bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enhanced Stability of Lithium Metal Anode by using a 3D Porous Nickel Substrate
Authors: Yu Lu , Canfield Nathan L. , Chen Shuru , Lee Hongkyung , Ren Xiaodi , Engelhard Mark H. , Li Qiuyan , Liu Jun , Xu Wu , Zhang Ji‐Guang 
Published: January 2018

AbstractLithium (Li) metal is considered as the “holy grail” anode for high energy density batteries, but its applications in rechargeable Li metal batteries are still hindered by the formation of Li dendrites and low coulombic efficiency for Li plating/stripping. An effective strategy to stabilize Li metal is to embed a Li metal anode in a three‐dimensional (3D) current collector. Here, a highly porous 3D Ni substrate is reported to effectively stabilize a Li metal anode. By using a galvanostatic intermittent titration technique combined with scanning electron microscopy, the underlying mechanism of the improved stability of the Li metal anode is revealed. It is clearly demonstrated that the porous 3D Ni substrate can effectively suppress the formation of “dead” Li and support the generation of a dense surface passivation layer, while a highly porous “dead” Li layer is accumulated on the two‐dimensional (2D) Li metal, which eventually limits mass transport. X‐ray photoelectron spectroscopy results further reveal the compositional differences in the solid‐electrolyte interphase layer formed on the Li metal embedded in the porous 3D Ni substrate and the 2D Li metal substrate. These results indicate that the use of 3D conductive host is critical for the long‐term stability of Li metal batteries.
Understanding the Unexpected Product Distribution in the Aerial Oxidation of Carbene‐Stabilized Diphosphorus Complex
Authors: Ghosh Boyli , Banerjee Ambar , Paul Ankan 
Published: January 2018

AbstractOxidation of nonmetallic singlet molecules by oxygen has its own share of intricacies. Herein, by means of DFT and ab initio techniques, mechanistic details of the aerial oxidation of an N‐heterocyclic carbene (NHC) stabilized diphosphorus complex are revealed. This particular oxidation process is known to produce an unexpected P−P bond containing diphosphorus tetroxide complex, instead of the more thermodynamically stable oxo‐bridged (P−O−P) compound. These findings suggest that the P−P bond containing less stabilized species is a kinetically controlled product (KCP) and obtained due to the presence of lower lying transition states (TSs) in the pathway leading to its formation, relative to the higher lying corresponding minimum‐energy crossing points (MECPs) present in the pathway involved in the formation of the oxo‐bridged species, which is the thermodynamically controlled product (TCP). Thus, an intriguing variant of the well‐known KCP/TCP phenomenon is presented here, in which the KCP is formed not by merely traditionally known lower barrier heights of TSs involved in the formation of KCP, but by faster transmission of a system through a low barrier TS relative to a higher lying MECP. Additionally, the faster kinetics of an irreversible unimolecular O−O dissociation step, which avoids the formation of the TCP is a contributing factor in dictating the fate of the reaction. The insights provided herein may help to understand the oxidation of other P−P‐containing species, such as black phosphorene.
Selective Single‐Site Pd−In Hydrogenation Catalyst for Production of Enhanced Magnetic Resonance Signals using Parahydrogen
Authors: Burueva Dudari B. , Kovtunov Kirill V. , Bukhtiyarov Andrey V. , Barskiy Danila A. , Prosvirin Igor P. , Mashkovsky Igor S. , Baeva Galina N. , Bukhtiyarov Valerii I. , Stakheev Aleksandr Yu. , Koptyug Igor V. 
Published: January 2018

AbstractPd−In/Al2O3 single‐site catalyst was able to show high selectivity (up to 98 %) in the gas phase semihydrogenation of propyne. Formation of intermetallic Pd−In compound was studied by XPS during reduction of the catalyst. FTIR−CO spectroscopy confirmed single‐site nature of the intermetallic Pd−In phase reduced at high temperature. Utilization of Pd−In/Al2O3 in semihydrogenation of propyne with parahydrogen allowed to produce ≈3400‐fold NMR signal enhancement for reaction product propene (polarization=9.3 %), demonstrating the large contribution of pairwise hydrogen addition route. Significant signal enhancement as well as the high catalytic activity of the Pd−In catalyst allowed to acquire 1H MR images of flowing hyperpolarized propene gas selectively for protons in CH, CH2 and CH3 groups. This observation is unique and can be easily transferred to the development of a useful MRI technique for an in situ investigation of selective semihydrogenation in catalytic reactors.
A Synthetic Binder of Breast Cancer Stem Cells
Authors: Chen Luxi , Long Chao , Tran Kha Andy Minh , Lee Jiyong 
Published: January 2018

