen von Alkoholen zu Alkylchloriden mit Benzoylchlorid als einzigem Reagenz. Diese nukleophilen Substitutionsreaktionen verlaufen über iminiumaktivierte Alkohole als Intermediate. Die neue Methode, die sogar lösungsmittelfrei durchgeführt werden kann, zeichnet sich durch eine exzellente Kompatibilität mit funktionellen Gruppen, Skalierbarkeit (>100 g) und Abfallbilanz aus (E‐Faktor bis zu 2). Chirale Substrate werden unter einem hohen Grad an stereochemischer Inversion in die entsprechenden Chloride überführt (99 %→≥95 % ee). In einem praktischen Eintopfverfahren konnten die primär gebildeten Chloride direkt zu Aminen, Aziden, Ethern, Sulfiden und Nitrilen weiter umgesetzt werden. Der praktische Nutzen der Methode wurde darüber hinaus in kurzen Synthesen von rac‐Clopidogrel und S‐Fendilin bewiesen.
Emerging Targets in Photopharmacology
Authors: Lerch Michael M. , Hansen Mickel J. , van Dam Gooitzen M. , Szymanski Wiktor , Feringa Ben L. 
Published: July 2016

AbstractThe field of photopharmacology uses molecular photoswitches to establish control over the action of bioactive molecules. It aims to reduce systemic drug toxicity and the emergence of resistance, while achieving unprecedented precision in treatment. By using small molecules, photopharmacology provides a viable alternative to optogenetics. We present here a critical overview of the different pharmacological targets in various organs and a survey of organ systems in the human body that can be addressed in a non‐invasive manner. We discuss the prospects for the selective delivery of light to these organs and the specific requirements for light‐activatable drugs. We also aim to illustrate the druggability of medicinal targets with recent findings and emphasize where conceptually new approaches have to be explored to provide photopharmacology with future opportunities to bring “smart” molecular design ultimately to the realm of clinical use.
Quantum chemistry mechanism study on preventing slag‐bonding via modifying the material surface properties
Authors: Li Mingqiang , Zhang Zhongxiao , Wu Xiaojiang , Fan Junjie 
Published: July 2016

AbstractA huge amount of coal with high content of Na and K in ash was found in Xinjiang Province, China. However, the most serious ash fouling/slagging problems of that kind of coal usually cause the increasing of operating costs and energy consumption in a power plant. In order to clarify the mechanism of the effect on ash deposition behavior on different material surfaces, the experimental study, as well as quantum chemistry calculation, was used in this study. The results show that the nickel‐based material can significantly alleviate the ash deposition of high‐alkali coal. The adsorption energy between Na atom and NiO is much higher than that between Na atom and Fe2O3. The much lower system energy between Na atom and Fe2O3 will cause more stable system of Na‐Fe2O3. However, for nickel‐based material, the electrons of Na‐NiO system are being at a higher energy status, which will cause the system to stay at a relative unstable status. The quantum chemistry calculation results can well explain the phenomena of the experimental result. Furthermore, the interaction mechanisms between Na and Al‐based materials were also calculated to predict the effect of Al‐based material on preventing ash fouling and slagging. Copyright © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Effects of elevated temperature and crude oil on the properties of a hydrogenated nitrile butadiene rubber elastomer
Authors: Pan Long , Tan Jinzhu , Han Xuemei , Li Peng , Zhang Wujian 
Published: July 2016

ABSTRACTThe stability and durability of hydrogenated nitrile butadiene rubber (HNBR) material in crude oil environments are of great importance for petroleum equipment to resist leakage and to ensure reliability. In this paper, an HNBR material was fabricated, and the degradation of the HNBR material was investigated in simulated crude oil environments. One crude oil and three temperatures (50 °C, 75 °C, and 100 °C, based on actual crude oil operations, were used in this study. Weight changes for the HNBR specimens were monitored after exposure to the environments over time. Optical microscopy was used to show the topographical changes on the specimen surfaces. Attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy was employed to study the surface chemistry of the HNBR material before and after exposure to the simulated crude oil environments at selected times. Mechanical property tests (tensile and compressive stress–strain tests, tear strength test, and compression set test) were conducted to assess the changes in mechanical properties of the HNBR specimens before and after exposure to the environments. The test results show that the physical–mechanical properties of the HNBR material changed significantly. The temperature and the crude oil had a direct effect on the degradation of the mechanical properties. The ATR‐FTIR test results indicate that the surface chemistry changed via chain crosslinking in the material after exposure to the environments over time. The degradation mechanisms of the HNBR material after exposure to the crude oil could be due to the presence of chain crosslinking, chain mobility, and backbone scission. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44012.
Fabrication and characterization of hybrid films based on polyaniline and graphitic carbon nitride nanosheet
Authors: Dinari Mohammad , Momeni Mohamad Mohsen , Afshari Mohaddeseh 
Published: July 2016

