bluuebunny/crossref_metadata_2025 huggingface dataset:
Fabrication of a Dendrite‐Free all Solid‐State Li Metal Battery via Polymer Composite/Garnet/Polymer Composite Layered Electrolyte
Authors: Pervez Syed Atif , Ganjeh‐Anzabi Pejman , Farooq Umer , Trifkovic Milana , Roberts Edward P. L. , Thangadurai Venkataraman
Published: May 2019

While all‐solid‐state Li metal batteries based on ceramic solid‐electrolytes offer higher energy density and better safety features over their liquid counterparts, critical challenges in their design such as high electrode–electrolyte interface resistance and formation of Li‐dendrites still remain unsolved. To address the issues, an intimate contact between Li and the solid‐state electrolyte is necessary. Herein, a flexible and mechanically robust polymer membrane comprising of poly(ethylene oxide), lithium perchlorate, and garnet particles is used as an interlayer between Li metal and garnet ceramic electrolyte. The Li salt enhances the ionic conductivity of the membranes and ensures their flexible nature while garnet particles enhance their mechanical strength. The cells comprising of composite membranes results in four times smaller charge transfer resistance at the interface and demonstrate stable and reversible Li plating/stripping voltage profiles. Further, the polymer composite membrane mechanically blocks the formation of Li dendrites at reasonably high currents (0.1 mA cm−2) in the structures even after prolonged cycling (140 h) owing to their enhanced toughness. With smaller charge transfer resistance (≈400 Ω cm2 at room temperature), stability at extended periods of cycling and no Li‐dendrite formations, the structures can prove a viable electrolyte candidate for advanced solid‐state Li metal batteries.
Symmetry‐Protected Dual Bound States in the Continuum in Metamaterials
Authors: Cong Longqing , Singh Ranjan
Published: May 2019

Bound state in the continuum (BIC) is a mathematical concept with an infinite radiative quality factor (Q) that exists only in an ideal infinite array of resonators. In photonics, it is essential to achieve high Q resonances for enhanced light‐mater interactions that could enable low‐threshold lasers, ultrasensitive sensors, and optical tweezers. Hence, it is important to explore BICs in different photonic systems including subwavelength metamaterials where symmetry‐protected dual BICs exist. The spectral features of dual BICs are experimentally verified in the terahertz domain by breaking the C2 symmetry that invokes a leakage channel in the form of weakly radiating Fano resonance and electromagnetically induced transparency. The radiative Q factors tend to infinity at discrete symmetry‐restoring points and obey an inverse square dependence on the structural asymmetry. BICs in metamaterials allow extreme field confinement with small mode volumes, thereby improving the rate of spontaneous emission in the cavity with much larger Purcell factor. In addition, the topological nature enables a robust existence of BICs with a vector beam profile that is ideal for lasing. The symmetry‐protected BICs in metamaterials also possess a unique advantage of scalability at different wavelengths for potential applications in sensing, lasing, switching, and spectral filtering.
Copper‐Catalyzed Homocoupling of Alkyl Halides in the Presence of Samarium
Authors: Liu Yongjun , Zhang Dianming , Xiao Shuhuan , Qi Yan , Liu Shufeng
Published: May 2019

By virtue of the reductive coupling reactivity of samarium, cuprous chloride can effectively catalyze the homocoupling of alkylhalides, including the Csp3‐Csp3 coupling of benzyl halides and the Csp2‐Csp2 coupling of aryl halides. Under mild conditions, the homocoupling reactions of benzyl halides proceeded with excellent yields, while aryl halides and heteroaryl halides formed the coupling products in moderate yields. Only 10 mol% cuprous chloride was enough to catalyze the reaction and potassium iodide proved to be necessary. The mechanism of the catalytic process was also discussed.
Progress in Symmetric and Asymmetric Superlattice Quantum Well Infrared Photodetectors
Authors: Penello Germano M. , Pereira Pedro H. , Guerra Lesslie , Pinto Luciana D. , Jakomin Roberto , Mourão Renato T. , Degani Marcos H. , Maialle Marcelo Z. , Sivco Deborah , Gmachl Claire , Pires Mauricio P. , Souza Patricia L.
Published: May 2019

Herein, two challenges are addressed, which quantum well infrared photodetectors (QWIPs), based on III‐V semiconductors, face, namely: photodetection within the so‐called “forbidden gap”, between 1.7 and 2.5 microns, and room temperature operation using thermal sources. First, to reach this forbidden wavelength range, a QWIP which consists of a superlattice structure with a central quantum well (QW) with a different thickness is presented. The different QW in the symmetric structure, which plays the role of a defect in the otherwise periodic structure, gives rise to localized states in the continuum. The proposed InGaAs/InAlAs superlattice QWIP detects radiation around 2.1 microns, beyond the materials bandoffset. Additionally, the wavefunction parity anomaly is explored to increase the oscillator strength of the optical transitions involving higher order states. Second, with the purpose of achieving room temperature operation, an asymmetric InGaAs/InAlAs superlattice, in which the QW with a different thickness is not in the center, is used to detect infrared radiation around 4 microns at 300 K. This structure operates in the photovoltaic mode because it gives rise to states in the continuum which are localized in one direction and extended in the other, leading to a preferential direction for current flow.
Von Polyhalogeniden zu Polypseudohalogeniden: Chemie basierend auf Bromcyan
Authors: Schmidt Benjamin , Schröder Benjamin , Sonnenberg Karsten , Steinhauer Simon , Riedel Sebastian
Published: May 2019

