bluuebunny/crossref_metadata_2025 huggingface dataset:
Epitope‐Targeted Macrocyclic Peptide Ligand with Picomolar Cooperative Binding to Interleukin‐17F
Authors: Lai Bert T. , Wilson Jeré A. , Malette Loredo Jacquie , Pitram Suresh M. , LaBerge Nicole A. , Heath James R. , Agnew Heather D.
Published: January 2018

The IL‐17 cytokine family is associated with multiple immune and autoimmune diseases and comprises important diagnostic and therapeutic targets. This work reports the development of epitope‐targeted ligands designed for differential detection of human IL‐17F and its closest homologue IL‐17A. Non‐overlapping and unique epitopes on IL‐17F and IL‐17A were identified by comparative sequence analysis of the two proteins. Synthetic variants of these epitopes were utilized as targets for in situ click screens against a comprehensive library of synthetic peptide macrocycles with 5‐mer variable regions. Single generation screens yielded selective binders for IL‐17F and IL‐17A with low cross‐reactivity. Macrocyclic peptide binders against two distinct IL‐17F epitopes were coupled using variable length chemical linkers to explore the physical chemistry of cooperative binding. The optimized linker length yielded a picomolar affinity binder, while retaining high selectivity. The presented method provides a rational approach towards targeting discontinuous epitopes, similar to what is naturally achieved by many B cell receptors.
Water–Tryptophan Interactions: Lone‐pair⋅⋅⋅π or O−H⋅⋅⋅π? Molecular Dynamics Simulations of β‐Galactosidase Suggest that Both Modes Can Co‐exist
Authors: Durec Matúš , Marek Radek , Kozelka Jiří
Published: January 2018

In proteins, the indole side chain of tryptophan can interact with water molecules either in‐plane, forming hydrogen bonds, or out‐of‐plane, with the water molecule contacting the aromatic π face. The latter interaction can be either of the lone pair⋅⋅⋅π (lp⋅⋅⋅π) type or corresponds to the O−H⋅⋅⋅π binding mode, an ambiguity that X‐ray structures usually do not resolve. Here, we report molecular dynamics (MD) simulations of a solvated β‐galactosidase monomer, which illustrate how a water molecule located at the π face of an indole side chain of tryptophan can adapt to the position of proximate residues and “select” its binding mode. In one such site, the water molecule is predicted to rapidly oscillate between the O−H⋅⋅⋅π and lp⋅⋅⋅π binding modes, thus gaining entropic advantage. Our MD simulations provide support for the role of lp⋅⋅⋅π interactions in the stabilization of protein structures.
Ultrafine and Ligand‐Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus‐Doped Carbon
Authors: Liu Ben , Jin Lei , Zhong Wei , Lopes Aaron , Suib Steven L. , He Jie
Published: January 2018

We report the use of phosphorus‐doped carbon (P‐C) as support to grow ultrasmall (1–3 nm) and ligand‐free precious metal nanocrystals (PMNCs) via chemical reduction. We show that the valence states of surface phosphorus species are critical in tuning the affinity between the carbon support and metal precursors, which rationally controls the loading size and uniformity of resultant PMNCs. Five kinds of PMNCs, including Ru, Ag, Au, Rh, and Pd, were grown in situ to demonstrate the key role of surface phosphorus sites on the P‐C support. As a proof‐of‐concept application, Ru nanocatalysts with an average diameter of 1.0±0.2 nm supported on P‐C were examined for the electrocatalytic hydrogen evolution reaction (HER). Ultrasmall and ligand‐free Ru nanocatalysts exhibited superior HER activity and stability compared to its counterparts with surface agents or larger sizes. An overpotential of 27.6 mV (vs. reversible hydrogen electrode) for Ru nanocatalysts was achieved at a current density of 10 mA cm−2. This novel method opens a new avenue to immobilize ligand‐free and well‐dispersed PMNCs on carbon; and, more importantly, it provides a new library of supported PMNCs with high catalytic activity.
Self‐Assembled Cofacial Zinc–Porphyrin Supramolecular Nanocapsules as Tuneable 1O2 Photosensitizers
Authors: Colomban Cédric , Fuertes‐Espinosa Carles , Goeb Sébastien , Sallé Marc , Costas Miquel , Blancafort Lluís , Ribas Xavi
Published: January 2018

We demonstrate the benefits of using cofacial Zn–porphyrins as structural synthons in coordination‐driven self‐assembled prisms to produce cage‐like singlet oxygen (1O2) photosensitizers with tunable properties. In particular, we describe the photosensitizing and emission properties of palladium‐ and copper‐based supramolecular capsules, and demonstrate that the nature of the bridging metal nodes in these discrete self‐assembled prisms strongly influences 1O2 generation at the Zn–porphyrin centers. The PdII‐based prism is a particularly robust photosensitizer, whereas the CuII self‐assembled prism is a dormant photosensitizer that could be switched to a ON state upon disassembly of the suprastructure. Furthermore, the well‐defined cavity within the prisms allowed encapsulation of pyridine‐based ligands and fullerene derivatives, which led to a remarkable guest tuning of the 1O2 production.
Effect of Crystal Packing on the Thermosalient Effect of the Pincer‐Type Diester Naphthalene‐2,3‐diyl‐bis(4‐fluorobenzoate): A New Class II Thermosalient Solid
Authors: Tamboli Majid I. , Karothu Durga Prasad , Shashidhar Mysore S. , Gonnade Rajesh G. , Naumov Panče
Published: January 2018

