bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction
Authors: Deng Shengjue , Yang Fan , Zhang Qinghua , Zhong Yu , Zeng Yinxiang , Lin Shiwei , Wang Xiuli , Lu Xihong , Wang Cai‐Zhuang , Gu Lin , Xia Xinhui , Tu Jiangping 
Published: July 2018

AbstractTailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe2/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe2 nanosheets to form high‐quality MoSe2/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe2 is realized on the MoSe2/TiC‐C arrays. Except for the pure 1T‐MoSe2 and 2H‐MoSe2, mixed (1T‐2H)‐MoSe2 nanosheets are achieved in the N‐MoSe2 by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer HSe bond length, and diminished bandgap endow N‐MoSe2/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe2/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm−2, and a small Tafel slope of 32 mV dec−1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.
In Situ Formed Protective Barrier Enabled by Sulfur@Titanium Carbide (MXene) Ink for Achieving High‐Capacity, Long Lifetime Li‐S Batteries
Authors: Tang Huan , Li Wenlong , Pan Limei , Cullen Conor P. , Liu Yu , Pakdel Amir , Long Donghui , Yang Jian , McEvoy Niall , Duesberg Georg S. , Nicolosi Valeria , Zhang Chuanfang (John) 
Published: July 2018

AbstractSulfur (S) is an attractive cathode material with advantages including high theoretical capacity and low cost. However, issues such as the lithium polysulfide shuttle effect and its insulating properties greatly limit the future applications of lithium‐sulfur (Li‐S) batteries. Here, a viscous aqueous ink with nanoscale S uniformly decorated on the polar, metallically conductive titanium carbide MXene nanosheets (S@Ti3C2Tx) is reported to address these issues. Importantly, it is observed that the conductive Ti3C2Tx mediator efficiently chemisorbs the soluble polysulfides and converts them into thiosulfate/sulfate. The in situ formed sulfate complex layer acts as a thick protective barrier, which significantly retards the shuttling of polysulfides upon cycling and improves the sulfur utilization. Consequently, the binder‐free, robust, highly electrically conductive composite film exhibits outstanding electrochemical performance, including high capacities (1244–1350 mAh g‐1), excellent rate handling, and impressive cycling stability (0.035–0.048% capacity loss per cycle), surpassing the best MXene‐S batteries known. The fabrication of a pouch cell based on the freestanding S@Ti3C2Tx film is also reported. The prototype device showcases high capacities and excellent mechanical flexibility. Considering the broad family of MXenes and their unique roles in immobilizing the polysulfides, various S@MXene composites can be similarly fabricated with promising Li+ storage capability and long lifetime performance.
Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials
Authors: Rice Allison M. , Dolgopolova Ekaterina A. , Yarbrough Brandon J. , Leith Gabrielle A. , Martin Corey R. , Stephenson Kenneth S. , Heugh Rebecca A. , Brandt Amy J. , Chen Donna A. , Karakalos Stavros G. , Smith Mark D. , Hatzell Kelsey B. , Pellechia Perry J. , Garashchuk Sophya , Shustova Natalia B. 
Published: July 2018

AbstractWe report the first examples of purely organic donor–acceptor materials with integrated π‐bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four‐orders‐of‐magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.
Tunable Water‐Soluble Supramolecular Polymers by Visible‐Light‐Regulated Host–Guest Interactions
Authors: Jin Ting‐Ting , Zhou Xiao‐He , Yin Yong‐Fei , Zhan Tian‐Guang , Cui Jiecheng , Liu Li‐Juan , Kong Li‐Chun , Zhang Kang‐Da 
Published: July 2018

AbstractThe development of artificial self‐assembling systems with dynamic photo‐regulation features in aqueous solutions has drawn great attention owing to the potential applications in fabricating elaborate biological materials. Here we demonstrate the fabrication of water‐soluble cucurbit[8]uril (CB[8])‐mediated supramolecular polymers by connecting the fluorinated azobenzene (FAB) containing monomers through host‐enhanced heteroternary π–π stacking interactions. Benefiting from the unique visible‐light‐induced E→Z photoisomerization of the FAB photochromophores, the encapsulation behaviors between the CB[8] macrocycle and the monomers could be regulated upon visible light irradiation, resulting in the depolymerization of such CB[8]‐mediated supramolecular polymers.
Validation of an LC‐MS/MS method for simultaneous determination of icotinib and its four major circulating metabolites in human plasma and its application in a pharmacokinetic study
Authors: Xiao Ying , Maiolino Piera , Yan Jin‐Hua , Ma Jie , Li Jin , Chen Li 
Published: July 2018

