bluuebunny/crossref_metadata_2025 huggingface dataset:
Multi‐rate observer design for process monitoring using asynchronous inter‐sample output predictions
Authors: Ling Chen , Kravaris Costas
Published: March 2017

In this article, the problem of observer design in linear multi‐output systems with asynchronous sampling is addressed. The proposed multi‐rate observer is based on a continuous‐time Luenberger observer design coupled with an inter‐sample predictor for each sampled measurement, which generates an estimate of the output in between consecutive measurements. The sampling times are not necessarily uniformly spaced, but there exists a maximum sampling period among all the sensors. Sufficient and explicit conditions are derived to guarantee exponential stability of the multi‐rate observer. The proposed framework of multi‐rate observer design is examined through a mathematical example and a gas‐phase polyethylene reactor. In the latter case, the amount of active catalyst sites is estimated, with a convergence rate that is comparable to the case of continuous measurements. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3384–3394, 2017
Microscopic insights into the efficiency of capacitive mixing process
Authors: Ma Manman , Zhao Shuangliang , Liu Honglai , Xu Zhenli
Published: March 2017

Significance

By means of an advanced molecular model, we identify the optimum conditions under which the Capacitive mixing technique can output maximum energies. In accord with experimental observations, we show that, when the salinity difference is fixed, a hydrophilic electrode surface can promote the energy extraction, the electrolyte solution containing monovalent ions with smaller ionic size will give larger energy output, and the temperature gradient between the salt water and fresh water should make significant contribution. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1785–1791, 2017
A new model for correlation and prediction of equilibrium CO2 solubility in N‐methyl‐4‐piperidinol solvent
Authors: Xiao Min , Cui Ding , Liu Helei , Tontiwachwuthikul Paitoon , Liang Zhiwu
Published: March 2017

In this work, the equilibrium CO2 solubility in the aqueous tertiary amine, N‐methyl‐4‐piperidinol (MPDL) was measured over a range of temperatures, CO2 partial pressures and amine concentrations. The dissociation constant of the MPDL solution was determined as well. A new thermodynamic model was developed to predict the equilibrium CO2 solubility in the MPDL‐H2O‐CO2 system. This model, equipped with the correction factor (Cf), can give reasonable prediction with an average absolute deviation of 2.0%, and performs better than other models (i.e., KE model, Li‐Shen model, and Hu‐Chakma). The second‐order reaction rate constant (k2) of MPDL and the heat of CO2 absorption (–ΔHabs) into aqueous MPDL solutions were evaluated as well. Based on the comparison with some conventional amines, MPDL revealed a high‐equilibrium CO2 loading, reasonably fast absorption rate when compared with other tertiary amines, and a low energy requirement for regeneration. It may, therefore, be considered to be an alternative solvent for CO2 capture. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3395–3403, 2017
Kationische Polymerisation: von der Photoinitiierung zur Steuerung durch Licht
Authors: Michaudel Quentin , Kottisch Veronika , Fors Brett P.
Published: March 2017

Während der letzten 40 Jahre erzielten Forscher bei der Untersuchung photoinitiierter kationischer Polymerisationen enorme Erfolge sowohl im industriellen Bereich als auch im akademischen Umfeld. Unzählige Photoinitiierungssysteme wurden entwickelt, wodurch die Polymerisation eines breiten Spektrums von Monomeren (z. B. Epoxiden, Vinylethern, Alkenen, cyclischen Ethern und Lactonen) unter praktischen, kostengünstigen und umweltschonenden Bedingungen ermöglicht wurde. Aufgrund der Fortschritte in der Photoredoxkatalyse hat sich in jüngerer Zeit die lichtgesteuerte kationische Polymerisation als Weg zur präzisen Steuerung des Polymerkettenwachstums herausgebildet. Dieser Kurzaufsatz gibt einen Überblick über die historische Entwicklung der lichtinduzierten kationischen Polymerisation und erörtert die neuesten Fortschritte bei photoinitiierten und lichtgesteuerten Verfahren. Letztere sind hochinteressante neue Richtungen auf dem Gebiet mit potenziellen Auswirkungen auf industrielle Bereiche, von der Mikrostrukturierung bis zur Synthese von komplexen Biomaterialien und sequenzgesteuerten Polymeren.
Cationic Polymerization: From Photoinitiation to Photocontrol
Authors: Michaudel Quentin , Kottisch Veronika , Fors Brett P.
Published: March 2017