ABSTRACTHybrid films of polyaniline/graphitic carbon nitride (PANI/g‐C3N4) deposited on titanium was fabricated. First, g‐C3N4 as a two‐dimensional graphite‐like structure was synthesized by the stepwise condensation reaction of melamine and cyanuric chloride in the presence of N,N‐dimethylmethanamide as a high boiling point nonnucleophilic base. Then composite films of PANI/g‐C3N4 were prepared by in situ electrochemical polymerization of an aniline solution containing g‐C3N4. Different concentrations of g‐C3N4 were utilized to improve the electrochemical performances of the hybrids. The resulting PANI/g‐C3N4 composite films were characterized by X‐ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and ultraviolet–visible diffuse reflection spectroscopy techniques. The electrochemical performance of the composites was evaluated by cyclic voltammetry (CV). Application of the prepared samples has been evaluated as supercapacitor material in 0.5 M H2SO4 solution using CV technique. The specific capacitances of PANI/g‐C3N4 composite films were higher than obtained for pure PANI films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44059.
A model‐based demand‐balancing control for dynamically divided multiple urban subnetworks
Authors: Lin Shu , Kong Qing‐Jie , Huang Qingming 
Published: July 2016

SummaryTraffic control is an effective and efficient method for the problem of traffic congestion. It is necessary to design a high‐level controller to regulate the network traffic demands, because traffic congestion is not only caused by the improper management of the traffic network but also to a great extent caused by excessive network traffic demands. Therefore, we design a demand‐balance model predictive controller based on the macroscopic fundamental diagram‐based multi‐subnetwork model, which can optimize the network traffic mobility and the network traffic throughput by regulating the input traffic flows of the subnetworks. Because the transferring traffic flows among subnetworks are indirectly controlled and coordinated by the demand‐balance model predictive controller, the subnetwork division can variate dynamically according to real traffic states, and a global optimality can be achieved for the entire traffic network. The simulation results show the effectiveness of the proposed controller in improving the network traffic throughput. Copyright © 2016 John Wiley & Sons, Ltd.
FK506 binding protein 51 integrates pathways of adaptation
Authors: Rein Theo 
Published: July 2016

This review portraits FK506 binding protein (FKBP) 51 as “reactivity protein” and collates recent publications to develop the concept of FKBP51 as contributor to different levels of adaptation. Adaptation is a fundamental process that enables unicellular and multicellular organisms to adjust their molecular circuits and structural conditions in reaction to environmental changes threatening their homeostasis. FKBP51 is known as chaperone and co‐chaperone of heat shock protein (HSP) 90, thus involved in processes ensuring correct protein folding in response to proteotoxic stress. In mammals, FKBP51 both shapes the stress response and is calibrated by the stress levels through an ultrashort molecular feedback loop. More recently, it has been linked to several intracellular pathways related to the reactivity to drug exposure and stress. Through its role in autophagy and DNA methylation in particular it influences adaptive pathways, possibly also in a transgenerational fashion.Also see the video abstract here.
Early‐life single‐episode sevoflurane exposure impairs social behavior and cognition later in life
Authors: Lin Daisy , Liu Jinyang , Kramberg Lea , Ruggiero Andrea , Cottrell James , Kass Ira S. 
Published: July 2016

