bluuebunny/crossref_metadata_2025 huggingface dataset:
Modulating silica‐rubber interface by a biorenewable urushiol derivative. Synthesis, surface modification, and mechanical and dynamic mechanical properties of vulcanizates therefrom
Authors: Yan Xuesong , Hamed Gary R. , Jia Li
Published: November 2017

Hydrogenated urushiol (i.e., 3‐pentadecylcatechol) can be used to directly modify silica particles via surface complexation with silicon. The degree of surface coverage can be varied by experimental conditions. Mooney viscosity and Payne effect studies of uncured rubber compounds show that dispersion of silica filler completely covered by hydrogenated urushiol in the absence of coupling agent bis[3‐(triethoxysilyl)propyl] tetrasulfide (TESPT) is as effective as dispersion of standard unmodified silica in the presence of TESPT under otherwise identical mixing conditions. Low bound rubber content and observation of filler flocculation at the early stage of vulcanization demonstrate that the filler‐rubber interaction is physical in nature as the result of surface modification by hydrogenated urushiol. When silica is partially covered by hydrogenated urushiol, it can be used in conjunction with TESPT. Judicial combination of partially covered silica and TESPT can give optimal properties to the resultant vulcanizate, including reduced Payne effect and improved cut resistance while maintaining other key parameters the same in comparison with a standard silica‐TESPT reinforced rubber. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45937.
Online prediction of the filtration performance of polypropylene melt blown nonwovens by blue‐colored glow
Authors: Zhang Haifeng , Liu Jinxin , Zhang Xing , Huang Chen , Jin Xiangyu
Published: November 2017

In recently years, fine particulate matter (PM) pollution has drawn worldwide attention due to its serious threat to public health, visibility, climate, and ecosystems. The electret filter that can significantly improve the filtration efficiency without increasing the pressure drop has been widely used to for PM filtration. However, there were still some blind spots in the corona charging process, such as the interaction effects between the charging factors on the electret performances and the electric spark phenomenon during charging, which generate challenges for further improving the electret performance. Herein, we report an inconspicuous charging phenomenon that a blue‐colored glow was observed during corona charging process. We named it as “Waterfall glow”, because a lot of charges appear to flow. The relationship between the blue‐colored glow and the filtration efficiency was investigated. The results showed that the filtration performance of the electret melt blown was positively correlated to the intensity of blue‐colored glow. The phenomenon enables us to online predict the filtration performance of the electret material in the actual production. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45948.
Crystal and NMR Structures of a Peptidomimetic β‐Turn That Provides Facile Synthesis of 13‐Membered Cyclic Tetrapeptides
Authors: Cameron Alan J. , Squire Christopher J. , Edwards Patrick J. B. , Harjes Elena , Sarojini Vijayalekshmi
Published: November 2017

Herein we report the unique conformations adopted by linear and cyclic tetrapeptides (CTPs) containing 2‐aminobenzoic acid (2‐Abz) in solution and as single crystals. The crystal structure of the linear tetrapeptide H2N‐d‐Leu‐d‐Phe‐2‐Abz‐d‐Ala‐COOH (1) reveals a novel planar peptidomimetic β‐turn stabilized by three hydrogen bonds and is in agreement with its NMR structure in solution. While CTPs are often synthetically inaccessible or cyclize in poor yield, both 1 and its N‐Me‐d‐Phe analogue (2) adopt pseudo‐cyclic frameworks enabling near quantitative conversion to the corresponding CTPs 3 and 4. The crystal structure of the N‐methylated peptide (4) is the first reported for a CTP containing 2‐Abz and reveals a distinctly planar 13‐membered ring, which is also evident in solution. The N‐methylation of d‐Phe results in a peptide bond inversion compared to the conformation of 3 in solution.
Excited‐State Proton Transfer Reaction of Pyranine in Aqueous Sugar and Alcohol Solutions Investigated by Fluorescence Spectroscopy
Authors: Hong Young‐Ho , Cheong Byeong‐Seo , Cho Han‐Gook
Published: November 2017

The fluorescence emission behaviors of excited pyranine (PyOH*) and deprotonated pyranine (PyO−*) were studied to explore the effects of sugar or alcohol on the excited‐state proton transfer (ESPT) reaction of pyranine in aqueous solutions. The fluorescence intensity ratio, Q between the two emission bands of pyranine varies significantly with the type and concentration of sugar or alcohol in aqueous solution. The results clearly show that a higher Q value (more PyOH* and less PyO−*) reflects a lower ESPT rate due to less free water molecules for solvation of PyO−* and H+. Higher Q values were observed in sugar solutions while lower values in alcohol solutions. Larger alcohols yielded higher Q values and the values for polyols (ethylene glycol and glycerin) were between those of methanol and ethanol, revealing that the hydroxyl groups in polyols form intramolecular hydrogen‐bond. The location of the hydroxyl group was also found to affect the intensity ratio, Q. The conductivities of 0.01 M HCl in aqueous sugar and alcohol solutions are consistent with the Q values observed, and the inverse of Q show a quadratic relation with conductivity. The enthalpy and entropy changes for the deprotonation reaction of PyOH* in fructose and ethanol aqueous solutions were also determined, assuming that the deprotonation reaction was an equilibrated process. The higher ΔH in fructose solution reveal that deprotonation of PyOH* in sugar solution is energetically less favored than in ethanol solution because solvation of fructose requires more water molecules.
Racial disparity in utilization of therapeutic modalities among multiple myeloma patients: a SEER‐medicare analysis
Authors: Ailawadhi Sikander , Frank Ryan D. , Advani Pooja , Swaika Abhisek , Temkit M'hamed , Menghani Richa , Sharma Mayank , Meghji Zahara , Paulus Shumail , Khera Nandita , Hashmi Shahrukh K. , Paulus Aneel , Kakar Tanya S. , Hodge David O. , Colibaseanu Dorin T. , Vizzini Michael R. , Roy Vivek , Colon‐Otero Gerardo , Chanan‐Khan Asher A.
Published: November 2017

