bluuebunny/crossref_metadata_2025_split huggingface dataset:
SERS‐Based Plasmon‐Driven Reaction and Molecule Detection on a Single Ag@MoS2 Microsphere: Effect of Thickness and Crystallinity of MoS2
Authors: Shen Yunfeng , Miao Peng , Hu Chang , Wu Jie , Gao Mansha , Xu Ping 
Published: June 2018

AbstractPlasmon‐driven catalysis on a single particle has attracted great attention in recent years, while the relationship between reaction efficiency and substrate remains to be deeply studied. Here, we demonstrate the fabrication of a novel Ag@MoS2 core‐shell single particle SERS substrate by coating MoS2 film on Ag microspheres through the pulsed laser deposition (PLD) technique, where the thickness and crystallinity of MoS2 can be effectively controlled by the PLD time and temperature. It is revealed that both the thickness and crystallinity of MoS2 can greatly influence the hot electron transfer process, and thus the plasmon‐driven reaction (4‐NTP into DMAB) efficiency and Raman enhancement of dye molecules on Ag@MoS2 substrates. Generally, high crystallinity and thin thickness of MoS2 can lead to accelerated plasmon‐driven reaction efficiency and greatly enhanced Raman signals of target molecules. This study opens up a new avenue for broadening the research area of the plasmon‐driven catalysis and Raman enhancement on the hybrid system of two‐dimensional materials and metal nanostructures.
Palladium‐Catalyzed Carbonylative Synthesis of N‐Acetyl Benzoxazinones
Authors: Qi Xinxin , Li Rui , Li Hao‐Peng , Peng Jin‐Bao , Ying Jun , Wu Xiao‐Feng 
Published: June 2018

AbstractA palladium‐catalyzed intramolecular carbonylation reaction for the synthesis of N‐acetyl benzoxazinones has been achieved for the first time. To avoid the using of toxic and flammable CO gas, formic acid was utilized as the CO source here. This carbonylative process is conducted under mild reaction conditions with high reaction efficiency. A variety of the desired N‐acetyl benzoxazinone products were obtained in moderate to excellent yields with very good functional group compatibility. The presents of acid anhydride holds two roles here: formic acid activator and acyl source.
Direct Methylation of Benzene with Methane Catalyzed by Co/MFI Zeolite
Authors: Nakamura Koshiro , Okuda Akihito , Ohta Kiyotaka , Matsubara Hitoshi , Okumura Kazu , Yamamoto Kana , Itagaki Ryosuke , Suganuma Satoshi , Tsuji Etsushi , Katada Naonobu 
Published: June 2018

AbstractCobalt‐loaded MFI zeolite showed distinct activity for direct methylation of benzene with methane into toluene. High activity was found at around 0.6 of Co/Al molar ratio. Incorporation of carbon from methane into the methyl group of toluene was confirmed with isotope tracer experiments and mass spectroscopy. Ammonia infrared‐mass spectroscopy temperature‐programmed desorption, transmission electron microscopy, X‐ray absorption near edge spectroscopy and extended X‐ray absorption fine structure indicated that Lewis acidic divalent (+II of oxidation state) Co species mono‐atomically dispersed on the ion exchange site of MFI zeolite was the active species.
Highly Efficient Aromatic C−H Oxidation with H2O2 in the Presence of Iron Complexes of the PDP Family
Authors: Tkachenko Nikolay V. , Ottenbacher Roman V. , Lyakin Oleg Y. , Zima Alexandra M. , Samsonenko Denis G. , Talsi Evgenii P. , Bryliakov Konstantin P. 
Published: June 2018

