bluuebunny/crossref_metadata_2025 huggingface dataset:
Galactic cosmic ray variations in the inner heliosphere from solar distances less than 0.5 AU: Measurements from the MESSENGER Neutron Spectrometer
Authors: Lawrence David J. , Peplowski Patrick N. , Feldman William C. , Schwadron Nathan A. , Spence Harlan E.
Published: July 2016

The Neutron Spectrometer (NS) on board NASA's MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft is sensitive to galactic cosmic ray (GCR) protons greater than 125 MeV. During the MESSENGER orbital mission of Mercury, which lasted from March 2011 to April 2015, the NS made continual measurements of GCR variations, which represent the first long‐term GCR measurements for solar distances less than 0.5 AU. These relative GCR variations are compared to GCR variations measured by the Cosmic Ray Telescope for Environmental Radiation (CRaTER) on the Lunar Reconnaissance Orbiter. The two data sets are highly correlated, with correlation coefficients ranging from 0.91 to 0.98 for time integrations ranging from 1 to 25 days. The MESSENGER NS and CRaTER measurements of GCR variations are used to investigate the GCR radial gradient within the inner solar system. We find that the GCR radial gradient is less than 10% per AU, which is consistent with GCR radial gradients measured for solar distances greater than 1 AU.
Insights into shallow magmatic processes at Kīlauea Volcano, Hawaiʻi, from a multiyear continuous gravity time series
Authors: Poland Michael P. , Carbone Daniele
Published: July 2016

Continuous gravity data collected near the summit eruptive vent at Kīlauea Volcano, Hawaiʻi, during 2011–2015 show a strong correlation with summit‐area surface deformation and the level of the lava lake within the vent over periods of days to weeks, suggesting that changes in gravity reflect variations in volcanic activity. Joint analysis of gravity and lava level time series data indicates that over the entire time period studied, the average density of the lava within the upper tens to hundreds of meters of the summit eruptive vent remained low—approximately 1000–1500 kg/m3. The ratio of gravity change (adjusted for Earth tides and instrumental drift) to lava level change measured over 15 day windows rose gradually over the course of 2011–2015, probably reflecting either (1) a small increase in the density of lava within the eruptive vent or (2) an increase in the volume of lava within the vent due to gradual vent enlargement. Superimposed on the overall time series were transient spikes of mass change associated with inflation and deflation of Kīlauea's summit and coincident changes in lava level. The unexpectedly strong mass variations during these episodes suggest magma flux to and from the shallow magmatic system without commensurate deformation, perhaps indicating magma accumulation within, and withdrawal from, void space—a process that might not otherwise be apparent from lava level and deformation data alone. Continuous gravity data thus provide unique insights into magmatic processes, arguing for continued application of the method at other frequently active volcanoes.
Transient deformation in the Asal‐Ghoubbet Rift (Djibouti) since the 1978 diking event: Is deformation controlled by magma supply rates?
Authors: Smittarello D. , Grandin R. , De Chabalier J.‐B. , Doubre C. , Deprez A. , Masson F. , Socquet A. , Saad I. A.
Published: July 2016

The Asal‐Ghoubbet Rift (AG Rift) in Djibouti lies in the subaerial continuation of the Aden ridge system, thereby constituting a unique location to study rifting processes and mechanisms involved in continental breakup and oceanic spreading. Continually upgraded and expanded geodetic technology has been used to record the 1978 Asal rifting event and postdiking deformation. In light of recent results obtained for the Manda Hararo‐Dabbahu rifting event (2005–2010), we propose that the horizontal and vertical geodetic data can be modeled with a double source, involving a dike‐like inflation component aligned along the rift axis and a spherical pressure source located at midsegment below the Fieale caldera. By revisiting the codiking data, we propose that the reservoir below Fieale could have fed, at least partially, the 1978 injection and the contemporaneous Ardoukôba eruption and potentially induced local subsidence due to magma draining out of the central reservoir. As an alternative to previously proposed viscoelastic relaxation models, we reinterpret postdiking observations using a purely elastic rheology. We determine the relative contribution of a midsegment reservoir inflation and a dike‐like opening component, together with their respective time evolutions. Our results suggest that interactions between steadily accumulating tectonic strain and temporal variations in melt supply to the shallow magma plumbing system below the AG Rift may entirely explain the geodetic observations and that viscoelastic deformation processes played a minor role in the 30 years following the 1978 rifting event.
Tidal deformation of Ganymede: Sensitivity of Love numbers on the interior structure
Authors: Kamata Shunichi , Kimura Jun , Matsumoto Koji , Nimmo Francis , Kuramoto Kiyoshi , Namiki Noriyuki
Published: July 2016

Tidal deformation of icy satellites provides crucial information on their subsurface structures. In this study, we investigate the parameter dependence of the tidal displacement and potential Love numbers (i.e., h2 and k2, respectively) of Ganymede. Our results indicate that Love numbers for Ganymede models without a subsurface ocean are not necessarily smaller than those with a subsurface ocean. The phase lag, however, depends primarily on the presence/absence of a subsurface ocean. Thus, the determination of the phase lag would be of importance to infer whether Ganymede possesses a subsurface ocean or not based only on geodetic measurements. Our results also indicate that the major control on Love numbers is the thickness of the ice shell if Ganymede possesses a subsurface ocean. This result, however, does not necessarily indicate that measurement of either of h2 or k2 alone is sufficient to estimate the shell thickness; while a thin shell leads to large h2 and k2 independent of parameters, a thick shell does not necessarily lead to small h2 and k2. We found that to reduce the uncertainty in the shell thickness, constraining k2 in addition to h2 is necessary, highlighting the importance of collaborative analyses of topography and gravity field data.
Electrically Tunable Goos–Hänchen Effect with Graphene in the Terahertz Regime
Authors: Fan Yuancheng , Shen Nian‐Hai , Zhang Fuli , Wei Zeyong , Li Hongqiang , Zhao Qian , Fu Quanhong , Zhang Peng , Koschny Thomas , Soukoulis Costas M.
Published: July 2016