Pseudohalogene sind molekulare Einheiten mit ähnlichen chemischen Eigenschaften wie die der Halogene. Während unser Verständnis der Polyhalogenchemie in den letzten Jahren zugenommen hat, ist die Forschung an Polypseudohalogenverbindungen deutlich weniger entwickelt. Das Pseudohalogen BrCN besitzt ein stark ausgeprägtes, bromzentriertes σ‐Loch, das die Ausbildung starker Halogenbrücken fördert. Dies ermöglicht die Synthese und Charakterisierung neuer Polypseudohalogenanionen, wie die Einkristall‐Röntgenstrukturanalysen von [PNP][Br(BrCN)] und [PNP][Br(BrCN)3] zeigt. Sowohl das nahezu lineare [Br(BrCN)]−, als auch das verzerrt pyramidale [Br(BrCN)3]− wurden mithilfe der Ramanspektroskopie und quantenchemischer Rechnungen charakterisiert. 13C‐ und 15N‐NMR‐spektroskopische Studien untersuchten zudem das Verhalten der Polypseudohalogenverbindungen in Lösung sowie als Raumtemperatur‐ionische‐Flüssigkeiten (RT‐ILs) mit [NBu4]+ als Kation. Diese ILs sind in der Lage elementares Gold aufzulösen und bieten sich somit als vielversprechende Verbindungen im Metallrecycling an.
Enantioselective Phenol Coupling by Laccases in the Biosynthesis of Fungal Dimeric Naphthopyrones
Authors: Obermaier Sebastian , Thiele Wiebke , Fürtges Leon , Müller Michael
Published: May 2019

Biaryl compounds are ubiquitous metabolites that are often formed by dimerization through oxidative phenol coupling. Hindered rotation around the biaryl bond can cause axial chirality. In nature, dimerizations are catalyzed by oxidative enzymes such as laccases. This class of enzymes is known for non‐specific oxidase reactions while inherent enantioselectivity is hitherto unknown. Here, we describe four related fungal laccases that catalyze γ‐naphthopyrone dimerization in a regio‐ and atropselective manner. In vitro assays revealed that three enzymes were highly P‐selective (ee >95 %), while one enzyme showed remarkable flexibility. Its selectivity for M‐ or P‐configured dimers varied depending on the reaction conditions. For example, a lower enzyme concentration yielded primarily (P)‐ustilaginoidin A, whereas the M atropisomer was favored at higher concentration. These results demonstrate inherent enantioselectivity in an enzyme class that was previously thought to comprise only non‐selective oxidases.
Direct Synthesis of Hydroquinones from Quinones through Sequential and Continuous‐Flow Hydrogenation‐Derivatization Using Heterogeneous Au–Pt Nanoparticles as Catalysts
Authors: Miyamura Hiroyuki , Tobita Fumiya , Suzuki Aya , Kobayashi Shū
Published: May 2019

Pt–Au bimetallic nanoparticle catalysts immobilized on dimethyl polysilane (Pt–Au/(DMPSi‐Al2O3)) have been developed for selective hydrogenation of quinones to hydroquinones. High reactivity, selectivity, and robustness of the catalysts were confirmed under continuous‐flow conditions. Various direct derivatizations of quinones, such as methylation, acetylation, trifluoromethanesulfonylation, methacrylation, and benzoylation were successfully performed under sequential and continuous‐flow conditions to afford the desired products in good to excellent yields. Especially, air‐sensitive hydroquinones, such as anthrahydroquinones and naphthohydroquinones, could be successfully generated and derivatized under closed sequential and continuous‐flow conditions without decomposition.
Drastische Verlangsamung der magnetischen Relaxation durch starke Austauschkopplungen in einem luftstabilen, radikalverbrückten Cobalt(II)‐Einzelmolekülmagneten
Authors: Albold Uta , Bamberger Heiko , Hallmen Philipp P. , van Slageren Joris , Sarkar Biprajit
Published: May 2019

Die zur magnetischen Bistabilität führende Energiebarriere wird in molekularen Clustern durch die magnetische Anisotropie der einzelnen Komponenten des Clusters bestimmt. Die Verwendung eines anisotropen, vierfach koordinierten Cobalt(II)‐Bausteines ermöglichte die Darstellung eines luft‐ und hydrolysestabilen, stark gekoppelten Drei‐Spin‐Systems. Dieses konnte den Raman‐Relaxationsprozess erheblich unterdrücken, wodurch die Relaxation der Magnetisierung gegenüber der des verwendeten Bausteins um ein 350‐faches verlängert wurde, mit dem gleichzeitigen Auftreten einer ausgeprägten Hysterese. Bei niedrigen Temperaturen konnte somit eine Relaxationszeit von bis zu 9 Stunden beobachtet werden.
Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework
Authors: Nuñez‐Lopez Alejandro , Galbiati Marta , Padial Natalia M. , Ganivet Carolina R. , Tatay Sergio , Pardo Emilio , Armentano Donatella , Martí‐Gastaldo Carlos
Published: May 2019

Metal–organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single‐crystal X‐ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.
A Yolk–Shell Structured Silicon Anode with Superior Conductivity and High Tap Density for Full Lithium‐Ion Batteries
Authors: Zhang Lei , Wang Chengrui , Dou Yuhai , Cheng Ningyan , Cui Dandan , Du Yi , Liu Porun , Al‐Mamun Mohammad , Zhang Shanqing , Zhao Huijun
Published: May 2019