AbstractCancer stem cells (CSCs) are associated with drug resistance, metastasis and recurrence of cancer. A synthetic binder of CSCs can provide a valuable tool to study the biology of CSCs and a lead to develop imaging, diagnostic and therapeutic agents targeting CSCs. Herein, a synthetic ligand (1) that specifically binds to CSCs over non‐CSCs of breast cancer cells was identified for the first time via a cell‐binding screening of a chemical library. The ligand 1 showed specific binding to CD24−/CD44+/ALDH+ CSC population of MCF‐7 and MDA‐MB‐231. We have demonstrated that 1‐immobilized beads can be used as matrices for affinity isolation of 1‐binding CSC population from breast cancer cells. The 1‐binding population showed significantly increased expressions of stemness‐associated transcription factors. Importantly, the 1‐binding population demonstrated accelerated tumor growth in vivo, and the resulting tumor displayed an increased migratory activity and high expressions of CSC markers.
Synthesis of Benzofuranones via Palladium‐Catalyzed Intramolecular Alkoxycarbonylation of Alkenylphenols
Authors: Hirschbeck Vera , Fleischer Ivana 
Published: January 2018

AbstractHerein, a new catalytic system to synthesize benzofuranones is reported. A palladium‐catalyzed intramolecular alkoxycarbonylation is employed to generate 3‐substituted‐benzofuran‐2(3H)‐ones from alkenylphenols under mild reaction conditions, linked to an ex situ formation of CO from N‐formylsaccharin. The carefully chosen catalytic system enables an efficient reaction with a novel functional group tolerance, despite the high polymerization tendency of the starting material.
Two‐Pot Synthesis of Chiral 1,3‐syn‐Diols through Asymmetric Organocatalytic Aldol and Wittig Reactions Followed by Domino Hemiacetal/Oxy‐Michael Reactions
Authors: Hayashi Yujiro , Saitoh Takanobu , Arase Hiromu , Kawauchi Genki , Takeda Naohiro , Shimasaki Yasuharu , Sato Itaru 
Published: January 2018

AbstractA two‐pot synthetic method to construct the chiral syn‐1,3‐diol unit has been developed from three aldehydes and either Wittig or Horner–Wadsworth–Emmons reagents. In the first pot, chiral δ‐hydroxy α,β‐unsaturated ketones are synthesized with excellent enantioselectivity by the organocatalyst‐mediated asymmetric direct aldol reaction of two different aldehydes, followed by either Wittig or Horner–Wadsworth–Emmons reactions. In the second pot, domino acetalization with an aldehyde and subsequent oxy‐Michael reaction proceeds in the presence of NaClO4 and a catalytic amount of Bi(OTf)3 (OTf=trifluoromethanesulfonate) to provide the chiral 1,3‐syn‐diol derivative with excellent diastereoselectivity. Diospongin C and yashabushidiol A have been synthesized efficiently by using the present method as a key step.
Highly Stable, New, Organic‐Inorganic Perovskite (CH3NH3)2PdBr4: Synthesis, Structure, and Physical Properties
Authors: Liu Xixia , Huang Tang Jiao , Zhang Liuyang , Tang Baoshan , Zhang Nengduo , Shi Diwen , Gong Hao 
Published: January 2018

AbstractLead halide perovskites have attracted striking attention recently, due to their appealing properties. However, toxicity and stability are two main factors restricting their application. In this work, a less toxic and highly stable Pd‐based hybrid perovskite was experimentally synthesized, after exploring different experimental conditions. This new hybrid organic‐inorganic perovskite (CH3NH3)2PdBr4 was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00, b=7.99, c=18.89 Å. The Cmce symmetry and lattice parameters were confirmed using Pawley refinement and the atoms positions were confirmed based on DFT calculation. This perovskite compound was determined to be a p‐type semiconductor, with a resistivity of 102.9 kΩ cm, a carrier concentration of 3.4 ×1012 cm−3, and a mobility of 23.4 cm2 (V s)−1. Interestingly, XRD and UV/Vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60 % for 4 days, and unchanged for months in N2 atmosphere; much more stable than most existing organic‐inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH3NH3)2PdBr4 organic‐inorganic hybrid perovskite material.
Revisiting empirical rules for the determination of the absolute configuration of cascarosides and other (ox‐)anthrones
Authors: Demarque Daniel P. , Pinho Danielle R. , Lopes Norberto P. , Merten Christian 
Published: January 2018

