bluuebunny/crossref_metadata_2025_split huggingface dataset:
Epileptic networks in action: Synchrony between distant hemodynamic responses
Authors: Khoo Hui Ming , von Ellenrieder Nicolás , Zazubovits Natalja , Dubeau François , Gotman Jean 
Published: June 2017

ObjectiveStructural and functional imaging studies in focal epilepsy often reveal distributed regions of abnormality. These are interpreted as representing the existence of epileptic networks, but the presence of actual neuronal interactions between these regions has not been demonstrated. We sought to determine whether the distributed hemodynamic responses often seen in functional magnetic resonance imaging (fMRI) studies of scalp interictal epileptic discharges (IEDs) actually correspond to synchronized neuronal activities when examining the intracerebral electroencephalogram (iEEG) at distant nodes of the network.MethodsWe studied 28 patients who underwent first EEG‐fMRI and then iEEG, and had significant hemodynamic responses in the gray matter. We coregistered the hemodynamic responses to the iEEG electrode contact positions and analyzed synchrony, measured by correlation, between IEDs recorded by iEEG in regions with and without hemodynamic responses.ResultsThe synchrony of intracerebral IED activity between pairs of regions showing a hemodynamic response was higher compared to that between pairs of regions without (p < 0.0001) and between pairs of regions, one with and one without hemodynamic response (p < 0.0001). These differences were found during the interictal periods with IEDs but were absent during the interictal periods without IEDs. Higher synchrony was also observed between regions involved at seizure onset (p < 0.0001).InterpretationEEG‐fMRI studies are unique in their ability to reveal hemodynamic concomitants of IEDs anywhere in the brain. This study proves that iEEG activity is synchronized between these regions of hemodynamic response, thus demonstrating the existence of an actual neuronally based interictal epileptic network. This also validates the EEG‐fMRI approach to reveal this network noninvasively. Ann Neurol 2017;82:57–66
Synthesis and Reactivity of Fluoroalkyl Copper Complexes by the Oxycupration of Tetrafluoroethylene
Authors: Ohashi Masato , Adachi Takuya , Ishida Naoyoshi , Kikushima Kotaro , Ogoshi Sensuke 
Published: June 2017

AbstractThe copper(I)‐mediated generation of ‐OCF2CF2‐ moieties by the oxycupration of tetrafluoroethylene (TFE) using either copper aryloxides or alkoxides is disclosed. The key intermediates, 2‐aryloxy‐1,1,2,2‐tetrafluoroethyl and 2‐alkoxy‐1,1,2,2‐tetrafluoroethyl copper complexes, were obtained from the reaction of the corresponding aryloxy and alkoxy copper complexes with TFE, and their structures in solution and in the solid state were unambiguously determined by multinuclear NMR spectroscopy and X‐ray diffraction analysis. These copper complexes subsequently reacted with aryl iodides (ArI) to afford ROCF2CF2Ar (R=aryl or alkyl) in high yields.
1,4‐Diphosphinine aus Imidazol‐2‐thionen
Authors: Koner Abhishek , Pfeifer Gregor , Kelemen Zsolt , Schnakenburg Gregor , Nyulászi László , Sasamori Takahiro , Streubel Rainer 
Published: June 2017

Abstract1,4‐Diphosphinine, substituiert mit zwei Thioharnstoff‐Gruppen, wurden aus tricyclischen 1,4‐Dichlor‐1,4‐dihydro‐1,4‐diphosphininen synthetisiert. Ihre Strukturen und spektroskopischen Eigenschaften werden beschrieben. Elektrochemische Untersuchungen zeigen sehr niedrige Oxidationspotentiale, bedingt durch effektive π‐Wechselwirkungen zwischen dem 1,4‐Diphosphinin‐Ring und den Orbitalen der beiden ylidischen C=S‐Bindungen. In Übereinstimmung mit dem niedrig liegenden LUMO, das größtenteils an den zwei Phosphorzentren lokalisiert ist, wird die Dianion‐Bildung stark bevorzugt. Trotz des kleinen HOMO‐LUMO‐Abstands, der in Einklang mit der roten Farbe der Titelverbindung ist, legen theoretische Rechnungen eine beträchtliche Aromatizität des 1,4‐Diphosphinin‐Ringes nahe.
One Model, Two Enzymes: Activation of Hydrogen and Carbon Monoxide
Authors: Ogo Seiji , Mori Yuki , Ando Tatsuya , Matsumoto Takahiro , Yatabe Takeshi , Yoon Ki‐Seok , Hayashi Hideki , Asano Masashi 
Published: June 2017