Outcomes have improved considerably in multiple myeloma (MM), but disparities among racial‐ethnic groups exist. Differences in utilization of novel therapeutics are likely contributing factors. We explored such differences from the SEER‐Medicare database. A utilization analysis of lenalidomide, thalidomide, bortezomib, and stem cell transplant (SCT) was performed for patients diagnosed with MM between 2007 and 2009, including use over time, use by race, time‐dependent trends for each racial subgroup, and survival analysis. A total of 5338 MM patients were included with median 2.4‐year follow‐up. Within the first year of MM diagnosis, utilization of lenalidomide, bortezomib, SCT, and more than one novel agent increased over time while utilization of thalidomide decreased. There was significantly lower utilization of lenalidomide among African‐Americans (P < 0.01), higher thalidomide use among Hispanics and Asians (P < 0.01), and lower bortezomib use among Asians (P < 0.01). Hispanics had the highest median number of days to first dose of bortezomib (P = 0.02) and the lowest utilization of SCT (P < 0.01). Hispanics and Asians were the only groups without notable increases in lenalidomide and bortezomib use, respectively. SCT utilization increased over time for all except African‐Americans. SCT use within the first year after diagnosis was associated with better overall survival (HR 0.52; 95% CI: 0.4–0.68), while bortezomib use was associated with inferior survival (HR 1.14; 95% CI 1.02–1.28). We noted considerable variability in MM therapeutics utilization with seeming inequity for racial‐ethnic minorities. These trends should be considered to eliminate drug access and utilization disparities and achieve equitable benefit of therapeutic advances across all races.
Aerobic Oxygenation of Alkylarenes over Ultrafine Transition‐Metal‐Containing Manganese‐Based Oxides
Authors: Nakai Satoru , Uematsu Tsubasa , Ogasawara Yoshiyuki , Suzuki Kosuke , Yamaguchi Kazuya , Mizuno Noritaka
Published: November 2017

The oxygenation of alkylarenes to the corresponding aryl ketones is an important reaction, and the development of efficient heterogeneous catalysts that can utilize O2 as the sole oxidant is highly desired. In this study, we developed an efficient alkylarene oxygenation process catalyzed by ultrafine transition‐metal‐containing Mn‐based oxides with spinel or spinel‐like structures (M‐MnOx, M=Fe, Co, Ni, Cu). These M‐MnOx catalysts were prepared by a low‐temperature reduction method in 2‐propanol‐based solutions using tetra‐n‐butyl ammonium permanganate (TBAMnO4) as the Mn source, and they exhibited high Brunauer–Emmett–Teller surface areas (typically >400 m2 g−1). Using fluorene as the model substrate, the catalytic activities of M‐MnOx and Mn3O4 were compared. The catalytic activities of M‐MnOx were significantly higher than that of Mn3O4, which demonstrates that the incorporation of transition metals in manganese oxide was critical. Among the series of M‐MnOx catalysts examined, Ni‐MnOx exhibited the highest catalytic activity for the oxygenation. In addition, the catalytic activity of Ni‐MnOx was higher than that of a physical mixture of Mn3O4 and NiO. Furthermore, Ni‐MnOx exhibited a broad substrate scope with respect to various types of structurally diverse (hetero)alkylarenes (16 examples). The observed catalysis was truly heterogeneous, and the Ni‐MnOx catalyst was reusable for the oxygenation of fluorene at least three times and its high catalytic performance was preserved, for example, the reaction rate, final product yield, and product selectivity. The present Ni‐MnOx‐catalyzed oxygenation process is possibly initiated by a single‐electron oxidation process, and herein a plausible oxygen‐transfer mechanism is proposed based on several pieces of experimental evidence.
Porous Materials as Highly Efficient Electrocatalysts for the Oxygen Evolution Reaction
Authors: Qi Jing , Zhang Wei , Cao Rui
Published: November 2017

Carbon‐neutral hydrogen has potential to alleviate the energy crisis and ease environmental problems. Water electrolysis is a sustainable way for large‐scale hydrogen production when electricity is generated from renewable energy resources. The key challenge in water splitting is the sluggish kinetics of the oxygen evolution reaction (OER). Thus, it is important and necessary to develop highly efficient electrocatalysts in a cost‐effective way for OER. Porous materials have proven to be versatile in catalysis due to their large surface area, the fast mass diffusion, and the buffer ability of volume change. Herein, we summarize the recent progress of representative methodologies for the synthesis of porous materials toward electrocatalytic OER. The materials discussed in this Review include the cheap transition‐metal‐based (Co, Ni, and Fe) and metal‐free porous materials. This Review sheds light on the different strategies to construct catalysts with porous structures to facilitate OER.
A PNNH Pincer Ligand Allows Access to Monovalent Iron
Authors: Polezhaev Alexander V. , Liss Cameron J. , Telser Joshua , Chen Chun‐Hsing , Caulton Kenneth G.
Published: November 2017