AbstractThe catalytic activity of a series of iron complexes of the PDP family (PDP=N,N′‐bis(2‐pyridylmethyl)‐2,2′‐bipyrrolidine) in the oxidation of aromatic substrates with H2O2 has been studied. In the presence of acetic acid, these complexes efficiently catalyze the oxidation of benzene and alkylbenzenes with high selectivity for oxygen incorporation into the aromatic ring (up to 93 %), performing up to 84 catalytic turnovers. The parent complex, [(PDP)(OTf)2], has demonstrated the highest catalytic efficiency and aromatic oxidation selectivity. The yield of products of oxidation of different substrates increases in line with increasing number of electron‐donating alkyl groups of the substrates: halogenbenzenes<benzene<monoalkylbenzenes<dialkylbenzenes, which, together with the results of competitive oxidation experiments and the observation of inverse primary kH/kD (0.90–0.92), agrees with the SEAr oxidation mechanism. Low‐temperature EPR studies have witnessed the presence of low‐spin (g1=2.071, g2=2.008, g3=1.960) perferryl intermediates, demonstrating direct reactivity toward benzene. The oxidation of m‐xylene in the presence of H218O has shown the same probability of 18O incorporation into the aromatic ring and the aliphatic moieties, which is indicative that both the aromatic and aliphatic oxidations are conducted by the same active species.
Stable Bifunctional Perylene Imide Radicals for High‐Performance Organic–Lithium Redox‐Flow Batteries
Authors: Li Lei , Gong Hai‐Xian , Chen Dong‐Yang , Lin Mei‐Jin 
Published: June 2018

AbstractThe search for high‐performance organic redox‐active materials for non‐aqueous redox‐flow batteries remains a key challenge. Organic radicals and aromatic imides are two promising classes of redox‐active materials with complementary advantages, such as the specific capacity, operating voltage, and stability, etc. Herein, this work reports two stable bifunctional radicals synthesized by the C−C coupling of redox‐active phenoxyl radicals and perylene diimides (PDIs, 1.) or benzo[ghi]perylene triimides (BPTIs, 2.). The incorporation of electron‐deficient PDIs or BPTIs into phenoxyl radicals is desired, to not only increase the number of redox‐active groups per molecule and, thus, improve their specific capacities, but also to increase the redox potential and the stability of the phenoxyl radicals and, thus, enhances their battery voltages and cycle lives. When serving as the redox‐active species in the catholyte of a non‐aqueous static redox‐flow battery, both radicals 1. and 2. exhibited a cooperatively enhanced performance with an unprecedented initial discharge voltage up to 3.12 V versus Li+/Li, which is the hitherto most presentable potential for imide‐ and radical‐based energy storage materials in redox‐flow batteries.
Does obesity affect the outcomes in takotsubo cardiomyopathy? Analysis of the Nationwide Inpatient Sample database, 2010‐2014
Authors: Desai Rupak , Singh Sandeep , Baikpour Maryam , Goyal Hemant , Dhoble Abhijeet , Deshmukh Abhishek , Kumar Gautam , Sachdeva Rajesh 
Published: June 2018