Goos–Hänchen (G–H) effect is of great interest in the manipulation of optical beams. However, it is still fairly challenging to attain efficient controls of the G–H shift for diverse applications. Here, a mechanism to realize tunable G–H shift in the terahertz regime with electrically controllable graphene is proposed. Taking monolayer graphene covered epsilon‐near‐zero metamaterial as a planar model system, it is found that the G–H shifts for the orthogonal s‐polarized and p‐polarized terahertz beams at oblique incidence are positive and negative, respectively. The G–H shift can be modified substantially by electrically controlling the Fermi energy of the monolayer graphene. Reversely, the Fermi energy dependent G–H effect can also be used as a strategy for measuring the doping level of graphene. In addition, the G–H shifts of the system are of strong frequency‐dependence at oblique angles of incidence, therefore the proposed graphene hybrid system can potentially be used for the generation of terahertz “rainbow,” a flat analog of the dispersive prism in optics. The proposed scheme of hybrid system involving graphene for dynamic control of G–H shift will have potential applications in the manipulation of terahertz waves.
Redox Shuttles with Axisymmetric Scaffold for Overcharge Protection of Lithium‐Ion Batteries
Authors: Weng Wei , Huang Jinhua , Shkrob Ilya A. , Zhang Lu , Zhang Zhengcheng
Published: July 2016

The derivatives of 1,4‐dimethoxybenzene are thus far the best performing redox shuttle additives for overcharge protection of Li‐ion batteries. The most durable molecules of this kind typically possess two in‐plane methoxy groups that are equivalent by inversion symmetry. However, such geometry leads to a vanishing average dipole moment that causes poor solubility of these molecules in carbonate‐based electrolytes. In this study, a novel redox shuttle additive, 1,2,3,4‐tetrahydro‐6,7‐dimethoxy‐1,1,4,4‐tetramethyl‐naphthalene (TDTN), is introduced. It has been demonstrated that reversible oxidation at 4.05 V versus Li+/Li, high polarity, high solubility (around 0.4 m), and excellent electrochemical stability (150 overcharge cycles at C/2 rate with 100% overcharge) can all be achieved simultaneously by the imposition of axial symmetry in the corresponding radical cation that is generated by electrochemical oxidation of TDTN in the battery. The intricate interplay between the symmetry and the chemical stability of the radical cation is scrutinized using magnetic resonance spectroscopy and electron structure modeling.
Simulation of dry powder inhalers: Combining micro‐scale, meso‐scale and macro‐scale modeling
Authors: van Wachem Berend , Thalberg Kyrre , Remmelgas Johan , Niklasson‐Björn Ingela
Published: July 2016

The flow of carrier particles, coated with active drug particles, is studied in a prototype dry powder inhaler. A novel, multiscale approach consisting of a discrete element model (DEM) to describe the particles coupled with a dynamic large eddy simulation (LES) model to describe the dynamic nature of the flow is applied. The model consists of three different scales: the micro‐scale, the meso‐scale, and the macro‐scale. At the micro‐scale, the interactions of the small active drug particles with larger carrier particles, with the wall, with the air flow, and with each other is thoroughly studied using discrete element modeling and detailed computational fluid dynamics (CFD), i.e., resolving the flow structures around the particles. This has led to the development of coarse‐grained models, describing the interaction of the small active drug particles at the larger scales. At the meso‐scale the larger carrier particles, and all of their interactions are modeled individually using DEM and CFD‐LES. Collisions are modeled using a visco‐elastic model to describe the local deformation at each point of particle‐particle contact in conjunction with a model to account for cohesion. At the macro‐scale, simulations of a complete prototype inhaler are carried out. By combining the relevant information of each of the scales, simulations of the inhalation of one dose from a prototype inhaler using a patient relevant air flow profile show that fines leave the inhaler faster than the carrier particles. The results also show that collisions are not important for particle‐particle momentum exchange initially but become more important as the particles accelerate. It is shown that for the studied prototype inhaler the total release efficiency of the fine particles is between 10 and 30%, depending on the Hamaker constant, using typical settings for the properties of both particles. The results are also used to study regions of recirculation, where carrier particles can become trapped, and regions where fines adhere to the wall of the device. © 2016 American Institute of Chemical Engineers AIChE J, 63: 501–516, 2017
Structure‐based model for prediction of electrical conductivity of pure ionic liquids
Authors: Wu Ke‐Jun , Luo Haitang , Yang Lingjian
Published: July 2016

A structure‐based method was proposed to estimate the electrical conductivity of ionic liquids covering wide ranges of temperature (238.15–484.1 K) and electrical conductivity (0.0001524–19.3 S/m) based on experimental data collect from literature from 1998 to 2015. The influences of temperature and ion structure on electrical conductivity were also discussed. The mean absolute percentage error between the calculated and literature data was 6.02%, with 6.12% for the training set (1978 data points, 177 ILs) and 5.10% for the test set (217 data points, 11 ILs). © 2016 American Institute of Chemical Engineers AIChE J, 62: 3751–3762, 2016
Histological transformation to diffuse large B‐cell lymphoma in patients with Waldenström macroglobulinemia
Authors: Castillo Jorge J. , Gustine Joshua , Meid Kirsten , Dubeau Toni , Hunter Zachary R. , Treon Steven P.
Published: July 2016