Reaction of the unsymmetrically armed pincer PNNH (phosphine‐pyridyl‐pyrazole) ligand with FeCl2 yielded the five‐coordinate monomer [(PNNH)FeCl2], the NH proton of which captures THF through the formation of a hydrogen bond. Deprotonation of this NH functionality with Li[N(SiMe3)2] did not give the four‐coordinate [(PNN)FeCl], but instead retained LiCl to yield [(PNNLi)FeCl2], in which the lithium bridges between the pyrazolate β‐nitrogen and one of the chlorides on iron. One‐electron reduction of this compound under CO occurred with the loss of LiCl to form the square‐pyramidal monovalent iron in [(PNN)Fe(CO)2], which was characterized by IR, Mössbauer, and EPR spectroscopy, X‐ray diffraction, and DFT calculations. Cyclic voltammetry studies of [(PNN)Fe(CO)2] showed a reversible reduction wave and the reduction product was synthesized by using KC8. The product K[(PNN)Fe(CO)2] contains saturated, five‐coordinate Fe0; the (PNN)Fe subunit is anionic and the K+ cations cluster close to the pyrazolate side of the two CO ligands. Potassium electrophile complete its coordination sphere through interactions with the oxygen atom of a CO of a neighboring unit, thereby creating a polymeric chain. The reaction of [(PNN)Fe(CO)2] with HBpin (4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane) resulted in the reduction of the metal center (by release of H2) and borylation of the pyrazole β‐nitrogen atom. This redox‐active addition of the H−B bond across the metal–ligand assembly is an unusual example of metal–ligand cooperativity and establishes a ligand that supports iron in three different oxidation states.
Structural Tuning and Conformational Stability of Aromatic Oligoamide Foldamers
Authors: Annala Riia , Suhonen Aku , Laakkonen Heikki , Permi Perttu , Nissinen Maija
Published: November 2017

A series of aromatic oligoamide foldamers with two or three pyridine‐2,6‐dicarboxamide units as their main folding motifs and varying aromatic building blocks as linkers have been synthetized to study the effects of the structural variation on the folding properties and conformational stability. Crystallographic studies showed that in the solid state the central linker unit either elongates the helices and more open S‐shaped conformations, compresses the helices to more compact conformations, or acts as a rigid spacer separating the pyridine‐2,6‐dicarboxamide units, which for their part add the predictability of the conformational properties. Multidimensional NMR studies showed that, even in solution, foldamers show conformational stability and folded conformations comparable to the solid‐state structures.
The First Alkaline‐Earth Fluorooxoborate Ba[B4O6F2]—Characterisation and Doping with Eu2+
Authors: Jantz Stephan G. , Pielnhofer Florian , van Wüllen Leo , Weihrich Richard , Schäfer Martin J. , Höppe Henning A.
Published: November 2017

The very first alkaline‐earth fluorooxoborate Ba[B4O6F2] was synthesised by solid state methods starting from Ba(BF4)2, β‐BaB2O4, and B2O3. The crystal structure derived from single‐crystal X‐ray diffraction (P21/n, a=6.6384(2) Å, b=7.6733(3) Å, c=11.3385(4) Å, β=91.281(2)°, Z=4, Rint=0.0269, R1=0.018, wR2=0.034) comprises layers of BO3F tetrahedra condensed through triangular BO3 units according to the descriptor 2Δ2□:<Δ2□>Δ. The extraordinary thirteen‐fold coordination of barium by oxygen and fluorine leads to interesting optical properties of a sample doped with divalent europium, where a 4f→4f emission was recorded around 359 nm together with a broad emission band of a 5d→4f emission peaking at 366 nm. The compound is further characterised by IR‐, Raman‐, and solid‐state NMR‐spectroscopic methods. Moreover, DFT calculations as well as TGA and DSC measurements were performed.
Au‐Coated Honeycomb Structure as an Efficient TCO‐Free Counter‐Electrode for Quantum‐Dot‐Sensitized Solar Cells
Authors: Dao Van‐Duong , Bui Van‐Tien , Baek Minki , Phan The‐Long , Yong Kijung , Choi Ho‐Suk
Published: November 2017

This study reports the fabrication of a Petri dish patterned with cylindrical micro‐cavities that are produced using a one‐step solvent‐immersion phase‐separation process. The developed 3D honeycomb Petri dish is coated with a Au film through a sputtering method to be an efficient Au‐coated FTO‐free electrode for quantum‐dot‐sensitized solar cells. Due to the high specific active surface area of the electrode with the Au‐coated honeycomb structure, the energy conversion efficiency of devices that use this electrode is 5.2 % compared to 4.4 and 4.7 % by devices using an Au‐coated flat Petri dish and an Au‐coated FTO electrode, respectively. This design strategy offers excellent potential for the fabrication of highly efficient counter electrodes with FTO‐free substrates of flexible photovoltaic devices.
Solar‐Driven Production of Hydrogen Peroxide from Water and Dioxygen
Authors: Fukuzumi Shunichi , Lee Yong‐Min , Nam Wonwoo
Published: November 2017