BackgroundObesity can lead to increased oxidative stress which is one of the proposed mechanisms in the etiopathogenesis of takotsubo cardiomyopathy (TCM).HypothesisThe presence of obesity adversely impacts clinical outcomes in TCM patients.MethodsWe queried the Nationwide Inpatient Sample database (2010‐2014) to identify adult patients admitted with a principal diagnosis of TCM with and without obesity. We compared the categorical and continuous variables by Pearson χ2 and Student t test, respectively, in propensity‐score matched cohorts.ResultsThe study cohort comprised 612 obese TCM (weighted n = 3034) and 5696 nonobese TCM (weighted n = 28 186) patients. Obese TCM patients were more often younger and private‐insurance enrollees. Cardiac complications including acute myocardial infarction (9.0% vs 7.4%; P = 0.04), cardiac arrest (2.3% vs. 0.4%; P < 0.001), cardiogenic shock (4.3% vs. 3.2%; P = 0.03), congestive heart failure (5.0% vs. 3.8%; P = 0.02), respiratory failure (12.9% vs. 11.0%; P = 0.021) and use of mechanical hemodynamic support (Impella; 0.2% vs. 0.0%, P = 0.02) were significantly higher among obese TCM patients. There were no significant differences between the 2 groups in all‐cause mortality (1.0% vs. 0.8%; P = 0.35), arrhythmia (24.5% vs. 22.7%, P = 0.123), length of stay (3.7 ±3.5 vs. 3.7 ±3.6 days; P = 0.68), and total hospital charges ($40 780.16 vs. $42 575.14; P = 0.08).ConclusionsObese TCM patients were more susceptible to developing TCM‐related cardiac complications than were nonobese TCM patients, without any impact on all‐cause in‐hospital mortality, LOS, and hospital charges.
False‐positive stress testing: Does endothelial vascular dysfunction contribute to ST‐segment depression in women? A pilot study
Authors: Sharma Shilpa , Mehta Puja K. , Arsanjani Reza , Sedlak Tara , Hobel Zachary , Shufelt Chrisandra , Jones Erika , Kligfield Paul , Mortara David , Laks Michael , Diniz Márcio , Bairey Merz C. Noel 
Published: June 2018

BackgroundThe utility of exercise‐induced ST‐segment depression for diagnosing ischemic heart disease (IHD) in women is unclear.HypothesisBased on evidence that IHD pathophysiology in women involves coronary vascular dysfunction, we hypothesized that coronary vascular dysfunction contributes to exercise electrocardiography (Ex‐ECG) ST‐depression in the absence of obstructive coronary artery disease, so‐called false positive results. We tested our hypothesis in a pilot study evaluating the relationship between peripheral vascular endothelial function and Ex‐ECG.MethodsTwenty‐nine asymptomatic women without cardiac risk factors underwent maximal Bruce protocol exercise treadmill testing and peripheral endothelial function assessment using peripheral arterial tonometry (Itamar EndoPAT 2000) to measure reactive hyperemia index (RHI). The relationship between RHI and Ex‐ECG ST‐segment depression was evaluated using logistic regression and differences in subgroups using 2‐tailed t tests.ResultsMean age was 54 ± 7 years, body mass index 25 ± 4 kg/m2, and RHI 2.51 ± 0.66. Three women (10%) had RHI <1.68, consistent with abnormal peripheral endothelial function, whereas 18 women (62%) met criteria for positive Ex‐ECG based on ST‐segment depression in contiguous leads. Women with and without ST‐segment depression had similar baseline and exercise vital signs, metabolic equivalents achieved, and RHI (all P > 0.05). RHI did not predict ST‐segment depression.ConclusionsOur pilot study demonstrates high prevalence of exercise‐induced ST‐segment depression in asymptomatic, middle‐aged, overweight women. Peripheral vascular endothelial dysfunction did not predict Ex‐ECG ST‐segment depression. Further work is needed to investigate the utility of vascular endothelial testing and Ex‐ECG for IHD diagnostic and management purposes in women.
A Compact and Synthetically Accessible Fluorine‐18 Labelled Cyclooctyne Prosthetic Group for Labelling of Biomolecules by Copper‐Free Click Chemistry
Authors: Murrell Emily , Kovacs Michael S. , Luyt Leonard G. 
Published: June 2018

AbstractA new fluorine‐containing azadibenzocyclooctyne (ADIBO‐F) was designed using a synthetically accessible pathway. The fluorine‐18 prosthetic group was prepared from its toluenesulfonate precursor and isolated in 21–35 % radiochemical yield in 30 minutes of synthetic time. ADIBO‐F has been incorporated into azide‐functionalized, cancer‐targeting peptides through a strain‐promoted alkyne–azide cycloaddition with high radiochemical yields and purities. The final products are novel peptide‐based positron emission tomography (PET) imaging agents that possess high affinities for their targets, growth hormone secretagogue receptor 1a (GHSR‐1a) and gastrin‐releasing peptide receptor (GRPR), with IC50 values of 9.7 and 0.50 nm, respectively. This is a new and rapid labelling option for the incorporation of fluorine‐18 into biomolecules for PET imaging.
Comprehensive Theoretical Study of Interactions between Ag+ and Polycyclic Aromatic Hydrocarbons
Authors: Liu Shuyang , Rogachev Andrey Yu. 
Published: June 2018