AbstractThe introduction of the C10‐stereocenter of (ox‐)anthrones by plant organisms is not stereospecific. Consequently, often, both (10S)‐ and (10R)‐diastereomers can be found in the same plant. Motivated by the importance of a correct assignment of the configuration at C10, this study revisits the nuclear magnetic resonance and electronic circular dichroism‐based empirical rules for the determination of the absolute configuration by molecular dynamic simulations and electronic circular dichroism spectrum calculations. Furthermore, a vibrational circular dichroism spectroscopic characterization of these large and conformationally very flexible molecules reveals spectral signatures, which can be used to specifically distinguish the C10 stereochemistry. A detailed analysis of the underlying vibrational modes suggests that the observed spectral pattern of the investigated cascarosides may be generally characteristic for the C10‐stereocenter of (ox‐)anthrones and that they can be used for empirical spectra‐structure correlations.
A Pharmacokinetic Study of an Ibuprofen Topical Patch in Healthy Male and Female Adult Volunteers
Authors: Lewis Fraser , Connolly Mark P. , Bhatt Aomesh 
Published: January 2018

AbstractThe pharmacokinetics of a novel locally applied ibuprofen topical patch was evaluated. Healthy subjects (n = 28) were administered a 200‐mg ibuprofen patch every 24 hours for 5 days, and steady‐state pharmacokinetics was determined. The amount of ibuprofen remaining in the patch following each patch removal was also assessed. The maximum steady‐state drug concentration and area under the concentration curve from time 0 on day 5 (t = 0) to the 24‐hours sample on day 6 were 514 ng/mL (95% CI 439 to 603 ng/mL) and 9.78 kg·h/mL (95% CI 8.43 to 11.4 kg·h/mL), respectively. Maximum ibuprofen concentration on day 5 occurred at 20 hours post–patch application. No evidence of drug accumulation was observed, and steady state was achieved between days 2 and 5. Ibuprofen levels attenuated rapidly to baseline within 24 hours after treatment discontinuation. The amount of ibuprofen remaining in the patch was high (≥80%). Treatment‐emergent adverse events were generally mild, with the most prevalent being headache (n = 6; 21.4%). Only 4 TEAEs were considered related to the ibuprofen patch: paresthesia (n = 1), headache (n = 2), and pruritic rash (n = 1). The study found that the systematic absorption of ibuprofen from a 200‐mg patch was low and that the levels of ibuprofen leaving the patch over a 24‐hour period are consistent with levels required for therapeutic relief as shown in other studies.
Theoretical Investigation of the Infrared Spectrum of 5‐Bromo‐2,4‐pentadiynenitrile from a CCSD(T)/B3LYP Anharmonic Potential
Authors: Dargelos Alain , Karamanis Panaghiotis , Pouchan Claude 
Published: January 2018

AbstractOn the grounds of a hybrid CCSD(T)/B3LYP/aug‐cc‐pVTZ anharmonic potential and the use of a variational and variational–perturbational methods, the IR spectra of 5‐bromo‐2,4‐pentadiynenitrile (BrC5N) is revisited in the mid‐infrared region up to 4500 cm−1. A position and intensity analysis of our theoretical results allow us to assign the fundamental bands together with their combinations and overtones, in the aforementioned range of frequencies. The main objective of this work is to give an “a priori” complete IR spectrum of BrC5N, which can be used as a guide for the low‐intensity bands in areas not completely studied so far.
Ultrathin Bismuth Nanosheets as a Highly Efficient CO2 Reduction Electrocatalyst
Authors: Su Panpan , Xu Wenbin , Qiu Yanling , Zhang Taotao , Li Xianfeng , Zhang Huamin 
Published: January 2018