Hydrogen peroxide, which is a green oxidant and fuel, is produced by a two‐electron/two‐proton reduction of dioxygen, two‐electron/two‐proton oxidation of water, or a combination of four‐electron/four‐proton or/and two‐electron/two‐proton oxidation of water and two‐electron/two‐proton reduction of dioxygen. There are many reports on electrocatalysts for selective two‐electron/two‐proton reduction of dioxygen to produce hydrogen peroxide instead of four‐electron/four‐proton reduction of dioxygen to produce water. As compared with the two‐electron/two‐proton reduction of dioxygen to produce hydrogen peroxide, fewer catalysts are known for the selective two‐electron/two‐proton oxidation of water to produce hydrogen peroxide instead of four‐electron/four‐proton oxidation of water to evolve dioxygen. Thus, solar‐driven production of hydrogen peroxide mainly consists of the catalytic four‐electron/four‐proton oxidation of water and the catalytic two‐electron/two‐proton reduction of dioxygen. The overall reaction is the solar‐driven oxidation of water by dioxygen to produce hydrogen peroxide. Either or both the four‐electron/four‐proton or/and the two‐electron/two‐proton oxidation of water and the two‐electron/two‐proton reduction of dioxygen requires photocatalysts. The yield of hydrogen peroxide is improved when the compartment for the photocatalytic four‐electron/four‐proton or/and two‐electron/two‐proton oxidation of water is separated from that for the catalytic two‐electron/two‐proton reduction of dioxygen using a two‐compartment cell separated by a membrane. The overall solar‐driven oxidation of water by dioxygen, which is the greenest oxidant, to produce hydrogen peroxide can be combined with catalytic oxidation of various substrates by hydrogen peroxide
Photomodulation of DNA‐Templated Supramolecular Assemblies
Authors: Rubio‐Magnieto Jenifer , Phan Tuan‐Anh , Fossépré Mathieu , Matot Valérie , Knoops Jérémie , Jarrosson Thibaut , Dumy Pascal , Serein‐Spirau Françoise , Niebel Claude , Ulrich Sébastien , Surin Mathieu
Published: November 2017

A new type of DNA ligand that contains a phosphate‐binding group and a photoresponsive azobenzene moiety is reported. When the azobenzene is in trans configuration, the ligand binds to the minor groove of a double‐stranded DNA, whereas it partially desorbs upon trans–cis isomerisation with light. The ability to photoswitch the ligand upon interaction with DNA is evidenced by (chir)optical signatures, and deciphered by the differences of binding geometry, stability, and dynamics of the DNA/ligand complexes for the two isomers. We exploit these properties to photomodulate DNA‐templated self‐assembly, through the incorporation of another π‐stacking DNA ligand, which together with the photoresponsive ligand form mixed supramolecular complexes along DNA. Our study demonstrates that well‐designed photoresponsive DNA binders can be used to modulate multicomponent supramolecular DNA assemblies.
Electronic and Structural Dynamics During the Switching of the Photomagnetic Complex [Fe(L222N5)(CN)2]
Authors: Zerdane Serhane , Collet Eric , Dong Xu , Matar Samir F. , Wang Hong Feng , Desplanches Cedric , Chastanet Guillaume , Chollet Matthieu , Glownia James M. , Lemke Henrick T. , Lorenc Maciej , Cammarata Marco
Published: November 2017

The [Fe(L222N5)(CN)2] compound, where L222N5 refers to the macrocyclic Schiff‐base ligand, 2,13‐dimethyl‐3,6,9,‐12,18‐pentaazabicyclo[12.3.1]octadeca‐1(18),2,12,14,‐ 16‐pentaene, is a photomagnetic FeII based coordination compound, which undergoes light‐induced excited spin‐state trapping (LIESST). The low spin state is hexacoordinated and the high spin state heptacoordinated. This system also serves as complex for the design of trinuclear or one‐dimensional compounds made of other types of bricks with diverse coordinated metals. Here its ultrafast spin‐state photoswitching dynamics are studied, by combining femtosecond optical spectroscopy and femtosecond X‐ray absorption measurements at the XPP station of the X‐ray free‐electron laser LCLS. DFT and TD‐DFT calculations are used to interpret experimental findings. These studies, performed in the solution phase, show that LIESST in [Fe(L222N5)(CN)2] occurs on the 100 fs timescale under different types of photoexcitation. In addition, coherent oscillations were observed, resulting from the structural dynamics accompanying LIESST, which were recently evidenced in more conventional octahedral FeIIN6 systems.
Tomographic Visualization of Single Droplets Inside Liquid‐Liquid Extraction Columns
Authors: Kögl Thilo , Arlt Wolfgang
Published: November 2017

Mithilfe der Röntgencomputertomographie kann die Fluiddynamik in verfahrenstechnischen Apparaten nicht‐invasiv untersucht werden. Durch die Wahl eines geeigneten Stoffsystems wird die disperse Tropfenströmung in Extraktionskolonnen tomographisch visualisiert. Die automatisierte Bildauswertung ermöglicht so zum ersten Mal den nicht‐invasiven Zugang zu Tropfengrößen, ‐formen und der örtlichen Verteilung der Tropfen im Inneren der strukturierten Metallpackungen. Entlang der Packungshöhe kann der Einfluss der strukturierten Packung auf die Tropfenverteilung detailliert untersucht werden.
Exploring the relationship between upgrading and capturing profits from GVC participation for disadvantaged suppliers in developing countries
Authors: Choksy Umair Shafi , Sinkovics Noemi , Sinkovics Rudolf R.
Published: November 2017

The existing literature on global value chains (GVCs) suggests that functional upgrading is a key determinant of whether suppliers are able to capture higher profits in GVCs. However, it is unclear whether the same argument holds for disadvantaged suppliers who face high barriers to achieving functional upgrading. Through a review of existing empirical studies, the present paper aims to explore how disadvantaged suppliers in developing countries increase their profits in the face of barriers to functional upgrading. The findings from the literature analysis suggest that the ability of disadvantaged suppliers to benefit from GVC participation depends on the extent of their managerial agency and their ability to leverage multiple upgrading/downgrading trajectories (whether product, process, or functional) and transform them into profitable outcomes. Copyright © 2017 ASAC. Published by John Wiley & Sons, Ltd.
Long‐term sequelae in survivors of childhood leukemia with Down syndrome: A childhood cancer survivor study report
Authors: Goldsby Robert E. , Stratton Kayla L. , Raber Shannon , Ablin Arthur , Strong Louise C. , Oeffinger Kevin , Sklar Charles A. , Armstrong Gregory T. , Robison Leslie L. , Bhatia Smita , Leisenring Wendy M.
Published: November 2017

BACKGROUND

Children with Down syndrome (DS) are at increased risk of developing acute leukemia and are more prone to acute toxicities. We studied the incidence and severity of chronic health conditions among survivors of childhood leukemia with DS compared with those without DS.