AbstractThe first comprehensive and systematic theoretical exploration of the bonding nature and energetics of the interactions between Ag(I) cation and a wide set of π‐ligands was accomplished. This set ranges from simple ethylene and aromatic benzene to planar and curved polyaromatic molecules and to closed‐cage C60‐fullerene. Simultaneous application of two energy decomposition schemes based on different ideas, namely, NBO‐NEDA and EDA‐NOCV, allowed shedding light on the nature of the bonding and its energetics. Importantly, our results unambiguously indicate that reliable results can be obtained only if using more than one theoretical approach. All methods clearly revealed the importance and even domination of the ionic contribution of the bonding in all adducts, except for those of C60‐fullerene, in which the covalent component was found to be the largest. Subsequent decomposition of the orbital term onto components showed that it consists of two major parts: (i) ligand‐to‐metal (π(C=C)→s(Ag), L→M) and (ii) metal‐to‐ligand (M→L) terms, with significant domination of the former. Interestingly, while the L→M component is essentially the same for all systems considered, the nature of the M→L one depends on the coordination site of the polycyclic aromatic hydrocarbons (PAH). In most of adducts, the M→L can be described as dxy(Ag)→π*(C=C) donation, whereas for systems [Ag‐spoke‐C12H8]+ and [Ag‐spoke‐C20H10]+ it corresponds to the dz2(Ag)→π*(C=C) type of interaction. As a result, the coordination mode in such complexes is switched from η2‐type to η1. Thus, the nature of the bonding, its energetics and even coordination mode in adducts of unsaturated hydrocarbons with late transition metal cations should be considered as a function of many components, which primarily includes the topology and aromaticity of the (poly)aromatic molecules.
Hierarchical Porous NiO/β‐NiMoO4 Heterostructure as Superior Anode Material for Lithium Storage
Authors: Wang Zhijian , Zhang Shilin , Zeng Hai , Zhao Haimin , Sun Wei , Jiang Meng , Feng Chuanqi , Liu Jianwen , Zhou Tengfei , Zheng Yang , Guo Zaiping 
Published: June 2018

AbstractTernary transition metal oxides (TTMOs) have attracted considerable attention for rechargeable batteries because of their fascinating properties. However, the unsatisfactory electrochemical performance originating from the poor intrinsic electronic conductivity and inferior structural stability impedes their practical applications. Here, the novel hierarchical porous NiO/β‐NiMoO4 heterostructure is fabricated, and exhibits high reversible capacity, superior rate capability, and excellent cycling stability in Li‐ion batteries (LIBs), which is much better than the corresponding single‐phase NiMoO4 and NiO materials. The significantly enhanced electrochemical properties can be attributed to its superior structural characteristics, including the large surface area, abundant pores, fast charge transfer, and catalytic effect of the intermediate product of metallic nickel. The NiO/β‐NiMoO4 heterostructure delivers a high capacity of 1314 mA h g−1 at 0.2 A g−1 after 100 cycles. Furthermore, even after 400 cycles at 1 A g−1, the reversible capacity remains at around 500 mA h g−1. These results indicate that the NiO/β‐NiMoO4 heterostructure shows great potential as an anode material for high‐performance LIBs.
Molecular Engineering of Zinc‐Porphyrin Sensitisers for p‐Type Dye‐Sensitised Solar Cells
Authors: Lu Jianfeng , Liu Zonghao , Pai Narendra , Jiang Liangcong , Bach Udo , Simonov Alexandr N. , Cheng Yi‐Bing , Spiccia Leone 
Published: June 2018