Histological transformation to diffuse large B‐cell lymphoma (DLBCL) rarely occurs in patients with Waldenström Macroglobulinemia (WM). We identified 20 patients out of a cohort of 1,466 WM patients who experienced histologic transformation. The 5, 10, and 15‐year cumulative incidence rates were 1, 2.4, and 3.8%, respectively. Approximately half of the patients were naive to nucleoside analogues, and a quarter were previously untreated for WM at the time of transformation. More than 80% of patients presented with extranodal involvement, 65% with high IPI scores. DLBCL cells did not express CD10 but expressed BCL6 and BCL2. All patients were treated with chemoimmunotherapy. The median survival from histological transformation was 2.7 years. The median overall survival was shorter for transformed patients versus those who did not transform (estimated 9 vs. 16 years; P = 0.09). Histological transformation to DLBCL is rare, and is associated with inferior survival in WM. Am. J. Hematol. 91:1032–1035, 2016. © 2016 Wiley Periodicals, Inc.
Management of relapsed and refractory multiple myeloma in modern times: Incorporating new agents into decision‐making
Authors: Clark Charles A. , Cornell Robert F. , Scott Emma C. , Chung Jae , Costa Luciano J.
Published: July 2016

Although upfront treatment of multiple myeloma has become more effective, relapses are the norm, often driven by the emergence of a genetically divergent clone selected by the initial therapy. Recent trials have demonstrated the safety and efficacy of combination therapy also in the relapsed and refractory setting and supported the regulatory approval of several new agents including new proteasome inhibitors, immunomodulatory agents, and monoclonal antibodies. We provide a detailed summary of recent practice‐changing trials in relapsed and refractory MM and share a practical approach to assimilate disease and patient‐features into treatment decision. Am. J. Hematol. 91:1044–1051, 2016. © 2016 Wiley Periodicals, Inc.
Sustainable polyacetals from erythritol and bioaromatics
Authors: Rostagno Mayra , Price Erik J. , Pemba Alexander G. , Ghiriviga Ion , Abboud Khalil A. , Miller Stephen A.
Published: July 2016

The polymerization of biorenewable molecules to polymers with hydrolyzable main‐chain functionality is one approach to identifying sustainable replacements for common, environmentally unsound packaging plastics. Bioaromatic polyacetals were synthesized via acid‐catalyzed acetal formation from dialdehydes and tetraols. Ethylene linked dialdehyde monomers VV and SS were constructed from bioaromatics vanillin and syringaldehyde, respectively. Tetraol monomers included biogenic erythritol (E), along with pentaerythritol (P), and ditrimethylolpropane (D). Four copolymer series were prepared with varying tetraol content: E/P‐VV; E/D‐VV; E/P‐SS; and E/D‐SS. Number average molecular weights (Mn) ranged from 1,400 to 27,100 Da. Generally, the copolymerization yields were inversely proportional to the feed fraction of erythritol (E), implying that tetraols P and D react more readily. The materials were typically amorphous and exhibited glass transition temperatures (Tg) ranging from 57 to 159 °C, suitably mimicking the Tg values of several commodity plastics. The syringaldehyde‐based copolymers exhibited a higher Tg range (71–159 °C) than the vanillin‐based copolymers (57–110 °C). Accelerated degradation studies in aqueous HCl (3 M, 6 M, concentrated) over 24 h showed that degradation (Mn decrease) was proportional to the acid concentration. A one‐year degradation study of E50/D50‐SS (from 50% feed of erythritol) in seawater, deionized water, tap water, or pH 5 buffer showed no Mn decrease; but in pH 1 buffer, the decrease was 40% (18,800 to 11,200). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44089.
Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam
Authors: Wang Mingyi , Xie Linsheng , Qian Bo , Ma Yulu , Zhou Nanqiao
Published: July 2016

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO2) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO2 was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44094.
Montmorillonite as support for peroxide in the melt grafting of maleic anhydride onto polypropylene
Authors: Muñoz Pablo Andres Riveros , Bettini Sílvia Helena Prado
Published: July 2016

Grafting of maleic anhydride onto polypropylene was performed in a Haake torque rheometer, in the presence of organically modified montmorillonite, MMT (used as support for the peroxide), according to a 23 factorial design, where the maleic anhydride concentration (CMA), peroxide concentration (Cper) and reaction time (tr) were varied. For comparison, the reaction in the absence of MMT was also conducted. Polypropylene degradation was assessed by parallel plate rheometry and size exclusion chromatography (SEC) and percentage of reacted maleic anhydride (%MAg) was obtained by titration and FTIR spectroscopy. The results showed differences in both systems, conventional and in the presence of MMT. The structure of polypropylene grafted with maleic anhydride, PP‐g‐MA, indicates longer branches are formed in the presence of MMT compared to in its absence, demonstrated by FTIR analysis. As in conventional reaction systems, an increase in Cper caused an increase in %MAg and a reduction in molar mass. The variable CMA showed to be not significant in the grafting reaction in the presence of MMT, even at high DCP levels, at a 5% significance level. On the other hand, increase in CMA resulted in significant increase in viscosity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44134.
Temporal regularity of intrinsic cerebral activity in patients with chronic primary insomnia: a brain entropy study using resting‐state fMRI
Authors: Zhou Fuqing , Huang Suhua , Gao Lei , Zhuang Ying , Ding Shan , Gong Honghan
Published: July 2016

Introduction

Several neuroimaging studies have suggested that patients with chronic primary insomnia (CPI) exhibit anatomical and functional alterations of the brain, but the temporal regularity in spontaneous neuronal activity remains unknown. Here, brain entropy (BEN), a data‐driven method used to measure the signal regularity of a time series, was applied for the first time to investigate changes in the entire brain at the voxel level.