The pincer‐like double ester naphthalene‐2,3‐diyl‐bis(4‐fluorobenzoate) (2) is pentamorphic. Upon heating crystals of form I to below their melting point (441–443 K), they undergo a phase transition accompanied by a thermosalient effect, that is, rare and visually striking motility whereby the crystals jump or disintegrate. The phase transition and the thermosalient effect are reversible. Analysis of the crystal structure revealed that form I is a class II thermosalient solid. Crystals of form III also underwent a reversible phase transition in the temperature range of 160 to 170 K; however, they were not thermosalient. Comparison of the structures and the mechanical responses of the two polymorphs revealed that the thermosalient effect of form I was due to reversible closing and opening of the arms of the diester molecules in a tweezer‐like action.
A BODIPY‐Based Fluorescent Probe to Visually Detect Phosgene: Toward the Development of a Handheld Phosgene Detector
Authors: Sayar Melike , Karakuş Erman , Güner Tuğrul , Yildiz Busra , Yildiz Umit Hakan , Emrullahoğlu Mustafa
Published: January 2018

A boron‐dipyrromethene (BODIPY)‐based fluorescent probe with a phosgene‐specific reactive motif shows remarkable selectivity toward phosgene, in the presence of which the nonfluorescent dye rapidly transforms into a new structure and induces a fluorescent response clearly observable to the naked eye under ultraviolet light. Given that dynamic, a prototypical handheld phosgene detector with a promising sensing capability that expedites the detection of gaseous phosgene without sophisticated instrumentation was developed. The proposed method using the handheld detector involves a rapid response period suitable for issuing early warnings during emergency situations.
Theoretical Investigations on the Mechanistic Aspects of O2 Activation by a Biomimetic Dinitrosyl Iron Complex
Authors: Banerjee Ambar , Sen Souloke , Paul Ankan
Published: January 2018

Though dinitrosyl‐iron complexes (DNICs) are largely believed to act as NO carriers, several experiments on model DNICs have suggested that they can also act as nitrating agents in presence of dioxygen. Oxygen activation by DNICs has been implicated as a possible route for protein tyrosine nitration (PTN), which leads to neurodegenerative disorders. Herein using static and dynamic theoretical techniques we unravel a previously unknown dual state mechanistic paradigm for dioxygen activation of a biomimetic nitrating DNIC complex leading to phenolic nitration. Our computations reveal that the model DNIC, the ground electronic state of which is singlet, has a low‐lying triplet state and an inherent singlet–triplet spin‐crossover of DNICs can be triggered by fluxional changes in the bite angle of the two NO ligands. The presence of a low‐lying triplet state in the DNIC affords an avenue for O2 activation other than a direct O2 activation by O2‐induced spin‐crossover of the singlet ground state. These two low‐lying channels facilitate the formation of a peroxynitrite species. Nitration of phenolic substrates is facilitated by the release of NO2. The corresponding minimum energy crossing points (MECP) have been located. Along the reaction path, the changes in the electronic structure scenarios have been studied and interpreted. Our report also sheds light on the plausible mechanistic pathway of PTN by reactive species formed once O2 activation by DNICs have been achieved.
Formation of Cyanamide–Glyoxal Oligomers in Aqueous Environments Relevant to Primeval and Astrochemical Scenarios: A Spectroscopic and Theoretical Study
Authors: Lavado Nieves , García de la Concepción Juan , Babiano Reyes , Cintas Pedro
Published: January 2018

The condensation of cyanamide and glyoxal, two well‐known prebiotic monomers, in an aqueous phase has been investigated in great detail, demonstrating the formation of oligomeric species of varied structure, though consistent with generalizable patterns. This chemistry involving structurally simple substances also illustrates the possibility of building molecular complexity under prebiotically plausible conditions, not only on Earth, but also in extraterrestrial scenarios. We show that cyanamide–glyoxal reactions in water lead to mixtures comprising both acyclic and cyclic fragments, largely based on fused five‐ and six‐membered rings, which can be predicted by computation. Remarkably, such a mixture could be identified using high‐resolution electrospray ionization (ESI) mass spectrometry and spectroscopic methods. A few mechanistic pathways can be postulated, most involving the intermediacy of glyoxal cyanoimine and further chain growth, thus increasing the diversity of the observed products. This rationale is supported by theoretical analyses with clear‐cut identification of all of the stationary points and transition‐state structures. The properties and structural differences of oligomers obtained under thermodynamic conditions in water as opposed to those isolated by precipitation from organic media are also discussed.
Cp*Co(III)‐Catalyzed Coupling of Benzamides with α,β‐Unsaturated Carbonyl Compounds: Preparation of Aliphatic Ketones and Azepinones
Authors: Chirila Paula G. , Adams Joshua , Dirjal Amir , Hamilton Alex , Whiteoak Christopher J.
Published: January 2018

A Cp*CoIII‐catalyzed C−H functionalization of benzamide substrates with α,β‐unsaturated ketones has been optimized, providing a facile route towards aliphatic ketone products. When employing α,β‐unsaturated aldehydes as coupling partners, under the optimized protocol, a cascade reaction forming azepinones has also been developed. Finally, DFT studies have demonstrated how stabilization of a metallo‐enol intermediate when employing α,β‐unsaturated ketones is the driving force leading to the observed aliphatic ketone product rather than olefinic products reported using α,β‐unsaturated esters as coupling partners.
Structural and Magnetic Variations in a Family of Isoskeletal, Oximate‐Bridged {MnIV2MIII} Complexes (MIII=Mn, Gd, Dy)
Authors: Alaimo Alysha A. , Worrell Anne , Gupta Sayak Das , Abboud Khalil A. , Lampropoulos Christos , Christou George , Stamatatos Theocharis C.
Published: January 2018