METHODS

Chronic health conditions reported by questionnaire were compared between 154 pediatric leukemia survivors with DS and 581 without DS, matched by leukemia, age at diagnosis, race/ethnicity, sex, radiation location and chemotherapy exposure using Cox models to estimate hazard ratios (HRs) and 95% confidence intervals (CIs). Subjects were selected from 7139 5‐year survivors of leukemia in the Childhood Cancer Survivor Study.

RESULTS

Risk of at least 1 late onset chronic health condition (grade 1‐5) was similar in the DS population compared with the non‐DS group (HR, 1.1; 95% CI, 0.7‐1.5). Serious chronic health conditions (grade 3‐5) were more common in DS survivors (HR, 1.7; 95% CI, 1.1‐2.6), as were ≥ 3 chronic health conditions (grades 1‐5) (HR, 1.7; 95% CI, 1.2‐2.4). The 25‐year cumulative incidence of any condition (grades 1‐5) was 83% for DS survivors and 69% for non‐DS survivors.

CONCLUSION

Leukemia survivors with DS have therapy‐related chronic health conditions comparable to those of similarly treated survivors without DS, with a few notable exceptions: 1) an increased risk of cataracts, hearing loss, and thyroid dysfunction compared with survivors without DS (though these are known risks in the DS population), 2) decreased risk of second cancers, and 3) increased risk of severe or multiple conditions. Practitioners should be aware of these risks during and after therapy. Cancer 2018;124:617‐25. © 2017 American Cancer Society.
Reducing the number of response time service level objective violations by a cloud‐HPC convergence scheduler
Authors: Kraemer Alessandro , Maziero Carlos , Richard Olivier , Trystram Denis
Published: November 2017

Job scheduling is an old topic in High‐Performance Computing (HPC), and it is more and more studied in data centers. Large data centers are often split into separate partitions for cloud computing and HPC; each partition normally has its specific scheduler. The possibility of migrating jobs from the HPC partition to the cloud one is a topic widely discussed in the literature. However, job migration from cloud to HPC is a much less explored topic. Nevertheless, such migration may be useful in many situations, in particular when the HPC platform has a low resource usage level, and the cloud usage level is high. A large number of jobs that could migrate from the cloud to the HPC partition may be observed in Google data center workloads. Job scheduling using overbooking strategy is seen as the main reason for the high resource usage level in clouds. However, overbooking can lead to a high rate of rescheduling and job dumping, which potentially causes response time violations. This work shows that HPC platforms can host and execute some cloud jobs with low interference in HPC jobs and a low number of response time violations. We introduce the definition of a cloud‐HPC convergence area and propose a job scheduling strategy for it, aiming at reducing the number of response time violations of cloud jobs without interfering with HPC jobs execution. Our proposal is formally defined and then evaluated in different execution scenarios, using the SimGrid simulation framework, with workload data from production HPC grid. The experimental results show that often, there is a large number of empty areas in the scheduling plan of HPC platforms, which makes it possible to allocate cloud jobs by backfilling. This is due to the sparse HPC job submission pattern and the low resource usage level in some HPC platforms. One performed simulation scenario considered a set of 11K parallel HPC jobs running on a 2560‐processor platform having an average resource usage level of 38.0%. The proposed convergence scheduler succeeded to inject around 267K cloud jobs in the HPC platform, with a response time violation rate under 0.00094% for such jobs, considering 80 processors in the convergence area and no effects on the HPC workload. This experiment considered cloud jobs based on job features of Google public cloud workloads, with a processing time slack factor of 1.25 (which is considered as high priority in the Google cloud SLA—Service Level Agreement). Usually, most cloud jobs show a slack factor higher than 1.25 (most cloud jobs are medium or low priority). The same simulation, repeated with a higher slack factor (4), showed no response time violations.
Sensor data management in the cloud: Data storage, data ingestion, and data retrieval
Authors: Sangat Prajwol , Indrawan‐Santiago Maria , Taniar David
Published: November 2017

Sensors are widely used in the field of manufacturing, railways, aerospace, cars, medicines, robotics, and many other aspects of our everyday life. There is an increasing need to capture, store, and analyse the dynamic semi‐structured data from those sensors. A similar growth of semi‐structured data in the modern web has led to the creation of NoSQL data stores for scalability, availability, and performance, whereas large‐scale data processing frameworks for parallel analysis. NoSQL data store such as MongoDB and data processing framework such as Apache Hadoop has been studied for scientific data analysis. However, there has been no study on MongoDB with Apache Spark, and there is a limited understanding of how sensor data management can benefit from these technologies, specifically for ingesting high‐velocity sensor data and parallel retrieval of high volume data. In this paper, we evaluate the performance of MongoDB sharding and no‐sharding databases with Apache Spark, to identify the right software environment for sensor data management.
Preservation of Nuclear Spin Order by Precipitation
Authors: Eills James , Alonso‐Valdesueiro Javier , Salazar Marcano David E. , Ferreira da Silva Jesse , Alom Shamim , Rees Gregory J. , Hanna John V. , Carravetta Marina , Levitt Malcolm H.
Published: November 2017