The poor cycling stability resulting from the large volume expansion caused by lithiation is a critical issue for Si‐based anodes. Herein, we report for the first time of a new yolk–shell structured high tap density composite made of a carbon‐coated rigid SiO2 outer shell to confine multiple Si NPs (yolks) and carbon nanotubes (CNTs) with embedded Fe2O3 nanoparticles (NPs). The high tap density achieved and superior conductivity can be attributed to the efficiently utilised inner void containing multiple Si yolks, Fe2O3 NPs, and CNTs Li+ storage materials, and the bridged spaces between the inner Si yolks and outer shell through a conductive CNTs “highway”. Half cells can achieve a high area capacity of 3.6 mAh cm−2 and 95 % reversible capacity retention after 450 cycles. The full cell constructed using a Li‐rich Li2V2O5 cathode can achieve a high reversible capacity of 260 mAh g−1 after 300 cycles.
Staged Surface Patterning and Self‐Assembly of Nanoparticles Functionalized with End‐Grafted Block Copolymer Ligands
Authors: Rossner Christian , Zhulina Ekaterina B. , Kumacheva Eugenia
Published: May 2019

Using two orthogonal external stimuli, programmable staged surface patterning and self‐assembly of inorganic nanoparticles (NPs) was achieved. For gold NPs capped with end‐grafted poly(styrene‐block‐(4‐vinylbenzoic acid)), P(St‐block‐4VBA), block copolymer ligands, surface‐pinned micelles (patches) formed from NP‐adjacent PSt blocks under reduced solvency conditions (Stimulus 1); solvated NP‐remote P(4VBA) blocks stabilized the NPs against aggregation. Subsequent self‐assembly of patchy NPs was triggered by crosslinking the P(4VBA) blocks with copper(II) ions (Stimulus 2). Block copolymer ligand design has a strong effect on NP self‐assembly. Small, well‐defined clusters assembled from NPs functionalized with ligands with a short P(4VBA) block, while NPs tethered with ligands with a long P(4VBA) block formed large irregularly shaped assemblies. This approach is promising for high‐yield fabrication of colloidal molecules and their assemblies with structural and functional complexity.
Self‐healing polyurethane based on a difuranic monomer from biorenewable source
Authors: Platonova Elena O. , Vlasov Evgeny , Pavlov Alexander A. , Kireynov Alexey , Nelyub Vladimir A. , Polezhaev Alexander V.
Published: May 2019

New monomer difurfurylamine easily obtainable from furfural (inexpensive biorenewable feedstock) was used for the synthesis of the polyurethane preform. The latest was cross‐linked with different amount of BMI (bismaleimide) via Diels–Alder reaction, and polymers with a high and low degree of cross‐linking were obtained and characterized. The self‐healing efficiency was investigated with differential scanning calorimetry, scanning electronic microscopy, X‐ray tomography, and tensile strength measurement end up to 95% restoration of mechanical properties was demonstrated for one composition after thermal treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019,136, 47869.
Role of serine protease inhibitors in insect‐host‐pathogen interactions
Authors: Shakeel Muhammad , Xu Xiaoxia , De Mandal Surajit , Jin Fengliang
Published: May 2019

Serine protease inhibitors (serpins), evolutionary old, structurally conserved molecules, are a superfamily of proteins found in almost all living organisms. Serpins are relatively large, typically 350–500 amino acids in length, with three β‐sheets and seven to nine α‐helices folding into a conserved tertiary structure with a reactive center loop. Serpins perform various physiological functions in insects, including development, digestion, host‐pathogen interactions, and innate immune response. In insects, the innate immune system is characterized as the first and major defense system against the invasion of microorganisms. Serine protease cascades play a critical role in the initiation of innate immune responses, such as melanization and the production of antimicrobial peptides, and are strictly and precisely regulated by serpins. Herein, we provide a microreview on the role of serpins in the insect‐host‐pathogen interactions, emphasizing their role in immune responses, particularly in diamondback moth (Plutella xylostella), highlighting the important discoveries and also the gaps that remain to be explored in future studies.
Transition‐Metal‐Mediated Cleavage of C−C Bonds in Aromatic Rings
Authors: Jakoobi Martin , Sergeev Alexey G.
Published: May 2019

Metal‐mediated cleavage of aromatic C−C bonds has a range of potential synthetic applications: from direct coal liquefaction to synthesis of natural products. However, in contrast to the activation of aromatic C−H bonds, which has already been widely studied and exploited in diverse set of functionalization reactions, cleavage of aromatic C−C bonds remainsTerra incognita. This Minireview summarizes the recent progress in this field and outlines key challenges to be overcome to develop synthetic methods based on this fundamental organometallic transformation.
Global projective lag synchronization of fractional order memristor based BAM neural networks with mixed time varying delays
Authors: Pratap Anbalagan , Raja Ramachandran , Sowmiya Chandran , Bagdasar Ovidiu , Cao Jinde , Rajchakit Grienggrai
Published: May 2019

This paper addresses Master–Slave synchronization for some memristor‐based fractional‐order BAM neural networks (MFBNNs) with mixed time varying delays and switching jumps mismatch. Firstly, considering the inherent characteristic of FMNNs, a new type of fractional‐order differential inequality is proposed. Secondly, an adaptive switching control scheme is designed to realize the global projective lag synchronization goal of MFBNNs in the sense of Riemann‐Liouville derivative. Then, based on a suitable Lyapunov method, under the framework of set‐valued map, differential inclusions theory, fractional Barbalat's lemma and proposed control scheme, some new projective lag synchronization criteria for such MFBNNs are obtained. Finally, some numerical examples are presented to illustrate the effectiveness of the proposed theoretical analysis.
Oil palm cultivation and production in South America: status and perspectives
Authors: Medina Jesus David Coral , Magalhães Antonio Irineudo , Zamora Hernan Dario , Melo Jaime Dario Quijano
Published: May 2019