The self‐assembly reaction of MnCl2⋅4H2O, acenaphthenequinone dioxime (acndH2) and NEt3 has yielded an unprecedented, linear {MnIV2MnIII} complex with an S=5 spin ground state and non‐SMM behavior. The targeted replacement of the central MnIII ion with GdIII and DyIII ions has successfully increased the S and turned on the SMM dynamics without affecting the core structure and the nature of the magnetic exchange interactions.
Supramolecular solvent‐based vortex‐mixed microextraction: Determination of chiral triazole fungicide in beer samples
Authors: Zhao Wenting , Zhao Jianzhuang , Zhao Hanqing , Cao Yueyang , Liu Weitong
Published: January 2018

A supramolecular solvent composed of decanol in tetrahydrofuran/water was utilized for the simultaneous microextraction of chiral triadimefon and triadimenol in beer samples. Supramolecular solvents are nanostructured amphiphilic liquids that contain aqueous cavities, and the size of those cavities can be adjusted by the ratio of decanol, tetrahydrofuran, and water. The target analytes were mixed into the matrix sample and extracted in the supramolecular solvent phase, which was followed by separation and quantification by chiral liquid chromatography‐mass spectrometry. The influences of some analytical parameters and matrix components were all examined. Under the optimized conditions, the method detection limits were in the range of 0.24 to 0.98 μg L−1 (at a signal/noise of 3), with relative standard deviations between 1.6 and 5.7%. The linearities of the calibration plots were between 0.5 to 50 (triadimenol) and 1.0 to 100 μg L−1 (triadimefon). When this method was applied to a spiked beer sample, the recoveries ranged from 84 to 100%.
Enantioseparation and identification for the rationalization of the environmental impact of 4 polychlorinated biphenyls
Authors: Guo Fangjie , Tang Qiaozhi , Xie Jingqian , Zhao Lu , Liu Kai , Liu Weiping
Published: January 2018

Polychlorinated biphenyls (PCBs) are harmful and persistent organic pollutants that have long been used in industrial manufacturing. Their persistence leads to accumulation in the food chain causing potential toxic effects. As 19 out of 78 of the chiral congeners have stable atropisomers at ambient temperature, we studied some typical enantiomers: PCB45, PCB95, PCB136, and PCB149. The chiral stationary phases OD‐H and OJ‐H were used for separation in analytic high‐performance liquid chromatography (HPLC), as well as for collection in semi‐preparative HPLC. The resolution was optimized with respect to n‐hexane–based mobile phases, temperature, and flow rate. All pure enantiomers were recovered from semi‐preparative HPLC within 15 minutes for practical purpose. Characterization of the absolute configurations were conducted with a combination of theoretical and experimental electronic circular dichroism measurements. The enantiomers of PCB45, PCB95, PCB136, and PCB149 proved to be eluted as R > S, S > R, R > S, and S > R, respectively. Molecular structures (eg, substituent groups) and properties (eg, bond lengths, bond angles, and dipole moments) were quantitatively analyzed to understand the toxicity effect of PCBs. In summary, we have developed a well‐established methodology of collection and configuration identification for analogous PCB derivatives.
Chiroptical properties of 2,2’‐bioxirane
Authors: Daugey N. , De Rycke N. , Brotin T. , Buffeteau T.
Published: January 2018

The two enantiomers of 2,2′‐bioxirane were synthesized, and their chiroptical properties were thoroughly investigated in various solvents by polarimetry, vibrational circular dichroism (VCD), and Raman optical activity (ROA). Density functional theory (DFT) calculations at the B3LYP/aug‐cc‐pVTZ level revealed the presence of three conformers (G+, G−, and cis) with Gibbs populations of 51, 44, and 5% for the isolated molecule, respectively. The population ratios of the two main conformers were modified for solvents exhibiting higher dielectric constants (G− form decreases whereas G+ form increases). The behavior of the specific optical rotation values with the different solvents was correctly reproduced by time‐dependent DFT calculations using the polarizable continuum model (PCM), except for the benzene for which explicit solvent model should be necessary. Finally, VCD and ROA spectra were perfectly reproduced by the DFT/PCM calculations for the Boltzmann‐averaged G+ and G− conformers.
Microbial‐Enhanced Phytoremediation of Lead Contaminated Calcareous Soil by Centaurea cyanus L
Authors: Karimi Akbar , Khodaverdiloo Habib , Rasouli‐Sadaghiani Mir Hassan
Published: January 2018