Methods

Resting‐state functional MRI data were used to investigate insomnia‐related BEN alterations and the resting‐state functional connectivity (rsFC) pattern in seed regions with altered BEN in 29 patients with identified and untreated CPI and 29 matched healthy controls. Subsequently, within the CPI group, correlation analysis was conducted to evaluate the relationship between the clinical variables and the BEN and rsFC of the abnormal regions.

Results

Chronic primary insomnia patients showed significant increase in BEN in the central part of the default‐mode network (DMN), the anterior regions of the task‐positive network (TPN), the hippocampus (Hipp), and basal ganglia (BG), and decreases in BEN in the right postcentral gyrus (PoCG) and right temporal–occipital junction (TOJ). We also demonstrated that three altered resting‐state functional connectivity (rsFC) patterns were associated with abnormal BEN regions in CPI patients. Correlation analysis identified an association between the altered rsFC and clinical variables, such as the Pittsburgh Sleep Quality Index (PSQI), in CPI patients.

Conclusions

Together, these findings suggest that abnormal BEN‐related intrinsic functional plasticity in CPI patients corresponds to poor sleep quality during chronic insomnia. Alterations in both BEN and its affected connectivity may improve our understanding of treatment‐naïve CPI patients and promote the future development of new therapeutic strategies.
Sonographic evaluation of jugulodigastric and juguloomohyoid lymph nodes
Authors: Öztoprak Bilge , Öztoprak İbrahim , Sönmez Muhittin , Haydar Atalar Mehmet , Arslan Mübeccel
Published: July 2016

The jugulodigastric (JD) and juguloomohyoid (JO) lymph nodes are levels II and III cervical lymph nodes corresponding to the upper and middle internal jugular chains, respectively. The aim of this study is to delineate the sonographic properties of these two nodes, which are commonly encountered in routine neck sonography, in subjects with normal neck ultrasound findings. Atypical findings can make it difficult to differentiate benign from malignant lymph nodes. The JD and JO lymph nodes of 126 subjects were examined by ultrasonography, and size, shape, presence of echogenic hilus and Doppler activity were recorded. Among the lymph nodes examined, 31.6% were not elliptical. Proportionally more of the JO than the JD nodes were round; there was a significant difference in roundness index between them (P < 0.05). An echogenic hilus was demonstrated in 223 of the 252 JD nodes and in 161 of the 252 JO nodes. Significantly more of the lymph nodes with roundness index <2 lacked a visible echogenic hilus. There was a positive correlation between the visibility of an echogenic hilus and Doppler activity. Normal jugulodigastric and juguloomohyoid lymph nodes are relatively prominent in the upper and middle jugular chains, respectively. Awareness of variations in the sonographic appearance of these nodes could preclude unnecessary procedures. Clin. Anat. 29:943–948, 2016. © 2016 Wiley Periodicals, Inc.
Impurities in Nitrile Solvents Commonly Used for Electrochemistry, and their Effects on Voltammetric Data
Authors: Tessensohn Malcolm E. , Ng Shu Jun , Chan Kwok Kiong , Gan Sher Li , Sims Natalie F. , Koh Yu Rong , Webster Richard D.
Published: July 2016

Voltammetry experiments were performed on 1,4‐benzoquinone and 1,4‐phenylenediamine in acetonitrile, propionitrile (from five commercial suppliers: Acros Organics, Aldrich, Alfa Aesar, Fluka, and Merck), and butyronitrile, to which different electrochemical responses were collected across the three nitrile solvents and within the five commercial brands of propionitrile, owing to the reduced (1,4‐benzoquinone) or oxidized (1,4‐phenylenediamine) compounds reacting with impurities in the solvents. Of the three solvents, propionitrile suffered from the most impurities, which adversely affected the electrochemical results. Distillation of the propionitrile over phosphorus pentoxide or passing it through a flash column containing silica gel was partially effective in removing some of the impurities and resulted in the recovery of the familiar oxidation behavior of 1,4‐phenylenediamine. The reduction behavior of 1,4‐benzoquinone could be improved if propionitrile was purified by passing it through a column of basic activated alumina, thus a combination of distillation and flash chromatography is necessary to adequately purify propionitrile for reductive and oxidative voltammetry experiments. Purge and trap‐gas chromatography–mass spectrometry analyses positively identified 2‐methyl‐2‐pentenal among the impurities, but it was discovered to only have a mild effect on the voltammetric behavior of the quinone and not exert any influence on the electrochemical response of the phenylenediamine. The results of this study lead to the possibility of using the voltammetry of quinones and phenylenediamines as a sensitive method for determining the purity of organic solvents.
Electrocatalytic Oxidation of Alcohols, Tripropylamine, and DNA with Ligand‐Free Gold Nanoclusters on Nitrided Carbon
Authors: Yao Huiqin , Liu Ben , Mosa Islam M. , Bist Itti , He Jie , Rusling James F.
Published: July 2016