AbstractElectrochemical reduction of CO2 to value‐added products is an important and challenging reaction for sustainable energy study. Herein, bismuth nanosheets with thickness of around 10 nm were prepared through the electrochemical reduction of Bi3+. Ultrathin Bi nanosheets with numerous low‐coordination sites can efficiently reduce CO2 to formate in aqueous solution. Within the potential range of −0.9 to −1.2 V vs. reversible hydrogen electrode (RHE), the faradaic efficiency of formate is over 90 %, outperforming many Bi catalysts. At −0.7 V, the Bi nanosheets exhibit much higher current for formate generation than that of bulk Bi, attributed to a high surface area and also modified intrinsic electronic properties brought about by the ultrathin structure. DFT calculations demonstrate that Bi nanosheets have much higher density of states at the Fermi level compared to bulk Bi, favoring improved CO2 reduction on Bi nanosheets. At −1.0 V, Bi nanosheets exhibit high selectivity for formate and excellent stability during 5 h of electrolysis.
Low‐complexity energy efficient power allocation scheme for DAS with maximum power constraint
Authors: Yu Xiangbin , Wang Hao , Wen Benben , Liu Tao 
Published: January 2018

SummaryIn this paper, a low‐complexity optimal power allocation (PA) scheme is developed to maximize energy efficiency (EE) in a distributed antenna system (DAS) under maximum power constraint and target bit error rate (BER) requirement. Composite Rayleigh fading, multiple receive antennas, and dynamic circuit power consumption are all considered in the system. Unlike conventional schemes, the presented scheme provides a closed‐form expression of PA. Firstly, the optimization problem is formulated according to the definition of EE. Using the Karush‐Kuhn‐Tucker conditions, a general form of the optimal PA, in which the number of active antennas and corresponding power allocation are required only, is then proposed. With this general form, an effective algorithm is presented to yield the closed‐form PA. The proposed scheme can be applied to the system with static circuit power consumption and/or without target BER constraint to obtain optimal PA. Simulation results corroborate the effectiveness of the developed scheme, and the scheme can achieve the same EE performance as the existing optimal schemes with lower complexity. Moreover, the distributed antenna system with multiple receive antennas has higher EE than that with single receive antenna.
A series representation for multidimensional Rayleigh distributions
Authors: Wiegand Martin , Nadarajah Saralees 
Published: January 2018

SummaryThe Rayleigh distribution is of paramount importance in signal processing and many other areas, yet an expression for random variables of arbitrary dimensions has remained elusive. In this note, we generalise the results of Beard and Tekinay for quadrivariate random variables to cases of unconstrained order and provide a simple algorithm for evaluation. The assumptions of cross‐correlation between in‐phase and quadrature, as well as nonsingularity of the covariance matrix, are retained throughout our computations.
Ecological consequences of invasion across the freshwater–marine transition in a warming world
Authors: Crespo Daniel , Solan Martin , Leston Sara , Pardal Miguel A. , Dolbeth Marina 
Published: January 2018

AbstractThe freshwater–marine transition that characterizes an estuarine system can provide multiple entry options for invading species, yet the relative importance of this gradient in determining the functional contribution of invading species has received little attention. The ecological consequences of species invasion are routinely evaluated within a freshwater versus marine context, even though many invasive species can inhabit a wide range of salinities. We investigate the functional consequences of different sizes ofCorbicula fluminea—an invasive species able to adapt to a wide range of temperatures and salinity—across the freshwater–marine transition in the presence versus absence of warming. Specifically, we characterize howC. flumineaaffect fluid and particle transport, important processes in mediating nutrient cycling (NH4‐N,NO3‐N,PO4‐P). Results showed that sediment particle reworking (bioturbation) tends to be influenced by size and to a lesser extent, temperature and salinity; nutrient concentrations are influenced by different interactions between all variables (salinity, temperature, and size class). Our findings demonstrate the highly context‐dependent nature of the ecosystem consequences of invasion and highlight the potential for species to simultaneously occupy multiple components of an ecosystem. Recognizing of this aspect of invasibility is fundamental to management and conservation efforts, particularly as freshwater and marine systems tend to be compartmentalized rather than be treated as a contiguous unit. We conclude that more comprehensive appreciation of the distribution of invasive species across adjacent habitats and different seasons is urgently needed to allow the true extent of biological introductions, and their ecological consequences, to be fully realized.
Bottom‐up processes drive reproductive success in an apex predator
Authors: Schmidt Joshua H. , McIntyre Carol L. , Roland Carl A. , MacCluskie Margaret C. , Flamme Melanie J. 
Published: January 2018