Microbe‐assisted phytoremediation is a promising technology for remediation of potentially toxic element contaminated soils. A greenhouse study was conducted to assess the effect of Pseudomonas spp. and Glomus spp. on phytoremediation of a Pb‐contaminated calcareous soil by Centaurea cyanus L. The study was carried out as a factorial experiment arranged in a randomized complete block design with three replications. Factors are microbial inoculation in three levels (mix inoculation with Glomus spp. or Pseudomonas spp. and non‐inoculated) and four Pb concentrations (0, 250, 500, and 1000 mg kg−1) in soil. The results revealed that microbial inoculation significantly increased the shoot dry weight and Pb accumulation in C. cyanus compared to non‐inoculated plants. Comparison of microbial treatments indicated that higher shoot Pb concentration, shoot modified bioconcentration factor (shoot mBCF, 5.33–5.63) and translocation factor (TF, 1.09–1.2) are obtained for Pseudomonas spp. inoculation, while higher plant biomass, plant Pb accumulation, root Pb concentration, root mBCF (5.91–6.46) and lower TF (0.77–0.99) are recorded for Glomus spp. inoculation. These results show that Pseudomonas spp. and Glomus spp. are more effective in phyotoextraction and phytostabilization of Pb by C. cyanus, respectively. It could be concluded that Pseudomonas spp. and Glomus spp. would be a promising strategy in bioremediation of Pb‐contaminated soils, especially at medium levels of soil Pb contamination (250 and 500 mg kg−1).
Health care disparities among octogenarians and nonagenarians with stage III lung cancer
Authors: Cassidy Richard J. , Zhang Xinyan , Switchenko Jeffrey M. , Patel Pretesh R. , Shelton Joseph W. , Tian Sibo , Nanda Ronica H. , Steuer Conor E. , Pillai Rathi N. , Owonikoko Taofeek K. , Ramalingam Suresh S. , Fernandez Felix G. , Force Seth D. , Gillespie Theresa W. , Curran Walter J. , Higgins Kristin A.
Published: January 2018

BACKGROUND

To the authors' knowledge, the practice patterns for patients aged more than 80 years with stage III non–small cell lung cancer (NSCLC) is not well known. The purpose of the current study was to investigate factors predictive of and the impact on overall survival (OS) after concurrent chemoradiation (CRT) among patients aged ≥80 years with American Joint Committee on Cancer stage III NSCLC in the National Cancer Data Base (NCDB).

METHODS

In the NCDB, patients aged ≥80 years who were diagnosed with stage III NSCLC from 2004 to 2013 with complete treatment records were identified. Multivariable logistic regression and Cox proportional hazard models were generated and propensity score‐matched analysis was used.

RESULTS

A total of 12,641 patients met the entry criteria: 6018 (47.6%) had stage IIIA disease and 6623 (52.4%) had stage IIIB disease. The median age at the time of diagnosis was 83.0 years (range, 80‐91 years). A total of 7921 patients (62.7%) received no therapy. Black race (odds ratio [OR], 1.23; 95% confidence interval [95% CI], 1.06‐1.43) and living in a lower educated census tract of residence (OR, 1.20; 95% CI, 1.03‐1.40) were found to be associated with not receiving care, whereas treatment at an academic center (OR, 0.80; 95% CI, 0.70‐0.92) was associated with receiving cancer‐directed therapy. Receipt of no treatment (hazard ratio [HR], 2.69; 95% CI, 2.57‐2.82) or definitive radiation alone (HR, 1.15; 95% CI, 1.07‐1.24) compared with CRT was associated with worse OS. On propensity score matching, not receiving CRT was found to be associated with worse OS (HR, 1.58; 95% CI, 1.44‐1.72).

CONCLUSIONS

In this NCDB analysis, approximately 62.7% of patients aged ≥80 years with stage III NSCLC received no cancer‐directed care. Black race and living in a lower educated census tract were associated with not receiving cancer‐directed care. OS was found to be improved in patients receiving CRT. Cancer 2018;124:775‐84. © 2018 American Cancer Society.
The clinical implications of immunogenomics in colorectal cancer: A path for precision medicine
Authors: Riley Jenny M. , Cross Ashley W. , Paulos Chrystal M. , Rubinstein Mark P. , Wrangle John , Camp E. Ramsay
Published: January 2018

Colorectal cancer (CRC) remains the third most common malignancy and the second‐leading cause of cancer‐related deaths in the United States. Large multi‐omic databases, such as The Cancer Genome Atlas and the International Colorectal Cancer Subtyping Consortium, have identified distinct molecular subtypes related to anatomy. The identification of genomic alterations in CRC is now critical because of the recent success and US Food and Drug Administration approval of pembrolizumab and nivolumab for microsatellite‐instable tumors. In parallel, landmark studies have established the prognostic significance of the CRC tumor‐infiltrating lymphocyte and the clinical impact of the tumor immune microenvironment. As a result, there is a growing appreciation for immunogenomics, the interconnected relation between tumor genomics and the immune microenvironment. The clinical implications of CRC immunogenomics continue to expand, and it will likely serve as a guide for next‐generation immunotherapy strategies for improving outcomes for this disease. Cancer 2018;124:1650‐9. © 2018 American Cancer Society
Projections of three subcortical visual centers to marmoset lateral geniculate nucleus
Authors: Zeater Natalie , Buzás Péter , Dreher Bogdan , Grünert Ulrike , Martin Paul R.
Published: January 2018

The dorsal lateral geniculate nucleus receives projections from visuotopically organized subcortical nuclei, in addition to inputs from the retina, visual cortices, and the thalamic reticular nucleus. Here, we study subcortical projections to the geniculate from the superior colliculus (SC) and parabigeminal nucleus (PBG) in the midbrain, and the nucleus of the optic tract (NOT) in the pretectum of marmosets. Marmosets are New World diurnal foveate monkeys, and are an increasingly popular model for studying the primate visual system. Furthermore, the koniocellular geniculate layers in marmosets, unlike those in the geniculate of commonly studied diurnal Old World monkeys, are well differentiated from the parvocellular and magnocellular layers. Thus, in the present study, we have made small iontophoretic injections of the retrograde tracer microruby, targeted to the koniocellular layers in the geniculates of four marmosets. We found direct projections from the ipsilateral SC, PBG, and NOT to the koniocellular geniculate layers. The distribution of retrogradely labeled cells in the superficial, visual layers of SC is consistent with the idea that projections from the SC to the koniocellular layers are visuotopically organized. A little over 20 years ago, Vivien Casagrande () introduced the idea that koniocellular geniculate layers (rather than the parvocellular and magnocellular layers) are principal targets of visuotopically organized subcortical nuclei. Our results add to subsequent evidence assembled by Casagrande and others in favor of this hypothesis.
An adaptive hybridizable discontinuous Galerkin approach for cardiac electrophysiology
Authors: Hoermann Julia M. , Bertoglio Cristóbal , Kronbichler Martin , Pfaller Martin R. , Chabiniok Radomir , Wall Wolfgang A.
Published: January 2018