AbstractIn this study, a simple and sensitive LC‐MS/MS method was developed and validated for simultaneous determination of icotinib and its four circulating metabolites in human plasma. The analytes were extracted with acetonitrile and separated on a C18 column using 2 mm ammonium acetate containing 0.2% formic acid and acetonitrile as mobile phase. The analytes were introduced into the mass spectrometer via an electrospray ionization source operated in positive ion mode. Precursor‐to‐product transitions were optimized to be m/z 392.2 → 304.1 for icotinib, m/z 424.1 → 278.2 for M1 and M2, m/z 408.2 → 320.1 for M3, m/z 410.2 → 322.1 for M4 and m/z 394.4 → 278.1 for IS. The assay showed good linearity over the concentration ranges of 0.1–600 ng/mL for icotinib and 0.1–200 ng/mL for metabolites, with correlation coefficients >0.994 (r > 0.994). The LLOQ was 0.1 ng/mL for each analyte. The intra‐ and inter‐day precisions (RSD) were ≤12.98% while the accuracy (RE) ranged from −8.76 to 12.01%. No significant matrix effect was observed. The validated method was successfully applied for the pharmacokinetic study of icotinib and its four circulating metabolites in human plasma after oral administration of icotinib at a single dose of 125 mg.
Comparative study of chemical composition and active components against α‐glucosidase of various medicinal parts of Morus alba L.
Authors: Chen Zhiyong , Du Xia , Yang Yuanyuan , Cui Xiaomin , Zhang Zijia , Li Ye 
Published: July 2018

AbstractMorus alba L has long been used as fodder and as a traditional medicine. The different parts of M. alba (Cortex Mori, Ramulus Mori, Folium Mori and Fructus Mori) have different bioactivities; however, most current evidence is focused on anti‐diabetic properties. In spite of their widespread use, few studies have compared the chemical composition and activity against α‐glucosidase of the various medicinal parts of M. alba. In this study, we developed an HPLC method for simultaneous quality control and discrimination of Cortex Mori, Ramulus Mori, Folium Mori and Fructus Mori using 13 marker compounds. We found that quercetin, morin, kuwanon G, sanggenon C, morusin, mulberroside A and rutin were chemically distinct among the various medicinal parts of M. alba. A spectrum–effect relationship method was established to compare α‐glucosidase inhibitory activity of various batches of samples to determine the activity of the primary active components against α‐glucosidase. Taken together with molecular docking data, we found that prenylated flavonoids (morin, sanggenon C, kuwanon G and morusin), flavonols (kaempferol, quercetin, rutin and isoquercitrin) and alkaloids (1‐deoxynojirimycin) were small molecule α‐glucosidase inhibitory ingredients. In conclusion, we laid a solid foundation for effective substance identification in various parts of M. alba, and simultaneously provided a basis for their quality control.
Core‐Shell Structured NiCo2O4@FeOOH Nanowire Arrays as Bifunctional Electrocatalysts for Efficient Overall Water Splitting
Authors: Li Man , Tao Leiming , Xiao Xin , Lv Xiaowei , Jiang Xingxing , Wang Mingkui , Peng Zhangquan , Shen Yan 
Published: July 2018

AbstractExploring earth‐abundant and high‐performance catalysts for water‐splitting is extremely crucial to produce clean hydrogen fuel. In this work, FeOOH was electrodeposited on NiCo2O4 nanowire to form a three dimensional (3D) core‐shell structure on Ni foam (NiCo2O4@FeOOH/NF) as bifunctional catalyst for overall water splitting. To control the thickness of FeOOH shell layer by optimizing electrodeposition time, the NiCo2O4@FeOOH/NF(500s) with FeOOH layer of ∼7 nm thickness exhibits excellent catalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution. Moreover, in a two‐electrode water splitting system, extremely small potential of 1.52 V can be achieved for NiCo2O4@FeOOH/NF(500s), giving a current density of 10 mA cm−2. Detailed investigation reveals that the thickness of FeOOH layer, strong electronic interaction at the interface between NiCo2O4 and FeOOH play critical role in the excellent catalytic property.
Multiple Multicomponent Reactions: Unexplored Substrates, Selective Processes, and Versatile Chemotypes in Biomedicine
Authors: Ghashghaei Ouldouz , Caputo Samantha , Sintes Miquel , Revés Marc , Kielland Nicola , Estarellas Carolina , Luque F. Javier , Aviñó Anna , Eritja Ramón , Serna‐Gallego Ana , Marrugal‐Lorenzo José Antonio , Pachón Jerónimo , Sánchez‐Céspedes Javier , Treadwell Ryan , de Moliner Fabio , Vendrell Marc , Lavilla Rodolfo 
Published: July 2018