AbstractOne of the central goals of the field of population ecology is to identify the drivers of population dynamics, particularly in the context of predator–prey relationships. Understanding the relative role of top‐down versus bottom‐up drivers is of particular interest in understanding ecosystem dynamics. Our goal was to explore predator–prey relationships in a boreal ecosystem in interior Alaska through the use of multispecies long‐term monitoring data. We used 29 years of field data and a dynamic multistate site occupancy modeling approach to explore the trophic relationships between an apex predator, the golden eagle, and cyclic populations of the two primary prey species available to eagles early in the breeding season, snowshoe hare and willow ptarmigan. We found that golden eagle reproductive success was reliant on prey numbers, but also responded prior to changes in the phase of the snowshoe hare population cycle and failed to respond to variation in hare cycle amplitude. There was no lagged response to ptarmigan populations, and ptarmigan populations recovered quickly from the low phase. Together, these results suggested that eagle reproduction is largely driven by bottom‐up processes, with little evidence of top‐down control of either ptarmigan or hare populations. Although the relationship between golden eagle reproductive success and prey abundance had been previously established, here we established prey populations are likely driving eagle dynamics through bottom‐up processes. The key to this insight was our focus on golden eagle reproductive parameters rather than overall abundance. Although our inference is limited to the golden eagle–hare–ptarmigan relationships we studied, our results suggest caution in interpreting predator–prey abundance patterns among other species as strong evidence for top‐down control.
Properties of Liposomes Containing Natural and Synthetic Lipids Formed by Microfluidic Mixing
Authors: Zheng Mengxiu , Fyles Thomas M. 
Published: January 2018

Vesicle formation by a staggered herringbone microfluidic mixer is investigated in comparison to a sonication‐extrusion method. Experiments focused on the incorporation efficiency of lipid components, on dye entrapment efficiency, and on the barrier properties of the vesicle bilayers produced. The microfluidic method produces vesicles largely under the control of thermodynamic factors. As a result, the molecular parameters of the lipids (chain length, chain volume, head group area) directly control vesicle diameter. A hydrophobic branched chain sulfonate lipid is incorporated by microfluidic mixing but not by sonication‐extrusion. The vesicles produced by microfluidic mixing can be used to study ion transport by known ionophores and appear to have directly comparable barrier properties to those produced by sonication‐extrusion. Vesicles containing the branched chain sulfonate are highly permeable. The microfluidic mixing method produces predominantly unilamellar vesicles.Practical Applications: The microfluidic device examined offers a new method to reproducibly produce vesicles that are directly controlled by the molecular components of the lipid mixture. The authors show that this method produces vesicles that are equivalent to currently used methods in the study of synthetic ion channels and carriers. Looking forward, thermodynamically controlled self‐assembly will find application in the creation of new membrane systems and assemblies where the vesicles themselves are the building blocks in more extensive structures, and the active components in inter‐vesicle functions.A staggered herringbone microfluidic mixer reproducibly gives size‐controlled unilamellar vesicles having low‐permeability bilayer membranes.
Prediction analysis and quality assessment of microwell array images
Authors: Mazumdar Hirak , Kim Tae Hyeon , Lee Jong Min , Ha Jang Ho , Ahrberg Christian D. , Chung Bong Geun 
Published: January 2018

AbstractMicrowell arrays are widely used for the analysis of fluorescent‐labelled biomaterials. For rapid detection and automated analysis of microwell arrays, the computational image analysis is required. Support Vector Machines (SVM) can be used for this task. Here, we present a SVM‐based approach for the analysis of microwell arrays consisting of three distinct steps: labeling, training for feature selection, and classification into three classes. The three classes are filled, partially filled, and unfilled microwells. Next, the partially filled wells are analyzed by SVM and their tendency towards filled or unfilled tested through applying a Gaussian filter. Through this, all microwells can be categorized as either filled or unfilled by our algorithm. Therefore, this SVM‐based computational image analysis allows for an accurate and simple classification of microwell arrays.
Social Media May Empower Fisheries Students via Learning Networks
Authors: Orth Donald J 
Published: January 2018

Abstract
Social media has great, unrealized potential to improve student learning and engagement. Whereas some traditional face-to-face instruction may encourage “cram, pass, and forget” learning strategies, a holistic approach to student learning requires smart use of social media to facilitate long-term personal, professional, and scholarly development. In this paper, I advocate the alignment of learning objectives with assignments and learning environments that encourage a high level of involvement by the student in a community of practice. These learning activities are enhanced by use of social media in teaching. Five pedagogies that will benefit fisheries students and enhance social networks include public writing, Twitter and infographics, digital storytelling, online communities, and electronic portfolios. Social media application in a holistic, multi-modal approach respects student differences and enables more engaging, open learning networks.