Cardiac electrophysiology simulations are numerically challenging because of the propagation of a steep electrochemical wave front and thus require discretizations with small mesh sizes to obtain accurate results. In this work, we present an approach based on the hybridizable discontinuous Galerkin method (HDG), which allows an efficient implementation of high‐order discretizations into a computational framework. In particular, using the advantage of the discontinuous function space, we present an efficient p‐adaptive strategy for accurately tracking the wave front. The HDG allows to reduce the overall degrees of freedom in the final linear system to those only on the element interfaces. Additionally, we propose a rule for a suitable integration accuracy for the ionic current term depending on the polynomial order and the cell model to handle high‐order polynomials. Our results show that for the same number of degrees of freedom, coarse high‐order elements provide more accurate results than fine low‐order elements. Introducing p‐adaptivity further reduces computational costs while maintaining accuracy by restricting the use of high‐order elements to resolve the wave front. For a patient‐specific simulation of a cardiac cycle, p‐adaptivity reduces the average number of degrees of freedom by 95% compared to the nonadaptive model. In addition to reducing computational costs, using coarse meshes with our p‐adaptive high‐order HDG method also simplifies practical aspects of mesh generation and postprocessing.
A fast rank mutual information based decision tree and its implementation via Map‐Reduce
Authors: Mu Yashuang , Wang Lidong , Liu Xiaodong
Published: January 2018

To address the time‐consuming problem for the confirmation of splitting attributes and splitting points in classic rank mutual information based decision trees, this paper establishes a fast rank mutual information based decision tree (FRMIDT) for classification problems. First, the proposed FRMIDT algorithm improves the velocity by a max‐relevance and min‐redundancy criterion to remove the redundant attributes in each tree node building. Then, the fuzzy c‐means algorithm is employed to confirm the splitting points for further acceleration. Meanwhile, a parallel implementation is developed in the framework of Map‐Reduce (MR‐FRMIDT) for medium or large‐scale data classification. Several comparative studies are conducted on UCI benchmark data sets. In contrast to the classic rank mutual information based decision tree on 12 data sets, the proposed FRMIDT model effectively reduces the computational time on the premise of keeping testing accuracy. Furthermore, the proposed FRMIDT algorithm is comparable through comparing FRMIDT with other traditional decision tree classifiers including BFT, C4.5, LAD, NBT, and SC. Meanwhile, the comparison with 7 different popular splitting measures based monotonic decision trees on several data sets illustrates the effectiveness of FRMIDT in monotonic classification. At last, the experimental analysis on other 6 data sets shows that the proposed MR‐FRMIDT is feasible and has a good parallel performance on reducing execution time and avoiding memory restrictions.
On the Kubo‐Greenwood model for electron conductivity
Authors: Dufty James , Wrighton Jeffrey , Luo Kai , Trickey S.B.
Published: January 2018

Currently, the most common approach to calculate transport properties for materials under extreme conditions is based on the phenomenological Kubo‐Greenwood method. The results of an inquiry into the justification and context of that model are summarized here. Specifically, the basis for its connection to equilibrium density functional theory (DFT) and the assumption of static ions are discussed briefly.
Detection and defense of DDoS attack–based on deep learning in OpenFlow‐based SDN
Authors: Li Chuanhuang , Wu Yan , Yuan Xiaoyong , Sun Zhengjun , Wang Weiming , Li Xiaolin , Gong Liang
Published: January 2018

Distributed denial of service (DDoS) is a special form of denial of service attack. In this paper, a DDoS detection model and defense system based on deep learning in Software‐Defined Network (SDN) environment are introduced. The model can learn patterns from sequences of network traffic and trace network attack activities in a historical manner. By using the defense system based on the model, the DDoS attack traffic can be effectively cleaned in Software‐Defined Network. The experimental results demonstrate the much better performance of our model compared with conventional machine learning ways. It also reduces the degree of dependence on environment, simplifies the real‐time update of detection system, and decreases the difficulty of upgrading or changing detection strategy.
Reactive histiocytic proliferation in the pleural fluid mimicking metastatic signet ring adenocarcinoma
Authors: Mir Fatima , Naumaan Anam , Alnajar Hussein , Brickman Arlen , Reddy Vijaya , Park Ji‐Weon , Gattuso Paolo
Published: January 2018

Reactive nodular and diffuse histiocytic proliferations of mesothelial and non‐mesothelial lined sites have been sporadically reported in the literature. However, there is no cytologic literature describing this process. We report a case of reactive histiocytic proliferation mimicking a metastatic signet ring adenocarcinoma in pleural fluid from a 33‐year‐old white male. Ancillary studies such as immunohistochemistry should be used to elucidate the cell of origin and avoid diagnostic errors.
Absence of the Drosophila jump muscle actin Act79B is compensated by up‐regulation of Act88F
Authors: Dohn Tracy E. , Cripps Richard M.
Published: January 2018