AbstractMultiple multicomponent reactions rapidly assemble complex structures. Despite being very productive, the lack of selectivity and the reduced number of viable transformations restrict their general application in synthesis. Hereby, we describe a rationale for a selective version of these processes based in the preferential generation of intermediates which are less reactive than the initial substrates. In this way, applying the Groebke–Blackburn–Bienaymé reaction on a range of α‐polyamino‐polyazines, we prepared a family compact heterocyclic scaffolds with relevant applications in medicinal and biological chemistry (live cell imaging probes, selective binders for DNA quadruplexes, and antiviral agents against human adenoviruses). The approach has general character and yields complex molecular targets in a selective, tunable and direct manner.
Functional Control of Peptide Amphiphile Assemblies via Modulation of Internal Cohesion and Surface Chemistry Switch
Authors: Lu Sheng , Cui Weijia , Li Jason , Sheng Yuebiao , Chen Pu 
Published: July 2018

AbstractUnderstanding the impacts of the internal cohesion and surface chemistry of supramolecular systems on the collective behaviors in the contacts between the systems and biomolecules can greatly expand the functional diversity and adaptivity of supramolecular nanostructures. Here we show how the tuned molecular interactions modulate the morphologies and internal cohesion of peptide amphiphile (PA) self‐assemblies and their resultant functions. Circular dichroism spectroscopy, fluorescence probing, atomic force and electron microscopy, along with molecular dynamics simulations, revealed that the PA self‐assembly formed compact long fibers when surface charge repulsion was screened, but formed loose short fibers or micelle‐like assemblies when hydrogen bonding was disrupted or hydrophobic core was enhanced. More importantly, depending on the strength of the phospholipid affinity for the cationic segment of the PA, the same internal cohesion of PA nanostructures can lead to either cell death or cell survival, providing unique insights into the design of supramolecular materials.
Long‐term outcomes of partial prostate treatment with magnetic resonance imaging‐guided brachytherapy for patients with favorable‐risk prostate cancer
Authors: King Martin T. , Nguyen Paul L. , Boldbaatar Ninjin , Tempany Clare M. , Cormack Robert A. , Beard Clair J. , Hurwitz Mark D. , Suh W. Warren , D'Amico Anthony V. , Orio Peter F. 
Published: July 2018

BACKGROUNDPartial prostate treatment has emerged as a potential method for treating patients with favorable‐risk prostate cancer while minimizing toxicity. The authors previously demonstrated poor rates of biochemical disease control for patients with National Comprehensive Cancer Network (NCCN) intermediate‐risk disease using partial gland treatment with brachytherapy. The objective of the current study was to estimate the rates of distant metastasis and prostate cancer‐specific mortality (PCSM) for this cohort.METHODSBetween 1997 and 2007, a total of 354 men with clinical T1c disease, a prostate‐specific antigen (PSA) level < 15 ng/mL, and Gleason grade ≤3 + 4 prostate cancer underwent partial prostate treatment with brachytherapy to the peripheral zone under 0.5‐Tesla magnetic resonance guidance. The cumulative incidences of metastasis and PCSM for the NCCN very low‐risk, low‐risk, and intermediate‐risk groups were estimated. Fine and Gray competing risk regression was used to evaluate clinical factors associated with time to metastasis.RESULTSA total of 22 patients developed metastases at a median of 11.0 years (interquartile range, 6.9‐13.9 years). The 12‐year metastasis rates for patients with very low‐risk, low‐risk, and intermediate‐risk disease were 0.8% (95% confidence interval [95% CI], 0.1%‐4.4%), 8.7% (95% CI, 3.4%‐17.2%), and 15.7% (95% CI, 5.7%‐30.2%), respectively, and the 12‐year PCSM estimates were 1.6% (95% CI, 0.1%‐7.6%), 1.4% (95% CI, 0.1%‐6.8%), and 8.2% (95% CI, 1.9%‐20.7%), respectively. On multivariate analysis, NCCN risk category (low risk: hazard ratio, 6.34 [95% CI, 1.18‐34.06; P = .03] and intermediate risk: hazard ratio, 6.98 [95% CI, 1.23‐39.73; P = .03]) was found to be significantly associated with the time to metastasis.CONCLUSIONSPartial prostate treatment with brachytherapy may be associated with higher rates of distant metastasis and PCSM for patients with intermediate‐risk disease after long‐term follow‐up. Treatment of less than the full gland may not be appropriate for this cohort.
Effect of exercise on metabolic syndrome in black women by family history and predicted risk of breast cancer: The FIERCE Study
Authors: Dash Chiranjeev , Taylor Teletia R. , Makambi Kepher H. , Hicks Jennifer , Hagberg James M. , Adams‐Campbell Lucile L. 
Published: July 2018