We demonstrate that non‐equilibrium nuclear spin order survives precipitation from solution and redissolution. The effect is demonstrated on13C‐ and2H‐labeled sodium fumarate, with precipitation and dissolution achieved by altering the pH. The lifetime of the spin magnetization in the precipitate suspension is found to be much longer than in solution. Our preliminary results show an extension of the effective relaxation time T1for the metabolite fumarate by a factor of ≈6. We show that when the free radical agent TEMPO is present in the solution, it is not incorporated into the precipitate, suggesting that this procedure may provide a means to store and transport agents polarized by dynamic nuclear polarization. Although the relaxation time, T1, of the precipitate suspension is longer than that of the same molecules in solution, it is significantly shorter than that observed in the immobilized solid state.
Binder‐Free Hybrid Titanium–Niobium Oxide/Carbon Nanofiber Mats for Lithium‐Ion Battery Electrodes
Authors: Tolosa Aura , Fleischmann Simon , Grobelsek Ingrid , Quade Antje , Lim Eunho , Presser Volker
Published: November 2017

Free‐standing, binder‐free, titanium–niobium oxide/carbon hybrid nanofibers are prepared for Li‐ion battery applications. A one‐pot synthesis offers a significant reduction of processing steps and avoids the use of environmentally unfriendly binder materials, making the approach highly sustainable. Tetragonal Nb2O5/C and monoclinic Ti2Nb10O29/C hybrid nanofibers synthesized at 1000 °C displayed the highest electrochemical performance, with capacity values of 243 and 267 mAh g−1, respectively, normalized to the electrode mass. At 5 A g−1, the Nb2O5/C and Ti2Nb10O29/C hybrid fibers maintained 78 % and 53 % of the initial capacity, respectively. The higher rate performance and stability of tetragonal Nb2O5 compared to that of monoclinic Ti2Nb10O29 is related to the low energy barriers for Li+ transport in its crystal structure, with no phase transformation. The improved rate performance resulted from the excellent charge propagation in the continuous nanofiber network.
Synthesis of ZnII and AlIII Complexes of Diaminocyclohexane‐Derived Ligands and Their Exploitation for the Ring Opening Polymerisation of rac‐Lactide
Authors: Kirk Sarah M. , McKeown Paul , Mahon Mary F. , Kociok‐Köhn Gabriele , Woodman Timothy J. , Jones Matthew D.
Published: November 2017

Two series of ligands based on diaminocyclohexane (DACH) have been prepared and successfully complexed to AlIII and ZnII metal centres. Solution and solid‐state studies reveal a tendency to form mono‐ or bis‐ligated forms depending on the steric bulk of the ligand. These complexes have been tested for their ability to ring open rac‐lactide. AlIII based complexes generally gave atactic PLA after a polymerisation time of 1–2 days. The ZnII complexes, were found to be more active and furnished PLA with a slight heterotactic bias.
Total Syntheses of Basiliolide A1, Basiliolide A2, Basiliolide C, and their Structural Analogues
Authors: Ma Wenjing , Liang Xuefeng , Ye Wejian , Wang Yuena , Min Long , He Shuzhong , Lee Chi‐Sing
Published: November 2017

A small focussed library of basiliolides including basiliolide A1, basiliolide A2, basiliolide C, and their structural analogues have been prepared for structure–activity‐relationship studies. The synthesis features a cyclopropanation/ring‐opening strategy to establish the C‐8 stereogenic centre by using the cyclopropanation substrate with the appropriate alkene geometry; an IMDA (intramolecular Diels–Alder) reaction to construct the seco acid derivatives; and a biomimetic O‐acylation to form the unprecedented seven‐membered acyl ketene acetal ring. The des‐D‐ring analogues were prepared by an IMDA/decarboxylation strategy. Moreover, an asymmetric catalytic cyclopropanation reaction has been developed; this provided an optically enriched intermediate for asymmetric synthesis.
3,5‐Dimethylorsellinic Acid Derived Meroterpenoids from Eupenicillium sp. 6A‐9, a Fungus Isolated from the Marine Sponge Plakortis simplex
Authors: Gu Bin‐Bin , Wu Wei , Liu Li‐Yun , Tang Jie , Zeng Ya‐Jun , Wang Shu‐Ping , Sun Fan , Li Lei , Yang Fan , Lin Hou‐Wen
Published: November 2017

Two rare 6(D)/5(E) ring‐fused meroterpenoids, eupeniacetal A (1) and eupeniacetal B (2), and three new meroterpenoids, 1‐methoxy‐hydropreaustinoid A1 (3), hydroberkeleyone B (4), and 22‐deoxy‐10‐oxominiolutelide B (5), as well as five known meroterpenoids, 22‐deoxyminiolutelide B (6), preaustinoid A1 (7), berkeleyone C (8), berkeleyacetal A (9), and preaustinoid A3 (10), have been isolated, through the aid of LC–MS, from the sponge‐derived fungus Eupenicillium sp. 6A‐9. The structures of these meroterpenoids were elucidated by detailed spectroscopic analysis, comparison with literature data, and single‐crystal X‐ray diffraction. The absolute configurations were assigned by means of TDDFT/ECD and [α]D calculations as well as by X‐ray diffraction analysis. These compounds showed inhibitory activity towards TNF‐α production in the induced THP‐1 cell line but were inactive against normal tumor cell lines.
One‐step Synthesis of AuAg Alloy Nanodots and its Electrochemical Studies towards Nitrobenzene Reduction and Sensing
Authors: Manivannan Shanmugam , Jeong Juwon , Kang Dong‐Ku , Kim Kyuwon
Published: November 2017