Background: Actins are structural components of the cytoskeleton and muscle, and numerous actin isoforms are found in most organisms. However, many actin isoforms are expressed in distinct patterns allowing each actin to have a specialized function. Numerous studies have demonstrated that actin isoforms both can and cannot compensate for each other under specific circumstances. This allows for an ambiguity of whether isoforms are functionally distinct. Results: In this study, we analyzed mutants of Drosophila Act79B, the predominant actin expressed in the adult jump muscle. Functional and structural analysis of the Act79B mutants found the flies to have normal jumping ability and sarcomere structure. Analysis of actin gene expression determined that expression of Act88F, an actin gene normally expressed in the flight muscles, was significantly up‐regulated in the jump muscles of mutants. This indicated that loss of Act79B caused expansion of Act88F expression. When we created double mutants of Act79B and Act88F, this abolished the jump ability of the flies and resulted in severe defects in myofibril formation. Conclusions: These results indicate that Act88F can functionally substitute for Act79B in the jump muscle, and that the functional compensation in actin expression in the jump muscles only occurs through Act88F. Developmental Dynamics 247:642–649, 2018. © 2018 Wiley Periodicals, Inc.
Experimental estimation of snare detectability for robust threat monitoring
Authors: O'Kelly Hannah J. , Rowcliffe J. Marcus , Durant Sarah , Milner‐Gulland E. J.
Published: January 2018

Hunting with wire snares is rife within many tropical forest systems, and constitutes one of the severest threats to a wide range of vertebrate taxa. As for all threats, reliable monitoring of snaring levels is critical for assessing the relative effectiveness of management interventions. However, snares pose a particular challenge in terms of tracking spatial or temporal trends in their prevalence because they are extremely difficult to detect, and are typically spread across large, inaccessible areas. As with cryptic animal targets, any approach used to monitor snaring levels must address the issue of imperfect detection, but no standard method exists to do so. We carried out a field experiment in Keo Seima Wildlife Reserve in eastern Cambodia with the following objectives: (1) To estimate the detection probably of wire snares within a tropical forest context, and to investigate how detectability might be affected by habitat type, snare type, or observer. (2) To trial two sets of sampling protocols feasible to implement in a range of challenging field conditions. (3) To conduct a preliminary assessment of two potential analytical approaches to dealing with the resulting snare encounter data. We found that although different observers had no discernible effect on detection probability, detectability did vary between habitat type and snare type. We contend that simple repeated counts carried out at multiple sites and analyzed using binomial mixture models could represent a practical yet robust solution to the problem of monitoring snaring levels both inside and outside of protected areas. This experiment represents an important first step in developing improved methods of threat monitoring, and such methods are greatly needed in southeast Asia, as well as in as many other regions.
MEMS Magnetic Sensor with Bridge‐Type Resonator and Magnetostrictive Thin Film
Authors: OKADA NAOKI , SASABUCHI TAKASHI , KOIKE KUNIHIRO , MINETA TAKASHI
Published: January 2018

This paper reports on fabrication and characterization of resonant‐type mechanical MEMS magnetic sensors using magnetostrictive FePd sputtered film. The sensor has a thin Si resonator bridge with a PZT piezoelectric thin film element for excitation. The resonator is pulled by other bridges with the FePd film when magnetic flux is applied. The sensor was fabricated from an SOI wafer by sol‐gel PZT deposition, FePd sputtering, and Si etching processes. The completed sensor showed a resonant peak with a Q factor of 229 at 26.39 kHz. When magnetic flux was applied along the microbridges, resonant frequency drastically decreased due to relaxation of initial deflection of the resonant bridge. Magnetic flux can be detected by resonant frequency change with a sensing resolution of 0.2 G per 0.1 Hz. When excitation frequency was fixed at slightly below the resonant frequency, amplitude of the bridge vibration slightly decreased with increasing magnetic flux in low magnetic flux region. High sensitive sensing of magnetic flux was difficult by the amplitude change. It was found that the magnetic sensor showed large thermal drift.
Stand‐scale transpiration of a Eucalyptus urophylla × Eucalyptus grandis plantation and its potential hydrological implication
Authors: Ouyang Lei , Zhao Ping , Zhou Guangsheng , Zhu Liwei , Huang Yuqing , Zhao Xiuhua , Ni Guangyan
Published: January 2018