South America is responsible for 16% of the world's agricultural production and 21% of the world's livestock. Palm harvesting has been gaining special attention, with constant growth in Brazil, Colombia, and Ecuador. Fast expansion in palm plantations in the equatorial zone around the world has been motivated by an increase in farming of species such as
Elaeis guineensis, Elaeis oleifera
, and Elaeis odora. Parallel to the increase of oil‐palm harvesting, the generation of residues is an important aspect to take into consideration. This work presents an overview of palm cultivation in South America, focusing on the full use of the fruits of the palm for biodiesel production. It also discusses the status of the main projects in South America for second‐generation biofuels production from governmental agencies and private institutes. From the data consulted it was determined that Colombia, Ecuador, and Brazil have policies and incentives for the agrobusiness of oil‐palm production. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd
Facile Preparation of Ionic Liquid‐coated Copper Nanowire‐modified Carbon Paste Electrode for Electrochemical Detection of Etilefrine Drug
Authors: Venkateswarlu Sada , Venu Manthrapudi , Reddy Yenegu Veera Manohara , Sravani Bathinapatla , Mallikarjuna K. , Yoon Minyoung , Madhavi G.
Published: May 2019

A carbon paste electrode (CPE)/Cu nanowire (Cu NW)/poly(1‐ethyl‐3‐methylimidazolium methyl sulfate) based sensor was successfully fabricated by the electro‐polymerization of 1‐ethyl‐3‐methylimidazolium methyl sulfate (EMIMS) onto the surface of Cu nanowires‐modified carbon paste electrode. The morphology and chemical nature of Cu NWs were characterized by FTIR, FE‐SEM, TEM, XRD techniques. The CPE/CuNWs/poly(EMIMS) showed an electrocatalytic activity toward the determination of etilefrine hydrochloride (ET‐HCl) in the 0.11 M buffer solution of phosphate at pH 7.0. The CPE/CuNWs/poly(EMIMS) showed an excellent limit of detection (LOD) 2.3 μM over the linear dynamic range of 0.1 to 1.3 μM. The prepared CPE/CuNWs/poly(EMIMS) has exhibited high stability, good sensitivity, and low detection limit for the determination of ET‐HCl. The validity of this advanced method was checked by applying in the blood plasma samples, with satisfactory results. This novel CPE/CuNWs/poly(EMIMS) can be an attractive material for the applications in biomedical and sensor fields.
Prognostic factors for overall survival in patients with chronic myeloid leukemia treated with imatinib at the National Cancer Institute – Mexico, from 2000 to 2016
Authors: Ylescas‐Soria Jimena , de la Torre‐Lujan Alfredo H. , Herrera Luis A. , Miranda Daniela , Grimaldo Flavio , Rivas Silvia , Cervera Eduardo , Meneses‐García Abelardo , Leon-Sarmiento Fidias E. , Prada Diddier
Published: May 2019

To determine potential predictors of long‐term survival in a large set of Hispanic (Mexican) patients with chronic myeloid leukemia (CML) treated with imatinib. We conducted an analysis with data from 411 patients with CML treated at the National Cancer Institute – Mexico, between January 2000 and December 2016. We found a median age at diagnosis of 40 years (range: 18‐84 years). The survival rate at 150 months was 82.02%, and we found that phase at diagnosis (β: 0.447, 95% Confidence Interval [95% CI]: 0.088, 0.806; P = 0.015), prognostic scales (Sokal [P = 0.021] and Hasford [β: 0.369, 95% CI: 0.049, 0.688; P = 0.024]) and hematological response at 3 months (β: 0.717, 95% CI: 0.443, 0.991; P < 0.001), but not molecular response (P = 0.834 for 6 months, P = 0.927 for 12 months, P = 0.250 for 18 months), were independently associated with overall survival. Survival analysis in subsets, according to the initial phase (chronic, accelerated and blastic phase) did not show any effect according to prognostic scales (P > 0.05). Mexican patients with CML have repeatedly been diagnosed at earlier ages. Prognostic factors in CML may differ according to the ethnic or geographical context. We found that phase at diagnosis, prognostic scale and hematological response at 3 months were independent predictors of survival.
Synthesis andin VitroAntimicrobial Activity Screening of New 3‐Acetyl‐2,5‐disubstituted‐1,3,4‐oxadiazoline Derivatives
Authors: Popiołek Łukasz , Biernasiuk Anna , Paruch Kinga , Malm Anna , Wujec Monika
Published: May 2019

Thirteen new 3‐acetyl‐2,5‐disubstituted‐1,3,4‐oxadiazoline derivatives were synthesized from corresponding hydrazide‐hydrazones of isonicotinic acid in the reaction with acetic anhydride. The obtained compounds were identified with the use of spectral methods (IR,1H‐NMR,13C‐NMR, MS).In vitroantimicrobial activity screening of synthesized compounds against a panel of bacteria and fungi revealed interesting antibacterial and antifungal activity of tested 1,3,4‐oxadiazoline derivatives, which is comparable to that of commonly used antimicrobial agents.
WDR13 promotes the differentiation of bovine skeletal muscle‐derived satellite cells by affecting PI3K/AKT signaling
Authors: Fu Yuying , Li Shuang , Tong Huili , Li Shufeng , Yan Yunqin
Published: May 2019