AbstractInvited for this month's cover are the groups of Prof. Dr. Udo Bach, Prof. Dr. Yi‐Bing Cheng, and Prof. Dr. Leone Spiccia (Monash University, Australia), and Dr. Mingkui Wang (Huazhong University of Science and Technology, China). The cover picture shows the charge‐transfer processes between a novel porphyrin dye adsorbed on nickel oxide and tris(acetylacetonato) iron(III/II) redox mediator after excitation by sunlight. Read the full text of the article at 10.1002/cplu.201800104.
Prevalence and prognostic impact of non‐cardiac co‐morbidities in heart failure outpatients with preserved and reduced ejection fraction: a community‐based study
Authors: Iorio Annamaria , Senni Michele , Barbati Giulia , Greene Stephen J. , Poli Stefano , Zambon Elena , Di Nora Concetta , Cioffi Giovanni , Tarantini Luigi , Gavazzi Antonello , Sinagra Gianfranco , Di Lenarda Andrea 
Published: June 2018

AimTo assess adverse outcomes attributable to non‐cardiac co‐morbidities and to compare their effects by left ventricular ejection fraction (LVEF) group [LVEF <50% (heart failure with reduced ejection fraction, HFrEF), LVEF ≥50% (heart failure with preserved ejection fraction, HFpEF)] in a contemporary, unselected chronic heart failure population.Methods and resultsThis community‐based cohort enrolled patients from October 2009 to December 2013. Adjusted hazard ratio (HR) and the population attributable fraction (PAF) were used to compare the contribution of 15 non‐cardiac co‐morbidities to adverse outcome. Overall, 2314 patients (mean age 77 ±10 years, 57% men) were recruited [n = 941 (41%) HFrEF, n = 1373 (59%) HFpEF]. Non‐cardiac co‐morbidity rates were similarly high, except for obesity and hypertension which were more prevalent in HFpEF. At a median follow‐up of 31 (interquartile range 16–41) months, 472 (20%) patients died. Adjusted mortality rates were not significantly different between the HFrEF and HFpEF groups. After adjustment, an increasing number of non‐cardiac co‐morbidities was associated with a higher risk for all‐cause mortality [HR 1.25; 95% confidence interval (CI) 1.10–1.26; P < 0.001], all‐cause hospitalization (HR 1.17; 95% CI 1.12–1.23; P < 0.001), heart failure hospitalization (HR 1.28; 95% CI 1.19–1.38; P < 0.001), non‐cardiovascular hospitalization (HR 1.16; 95% CI 1.11–1.22; P < 0.001). The co‐morbidities contributing to high PAF were: anaemia, chronic kidney disease, chronic obstructive pulmonary disease, diabetes mellitus, and peripheral artery disease. These findings were similar for HFrEF and HFpEF. Interaction analysis yielded similar results.ConclusionsIn a contemporary community population with chronic heart failure, non‐cardiac co‐morbidities confer a similar contribution to outcomes in HFrEF and HFpEF. These observations suggest that quality improvement initiatives aimed at optimizing co‐morbidities may be similarly effective in HFrEF and HFpEF.
Electric Field Poling Effect on the Electrocatalytic Properties of Nitrogen‐Functionalized Graphene Nanosheets
Authors: Jahan Maryam , Li Kuo , Zhao Guang‐Lin 
Published: June 2018