BackgroundThis study examined the effects of supervised and home‐based exercise interventions on changes in metabolic syndrome (MetS) according to breast cancer risk (high vs low) in black women enrolled in the Focused Intervention on Exercise to Reduce Cancer (FIERCE) trial.MethodsPostmenopausal, obese, metabolically unhealthy black women, 45 to 65 years old, were randomized to supervised aerobic exercise (73 women), home‐based walking‐based exercise (69 women), or a control arm (71 women). Participants in the exercise arms underwent a 6‐month intervention with study assessments conducted at the baseline and 6 months. The primary outcome measure was MetS (fasting glucose, waist circumference, blood pressure, serum triglycerides, and high‐density lipoprotein [HDL]). The intervention effects on MetS, stratified by breast cancer risk as measured by the family history of breast cancer and model‐based projected breast cancer risk, were examined with intent‐to‐treat analyses using generalized estimating equation models.ResultsAmong women with a family history of breast cancer, the exercise arms had lower mean MetS z scores, which suggested an improvement in the metabolic profile, than controls at 6 months (controls, + 0.55; home‐based arm, –0.97, P < .01; supervised arm, –0.89, P < .01). Stratified analyses by projected breast cancer risk suggested similar but statistically nonsignificant findings, with those at high risk having more favorable changes in the MetS z score in the exercise arms versus the control arm. These changes were primarily attributable to changes in blood pressure, triglycerides, and HDL.ConclusionsShort‐term aerobic activity regimens may improve the metabolic profile and thereby reduce breast cancer risk in obese, metabolically unhealthy black women at high risk for cancer. © 2018 American Cancer Society.
Thermodynamic Limit for Directed Polymers and Stationary Solutions of the Burgers Equation
Authors: Bakhtin Yuri , Li Liying 
Published: July 2018

The first goal of this paper is to prove multiple asymptotic results for a time‐discrete and space‐continuous polymer model of a random walk in a random potential. These results include: existence of deterministic free energy density in the infinite‐volume limit for every fixed asymptotic slope, concentration inequalities for free energy implying a bound on its fluctuation exponent, and straightness estimates implying a bound on the transversal fluctuation exponent. The culmination of this program is almost sure existence and uniqueness of polymer measures on one‐sided infinite paths with given endpoint and slope, and interpretation of these infinite‐volume Gibbs measures as thermodynamic limits. Moreover, we prove that marginals of polymer measures with the same slope and different endpoints are asymptotic to each other.The second goal of the paper is to develop ergodic theory of the Burgers equation with positive viscosity and random kick forcing on the real line without any compactness assumptions. Namely, we prove a one force–one solution principle, using the infinite‐volume polymer measures to construct a family of stationary global solutions for this system, and proving that each of those solutions is a one‐point pullback attractor on the initial conditions with the same spatial average. This provides a natural extension of the same program realized for the inviscid Burgers equation with the help of action minimizers that can be viewed as zero temperature limits of polymer measures. © 2018 Wiley Periodicals, Inc.
β‐Cyclodextrin as a Precursor to Holey C‐Doped g‐C3N4 Nanosheets for Photocatalytic Hydrogen Generation
Authors: Da Silva Eliana S. , Moura Nuno M. M. , Coutinho Ana , Dražić Goran , Teixeira Bruno M. S. , Sobolev Nikolai A. , Silva Cláudia G. , Neves M. Graça P. M. S. , Prieto Manuel , Faria Joaquim L. 
Published: July 2018