Electrocatalytic properties of ligand‐free gold nanoclusters (AuNCs, <2 nm) grown on nitrided carbon supports (denoted as AuNCs@N‐C) were evaluated for the oxidation of representative organic molecules including alcohols, an amine, and deoxyguanosine in oligonucleotides. AuNCs@N‐C catalysts were incorporated into films of architecture {PDDA/AuNCs@N‐C}n by using layer‐by‐layer assembly with oppositely charged poly(diallyldimethylammonium) (PDDA) on pyrolytic graphite (PG) electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to survey the electrocatalytic properties of these AuNCs@N‐C films. Ligand‐free AuNCs in these films demonstrated excellent electrocatalytic oxidation activity with maximum peak currents and the lowest potentials for oxidizing ethanol, propanol, and tripropylamine (TprA) compared to controls with Au‐surface capping agents or to larger sized Au nanocrystals on the nitrided carbon supports. EIS kinetic studies showed that ligand‐free AuNCs films have the smallest charge‐transfer resistance, largest electrochemically active surface area, and largest apparent standard rate constants, as compared to the control films for all compounds examined. DNA films on AuNCs@N‐C were oxidized at deoxyguanosine moieties with good catalytic activity that depended on charge transport within the films.
Mechanochemical Cycloreversion of Cyclobutane Observed at the Single Molecule Level
Authors: Pill Michael F. , Holz Katharina , Preußke Nils , Berger Florian , Clausen‐Schaumann Hauke , Lüning Ulrich , Beyer Martin K.
Published: July 2016

Mechanochemical cycloreversion of cyclobutane is known from ultrasound experiments. It is, however, not clear which forces are required to induce the cycloreversion. In atomic force microscopy (AFM) experiments, on the other hand, it is notoriously difficult to assign the ruptured bond. We have solved this problem through the synthesis of tailored macrocycles, in which the cyclobutane mechanophore is bypassed by an ethylene glycol chain of specific length. This macrocycle is covalently anchored between a glass substrate and an AFM cantilever by polyethylene glycol linkers. Upon mechanical stretching of the macrocycle, cycloreversion occurs, which is identified by a defined length increase of the stretched polymer. The measured length change agrees with the value calculated with the external force explicitly included (EFEI) method. By using two different lengths for the ethylene glycol safety line, the assignment becomes unambiguous. Mechanochemical cycloreversion of cyclobutane is observed at forces above 1.7 nN.
1H NMR‐Guided Isolation of Formyl‐Phloroglucinol Meroterpenoids from the Leaves of Eucalyptus robusta
Authors: Shang Zhi‐Chun , Yang Ming‐Hua , Jian Kai‐Li , Wang Xiao‐Bing , Kong Ling‐Yi
Published: July 2016

Nine formyl‐phloroglucinolmeroterpenoids (FPMs), namely, eucalrobusones A–I (1–9), were isolated from the leaves of Eucalyptus robusta by tracking the phenolic hydroxyl 1H NMR peaks. The Snatzke helicity rules for the Cotton effects of twisted benzene rings were applied to elucidate the absolute configurations of the FPMs. These findings, along with NMR spectroscopy, the circular dichroism (CD) exciton chirality method, and CD calculations, allowed complete structures for the FPMs to be assigned. Eucalrobusones A–F (1–6) are novel adducts formed between a formyl‐derived carbon atom on the phloroglucinol ring and monoterpene and sesquiterpene components. Eucalrobusones G–I (7–9) are the first examples of FPMs with cubebane part structures connected by an unusual 1‐oxaspiro[5.5]undecane subunit. Among these isolates, eucalrobusone C (3) showed significant cytotoxicity against HepG2, MCF‐7, and U2OS cancer cell lines, with IC50 values less than 10 μm. Compound 3 significantly blocks cell proliferation in MCF‐7 cells and induces MCF‐7 cell death through apoptosis.
Toward the Rational Design of Galactosylated Glycoclusters That Target Pseudomonas aeruginosa Lectin A (LecA): Influence of Linker Arms That Lead to Low‐Nanomolar Multivalent Ligands
Authors: Wang Shuai , Dupin Lucie , Noël Mathieu , Carroux Cindy J. , Renaud Louis , Géhin Thomas , Meyer Albert , Souteyrand Eliane , Vasseur Jean‐Jacques , Vergoten Gérard , Chevolot Yann , Morvan François , Vidal Sébastien
Published: July 2016

Anti‐infectious strategies against pathogen infections can be achieved through antiadhesive strategies by using multivalent ligands of bacterial virulence factors. LecA and LecB are lectins of Pseudomonas aeruginosa implicated in biofilm formation. A series of 27 LecA‐targeting glycoclusters have been synthesized. Nine aromatic galactose aglycons were investigated with three different linker arms that connect the central mannopyranoside core. A low‐nanomolar (Kd=19 nm, microarray) ligand with a tyrosine‐based linker arm could be identified in a structure–activity relationship study. Molecular modeling of the glycoclusters bound to the lectin tetramer was also used to rationalize the binding properties observed.
High‐Performance Blue OLEDs Based on Phenanthroimidazole Emitters via Substitutions at the C6‐ and C9‐Positions for Improving Exciton Utilization
Authors: Liu Bin , Yuan Yi , He Dan , Huang De‐Yue , Luo Cheng‐Yuan , Zhu Ze‐Lin , Lu Feng , Tong Qing‐Xiao , Lee Chun‐Sing
Published: July 2016