AbstractBackgroundSingle‐episode anesthetic exposure is the most prevalent surgery‐related incidence among young children in the United States. Although numerous studies have used animals to model the effects of neonatal anesthetics on behavioral changes later on in life, our understanding of the functional consequences to the developing brain in a comprehensive and clinically relevant manner is unclear.MethodsThe volatile anesthetic, sevoflurane (sevo) was administered to C57BL6 postnatal day 7 (P7) mice in a 40% oxygen and 60% nitrogen gas mixture. In order to examine the effects of sevo alone on the developing brain in a clinically relevant manner, mice were exposed to an average of 2.38 ± 0.11% sevo for 2 h. No sevo (control) mice were treated in an identical manner without sevo exposure. Mice were examined for cognition and neuropsychiatric‐like behavioral changes at 1–5 months of age.ResultsUsing the active place avoidance (APA) test and the novel object recognition (NOR) test, we demonstrated that P7 sevo‐treated mice showed a deficit in learning and memory both during periadolescence and adulthood. We then employed a battery of neuropsychiatric‐like behavioral tests to examine social interaction, communication, and repetitive behavior. Interestingly, compared to the no‐sevo–treated group, sevo‐treated mice showed significant reductions in the time interacting with a novel mouse (push–crawl and following), time and interaction in a chamber with a novel mouse, and time sniffing a novel social odor.ConclusionsOur study established that single‐episode, 2‐h sevo treatment during early life impairs cognition later on in life. With this approach, we also observed neuropsychiatric‐like behavior changes such as social interaction deficits in the sevo‐treated mice. This study elucidated the effects of a clinically relevant single‐episode sevo application, given during the neonatal period, on neurodevelopmental behavioral changes later on in life.
High‐throughput screening of clinically approved drugs that prime polyethylenimine transfection reveals modulation of mitochondria dysfunction response improves gene transfer efficiencies
Authors: Nguyen Albert , Beyersdorf Jared , Riethoven Jean‐Jack , Pannier Angela K. 
Published: July 2016

AbstractNonviral gene delivery methods are advantageous over viral vectors in terms of safety, cost, and flexibility in design and application, but suffer from lower gene transfer efficiency. In addition to modifications to nucleic acid design and nonviral carriers, new tools are sought to enhance transfection. Priming is the pharmacological modulation of transfection efficiency and transgene expression, and has demonstrated transfection increase in several compounds, for example, chloroquine and glucocorticoids. To develop a library of transfection priming compounds, a high‐throughput screen was performed of the NIH Clinical Collection (NCC) to identify clinical compounds that prime polyethylenimine (PEI) transfection. HEK293T cells were treated with priming compounds, then transfected with enhanced green fluorescent protein (EGFP)‐encoding plasmid by PEI. After 48‐hr culture, primed and transfected cells were assayed for transfection, cell proliferation, and cell viability by fluorescence measurement of EGFP reporter, Hoechst 33342 nuclei stain, and resazurin metabolic assay. From the microscope image analysis and microplate measurements, transfection fold‐changes were determined, and compounds resulting in statistically significant transfection fold‐change were identified. NCC compounds were clustered using PubChem fingerprint similarity by Tanimoto coefficients in ChemmineTools. Fold‐changes for each compound were linked to drug clusters, from which drug classes that prime transfection were identified. Among the identified drugs classes that primed transfection increases were antioxidants, GABAA receptor modulators, and glucocorticoids. Resveratrol and piceid, stilbenoid antioxidants found in grapes, and zolpidem, a GABAA modulator, increased transfection nearly three‐fold. Literature indicate interaction of the identified transfection priming drug clusters with mitochondria, which may modulate mitochondrial dysfunction known to be associated with PEI transfection.
Reducing neuroinflammation by delivery of IL‐10 encoding lentivirus from multiple‐channel bridges
Authors: Margul Daniel J. , Park Jonghyuck , Boehler Ryan M. , Smith Dominique R. , Johnson Mitchell A. , McCreedy Dylan A. , He Ting , Ataliwala Aishani , Kukushliev Todor V. , Liang Jesse , Sohrabi Alireza , Goodman Ashley G. , Walthers Christopher M. , Shea Lonnie D. , Seidlits Stephanie K. 
Published: July 2016

AbstractThe spinal cord is unable to regenerate after injury largely due to growth‐inhibition by an inflammatory response to the injury that fails to resolve, resulting in secondary damage and cell death. An approach that prevents inhibition by attenuating the inflammatory response and promoting its resolution through the transition of macrophages to anti‐inflammatory phenotypes is essential for the creation of a growth permissive microenvironment. Viral gene delivery to induce the expression of anti‐inflammatory factors provides the potential to provide localized delivery to alter the host inflammatory response. Initially, we investigated the effect of the biomaterial and viral components of the delivery system to influence the extent of cell infiltration and the phenotype of these cells. Bridge implantation reduces antigen‐presenting cell infiltration at day 7, and lentivirus addition to the bridge induces a transient increase in neutrophils in the spinal cord at day 7 and macrophages at day 14. Delivery of a lentivirus encoding IL‐10, an anti‐inflammatory factor that inhibits immune cell activation and polarizes the macrophage population towards anti‐inflammatory phenotypes, reduced neutrophil infiltration at both day 7 and day 28. Though IL‐10 lentivirus did not affect macrophages number, it skewed the macrophage population toward an anti‐inflammatory M2 phenotype and altered macrophage morphology. Additionally, IL‐10 delivery resulted in improved motor function, suggesting reduced secondary damage and increased sparing. Taken together, these results indicate that localized expression of anti‐inflammatory factors, such as IL‐10, can modulate the inflammatory response following spinal cord injury, and may be a key component of a combinatorial approach that targets the multiple barriers to regeneration and functional recovery.
Performance evaluation of learning styles based on fuzzy logic inference system
Authors: Ozdemir Ali , Alaybeyoglu Aysegul , Mulayim Naciye , Balbal Kadriye Filiz 
Published: July 2016