AbstractA green, template‐free and easy‐to‐implement strategy was developed to access holey g‐C3N4 (GCN) nanosheets doped with carbon. The protocol involves heating dicyandiamide with β‐cyclodextrin (βCD) prior to polymerization. The local symmetry of the GCN skeleton is broken, yielding CxGCN (x corresponds to the initial amount of βCD used) with pores and a distorted structure. The electronic, emission, optical and textural properties of the best‐performing material, C2GCN, were significantly modified as compared to bulk GCN. The spectroscopic and luminescent features of C2GCN show the characteristic π–π* electronic transition of GCN, accompanied by much stronger n–π* electronic transitions owing to the porous and distorted network. These new electronic transitions, along with the presence of additional carbon synergistically contributed to enhanced visible light absorption and restrained recombination of electron–hole pairs. Steady‐state and time‐resolved photoluminescence showed an effective quench of the fluorescence emission, accompanied by a decrease of fluorescence lifetime of C2GCN (2.20 ns) in comparison with GCN (5.85 ns), owing to the delocalization of electron and holes to new recombination centers. The photocatalytic activity of C2GCN was attributed to efficient charge carrier separation and improved visible‐light absorbing ability. As result, C2GCN exhibited ∼5 times higher photocatalytic H2 generation under visible light than bulk GCN.
A Cobalt‐Based Metal–Organic Framework as Cocatalyst on BiVO4 Photoanode for Enhanced Photoelectrochemical Water Oxidation
Authors: Zhang Wang , Li Rui , Zhao Xin , Chen Zhong , Law Adrian Wing‐Keung , Zhou Kun 
Published: July 2018

AbstractA metal–organic framework (MOF)‐modified bismuth vanadate (BiVO4) photoanode is fabricated by an ultrathin sheet‐induced growth strategy, where ultrathin cobalt oxide sheets act as a metal source for the in situ synthesis of Co‐based MOF poly[Co2(benzimidazole)4] (denoted [Co2(bim)4]) nanoparticles on the surface of BiVO4. [Co2(bim)4] with small particle size and high dispersion can serve as a promising cocatalyst to accept holes transferred from BiVO4 and boost surface reaction kinetics for photoelectrochemical (PEC) water oxidation. The photocurrent density of a [Co2(bim)4]‐modified BiVO4 photoanode can achieve 3.1 mA cm−2 under AM 1.5G illumination at 1.23 V versus the reversible hydrogen electrode (RHE), which is better than those of pristine and cobalt‐based inorganic materials‐modified BiVO4 photoanodes. [Co2(bim)4], with porosity and abundant metal sites, exhibits a high surface charge‐separation efficiency (83 % at 1.2 V versus RHE), leading to the enhanced PEC activity. This work will bring new insight into the development of MOF materials as competent cocatalysts for PEC water splitting applications.
Hummingbirds and bumble bees exposed to neonicotinoid and organophosphate insecticides in the Fraser Valley, British Columbia, Canada
Authors: Bishop Christine A. , Moran Alison J. , Toshack Michelle C. , Elle Elizabeth , Maisonneuve France , Elliott John E. 
Published: July 2018

Abstract

To measure exposure to neonicotinoid and other pesticides in avian pollinators, we made novel use of cloacal fluid and fecal pellets from rufous (Selasphorus rufus) and Anna's (Calypte anna) hummingbirds living near blueberry fields in the Fraser River Valley and Vancouver Island, British Columbia, Canada. To examine on-farm exposure to pesticides in invertebrate pollinators, we also collected bumble bees native to Canada (Bombus mixtus, Bombus flavifrons, and Bombus melanopygus), their pollen, and blueberry leaves and flowers from within conventionally sprayed and organic blueberry farms. By sites and sample type, the results reported in the present study represent pooled samples (n = 1). In 2015 to 2016, the combined concentration of the neonicotinoid insecticides imidacloprid, thiamethoxam, and clothianidin detected in hummingbird cloacal fluid from sites near conventionally sprayed blueberry fields was 3.63 ng/mL (ppb). Among the 18 compounds measured in fecal pellets, including one neonicotinoid (imidacloprid), only piperonyl butoxide was detected (1.47–5.96 ng/g). Piperonyl butoxide is a cytochrome P450 inhibitor applied with some insecticides to increase their toxic efficacy. Only diazinon was detected in bumble bees (0.197 ng/g), whereas diazinon (1.54–1.7 ng/g) and imidacloprid (up to 18.4 ng/g) were detected in pollen collected from bumble bees including the bees from organic sites located near conventionally sprayed blueberry farms. Imidacloprid was also detected at 5.16 ng/g in blueberry flowers collected 1 yr post spray from 1 of 6 conventionally sprayed blueberry farms. Environ Toxicol Chem 2018;37:2143–2152. © 2018 SETAC
Abstract