Muscle satellite cells are usually at rest, and when externally stimulated or regulated, they can be further differentiated by cell fusion to form new myotubes and muscle fibers. WD repeat domain 13 (WDR13) is highly conserved in vertebrates. Studies have shown that mice lacking the Wdr13 gene develop mild obesity, hyperinsulinemia, and increased islet β cell proliferation. However, the role of WDR13 in bovine cells is unclear. Here, we investigated the effect of WDR13 on bovine skeletal muscle‐derived satellite cells (MDSCs). We found that WDR13 was upregulated in bovine MDSCs using western blotting and immunofluorescence experiments. Moreover, activation and inhibition of WDR13 expression increased and decreased cell differentiation, respectively, suggesting that WDR13 promotes bovine MDSC differentiation. To further understand the mechanism of action of WDR13, we examined changes in the PI3K/AKT signaling pathway following WDR13 activation or inhibition. In addition, cells were treated with a phosphoinositide kinase 3 (PI3K) inhibitor, LY294004, to observe cell differentiation. The results showed that activation of WDR13 inhibited the PI3K/AKT signaling pathway and enhanced cell differentiation. These data suggest that WDR13 can promote the differentiation of bovine MDSCs by affecting the PI3K/AKT signaling pathway.
Photoinduced Nonlinear Contraction Behavior in Metal–Organic Frameworks
Authors: Shi Yi‐Xiang , Chen Huan‐Huan , Zhang Wen‐Hua , Day Gregory S. , Lang Jian‐Ping , Zhou Hong‐Cai
Published: May 2019

The photoinduced dynamic behavior of flexible materials has received considerable attention for potential applications, such as in data storage or as smart optical devices and molecular mechanical actuators. Until now, precisely controlling expansion and contraction with light has remained a challenge. Unraveling the detailed mechanisms of photoinduced structural transformations remains a critical step necessary to understand the molecular architecture necessary for the design of sensitive photomechanical actuators. Herein, a two‐dimensional flexible metal–organic framework [Zn2(bdc)2(3‐CH3‐spy)2]⋅H2O (Zn2‐1; H2bdc=1,4‐benzenedicaboxylic acid; 3‐CH3‐spy=3‐methylstyrylpyridine) with a positive volumetric thermal expansion coefficient of +78.78×10−6 K−1 is reported. Upon light irradiation at different wavelengths, the MOF underwent a [2+2] cycloaddition, which afforded a family of isomeric, three‐dimensional MOFs (Zn2‐2 n, n=a–d) in a single‐crystal‐to‐single‐crystal (SCSC) manner. An unprecedented phenomenon, that is, photoinduced nonlinear contraction (PINC), was observed during this conversion. The PINC is caused by conformational changes in the 3‐CH3‐spy and bdc2− ligands, the bending of metal–ligand bonds, and the local distortion of the paddle‐wheel SBUs. The formation of a “wrinkle morphology” on the crystal surface after the photoreaction was observed by AFM. This PINC behavior can broaden the studies on materials expansion and offer a photodriven approach for the future design of supersensitive photomechanical actuators.
A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling
Authors: Hiller Markus , Sittel Thomas , Wadepohl Hubert , Enders Markus
Published: May 2019

Combination of three radical anionic Ph‐BIAN ligands (Ph‐BIAN=bis‐(phenylimino)‐acenaphthenequinone) with lanthanoid ions leads to a series of homoleptic, six‐coordinate complexes of the type Ln(Ph‐BIAN)3. Magnetic coupling data were measured by paramagnetic solution NMR spectroscopy. Combining 1H NMR with 2H NMR of partially deuterated compounds allowed a detailed study of the magnetic susceptibility anisotropies over a large temperature range. The observed chemical shifts were separated into ligand‐ and metal‐centered contributions by comparison with the Y analogue (diamagnetic at the metal). The metal‐centered contributions of the complexes with the paramagnetic ions could then be separated into pseudocontact and Fermi contact shifts. The latter is large within the Ph‐BIAN scaffold, which shows that magnetic coupling is significant between the lanthanide ion and the radical ligand. Pseudocontact shifts were further correlated to structural data obtained from X‐ray diffraction experiments. Ligand‐field parameters were determined by fitting the temperature dependence of the observed magnetic susceptibility anisotropies. The electronic structure determined by this approach shows, that the Er and Tm analogues are candidates for single molecule magnets (SMM). These results demonstrate the possibilities for the application of NMR spectroscopy in investigations of paramagnetic systems in general and single molecule magnets in particular.
Chemoenzymatic Dynamic Kinetic Resolution of Primary Benzylic Amines using Pd0‐CalB CLEA as a Biohybrid Catalyst
Authors: Gustafson Karl P. J. , Görbe Tamás , de Gonzalo‐Calvo Gonzalo , Yuan Ning , Schreiber Cynthia L. , Shchukarev Andrey , Tai Cheuk‐Wai , Persson Ingmar , Zou Xiaodong , Bäckvall Jan‐E.
Published: May 2019

Herein, we report on the use a biohybrid catalyst consisting of palladium nanoparticles immobilized on cross‐linked enzyme aggregates of lipase B of Candida antarctica (CalB CLEA) for the dynamic kinetic resolution (DKR) of benzylic amines. A set of amines were demonstrated to undergo an efficient DKR and the recyclability of the catalysts was studied. Extensive efforts to further elucidate the structure of the catalyst are presented.
Advanced stage at diagnosis and elevated mortality among US patients with cancer infected with HIV in the National Cancer Data Base
Authors: Coghill Anna E. , Han Xuesong , Suneja Gita , Lin Chun Chieh , Jemal Ahmedin , Shiels Meredith S.
Published: May 2019

Background

People living with HIV (PLWH) are at an increased risk of developing several cancers, but to the authors’ knowledge less is known regarding how HIV impacts the rate of progression to advanced cancer or death.