Donor–acceptor (D–A) molecular architecture has been shown to be an effective strategy for obtaining high‐performance electroluminescent materials. In this work, two D–A molecules, Ph‐BPA‐BPI and Py‐BPA‐BPI, have been synthesized by attaching highly fluorescent phenanthrene or pyrene groups to the C6‐ and C9‐positions of a locally excited‐state emitting phenylamine–phenanthroimidazole moiety. Equipped with good physical and hybridized local and charge‐transfer properties, both molecules show high performances as blue emitters in nondoped organic light‐emitting devices (OLEDs). An OLED using Ph‐BPA‐BPI as the emitting layer exhibits deep‐blue emission with CIE coordinates of (0.15, 0.08), and a maximum external quantum efficiency (EQE), current efficiency (CE), and power efficiency (PE) of 4.56 %, 3.60 cd A−1, and 3.66 lm W−1, respectively. On the other hand, a Py‐BPA‐BPI‐based, sky‐blue OLED delivers the best results among nondoped OLEDs with CIEy values of < 0.3 reported so far, for which a very low turn‐on voltage of 2.15 V, CIE coordinates of (0.17, 0.29), and maximum CE, PE, and EQE values of 10.9 cd A−1, 10.5 lm W−1, and 5.64 %, were achieved, respectively. More importantly, both devices show little or even no efficiency roll‐off and high singlet exciton‐utilizing efficiencies of 36.2 % for Ph‐BPA‐BPI and 39.2 % for Py‐BPA‐BPI.
Synthesis, Characterization and Properties of Expanded Pyriporphyrins: A New Family of Alkylidenyl Porphyrin Homologues Bearing meso‐Exocyclic Double Bonds
Authors: Abebayehu Abeje , Dutta Ranjan , Lee Chang‐Hee
Published: July 2016

We present the synthesis and characterization of a new family of expanded meso‐alkylidenyl (2,6‐pyri)porphyrinoids bearing multiple exocyclic double bonds at the meso‐positions. The synthesis was accomplished by using mixed pyrrole condensation. Similar to meso‐alkylidenyl porphyrinoids, this study revealed that pyriporphyrinoids do not possess a porphyrin‐like, global‐aromatic character. The synthesized 2,6‐pyripentaphyrin 1 displays selective ratiometric sensing of pyrophosphate anion in organic solvent.
Pt‐Catalyzed Synthesis of Functionalized Symmetrical and Unsymmetrical Disilazanes
Authors: Kuciński Krzysztof , Szudkowska‐Frątczak Justyna , Hreczycho Grzegorz
Published: July 2016

In nearly every total synthesis, silylating agents are employed in synthetic steps to protect sensitive functional groups. A Pt‐catalyzed hydrosilylation of various unsaturated substrates to prepare novel symmetrical and unsymmetrical disilazanes is described. The developed synthetic methodology is widely applicable and tolerates all manner of functional groups (e.g., amines, ethers, esters, halogens, silanes, etc.). To demonstrate the value of the described method, mono‐substituted 1,1,3,3‐tetramethyldisilazanes were further selectively converted to completely new unsymmetrical derivatives.
Near‐Infrared‐Emitting BODIPY‐trisDOTA111In as a Monomolecular Multifunctional Imaging Probe: From Synthesis to In Vivo Investigations
Authors: Maindron Nicolas , Ipuy Martin , Bernhard Claire , Lhenry Damien , Moreau Mathieu , Carme Sabin , Oudot Alexandra , Collin Bertrand , Vrigneaud Jean‐Marc , Provent Peggy , Brunotte François , Denat Franck , Goze Christine
Published: July 2016

A new generation of monomolecular imaging probes (MOMIP) based on a distyryl‐BODIPY (BODIPY=boron‐dipyrromethene) coupled with three DOTA macrocycles has been prepared (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The MOMIP presents good fluorescence properties and is very stable in serum. The bimodal probe was conjugated to trastuzumab, and an optical in vivo study showed high accumulation of the imaging agent at the tumor site. 111In radiometallation of the bioconjugate was performed in high radiochemical yield, highlighting the potential of this new BODIPY‐chelators derivative as a bimodal imaging probe.
A New Generation of Smart Amine Donors for Transaminase‐Mediated Biotransformations
Authors: Gomm Andrew , Lewis William , Green Anthony P. , O'Reilly Elaine
Published: July 2016

The application of ω‐transaminase biocatalysts for the synthesis of optically pure chiral amines presents a number of challenges, including difficulties associated with displacing the challenging reaction equilibria. Herein, we report a highly effective approach using low equivalents of the new diamine donor, cadaverine, which enables high conversions of challenging substrates to the corresponding chiral amines in excellent ee. This approach paves the way for the design of self‐sufficient fermentation processes combining transaminase biotransformations with existing strategies for cadaverine production by decarboxylation of endogenous lysine.
ZIF‐8 SURMOF Membranes Synthesized by Au‐Assisted Liquid Phase Epitaxy for Application in Gas Separation
Authors: Valadez Sánchez Elvia P. , Gliemann Hartmut , Haas‐Santo Katja , Wöll Christof , Dittmeyer Roland
Published: July 2016

Metal‐organic frameworks (MOFs) exhibit a huge potential for gas separation. ZIF‐8 is an interesting candidate due to its high thermal stability and its pore properties. By liquid phase epitaxy, the growth of the highly oriented surface‐anchored MOF ZIF‐8 on non‐porous and porous surfaces has been proven. The preparation of monolithic ZIF‐8 thin films supported by porous α‐Al2O3 substrates modified by a thin layer of Au is investigated. The layer‐by‐layer deposition process accomplished via a dipping procedure results in the formation of defect‐ or crack‐free membranes, preliminary characterized by the determination of ethane and ethene permeance.
Chlorophyll
Authors: Klaproth Anne , Najdanova Maria , Minceva Mirjana , Sicker Dieter , Siehl Hans‐Ullrich , Zeller Klaus‐Peter , Berger Stefan
Published: July 2016