Quantifying tree transpiration at a stand scale is important for understanding the hydrological impact of Eucalyptus plantations on the local water yield and water balance. In this study, we aimed to explore the seasonal and monthly changes in stand transpiration, its response to climatic factors, and hydrological impacts of a 5‐year‐old Eucalyptus urophylla × Eucalyptus grandis plantation in Guangxi Province, Southern China. Stand‐scale transpiration (Et) and potential evapotranspiration (ETo) were determined, and seasonal sensitivity of daily Et to vapour pressure deficit was analysed by using the monitored sap flux of the E. urophylla × E. grandis plantation and the associated environmental factors during a 2‐year experimental period from June 2012 to May 2014. The results showed that the monthly Et values in the wet seasons were higher than those in the dry seasons, and a temporal Et difference was observed between the 2 years of the experiment. Generally, within a whole experimental year, the highest water consumption mainly occurred from May to August, accounting for more than 40% of the annual total, and the lowest transpiration values (approximately 10 mm) mainly occurred from January to March. This monthly variation would be partly attributed to the difference of climatic factors. Clear seasonal variations were also observed for the ETo values, the Et/ETo and the Et/P (precipitation) ratios, and the dryness index (DI, ETo/P). Compared to the wet seasons, higher ETo and DI (>1) values occurred in the dry seasons. Moreover, the linear relationships between the daily stand‐scale transpiration and vapour pressure deficit for the selected months (representing spring, summer, autumn, and winter) suggest weak stomatal control of eucalypt trees. In consideration of the short rotation practices (5–7 years), the non‐conservative character of water use of eucalypt plantation, as well as the ratios of Et/ETo, Et/P, and DI, we suggested that Eucalyptus plantations in Guangxi Province might pose a potential threat to catchment water yield and management in this region. The findings of this study will assist in managing the increasing hydrological and water resource concerns related to the rapid expansion of Eucalyptus plantations in Southern China.
Economic Evaluation of Power System Flexibility by Commercial Air Conditioner Control with Large Penetration of Photovoltaic Generation
Authors: TAKAGI KENTARO , ASANO HIROSHI , BANDO SHIGERU
Published: January 2018

High penetration of intermittent renewable energy such as photovoltaic (PV) and wind power could cause shortage of power system flexibility. Demand response is expected to help supply ancillary service instead of the conventional power plant. Commercial air conditioners are a promising responsive load for demand response because they account for a large proportion of power consumption in the power system. We calculate a system operation cost and hourly operation pattern of each power plant by using the optimal power generation model considering flexibility supply from controlling commercial air conditioner. We obtained the following results as an effect of commercial air conditioner control. (1) The power generation of oil fired power plants decreases at peak time and annual fuel cost of oil fired plant is reduced by approximately 30% at most in Kanto area. (2) The percentage of rated operation mode of LNG combined cycle plants increases. (3) Curtailed energy rate of PV decreases because a power storage amount by pumped hydropower generation increases. (4) Required battery capacity to reduce PV curtailed amount decreased by combining battery energy storage system in case of high penetration of PV.
Determination of Physical Properties and Crystallization Kinetics of Oil From Allanblackia Seeds and Shea Nuts Under Different Thermal Conditions
Authors: Badu Mercy , Awudza Johannes , Budd Peter M. , Yeates Stephen
Published: January 2018

In this study, the fatty acid content, melting and cooling profiles, crystallization properties at different cooling rates and kinetics of crystallization of Allanblackia seed oil (ASO) and shea nut oil (SNO) are investigated. The fatty acid content is determined using gas chromatography coupled with mass spectrometry (GC/MS). The melting and cooling profiles, crystallization, and crystallization kinetics are investigated using differential scanning calorimetry (DSC) and the fat morphology is investigated using polarized light microscopy. The GC/MS results showed that ASO contains a high amount of saturated fats as compared with SNO. The DSC analysis revealed that ASO has a high melting temperature of 35.3 ± 2.1 °C and crystallizes earlier (16.8 ± 0.3 °C) in the constant rate cooling experiments. The crystallization patterns of both oils are observed to be dependent on the cooling rate. Under isothermal conditions, it is observed that both ASO and SNO shows high and low melting peaks with the low melting peak disappearing as the crystallization progressed. The Avrami model is used to estimate the crystallization kinetics of the oils under the isothermal conditions and it is inferred that ASO has a faster nucleation and subsequent crystal growth as compared with SNO. At room temperature SNO formed overlapping fat crystal particles while ASO gave distinct crystallized fat fractions during the crystallization at room temperature, as shown by the polarized light microscopy.

Practical Application: The high melting temperature, the rate and the nature of crystallization of Allanblackia seed oil gives it good material functionality and desired plasticity, properties associated with possible industrial application. Additionally, the presence of high stearic acid content makes the Allanblackia seed oil a healthy choice for food, hence, it can be used as a substitute for cocoa butter in the food industry.

The appearance of fat crystals during the crystallization at isothermal conditions at 16 °C of the Allanblackia seed oil.
Radical‐Mediated Formal C(sp2)–H Functionalization of Aldehyde‐Derived N,N‐Dialkylhydrazones
Authors: Prieto Alexis , Bouyssi Didier , Monteiro Nuno
Published: January 2018

Recent advances in formal C(sp2)–H functionalization of aldehyde‐derived N,N‐dialkylhydrazones (substitution at the azomethine carbon atom) are highlighted, with a focus on radical‐mediated processes that open up new opportunities for C–C bond formation, such as alkylation reactions with the aid of hypervalent iodonium reagents or polyhaloalkanes, as well as for carbon–heteroatom bond formation (C–N, C–P). Cascade sequences based on these reactions, and leading to (hetero)cyclic frameworks, are also discussed.
Molecular Transformation of 2‐Methylazulenes: An Efficient and Practical Synthesis of 2‐Formyl‐ and 2‐Ethynylazulenes
Authors: Shoji Taku , Araki Takanori , Iida Nanami , Kobayashi Yoshiaki , Ohta Akira , Sekiguchi Ryuta , Ito Shunji , Mori Shigeki , Okujima Tetsuo , Yasunami Masafumi
Published: January 2018