Methods

The authors compared stage of disease at the time of presentation and mortality after diagnosis between 14,453 PLWH and 6,368,126 HIV‐uninfected patients diagnosed with cancers of the oral cavity, stomach, colorectum, anus, liver, pancreas, lung, female breast, cervix, prostate, bladder, kidney, and thyroid and melanoma using data from the National Cancer Data Base (2004‐2014). Polytomous logistic regression and Cox proportional hazards regression were used to evaluate the association between HIV, cancer stage, and stage‐adjusted mortality after diagnosis, respectively. Regression models accounted for the type of health facility at which cancer treatment was administered and the type of individual health insurance.

Results

HIV‐infected patients with cancer were found to be more likely to be uninsured (HIV‐infected: 5.0% vs HIV‐uninfected: 3.3%; P < .0001) and were less likely to have private health insurance (25.4% vs 44.7%; P < .0001). Compared with those not infected with HIV, the odds of being diagnosed at an advanced stage of disease were significantly elevated in PLWH for melanoma and cancers of the oral cavity, liver, female breast, prostate, and thyroid (odds ratio for stage IV vs stage I range, 1.24‐2.06). PLWH who were diagnosed with stage I to stage III disease experienced elevated mortality after diagnosis across 13 of the 14 cancer sites evaluated, with hazard ratios ranging from 1.20 (95% CI, 1.14‐1.26) for lung cancer to 1.85 (95% CI, 1.68‐2.04), 1.85 (95% CI, 1.51‐2.27), and 2.93 (95% CI, 2.08‐4.13), respectively, for cancers of the female breast, cervix, and thyroid.

Conclusions

PLWH were more likely to be diagnosed with advanced‐stage cancers and to experience elevated mortality after a cancer diagnosis, even after accounting for health care–related factors.
Application of the Milan System for Reporting Submandibular Gland Cytopathology: An international, multi‐institutional study
Authors: Maleki Zahra , Baloch Zubair , Lu Ryan , Shafique Khurram , Song Sharon J. , Viswanathan Kartik , Rao Rema A. , Lefler Holly , Fatima Aisha , Wiles Austin , Jo Vickie Y. , Wang He , Fadda Guido , Powers Celeste N. , Ali Syed Z. , Pantanowitz Liron , Siddiqui Momin T. , Nayar Ritu , Klijanienko Jerzy , Barkan Guliz A. , Krane Jeffrey F. , Rossi Esther D. , Callegari Fabiano , Kholová Ivana , Bongiovanni Massimo , Faquin William C. , Pusztaszeri Marc P.
Published: May 2019

Background

The Milan System for Reporting Salivary Gland Cytopathology (MSRSGC) is a 6‐tier diagnostic category system with associated risks of malignancy (ROMs) and management recommendations. Submandibular gland fine‐needle aspiration (FNA) is uncommon with a higher frequency of inflammatory lesions and a higher relative proportion of malignancy, and this may affect the ROM and subsequent management. This study evaluated the application of the MSRSGC and the ROM for each diagnostic category for 734 submandibular gland FNAs.

Methods

Submandibular gland FNA cytology specimens from 15 international institutions (2013‐2017) were retrospectively assigned to an MSRSGC diagnostic category as follows: nondiagnostic, nonneoplastic, atypia of undetermined significance (AUS), benign neoplasm, salivary gland neoplasm of uncertain malignant potential (SUMP), suspicious for malignancy (SM), or malignant. A correlation with the available histopathologic follow‐up was performed, and the ROM was calculated for each MSRSGC diagnostic category.

Results

The case cohort of 734 aspirates was reclassified according to the MSRSGC as follows: nondiagnostic, 21.4% (0%‐50%); nonneoplastic, 24.2% (9.1%‐53.6%); AUS, 6.7% (0%‐14.3%); benign neoplasm, 18.3% (0%‐52.5%); SUMP, 12% (0%‐37.7%); SM, 3.5% (0%‐12.5%); and malignant, 13.9% (2%‐31.3%). The histopathologic follow‐up was available for 333 cases (45.4%). The ROMs were as follows: nondiagnostic, 10.6%; nonneoplastic, 7.5%; AUS, 27.6%; benign neoplasm, 3.2%; SUMP, 41.9%; SM, 82.3%; and malignant, 93.6%.

Conclusions

This multi‐institutional study shows that the ROM of each MSRSGC category for submandibular gland FNA is similar to that reported for parotid gland FNA, although the reported rates for the different MSRSGC categories were variable across institutions. Thus, the MSRSGC can be reliably applied to submandibular gland FNA.
The Next Stage in Colloidal Synthesis of Aqueous CdSe Quantum Dots: High Throughput and Intense Emissive Properties
Authors: Saha Arpita , Saini Abhishek , Vinas Clara , Teixidor Francesc
Published: May 2019