Efficient, stable, and low‐cost electrocatalysts for the degradation and sensing of environment pollutants are essential components of clean environment monitoring. Here we report, one‐step synthesis and characterization of 1–3 nm diameter sized bi‐metallic AuAg nanodots (NDs) embedded in amine functionalized silicate sol‐gel matrix (SSG) and its electrochemical studies toward nitrobenzene. The SSG was used as a reducing agent as well as stabilizer for the prepared mono‐ and bi‐metallic nanoparticles (NPs). From the HRTEM, STEM‐EDS and XPS analyses, the bi‐metallic AuAg NDs were identified as an alloy and not the mixtures of Au and Ag NPs. Characteristic surface plasmon resonance (SPR) band between the Au and Ag NPs SPR absorption region was noticed for the prepared AuAg NDs. The AuAg alloy NDs with different concentrations of Au and Ag (Au25Ag75, Au50Ag50 and Au75Ag25 NDs) modified electrodes exhibited synergistic electrocatalytic effect than did the Au and Ag NPs towards nitrobenzene reduction and detection. Together with ultra‐small size and exceptional colloidal stability features within these SSG‐AuAg NDs pave convenient way for nanotechnology‐based catalysts development and sensor applications.
A modified 384‐well‐device for versatile use in 3D cancer cell (co‐)cultivation and screening for investigations of tumor biology in vitro
Authors: Widder Miriam , Lemke Karen , Kekeç Bünyamin , Förster Tobias , Grodrian Andreas , Gastrock Gunter
Published: November 2017

Pancreatic cancer exhibits a worst prognosis owed to an aggressive tumor progression i.a. driven by chemoresistance or tumor‐stroma‐interactions. The identification of candidate genes, which promote this progression, can lead to new therapeutic targets and might improve patient's outcome. The identification of these candidates in a plethora of genes requires suitable screening protocols. The aim of the present study was to establish a universally usable device which ensures versatile cultivation, screening and handling protocols of cancer cells with the 3D spheroid model, an approved model to study tumor biology. By surface modification and alternative handling of a commercial 384‐well plate, a modified device enabling (i) 3D cultivation either by liquid overlay or by a modified hanging drop method for (ii) screening of substances as well as for tumor‐stroma‐interactions (iii) either with manual or automated handling was established. The here presented preliminary results of cell line dependent dose‐response‐relations and a stromal‐induced spheroid‐formation of the pancreatic cancer cells demonstrate the proof‐of‐principle of the versatile functionality of this device. By adapting the protocols to automation, a higher reproducibility and the ability for high‐throughput analyses were ensured.
Extraction Rate and Energy Efficiency of Supercritical Carbon Dioxide Recovery of Higher Alcohols from Dilute Aqueous Solution
Authors: Tompsett Geoffrey A. , Boock Jason T. , DiSpirito Cameron , Stolz Eric , Knutson David R. , Rivard Allison G. , Overdevest Mark R. , Conlon Chelsea N. , Prather Kristala L. J. , Thompson Janelle R. , Timko Michael T.
Published: November 2017

New biotechnologies have been developed to produce higher alcohols, including various isomers of butanol, pentanol, and hexanol. The thermodynamic properties of higher alcohols—i.e., low volatility and moderate water solubility—make them good candidates for extraction using supercritical carbon dioxide (scCO2). Here, we studied semi‐batch extraction of several representative higher alcohols, including n‐butanol, n‐pentanol, and n‐hexanol from dilute aqueous solutions using scCO2, measuring the initial extraction rates and extraction efficiencies, where the extraction efficiency was defined as the grams of alcohol recovered per gram of scCO2. In all cases, the extraction kinetics were well described by a simple first‐order disappearance model and the extraction rates were much greater than the published butanol bioproduction rates. Quantitatively, the initial extraction rates and efficiencies, respectively, for both n‐hexanol and n‐pentanol were 1.6±0.2 and 1.3±0.1 times greater than that for n‐butanol. These results were analyzed for semi‐continuous alcohol recovery and compared with previous literature on butanol gas stripping to evaluate the competitiveness of the scCO2 separation strategy.
To Go or Not to Go: A Proof of Concept Study Testing Food‐Specific Inhibition Training for Women with Eating and Weight Disorders
Authors: Turton Robert , Nazar Bruno P. , Burgess Emilee E. , Lawrence Natalia S. , Cardi Valentina , Treasure Janet , Hirsch Colette R.
Published: November 2017

Inefficient food‐specific inhibitory control is a potential mechanism that underlies binge eating in bulimia nervosa and binge eating disorder. Go/no‐go training tools have been developed to increase inhibitory control over eating impulses. Using a within‐subjects design, this study examined whether one session of food‐specific go/no‐go training,versusgeneral inhibitory control training, modifies eating behaviour. The primary outcome measure was food consumption on a taste test following each training session. Women with bulimia nervosa and binge eating disorder had small non‐significant reductions in high‐calorie food consumption on the taste test following the food‐specific compared with the general training. There were no effects on eating disorder symptomatic behaviour (i.e. binge eating/purging) in the 24 h post‐training. The training task was found to be acceptable by the clinical groups. More research is needed with larger sample sizes to determine the effectiveness of this training approach for clinical populations. Copyright © 2017 John Wiley & Sons, Ltd and Eating Disorders Association.
Regulation of mitochondrial dynamics in astrocytes: Mechanisms, consequences, and unknowns
Authors: Jackson Joshua G. , Robinson Michael B.
Published: November 2017