AbstractThe ability to catalyze the oxidation of both H2 and CO in one reaction pot would be a major boon to hydrogen technology since CO is a consistent contaminant of H2 supplies. Here, we report just such a catalyst, with the ability to catalyze the oxidation of either or both H2 and CO, based on the pH value. This catalyst is based on a NiIr core that mimics the chemical function of [NiFe]hydrogenase in acidic media (pH 4–7) and carbon monoxide dehydrogenase in basic media (pH 7–10). We have applied this catalyst in a demonstration fuel cell using H2, CO, and H2/CO (1/1) feeds as fuels for oxidation at the anode. The power density of the fuel cell depends on the pH value in the media of the fuel cell and shows a similar pH dependence in a flask. We have isolated and characterized all intermediates in our proposed catalytic cycles.
Diastereoselective Total Synthesis of the Euphorbia Diterpenoid Pepluanol A: A Reductive Annulation Approach
Authors: Xuan Jun , Liu Zhaobo , Zhu An , Rao Peirong , Yu Lei , Ding Hanfeng 
Published: June 2017

AbstractA new titanium(III)‐catalyzed reductive annulation constructed a series of diversely functionalized 1,5‐diols in good to excellent yields with respect to a wide scope of vinyl epoxide‐aldehyde substrates. Taken together with a Diels–Alder reaction and a substrate‐controlled diastereoselective cyclopropanation as additional key steps, the synthetic utility of this novel method has been preliminarily explored by the first and concise total synthesis of the Euphorbia diterpenoid (±)‐pepluanol A.
Alkyltin Keggin Clusters Templated by Sodium
Authors: Saha Sumit , Park Deok‐Hie , Hutchison Danielle C. , Olsen Morgan R. , Zakharov Lev N. , Marsh David , Goberna‐Ferrón Sara , Frederick Ryan T. , Diulus J. Trey , Kenane Nizan , Herman Gregory S. , Johnson Darren W. , Keszler Douglas A. , Nyman May 
Published: June 2017

AbstractDodecameric (Sn12) and hexameric topologies dominate monoalkyltin–oxo cluster chemistry. Their condensation, triggered by radiation exposure, recently produced unprecedented patterning performance in EUV lithography. A new cluster topology was crystallized from industrial n‐BuSnOOH, and additional characterization techniques indicate other clusters are present. Single‐crystal X‐ray analysis reveals a β‐Keggin cluster, which is known but less common than other Keggin isomers in polyoxometalate and polyoxocation chemistry. The structure is formulated [NaO4(BuSn)12(OH)3(O)9(OCH3)12(Sn(H2O)2)] (β‐NaSn13). SAXS, NMR, and ESI MS differentiate β‐NaSn13, Sn12, and other clusters present in crude “n‐BuSnOOH” and highlight the role of Na as a template for alkyltin Keggin clusters. Unlike other alkyltin clusters that are cationic, β‐NaSn13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.
Initiator‐Loaded Gold Nanocages as a Light‐Induced Free‐Radical Generator for Cancer Therapy
Authors: Wang Xiao‐Qiang , Gao Fan , Zhang Xian‐Zheng 
Published: June 2017

AbstractTumor hypoxia greatly suppresses the therapeutic efficacy of photodynamic therapy (PDT), mainly because the generation of toxic reactive oxygen species (ROS) in PDT is highly oxygen‐dependent. In contrast to ROS, the generation of oxygen‐irrelevant free radicals is oxygen‐independent. A new therapeutic strategy based on the light‐induced generation of free radicals for cancer therapy is reported. Initiator‐loaded gold nanocages (AuNCs) as the free‐radical generator were synthesized. Under near‐infrared light (NIR) irradiation, the plasmonic heating effect of AuNCs can induce the decomposition of the initiator to generate alkyl radicals (R.), which can elevate oxidative‐stress (OS) and cause DNA damages in cancer cells, and finally lead to apoptotic cell death under different oxygen tensions. As a proof of concept, this research opens up a new field to use various free radicals for cancer therapy.
Synthesis of [5,6]‐Bicyclic Heterocycles with a Ring‐Junction Nitrogen Atom: Rhodium(III)‐Catalyzed C−H Functionalization of Alkenyl Azoles
Authors: Halskov Kim Søholm , Roth Howard S. , Ellman Jonathan A. 
Published: June 2017