AbstractFuel cells are attractive new technologies for producing sustainable and green energy. However, the high cost of its components such as Pt electrocatalyst is a major challenge. Heteroatom doped carbon nano‐materials show potential applications for oxygen reduction reaction (ORR) which can be used for fuel cells and may be promising replacement of Pt catalyst. Recently, we implemented a facile method for preparing partially nitrogen functionalized graphene oxide (PNG) nano‐sheets. To achieve better nitrogen functionalization, graphene oxide was annealed in ammonia solution for 12 h at 220 oC. The electrochemical measurement data show that the PNG synthesized in NH3 environment possesses good electrocatalytic activities for ORR. In addition, we identified a physical method for the first time to drive the randomly oriented graphene nano‐sheets to be aligned parallel to the surface of electrode for electrocatalytic application by using an AC electric field. An additional effect of the applied electric field is the induction of a polarization on PNG nano‐sheets that create a dielectrophoresis phenomenon. The poling effect of the electric field on the sample shows much improved electrocatalytic performance. The enhanced catalysis can be used for ORR as an important reaction in fuel cells. The reported new method can achieve a low cost capability for preparing new electrocatalyst electrodes for large‐scale applications.
Validation of the nickel biotic ligand model for locally relevant species in Australian freshwaters
Authors: Peters Adam , Merrington Graham , Schlekat Christian , De Schamphelaere Karel , Stauber Jennifer , Batley Graeme , Harford Andrew , van Dam Rick , Pease Ceiwen , Mooney Tom , Warne Michael , Hickey Chris , Glazebrook Peter , Chapman John , Smith Ross , Krassoi Rick 
Published: June 2018

Abstract

Australian freshwaters have relatively low water hardness and different calcium (Ca) to magnesium (Mg) ratios compared with those in Europe. The hardness values of a substantial proportion of Australian freshwaters fall below the application boundary of the existing European nickel biotic ligand models (Ni BLMs) of 2 mg Ca/L. Toxicity testing was undertaken using Hydra viridissima to assess the predictive ability of the existing Ni BLM for this species in extremely soft waters. This testing revealed an increased competitive effect of Ca and Mg with Ni for binding to the biotic ligand in soft water (&lt;10 mg CaCO3/L) than at higher water hardness. Modifications were made to the Ni BLM by increasing the binding constants for Ca and Mg at the biotic ligand to account for softer waters encountered in Australia and the more important competitive effect of Ca and Mg on Ni toxicity. To validate the modified Ni BLM, ecotoxicity testing was performed on 5 Australian test species in 5 different natural Australian waters. Overall, no single water chemistry parameter was able to indicate the trends in toxicity to all of the test species. The modified Ni BLMs were able to predict the toxicity of Ni to the test species in the validation studies in natural waters better than the existing Ni BLMs. The present study suggests that the overarching mechanisms defining Ni bioavailability to freshwater species are globally similar and that Ni BLMs can be used in all freshwater systems with minor modifications. Environ Toxicol Chem 2018;37:2566–2574. © 2018 SETAC
A collaborative mobile edge computing and user solution for service composition in 5G systems
Authors: Al Ridhawi Ismaeel , Aloqaily Moayad , Kotb Yehia , Al Ridhawi Yousif , Jararweh Yaser 
Published: June 2018

AbstractMobile edge computing (MEC) is an emergent technology that has revolutionized traditional cloud service solutions. Mobile edge computing extends cloud computing by providing processing, storage, and networking capabilities at the edge of the mobile network. Delay‐sensitive and context‐aware applications are able to execute within close proximity of mobile users. Additionally, today's cloud services are not tailored to user specifications, but rather diversified toward a group of users. To guarantee delivery of user‐specific services in 5G networks, service composition techniques should be incorporated. This article envisions a real‐time, context‐aware, service‐composition collaborative framework that lies at the edge of the network, comprising MEC and user devices for fast composite service delivery. The proposed solution decomposes cloud data into a set of files and services, which are then replicated to MEC nodes. Frequently requested files and services are further cached onto user mobile devices for faster access. Both MEC nodes and mobile users advertise their services onto the collaborative edge/user space, where services are delivered either composite or unrendered according to users' requests. Service composition is achieved through a learning‐based workflow‐net approach that relies on previous composition results to build service composition models to be used for new compositions. The presented solution provides guaranteed and fast delivery of the requested cloud composite services to end users while sustaining QoS requirements and load balancing among edge and mobile nodes.