Astrocytes are the major glial cell in the central nervous system. These polarized cells possess numerous processes that ensheath the vasculature and contact synapses. Astrocytes play important roles in synaptic signaling, neurotransmitter synthesis and recycling, control of nutrient uptake, and control of local blood flow. Many of these processes depend on local metabolism and/or energy utilization. While astrocytes respond to increases in neuronal activity and metabolic demand by upregulating glycolysis and glycogenolysis, astrocytes also possess significant capacity for oxidative (mitochondrial) metabolism. Mitochondria mediate energy supply and metabolism, cellular survival, ionic homeostasis, and proliferation. These organelles are dynamic structures undergoing extensive fission and fusion, directed movement along cytoskeletal tracts, and degradation. While many of the mechanisms underlying the dynamics of these organelles and their physiologic roles have been characterized in neurons and other cells, the roles that mitochondrial dynamics play in glial physiology is less well understood. Recent work from several laboratories has demonstrated that mitochondria are present within the fine processes of astrocytes, that their movement is regulated, and that they contribute to local Ca2+ signaling within the astrocyte. They likely play a role in local ATP production and metabolism, particularly that of glutamate. Here we will review these and other findings describing the mechanism by which mitochondrial dynamics are regulated in astrocytes, how mitochondrial dynamics might influence astrocyte and brain metabolism, and draw parallels to mitochondrial dynamics in neurons. Additionally, we present new analyses of the size, distribution, and dynamics of mitochondria in astrocytes performed using in vivo using 2‐photon microscopy.
Preliminary study of a communication intervention for family caregivers and spouses with dementia
Authors: Williams Christine L. , Newman David , Hammar Lena Marmstål
Published: November 2017

Objective

This study was to designed to examine the feasibility and preliminary outcomes of CARE: Caring About Relationships and Emotions, a 10‐week, home‐based, intervention to support married couples affected by dementia.

Methods

Fifteen older couples participated in a single group repeated measures feasibility study. Weekly, video‐recorded conversations over 10 weeks were used to rate communication using the Verbal/Nonverbal Interaction Scale for caregivers and care receivers.

Results

Accounting for mental status of care recipients, the ratio of social to unsocial communication showed a significant improvement across sessions‐an average of 4.46 points per session [β = 4.46, t(10) = 1.96, p = .039]. Spouse caregiver (CG) communication showed a significant decrease in the number of disabling communications with approximately .65 decreased comments per session [β = 0.654, t(11) = −2.61, p = .024].

Conclusions

At home dyadic, relationship‐focused psychoeducational intervention to improve communication in spouses affected by dementia has the potential to improve communication outcomes. Creative ways of working with couples are needed to help them sustain their relationships and maintain their health.
A pilot study investigating the feasibility of symptom assessment manager (SAM), a Web‐based real‐time tool for monitoring challenging behaviors
Authors: Loi Samantha M. , Wanasinghage Sangeeth , Goh Anita , Lautenschlager Nicola T. , Darby David G. , Velakoulis Dennis
Published: November 2017

Objective

Improving and minimizing challenging behaviors seen in psychiatric conditions, including behavioral and psychological symptoms of dementia are important in the care of people with these conditions. Yet there is a lack of systematic evaluation of these as a part of routine clinical care. The Neuropsychiatric Inventory is a validated and reliable tool for rating the severity and disruptiveness of challenging behaviors. We report on the evaluation of a Web‐based symptom assessment manager (SAM), designed to address the limitation of previous tools using some of the Neuropsychiatric Inventory functions, to monitor behaviors by staff caring for people with dementia and other psychiatric conditions in inpatient and residential care settings.

Methods

The SAM was piloted in an 8‐bed inpatient neuropsychiatry unit over 5 months. Eleven nurses and 4 clinicians were trained in usage of SAM. Primary outcomes were usage of SAM and perceived usability, utility, and acceptance of SAM. Secondary outcomes were the frequencies of documented behavior. Usage data were analyzed using chi‐square and logistic regression analyses.

Results

The SAM was used for all admitted patients regardless of diagnosis, with a usage rate of 64% for nurses regularly employed in the unit. Staff provided positive feedback regarding the utility of SAM.

Conclusions

The SAM appeared to offer individualized behavior assessment by providing a quick, structured, and standardized platform for assessing behavior in a real‐world setting. Further research would involve trialing SAM with more staff in alternative settings such as in home or residential care settings.
Increased functional connectivity in the ventral and dorsal streams during retrieval of novel words in professional musicians
Authors: Dittinger Eva , Valizadeh Seyed Abolfazl , Jäncke Lutz , Besson Mireille , Elmer Stefan
Published: November 2017

Current models of speech and language processing postulate the involvement of two parallel processing streams (the dual stream model): a ventral stream involved in mapping sensory and phonological representations onto lexical and conceptual representations and a dorsal stream contributing to sound‐to‐motor mapping, articulation, and to how verbal information is encoded and manipulated in memory. Based on previous evidence showing that music training has an influence on language processing, cognitive functions, and word learning, we examined EEG‐based intracranial functional connectivity in the ventral and dorsal streams while musicians and nonmusicians learned the meaning of novel words through picture–word associations. In accordance with the dual stream model, word learning was generally associated with increased beta functional connectivity in the ventral stream compared to the dorsal stream. In addition, in the linguistically most demanding “semantic task,” musicians outperformed nonmusicians, and this behavioral advantage was accompanied by increased left‐hemispheric theta connectivity in both streams. Moreover, theta coherence in the left dorsal pathway was positively correlated with the number of years of music training. These results provide evidence for a complex interplay within a network of brain regions involved in semantic processing and verbal memory functions, and suggest that intensive music training can modify its functional architecture leading to advantages in novel word learning.