AbstractThe first syntheses of privileged [5,6]‐bicyclic heterocycles, with ring‐junction nitrogen atoms, by transition metal catalyzed C−H functionalization of C‐alkenyl azoles is disclosed. Several reactions are applied to alkenyl imidazoles, pyrazoles, and triazoles to provide products with nitrogen incorporated at different sites. Alkyne and diazoketone coupling partners give azolopyridines with various substitution patterns. In addition, 1,4,2‐dioxazolone coupling partners yield azolopyrimidines. Furthermore, the mechanisms for the reactions are discussed and the utility of the developed approach is demonstrated by iterative application of C−H functionalization for the rapid synthesis of a patented drug candidate.
Synthesis and Characterization of a Metallacyclic Framework with Three Fused Five‐membered Rings
Authors: Zhu Congqing , Wu Jingjing , Li Shenyan , Yang Yuhui , Zhu Jun , Lu Xin , Xia Haiping 
Published: June 2017

AbstractPolycyclic complexes containing a bridgehead transition metal are interesting species because the transition metal is shared by all the rings simultaneously. In this study, we present a novel osmium–bridgehead system with three fused five‐membered rings. This novel framework can be viewed as a 10‐atom carbon chain coordinating to the osmium center. In sharp contrast to the nonplanar organic analogue, this unique metallacycle exhibits good planarity, which was unambiguously verified by means of X‐ray diffraction. Interestingly, preliminary DFT calculations show that the aromaticity in the three 5MRs of these osmatricycles can be easily tuned by the ligand substitution. Finally, the broad UV/Vis absorption spectra of these novel polycyclic complexes were also reported.
1,4‐Diphosphinines from Imidazole‐2‐thiones
Authors: Koner Abhishek , Pfeifer Gregor , Kelemen Zsolt , Schnakenburg Gregor , Nyulászi László , Sasamori Takahiro , Streubel Rainer 
Published: June 2017

Abstract1,4‐Diphosphinines that are fused to two thiourea units were synthesized from the corresponding tricyclic 1,4‐dichloro‐1,4‐dihydro‐1,4‐diphosphinines, and their structures and spectroscopic features are described. Electrochemical studies revealed very low oxidation potentials, which are due to the effective π‐interaction between the 1,4‐diphosphinine ring and the orbitals of the two ylidic C=S bonds. In accordance with the low‐lying LUMO, which is largely localized at the two phosphorus centers, dianion formation is strongly preferred. Despite the small HOMO–LUMO gap, which is in accordance with the red color of the title compounds, theoretical calculations suggest considerable aromaticity for the 1,4‐diphosphinine ring.
Polytriazole polyether elastomers with widely tunable mechanical properties: The role of network structure and crystallization behavior
Authors: Zou Yecheng , Yang Rongjie , Zhai Jinxian 
Published: June 2017

ABSTRACTThe polytriazole polyether elastomers were prepared by the propargyl‐terminated ethylene oxide‐tetrahydrofuran [PTP(E‐co‐T)] prepolymer and the multi‐azide group glycidyl ether with different curing parameter R. The relationship between the network structure, mechanical properties, and crystallization behaviors of the elastomers were investigated by swelling testing, tensile testing machine, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and in situ wide‐angle X‐ray scattering at 60, 20, and −40 °C, respectively. The mechanical properties of the polytriazole elastomers exhibited obviously different dependences on R values at different testing temperatures. At 60 and 20 °C, with the increase of R, the tensile stress at breaking gives a parabola going downwards with a maximum at R = 1.1. However, at −40 °C, the stress exhibited an analogous parabola going upward with a minimum at R = 1.1. The DSC and WAXD results indicated that at 60 and 20 °C, the polytriazole elastomers was amorphous, but at −40 °C, the polytriazole elastomers were crystallizable and the crystallization capability of the polytriazole elastomers are also observed. Therefore, it can be inferred that at 60 and 20 °C, the mechanical properties of the polyether polytriazole elastomer depend on completeness of the network structures, while the crystallization behavior of the polytriazole elastomers induces its different mechanical properties at −40 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45298.
Single‐ and two‐step procedures of AGET emulsion ATRP of methyl methacrylate in a well‐mixed batch reactor
Authors: Upadhayay Regmi Kishor N. , Mehrvar Mehrab , Dhib Ramdhane 
Published: June 2017