Chlorophyll existiert seit ca. 3 Mrd. Jahren und steht mit am Beginn der Evolution. Dieser chirale, grüne Magnesium‐Porphyrin‐Komplex absorbiert als Photosensibilisator in den Antennen der Lichtsammelkomplexe der Chloroplasten alle Anteile des sichtbaren Lichts außer Grün. Diese Energie wird an die Reaktionszentren der oxygenen Photosynthese weitergeleitet. In dieser Redoxreaktion entstehen aus Kohlendioxid und Wasser Kohlenhydrate und Sauerstoff. Wir beschreiben die Strukturaufklärung der Chlorophylle, diskutieren Struktur und Eigenschaften, ihre Verwandtschaft zum Häm des Blutes, Alltagsanwendungen und denken über Grünes in der Sprache nach. Die Reinisolierung von Chlorophyll a aus Spinat ist eine experimentelle Herausforderung, die wir im Detail schildern. Alle analytischen Spektren werden vollständig entweder im Hauptteil oder in der supporting information wiedergegeben und interpretiert.
Rational design of a serum‐free culture medium for the growth of human myoblasts destined to cell therapy
Authors: Parent Victor A. , Tremblay Jacques P. , Garnier Alain
Published: July 2016

Cellular therapy of Duchenne muscular dystrophy is currently showing encouraging results. However, there is still no serum‐free medium that allows multiplying functional myoblasts, the cells required for this therapy, obtained from healthy donors, in sufficient number. A systematic screen for a defined culture medium that would allow expanding fully functional human myoblasts at the same rate and to the same extent as the existing serum‐containing medium has been undertaken. To this end, 6 basal media and more than 60 defined additives have been screened for their individual as well as synergistic effects. The medium developed in this study permits a 12‐log expansion of human myoblasts over a 60‐day period. The cells obtained have the same capacity to fuse and form myofibres as myoblasts multiplied in serum‐containing medium.
16‐Membered Macrolide Lactone Derivatives Bearing a Triazole‐Functionalized Arm at the Aglycone C13 Position as Antibacterial and Anticancer Agents
Authors: Domagalska Joanna , Janas Anna , Pyta Krystian , Pecyna Paulina , Ruszkowski Piotr , Celewicz Lech , Gajecka Marzena , Bartl Franz , Przybylski Piotr
Published: July 2016

A series of new C13‐triazole‐bridged and C13‐ether leucomycin analogues with a reduced aldehyde group were synthesized. Derivatives with the highest antibacterial [MIC values (S. epidermidis, S. pneumoniae): ∼2–4 μg mL−1; 2.55–5.09 μm] and cytotoxic [IC50 values (HeLa, KB, MCF‐7, A549, HepG2 cells): ∼1.35–3.70 μm] potencies were those with the best aqueous solubility and bearing a saccharide‐triazole arm at the C13 position of the aglycone. These derivatives preferentially bind at the ribosomal tunnel and show the most attractive selectivity indexes [SI; calculated relative to the human dermal fibroblast (HDF) cell line], even higher than that of the reference compound cytarabine. Results of molecular docking studies of this type of macrolide antibiotics at the ribosomal tunnel, together with experimentally determined lipophilicity and aqueous solubility values, as well as biological assay data revealed the importance of the introduced functional group at the aglycone C13 arm to the future design of anticancer and antibacterial drug candidates. Our results clearly indicate that the high antibacterial and anticancer activities of these types of macrolides do not necessarily depend on the presence of the aldehyde group at the aglycone lactone ring.
Progress in the Development of Lysine Methyltransferase SETD8 Inhibitors
Authors: Milite Ciro , Feoli Alessandra , Viviano Monica , Rescigno Donatella , Mai Antonello , Castellano Sabrina , Sbardella Gianluca
Published: July 2016

SETD8/SET8/Pr‐SET7/KMT5A is the only known lysine methyltransferase that monomethylates lysine 20 of histone H4 (H4K20) in vivo. The methyltransferase activity of SETD8 has been implicated in many essential cellular processes, including DNA replication, DNA damage response, transcription modulation, and cell cycle regulation. In addition to H4K20, SETD8 monomethylates non‐histone substrates including proliferating cell nuclear antigen and p53. During the past decade, different structural classes of inhibitors targeting various lysine methyltransferases have been designed and developed. However, the development of SETD8 inhibitors is still in its infancy. This review covers the progress made to date in inhibiting the activity of SETD8 by small molecules, with an emphasis on their discovery, selectivity over other methyltransferases, and cellular activity.
Direct Chemical Fine‐Tuning of Electronic Properties in Sc2Ir6−xPdxB
Authors: Koumoulis Dimitrios , Scheifers Jan P. , St. Touzani Rachid , Fokwa Boniface P. T. , Bouchard Louis‐S.
Published: July 2016

Crystal orbital Hamilton population (COHP) bonding analysis has predicted that ScPd3B0.5 is the least stable compound of the entire series Sc2Ir6−xPdxB. Here, we report a systematic study of Sc2Ir6−xPdxB (x=3, 5 and 6) by means of 11B nuclear magnetic resonance (NMR), Knight shift (K) and nuclear spin‐lattice relaxation rate (1/T1). NMR results combined with theoretical band structure calculations provide a measure of s‐ and non‐s‐character Fermi‐level density of states. We present direct evidence that the enhanced s‐state character of the Fermi level density of states (DOS) in ScPd3B0.5 reduces the strength of the B 2p and Pd 4d hybridized states across the entire Sc2Ir6−xPdxB series. This hybridization strength relates to the opening of a deep pseudogap in the density of states of Sc2IrPd5B and the chemical bonding instability of ScPd3B0.5. This study is an experimental realization of a chemical fine‐tuning of the electronic properties in intermetallic perovskites.
Light‐Induced Cell‐Sheet Harvest on TiO2 Films Sensitized with Carbon Quantum Dots
Authors: Wang Xiaozhao , Cheng Kui , Weng Wenjian , Wang Huiming , Lin Jun
Published: July 2016