2‐Formylazulene derivatives have been obtained in good yields by the reactions of 2‐methylazulenes with N,N‐dimethylformamide dimethyl acetal, followed by oxidative cleavage of the intermediately formed enamines with NaIO4. Vilsmeier formylation of 1‐phenyl‐3‐methylazulenes also afforded the corresponding 2‐formylazulenes in moderate yields. The treatment of a 2‐methylazulene derivative bearing a formyl group at the 1‐position with sodium methoxide led, through a self‐condensation reaction, to a trans‐1‐(azulen‐1‐yl)‐2‐(azulen‐2‐yl)ethylene derivative, the structure of which was verified by single‐crystal X‐ray diffraction analysis. The 2‐formylazulenes obtained were transformed into 2‐ethynylazulenes in good yields by a modified Seyferth–Gilbert reaction. The reactivity of a 1‐iodoazulene bearing a 2‐formyl function in palladium‐catalyzed cross‐coupling reactions has also been examined.
Metal‐Free N–H/C–H Coupling for Efficient Asymmetric Synthesis of Chiral Dihydroquinoxalinones from Readily Available α‐Amino Acids
Authors: Kanyiva Kyalo Stephen , Horiuchi Masashi , Shibata Takanori
Published: January 2018

We have developed a method for the synthesis of dihydroquinoxalinones via intramolecular N–H/C–H coupling using hypervalent iodine. The starting materials were prepared from inexpensive and readily available aniline and amino acid derivatives. Various functional groups were tolerated to give multisubstituted dihydroquinoxalinones in moderate to excellent yields. The chirality of the amino acid was transferred to the desired target compound without a loss of enantiomeric excess. Preliminary mechanistic studies indicated that the reaction proceeds via an ionic mechanism.
Study of isomeric pentacyclic triterpene acids in traditional Chinese medicine of Forsythiae Fructus and their binding constants with β‐cyclodextrin by capillary electrophoresis
Authors: Ren Tingjun , Xu Zhongqi
Published: January 2018

In this study, a capillary zone electrophoresis (CZE) method was first developed to identify three microconstituents of isomeric pentacyclic triterpene acids (PTAs including oleanolic acid (OA), ursolic acid (UA) and betulinic acid (BA)) in Forsythiae Fructus (FF). The baseline separation of PTAs by CZE were eventually achieved in a background electrolyte (BGE) containing 50.0 mmol/L borax and 0.5 mmol/L β‐cyclodextrin (β‐CD) at pH 9.5 within 13.0 min. Herein, it was not only the compositions of BGE were detail investigated for rapid and good separation, but also the binding ratio and the equilibrium constants (K) for OA, UA and BA with β‐CD was estimated by double reciprocal equation to well understand the separation mechanism. The proposed method allowed the LODs of PTAs were averaged at 1.50 μg/mL with UV detection (at 200 nm). The interday RSD of migration time and peak area were around 2.0 and 4.7% (n = 5), respectively. Thus, the content of PTAs in 19 FF real samples distinguished from maturation stages and geographical areas in China was quantified with the proposed method. Depending on the amount of each PTA in FF, it was demonstrated these microconstituents might benefit to identify their harvested time even qualities.
Electrochemical Performance of Structure‐Dependent LiNi1/3Co1/3Mn1/3O2 in Aqueous Rechargeable Lithium‐Ion Batteries
Authors: Li Yajie , Hou Xianhua , Zhou Yu , Han Weiqiang , Liang Chu , Wu Xu , Wang Shaofeng , Ru Qiang
Published: January 2018

This work is focused on the relationship between electrochemical performance and morphology of LiNi1/3Co1/3Mn1/3O2 (NCM) in an aqueous rechargeable lithium battery, and provides a reference for the selection of novel battery materials. In this work, NCM microrods, microspheres, and nanoblocks were successfully synthesized by solvothermal, coprecipitation, and sol–gel methods, respectively. Of the three samples, NCM nanoblocks, which are formed by agglomeration of a large number of nanoparticles, show the best electrochemical performance. During cycling, the NCM nanoblock exhibits an initial discharge capacity of 137.4 mAh g−1 and an impressive capacity of 130.8 mAh g−1 after 20 cycles at a current density of 1C (=160 mA g−1). Even at a high current density of 50C, this NCM nanoblock provides a capacity of 50.1 mAh g−1, which shows the great potential of the nanoblock as a cathode in aqueous rechargeable lithium‐ion batteries.
Nonparametric estimation of multivariate quantiles
Authors: Coblenz M. , Dyckerhoff R. , Grothe O.
Published: January 2018

In many applications of hydrology, quantiles provide important insights in the statistical problems considered. In this paper, we focus on the estimation of multivariate quantiles based on copulas. We provide a nonparametric estimation procedure for a notion of multivariate quantiles, which has been used in a series of papers. These quantiles are based on particular level sets of copulas and admit the usual probabilistic interpretation that a p‐quantile comprises a probability mass p. We also explore the usefulness of a smoothed bootstrap in the estimation process. Our simulation results show that the nonparametric estimation procedure yields excellent results and that the smoothed bootstrap can be beneficially applied. The main purpose of our paper is to provide an easily applicable method for practitioners and applied researchers in domains such as hydrology and coastal engineering.
Development of a national water‐energy system model with emphasis on the power sector for south africa
Authors: Ahjum Fadiel , Merven Bruno , Cullis James , Goldstein Gary , DeLaquil Pat , Stone Adrian
Published: January 2018

A comprehensive archive of information and data pertaining to the development process is available via the Energy Research Data Portal for South Africa. The portal hosts technical reports and data fully describing the model development, estimation of costs and technical parameters; and that of stakeholder engagement for model validation and scenario critique. http://energydata.uct.ac.za/organization/erc-water-energy-nexus © 2018 American Institute of Chemical Engineers Environ Prog, 37: 132–147, 2018