ABSTRACTDetermining best convenient learning style in accordance with the individual's capabilities and personalities is very important for learning rapidly, easily, and in high quality. When it is thought that each individual has different personality and ability, it can be recognized that each individual's best convenient learning style will be different. Because of the importance of lifelong learning, many methods and approaches have been developed to determine learning styles of the individuals. In this study, a rule based fuzzy logic inference system is developed to determine best convenient learning styles of the engineering faculty stuffs and the students. During studies, two different learning style models namely Honey&Mumford and McCarthy are used in implementations. This study is carried out with a total number of 60 and 26 engineering faculty students and stuffs, respectively. The personal information form and Learning Style Preference Survey of Honey&Mumford and McCarthy are used to collect the data which are analyzed using the techniques of frequency, percentage, mean, standard deviation, and t‐test. While Honey&Mumford learning style classifies engineering faculty students and stuffs as Activist, Reflector, Theorist, and Pragmatist; McCarthy learning style classifies them as Innovative, Analytic, Common Sense, and Dynamic. Gender, age, and department are selected as the metrics for evaluation of the system performance. © 2016 Wiley Periodicals, Inc Comput Appl Eng Educ 24:853–865, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21754
Diverse Ligand‐Functionalized Mixed‐Valent Hexamanganese Sandwiched Silicotungstates with Single‐Molecule Magnet Behavior
Authors: Xue Han , Zhao Jun‐Wei , Pan Rui , Yang Bai‐Feng , Yang Guo‐Yu , Liu Hong‐Sheng 
Published: July 2016

AbstractUnder hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed‐valent Mn6 sandwiched silicotungstate [(B‐α‐SiW9O34)2MnIII4MnII2O4(H2O)4]12− (1 a) with organic N ligands led to the isolation of five organic–inorganic hybrid, Mn6‐substituted polyoxometalates (POMs) 2–6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse‐reflectance spectroscopy, and powder and single‐crystal X‐ray diffraction. Compounds 2–6 represent the first series of mixed‐valent {MnIII4MnII2O4(H2O)4−n(L)n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1–6 not only indicates that the double‐cubane {MnIII4MnII2O4(H2O)4−n(L)n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed‐valent POMs substituted with transition‐metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single‐molecule magnet behavior.
A Hydrophobic Metal–Organic Framework Based on Cubane‐Type [Co4(μ3‐F)3(μ3‐SO4)]3+ Clusters for Gas Storage and Adsorption Selectivity of Benzene over Cyclohexane
Authors: Zhang Lei , Yang Wenbin , Wu Xiao‐Yuan , Lu Can‐Zhong , Chen Wen‐Zhe 
Published: July 2016

AbstractHydrophobic metal‐organic frameworks (MOFs) not only have high water stability, but also exhibit high adsorption capacity towards organic molecules, in particular hydrocarbons. Herein we report a rare metal fluoride organic framework MFOF‐1 with high hydrophobicity, which is constructed from unprecedented fluoride‐ and sulfate‐bridged cubane‐type tetranuclear cobalt clusters. MFOF‐1 consists of three types of polyhedral cages with face‐sharing configurations, and possesses a novel (3,9)‐connected 3D+3D→3D self‐interpenetrating array or the rare pyr topology. MFOF‐1 shows high thermal stability and high stability in water and even acid/base aqueous solutions, and exhibits rather high H2 and CO2 storage capacities at ambient pressure. Remarkably, MFOF‐1 shows little adsorption of water but considerably high uptakes of methanol, n‐hexane, cyclohexane, and benzene, and exhibits a certain degree of adsorption selectivity of benzene over cyclohexane.