Carbon quantum dots (CQDs) have been incorporated as a sensitizer into TiO2 films to regulate the light‐induced cell‐detachment performance. Depending on the amount of CQDs incorporated, nanodots or porous films are obtained. It was found that the right amount of CQDs incorporation significantly improves the cell‐sheet detachment efficiency, and an intact cell sheet could be obtained after merely five minutes of UV illumination (365 nm, UV365), which is much faster than that from CQDs‐free TiO2 film. Furthermore, cell sheets on CQDs‐sensitized TiO2 films show improved viability, and alkaline phosphatase and collagen I activity either before or after light‐induced detachment. The improved cell‐detachment performance is ascribed to the effective inhibition of charge recombination of the TiO2 film and the microstructure variations, which increase the negative surface potential and change the secondary structure of the adsorbed extracellular protein molecules; this results in a faster release of cells. It is suggested that the faster release reduces the possible detrimental impact on cell functions during detachment and helps in maintaining the excellent cellular activity. This study demonstrates that CQDs sensitization is an effective approach for optimizing the performance of light‐induced cell‐sheet harvest.
Successful Comparison of US Food and Drug Administration Sentinel Analysis Tools to Traditional Approaches in Quantifying a Known Drug‐Adverse Event Association
Authors: Gagne JJ , Han X , Hennessy S , Leonard CE , Chrischilles EA , Carnahan RM , Wang SV , Fuller C , Iyer A , Katcoff H , Woodworth TS , Archdeacon P , Meyer TE , Schneeweiss S , Toh S
Published: July 2016

The US Food and Drug Administration's Sentinel system has developed the capability to conduct active safety surveillance of marketed medical products in a large network of electronic healthcare databases. We assessed the extent to which the newly developed, semiautomated Sentinel Propensity Score Matching (PSM) tool could produce the same results as a customized protocol‐driven assessment, which found an adjusted hazard ratio (HR) of 3.04 (95% confidence interval [CI], 2.81–3.27) comparing angioedema in patients initiating angiotensin‐converting enzyme (ACE) inhibitors vs. beta‐blockers. Using data from 13 Data Partners between 1 January 2008, and 30 September 2013, the PSM tool identified 2,211,215 eligible ACE inhibitor and 1,673,682 eligible beta‐blocker initiators. The tool produced an HR of 3.14 (95% CI, 2.86–3.44). This comparison provides initial evidence that Sentinel analytic tools can produce findings similar to those produced by a highly customized protocol‐driven assessment.
A new gain‐of‐function mouse line to study the role of Wnt3a in development and disease
Authors: Chalamalasetty Ravindra B. , Ajima Rieko , Garriock Robert J. , Kennedy Mark W. , Tessarollo Lino , Yamaguchi Terry P.
Published: July 2016

Wnt/β‐catenin signals are important regulators of embryonic and adult stem cell self‐renewal and differentiation and play causative roles in tumorigenesis. Purified recombinant Wnt3a protein, or Wnt3a‐conditioned culture medium, has been widely used to study canonical Wnt signaling in vitro or ex vivo. To study the role of Wnt3a in embryogenesis and cancer models, we developed a Cre recombinase activatable Rosa26Wnt3a allele, in which a Wnt3a cDNA was inserted into the Rosa26 locus to allow for conditional, spatiotemporally defined expression of Wnt3a ligand for gain‐of‐function (GOF) studies in mice. To validate this reagent, we ectopically overexpressed Wnt3a in early embryonic progenitors using the T‐Cre transgene. This resulted in up‐regulated expression of a β‐catenin/Tcf‐Lef reporter and of the universal Wnt/β‐catenin pathway target genes, Axin2 and Sp5. Importantly, T‐Cre; Rosa26Wnt3a mutants have expanded presomitic mesoderm (PSM) and compromised somitogenesis and closely resemble previously studied T‐Cre; Ctnnb1ex3 (β‐cateninGOF) mutants. These data indicate that the exogenously expressed Wnt3a stimulates the Wnt/β‐catenin signaling pathway, as expected. The Rosa26Wnt3a mouse line should prove to be an invaluable tool to study the function of Wnt3a in vivo.
Modeling stream fish distributions using interval‐censored detection times
Authors: Ferreira Mário , Filipe Ana Filipa , Bardos David C. , Magalhães Maria Filomena , Beja Pedro
Published: July 2016

Controlling for imperfect detection is important for developing species distribution models (SDMs). Occupancy‐detection models based on the time needed to detect a species can be used to address this problem, but this is hindered when times to detection are not known precisely. Here, we extend the time‐to‐detection model to deal with detections recorded in time intervals and illustrate the method using a case study on stream fish distribution modeling. We collected electrofishing samples of six fish species across a Mediterranean watershed in Northeast Portugal. Based on a Bayesian hierarchical framework, we modeled the probability of water presence in stream channels, and the probability of species occupancy conditional on water presence, in relation to environmental and spatial variables. We also modeled time‐to‐first detection conditional on occupancy in relation to local factors, using modified interval‐censored exponential survival models. Posterior distributions of occupancy probabilities derived from the models were used to produce species distribution maps. Simulations indicated that the modified time‐to‐detection model provided unbiased parameter estimates despite interval‐censoring. There was a tendency for spatial variation in detection rates to be primarily influenced by depth and, to a lesser extent, stream width. Species occupancies were consistently affected by stream order, elevation, and annual precipitation. BayesianP‐values andAUCs indicated that all models had adequate fit and high discrimination ability, respectively. Mapping of predicted occupancy probabilities showed widespread distribution by most species, but uncertainty was generally higher in tributaries and upper reaches. The interval‐censored time‐to‐detection model provides a practical solution to model occupancy‐detection when detections are recorded in time intervals. This modeling framework is useful for developingSDMs while controlling for variation in detection rates, as it uses simple data that can be readily collected by field ecologists.