ABSTRACTThis study investigates the atom transfer radical emulsion polymerization of methyl methacrylate in a 2 L well‐mixed stirred batch reactor using activators generated by electron transfer as the initiation technique. The polymerization was carried out with ethyl‐2‐bromoisobutyrate as the initiator, copper bromide with 4,4′‐di‐5‐nonyl‐2,2′‐bipyridine as the catalyst system, Brij 98 as the surfactant, and ascorbic acid as the reducing agent. The reaction was carried out at constant temperature in the range of 50 to 70 °C under a blanket of nitrogen to minimize the presence of air in the system. Polymerizations were carried out according to single‐step and two‐step procedures. The coagulation was found to be a major problem, especially at high monomer conversion. However, adding more surfactant and lowering the reaction temperature weakened the effect of the coagulation but at the expense of the low monomer conversion. Measurement of molecular weight distribution and Đ using gel permeation show that the two‐step techniques produced polymers with living features of atom transfer radical emulsion polymerization much better than those in the single‐step procedure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45308.
Lignin nanoparticles by ultrasonication and their incorporation in waterborne polymer nanocomposites
Authors: Garcia Gonzalez Maria Nelly , Levi Marinella , Turri Stefano , Griffini Gianmarco 
Published: June 2017

ABSTRACTLignin nanoparticles (nanolignin, NL) were prepared in this work by ultrasonic treatment of softwood kraft lignin to obtain lignin‐water dispersions with excellent colloidal stability. A thorough characterization of the chemical, physical, and morphological properties of the new NL particles allowed for direct comparisons with the untreated parent material. Such NL particles were incorporated into a waterborne thermoplastic polyurethane matrix at different concentrations to yield bio‐based nanocomposite materials. The effect of the bio‐filler type (NL vs. untreated lignin) and loading on the chemical, physical, thermal, and morphological characteristics of the resulting nanocomposites was extensively investigated. In addition, tensile tests carried out on these systems highlighted the superior mechanical properties of NL‐based nanocomposites compared to composite materials incorporating untreated lignin. The results of this study provide a direct demonstration of an easy and environmentally friendly approach to obtain waterborne polyurethane‐based nanocomposites reinforced with NL in a relatively straightforward and accessible way and clearly evidence the potential of lignin nanoparticles as fully bioderived fillers for advanced nanocomposite applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45318.
Inducing Thought Processes: Bringing Process Measures and Cognitive Processes Closer Together
Authors: Schulte‐Mecklenbeck Michael , Kühberger Anton , Gagl Benjamin , Hutzler Florian 
Published: June 2017

AbstractThe challenge in inferring cognitive processes from observational data is to correctly align overt behavior with its covert cognitive process. To improve our understanding of this overt–covert mapping in the domain of decision making, we collected eye‐movement data during decisions between gamble‐problems. Participants were either free to choose or instructed to use a specific choice strategy (maximizing expected value or a choice heuristic). We found large differences in looking patterns between free and instructed choices. Looking patterns provided no support for the common assumption that attention is equally distributed between outcomes and probabilities, even when participants were instructed to maximize expected value. Eye‐movement data are to some extent ambiguous with respect to underlying cognitive processes. Copyright © 2017 John Wiley & Sons, Ltd.
Molecular Containers Bind Drugs of Abuse in Vitro and Reverse the Hyperlocomotive Effect of Methamphetamine in Rats
Authors: Ganapati Shweta , Grabitz Stephanie D. , Murkli Steven , Scheffenbichler Flora , Rudolph Maíra I. , Zavalij Peter Y. , Eikermann Matthias , Isaacs Lyle 
Published: June 2017

AbstractWe measured the affinity of five molecular container compounds (calabadions 1 and 2, CB[7], sulfocalix[4]arene, and HP‐β‐CD) toward seven drugs of abuse in homogenous aqueous solution at physiological pH by various methods (1H NMR, UV/Vis, isothermal titration calorimetry [ITC]) and found binding constants (Ka values) spanning from <102 to >108 m−1. We also report X‐ray crystal structures of CB[7]⋅methamphetamine and 1⋅methamphetamine. We found that 2, but not CB[7], was able to ameliorate the hyperlocomotive activity of rats treated with methamphetamine. The bioavailability of the calabadions and their convergent building block synthesis suggest potential for further structural optimization as reversal agents for intoxication with nonopioid drugs of abuse for which no treatments are currently available.
Impact of the Co : Cu Ratio in CoCu‐Containing Oxidic Solids on their Activity for the Water‐Splitting Reaction
Authors: Polyakov Mykola , Surkus Annette‐Enrica , Maljusch Artjom , Hoch Sascha , Martin Andreas 
Published: June 2017