Quantum dots (QDs) of CdSe have been produced with high yield using common reagents in water at 150 °C. The QDs thus produced are water compatible, show intense fluorescence emission and have high quantum yields (QYs). Their size can be controlled similarly to the high temperature organometallic method of synthesizing QDs, and these QDs produced in organic solvents at high temperature and the QDs produced in water both show comparable QYs. The great advantage is that a green solvent, water, is used and their separation from the water is very simple. They can be stored dry very easily. Similar to the organic method their size can be controlled by time, producing QDs with distinct fluorescence. The size obtained by TEM for 30, 60 and 90 minutes of reaction is 4.18 nm, 6.7 nm and 8.6 nm, respectively. This parallels the change in the emission wavelength of the QDs produced; green, yellow and orange, respectively. TEM dimensions are very similar to these of DLS (dynamic light scattering). These QDs display the hexagonal wurtzite phase, common for the higher temperature synthesis of QDs in organic solvents, and not the zinc blende phase of CdSe QDs common for the lower temperature water synthesis of QDs. The prepared QDs have shown the same intense emission for over a year after being synthesized.
Ensemble approach for network threat detection and classification on cloud computing
Authors: Krishnaveni S. , Prabakaran S.
Published: May 2019

As Network traffic rises and attacks become more widespread and complicated, we must come across Innovative ways to enrich Intrusion Detection Systems in Cloud Computing. This paper proposes the Ensemble approaches for Network Intrusion Detection and Classification in Cloud. The major aids of the Ensemble Learning to improve the outcome of each Machine Learning Algorithms and to get a robust Classifier. Real Time Malicious Network Streams Samples were collected using Honeynet, which is deployed on cloud environment. We use supervised learning and Unsupervised learning algorithms for classifying the known malicious network streams and unknown malicious streams. Network related attacks can be segregated into four classes, namely, Denial of service (DOS), User to root (U2 R), Remote to local (R2L), and probe, and the vital constraints that must be overcome with the end goal to build efficient Intelligent Intrusion Detection. The motivation behind the proposed work is to enhance the accuracy rate with response time. The outcome obtained from the Ensemble method has better accuracy rate compared to the SVM, Naive Bayes, and Logistic regression method.
Continuous‐Flow Oxidation of HMF to FDCA by Resin‐Supported Platinum Catalysts in Neat Water
Authors: Liguori Francesca , Barbaro Pierluigi , Calisi Nicola
Published: May 2019

The oxidation reaction of 5‐hydroxymethylfurfural to the bioplastic monomer 2,5‐furandicarboxylic acid over heterogenous resin‐supported Pt catalysts was investigated in detail, under continuous flow, base‐free conditions, and in neat water. The product was continuously obtained in 99 % yield by running the reaction at 120 °C, 303 s residence time, 1.2 mL min−1 O2 flow rate, and 7.7 bar O2 pressure. The product was isolated with a high space‐time‐yield of 46.0 g L−1 h−1 without purifications or acid/base treatments.
Using alpha, beta, and zeta diversity in describing the health of stream‐based benthic macroinvertebrate communities
Authors: Simons Ariel Levi , Mazor Raphael , Stein Eric D. , Nuzhdin Sergey
Published: May 2019

Ecological monitoring of streams has frequently focused on measures describing the taxonomic, and sometimes functional, α diversity of benthic macroinvertebrates (BMIs) within a single sampled community. However, as many ecological processes effectively linkBMIstream communities there is a need to describe groups of communities using measures of regional diversity. Here we demonstrate a role for incorporating both a traditional pairwise measure of community turnover, β diversity, in assessing community health as well as ζ diversity, a more generalized framework for describing similarity between multiple communities. Using 4,395 samples ofBMIstream communities in California, we constructed a model using measures of α, β, and ζ diversity, which accounted for 71.7% of among‐watershed variation in the mean health of communities, as described by the California Streams Condition Index (CSCI). We also investigated the use of ζ diversity in assessing models of stochastic vs. niche assembly across communities ofBMIs within watersheds, with the niche assembly model found to be the likelier of the two.
Postrelease monitoring habitat selection by reintroduced burchell's zebra and blue wildebeest in southern Mozambique
Authors: Mandlate Luís Comissário , Cuamba Ezidio da Lucia , Rodrigues Flávio H. G.
Published: May 2019

Aim

In Africa, reintroduction of wild animal species to conservation areas is a common practice, for the recovery or restoration of populations. Effective monitoring of reintroduced species requires understanding of basic ecological requirements such as habitat selection of these species in the new environment. Therefore, the present study investigated the habitat selection of zebra and wildebeest following their reintroduction into Maputo Special Reserve, south Mozambique, and we use binary logistic analyses to investigate the relative influence of biotic and abiotic factors in determining the habitat use.

Location

Maputo Special Reserve, south Mozambique.

Methods

We conducted the study from July 2016 to June 2017. The data were collected by direct observation, driving the vehicle along the reserve's roads that covered the vegetation communities where zebras and wildebeest are known to commonly occur. Habitat selection was calculated using selection indices (Manly's alpha), and binary logistic analyses were used to investigate the relative influence of biotic and abiotic factors in determining the habitat use.

Results

The arboreal savanna was the preferred habitat by both herbivore species. Habitat use of zebra appeared to be strongly determined by characteristics such as high grass cover, high grass greenness, and distance to water, while the habitat use by wildebeest, was strongly affected by grass height.