During the last 40 years, researchers investigating photoinitiated cationic polymerizations have delivered tremendous success in both industrial and academic settings. A myriad of photoinitiating systems have been developed, thus allowing polymerization of a broad array of monomers (e.g., epoxides, vinyl ethers, alkenes, cyclic ethers, and lactones) under practical, inexpensive, and environmentally benign conditions. More recently, owing to progress in photoredox catalysis, photocontrolled cationic polymerization has emerged as a means to precisely regulate polymer chain growth. This Minireview provides a concise historical perspective on cationic polymerization induced by light and discusses the latest advances in both photoinitiated and photocontrolled processes. The latter are exciting new directions for the field that will likely impact industries ranging from micropatterning to the synthesis of complex biomaterials and sequence‐controlled polymers.
Analysis of the global wood‐chip trade's response to renewable energy policies using a spatial price equilibrium model
Authors: Jiang Wei , Searle Stephanie , Siddiqui Sauleh
Published: March 2017

Wood chip, mainly used to produce paper and other products traditionally, has also been used to produce biofuel. The global demand for wood chip is increasing as policies promote the use of biomass for renewable energy. The USA has been a major exporter of wood chip worldwide, but US exports of wood chip could decline if this resource is increasingly used for domestic electricity generation and cellulosic biofuel production. Meanwhile, European Union (EU) demand for wood chip is expected to increase rapidly in response to its renewable energy policy. In this paper, we build the first global trade model for wood chip using available wood chip trade data and analyze the combined effects of local renewable energy policies in these jurisdictions on the global market of wood chip. We find that the tropical regions of Latin America and Southeast Asia as well as the Former Soviet Union would increase their export of wood chip significantly in response to the policy scenarios. If forest governance in some of these countries is weak, US and EU renewable energy policy could inadvertently exacerbate deforestation in these regions, with an associated negative impact on carbon storage and other environmental services. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Old and New Directions in Strategy Selection
Authors: Busemeyer Jerome R.
Published: March 2017

Research on strategy selection, which has progressed a great deal over the past 50 years, is briefly reviewed. Past challenges that the field has faced, and new directions that have emerged in this field, are reviewed. As the articles featured in this special issue demonstrate, the topic of strategy selection continues to garner strong interest and make steady progress. Copyright © 2017 John Wiley & Sons, Ltd.
The Influence of Time Estimation and Time‐Saving Preferences on Learning to Make Temporally Dependent Decisions from Experience
Authors: Ashby Nathaniel J. S. , Gonzalez Cleotilde
Published: March 2017

In this paper, we merge research related to experiential learning, temporal perception, and the value of time and money by examining decisions where the timing of action (response) determines the outcome received. We predicted that time‐saving preferences and impatience would decrease maximization (i.e., taking action when it returned the largest reward), and that the constraints of temporal perception would compound their effects. Across three studies, participants undershot on average (i.e., responded earlier than the period of time during which a response would return the maximal reward) showed a preference for shorter‐delay options and often did not find the maximal reward. In addition, participants' reliance on temporal perception increased undershooting, increased preferences for shorter‐delay options, and reduced maximization. Nevertheless, participants who found the maximal reward continued to maximize at a high rate rather than opting for shorter delays and smaller rewards. Thus, while most participants appeared to have a preference for saving time, most behaved as reward maximizers rather than temporal discounters. Copyright © 2017 John Wiley & Sons, Ltd.
Central control of micturition in women: Brain‐bladder pathways in continence and urgency urinary incontinence
Authors: Arya Nisha G. , Weissbart Steven J.
Published: March 2017

Urinary incontinence disproportionately affects women. Anatomical textbooks typically describe continence mechanisms in women in the context of the pelvic floor support of the urinary bladder and the urethral sphincters. However, the urinary bladder and urethral sphincters are under the central control of the brain through a complex network of neurons that allow storage of urine followed by voiding when socially appropriate. Recent studies suggest that the most common type of urinary incontinence in women, urgency urinary incontinence, involves significant dysfunction of the central control of micturition. In this paper, we review the anatomy and functional connectivity of the nervous system structures involved in the control of micturition. Clinical application of this anatomy in the context of urgency urinary incontinence is also discussed. Understanding the anatomy of the neural structures that control continence will allow clinicians to better understand the underlying pathology of urge incontinence and consider new ways of treating this distressing condition. Clin. Anat. 30:373–384, 2017. © 2017 Wiley Periodicals, Inc.
Polymorphous ZnO Nanostructures: Zn Polar Surface‐Guided Size and Shape Evolution Mechanism and Enhanced Photocatalytic Activity
Authors: Zhao Yanting , Cui Tingting , Wu Tong , Jin Chen , Qiao Ru , Qian Yao , Tong Guoxiu
Published: March 2017