AbstractNoble metal free bimetallic CoCu‐containing water splitting catalysts for the oxygen evolution reaction (OER) in basic media with different Co : Cu ratios were synthesized. A simple sol‐gel method with citric acid as a multipurpose chelating and reduction agent was used. The subsequent thermal treatment was carried out in an oxygen‐deficient atmosphere (pyrolysis). The catalysts were characterized by rotating disc electrode (RDE) OER measurements, N2 adsorption, XRD, XPS, TEM, DLS and elemental analyses. The highest activity in the OER was achieved with a Co : Cu ratio of 5 (47 A gcatalyst−1 at 1.6 V versus the reversible hydrogen electrode). This is the first time that such high activity has been reported. These transition metal oxide catalysts might be promising candidates as an anode material in alkaline water electrolyzers. Higher and lower Co : Cu ratios revealed less activity.
Electrochemiluminescence Detection in Paper‐Based and Other Inexpensive Microfluidic Devices
Authors: Gross Erin M. , Durant Hannah E. , Hipp Kenneth N. , Lai Rebecca Y. 
Published: June 2017

AbstractThere is a need in the field of microfluidics for integration of analytical detection methods onto small fluidic chips. Electrogenerated chemiluminescence (ECL) is an effective method for detecting a wide range of analytes, including small molecules, metal ions and bacteria. This Minireview discusses recent applications of ECL‐based detection methods to inexpensive microfluidic devices. We discuss various paper and cloth based devices, including 3D‐origami devices and devices utilizing bipolar electrodes. We also discuss novel devices that have replaced traditional instrumentation with inexpensive and portable equipment, such as mobile phones.
Synthesis of Magnetic‐Nanoparticle/Ansamitocin Conjugates—Inductive Heating Leads to Decreased Cell Proliferation In Vitro and Attenuation Of Tumour Growth In Vivo
Authors: Seidel Katja , Balakrishnan Asha , Alexiou Christoph , Janko Christina , Komoll Ronja‐Melinda , Wang Liang‐Liang , Kirschning Andreas , Ott Michael 
Published: June 2017

AbstractConjugates based on nanostructured, superparamagnetic particles, a thermolabile linker and a cytotoxic maytansinoid were developed to serve as a model for tumour‐selective drug delivery and release. It combines chemo‐ with thermal therapy. The linker‐modified toxin was prepared by a combination of biotechnology and semisynthesis. Drug release was achieved by hyperthermia through an external oscillating electromagnetic field that induces heat inside the particles. Efficacy of this release concept was demonstrated both for cancer cell proliferation in vitro, and for tumour growth in vivo, in a xenograft mouse model. Biocompatibility studies for these magnetic‐nanoparticle/ansamitocin conjugates complement this work.
Differential neuronal and glial expression of nuclear factor I proteins in the cerebral cortex of adult mice
Authors: Chen Kok‐Siong , Harris Lachlan , Lim Jonathan W. C. , Harvey Tracey J. , Piper Michael , Gronostajski Richard M. , Richards Linda J. , Bunt Jens 
Published: June 2017

AbstractThe nuclear factor I (NFI) family of transcription factors plays an important role in the development of the cerebral cortex in humans and mice. Disruption of nuclear factor IA (NFIA), nuclear factor IB (NFIB), or nuclear factor IX (NFIX) results in abnormal development of the corpus callosum, lateral ventricles, and hippocampus. However, the expression or function of these genes has not been examined in detail in the adult brain, and the cell type‐specific expression of NFIA, NFIB, and NFIX is currently unknown. Here, we demonstrate that the expression of each NFI protein shows a distinct laminar pattern in the adult mouse neocortex and that their cell type‐specific expression differs depending on the family member. NFIA expression was more frequently observed in astrocytes and oligodendroglia, whereas NFIB expression was predominantly localized to astrocytes and neurons. NFIX expression was most commonly observed in neurons. The NFI proteins were equally distributed within microglia, and the ependymal cells lining the ventricles of the brain expressed all three proteins. In the hippocampus, the NFI proteins were expressed during all stages of neural stem cell differentiation in the dentate gyrus, with higher expression intensity in neuroblast cells as compared to quiescent stem cells and mature granule neurons. These findings suggest that the NFI proteins may play distinct roles in cell lineage specification or maintenance, and establish the basis for further investigation of their function in the adult brain and their emerging role in disease.