Main conclusions

Both zebra and wildebeest prefer arboreal savanna, forage selection likely drove preference of this habitat. Greater grass cover and greater percentage greenness of the grass both significantly increased the odds of zebra use of habitat, whereas the odds of use decreased with increases in distance to water, meaning an opportunity to ingest large amounts of grass biomass with higher quality, and this opportunity decreases with increasing in distance to water. Grass height was in the highest‐ranking model predicting habitat use by wildebeest, and during the dry season the use of habitat increased with increasing grass height, suggesting that selecting areas with tall grasses by wildebeest equated to choosing areas with higher grass quantity, as the food intake rate increases with grass height.
Give chance a chance: from coexistence to coviability in biodiversity theory
Authors: Jeltsch Florian , Grimm Volker , Reeg Jette , Schlägel Ulrike E.
Published: May 2019

A large part of biodiversity theory is driven by the basic question of what allows species to coexist in spite of a confined number of niches. A substantial theoretical background to this question is provided by modern coexistence theory (MCT), which rests on mathematical approaches of invasion analysis to categorize underlying mechanisms into factors that reduce either niche overlap (stabilizing mechanisms) or the average fitness differences of species (equalizing mechanisms). While MCT has inspired biodiversity theory in the search for these underlying mechanisms, we feel that the strong focus on coexistence causes a bias toward the most abundant species and neglects the plethora of species that are less abundant and often show high local turnover. Given the more stochastic nature of their occurrence, we advocate a complementary cross‐level approach that links individuals, small populations, and communities and explicitly takes into account (1) a more complete inclusion of environmental and demographic stochasticity affecting small populations, (2) intraspecific trait variation and behavioral plasticity, and (3) local heterogeneities, interactions, and feedbacks. Focusing on mechanisms that drive the temporary coviability of species rather than infinite coexistence, we suggest a new approach that could be dubbed coviability analysis (CVA). From a modeling perspective, CVA builds on the merged approaches of individual‐based modeling and population viability analysis but extends them to the community level. From an empirical viewpoint, CVA calls for a stronger integration of spatiotemporal data on variability and noise, changing drivers, and interactions at the level of individuals. The resulting large volumes of data from multiple sources could be strongly supported by novel techniques tailored to the discovery of complex patterns in high‐dimensional data. By complementing MCT through a stronger focus on the coviability of less common species, this approach can help make modern biodiversity theory more comprehensive, predictive, and relevant for applications.
The amphibian‐killing fungus in a biodiversity hotspot: identifying and validating high‐risk areas and refugia
Authors: Bacigalupe Leonardo D. , Vásquez Inao A. , Estay Sergio A. , Valenzuela‐Sánchez Andrés , Alvarado‐Rybak Mario , Peñafiel‐Ricaurte Alexandra , Cunningham Andrew A. , Soto‐Azat Claudio
Published: May 2019

Amphibian chytridiomycosis, due to infection with the fungusBatrachochytrium dendrobatidis(Bd), has been associated with the alarming decline and extinction crisis of amphibians worldwide. It is essential for conservation management to identify regions with high or low suitability forBd. We use a species distribution model to estimate the environmental suitability ofBdin the Chilean Winter Rainfall–Valdivian Forest biodiversity hotspot. Fourteen environmental variables were used as predictors in the statistical modeling (Maxent, generalized linear models, random forest) which also included 56 independentBd+ localities. High‐risk areas (i.e., suitability above a defined threshold) were validated through prospective field surveys conducted in 2017. As results from Maxent, which only uses presence data, were the only results retained, refugia (i.e., suitability below a defined threshold) were validated with theBdabsences (N = 12) used in the GLM and RF modeling. Our results showed that (1) suitability forBdincreased with human footprint and with shorter distances to urban centers and water bodies and decreased with elevation; (2) climate was not a major factor shaping the current distribution ofBd; and (3) the model predicted high‐risk and refugia areas fairly well. Surveys of 24 new localities in high‐risk areas confirmed that 23 wereBd+; hence, these areas warrant consideration for long‐termBdsurveillance, population monitoring, and disease mitigation. In addition, five localities with apparentBdabsence were found in the predicted high‐risk areas. Our models showed that refugia can exist near high‐risk areas andBd+ sites. Four localities with apparentBdabsence were located within the refugia predicted by the model. PreventingBdtransmission to such refugia is of paramount importance for persistence ofBd‐susceptible amphibian populations. The identification and validation through prospective field surveys of high‐risk areas and refugia are imperative to develop strategies to prevent further arrival and establishment ofBdand also, by identifying amphibian species or populations of conservation concern in such areas, will help to guide specific actions to reduce the biodiversity loss caused by chytridiomycosis.
Inferring critical thresholds of ecosystem transitions from spatial data
Authors: Majumder Sabiha , Tamma Krishnapriya , Ramaswamy Sriram , Guttal Vishwesha
Published: May 2019

Ecosystems can undergo abrupt transitions between alternative stable states when the driver crosses a critical threshold. Dynamical systems theory shows that when ecosystems approach the point of loss of stability associated with these transitions, they take a long time to recover from perturbations, a phenomenon known as critical slowing down. This generic feature of dynamical systems can offer early warning signals of abrupt transitions. However, these signals are qualitative and cannot quantify the thresholds of drivers at which transition may occur. Here, we propose a method to estimate critical thresholds from spatial data. We show that two spatial metrics, spatial variance and autocorrelation of ecosystem state variable, computed along driver gradients can be used to estimate critical thresholds. First, we investigate cellular‐automaton models of ecosystem dynamics that show a transition from a high‐density state to a bare state. Our models show that critical thresholds can be estimated as the ecosystem state and the driver values at which spatial variance and spatial autocorrelation of the ecosystem state are maximum. Next, to demonstrate the application of the method, we choose remotely sensed vegetation data (Enhanced Vegetation Index, EVI) from regions in central Africa and northeast Australia that exhibit alternative states in woody cover. We draw transects (8 × 90 km) that span alternative stable states along rainfall gradients. Our analyses of spatial variance and autocorrelation of EVI along transects yield estimates of critical thresholds. These estimates match reasonably well with those obtained by an independent method that uses large‐scale (250 × 200 km) spatial data sets. Given the generality of the principles that underlie our method, our method can be applied to a variety of ecosystems that exhibit alternative stable states.