This study proposes a simple, low‐temperature chemical etching method for selective preparation of monodispersed, hexagonal, single‐crystal ZnO nanostructures. The morphological evolution from nanoplates (NPs) to nanoseals (NSs), nanobowls (NBs), and nanorings (NRs) is initiated by positively charged (0 0 0 1) Zn polar surface and driven by the principle of minimum energy. The relationship among the morphology, dimensions, and function of ZnO was determined by investigating polar planes, surface areas, energy bands, defects, optical properties, and catalytic activity for rhodamine B degradation. The ZnO NBs and ZnO NRs exhibit improved photocatalytic performance because of enhanced light harvesting and plasmonic resonance enhanced absorption. Surface recombination plays a key role in the apparent rate constant k for ZnO NBs with small size and those formed at low reaction temperatures. The photocatalytic activity of ZnO NBs formed at high reaction temperatures decreases with increasing size because of the decreased surface area.
Inhibition by Inorganic Dopants of γ‐Alumina Chemical Weathering under Hydrothermal Conditions: Identification of Reactive Sites and their Influence in Fischer–Tropsch Synthesis
Authors: Abi Aad Jane , Courty Philippe , Decottignies Dominique , Michau Mathieu , Diehl Fabrice , Carrier Xavier , Marceau Eric
Published: March 2017

Understanding how alumina degradation to boehmite AlOOH can be prevented under hydrothermal conditions is key to design more stable catalysts supported on alumina for Fischer–Tropsch synthesis. We compare the effect of four inorganic dopants to inhibit γ‐alumina chemical weathering under hydrothermal conditions: three metal ions: Mg2+, Zr4+, Ni2+, introduced by impregnation, and nonmetal Si, introduced by the grafting of tetraethyl orthosilicate. Boehmite is formed by a mechanism of dissolution–precipitation. A significant decrease of alumina weathering to boehmite is evidenced for all dopants. For metal ions, the thermal conversion of doped γ‐Al2O3 into an alumina‐rich mixed oxide or the coverage of the alumina surface by particles of a poorly soluble oxide such as NiO contribute to the stabilization of the solid. Alumina dissolution and degradation are only inhibited fully through Si grafting. IR spectra in the OH stretching region suggest that the most reactive alumina sites toward dissolution are basic Al−OH sites located on lateral facets that are blocked upon Si introduction. Fischer–Tropsch reactivity shows that Co catalysts prepared on Mg2+‐ and Si‐doped supports are less active or, at best, as active as a reference Co/γ‐Al2O3 catalyst, which is explained by a lower reducibility of CoO on doped supports. The Co catalyst prepared on Mg2+‐doped γ‐Al2O3 calcined at 900 °C exhibits the best combination of catalytic activity, ease of preparation, and hydrothermal stability.
Chemical Synthesis of Glycoproteins with the Specific Installation of Gradient‐Enriched 15N‐Labeled Amino Acids for Getting Insights into Glycoprotein Behavior
Authors: Minh Hien Nguyen , Izumi Masayuki , Sato Hajime , Okamoto Ryo , Kajihara Yasuhiro
Published: March 2017

Elucidating the effects of oligosaccharides on glycoprotein properties, such as local conformational changes, stability, and dynamics, has still been challenging. In this paper, a novel partial 15N‐labeling method for the amide backbone of a synthetic glycoprotein is proposed. Using solid‐phase peptide synthesis (SPPS) and native chemical ligation (NCL), thirteen 15N‐labeled amino acids were inserted at specific positions of the protein backbone, while intentionally varying the enrichment of 15N atoms. This idea discriminated even the same type of amino acid based on the intensities of 1H‐15N HSQC signals, combined with classic homonuclear TOCSY and NOESY methods, thus allowing for understanding the dynamics of the local conformation of a synthetic homogeneous glycoprotein. Results suggested that the attachment of an oligosaccharide of either a bi‐antennary complex‐type or a high‐mannose‐type did not disturb protein conformation. However, T1 values suggested that the oligosaccharide influenced dynamics at the local conformation. Temperature‐varied circular dichroism (CD) spectra and T1 values clearly indicated that oligosaccharides appeared to inhibit protein fluctuation or, in other words, stabilize protein structure. This insight into oligosaccharide behavior suggests some further effects on binding affinity between a glycoprotein and its receptor.
Selective Targeting of G‐Quadruplex Structures by a Benzothiazole‐Based Binding Motif
Authors: Buchholz Ina , Karg Beatrice , Dickerhoff Jonathan , Sievers‐Engler Adrian , Lämmerhofer Michael , Weisz Klaus
Published: March 2017

A benzothiazole derivative was identified as potent ligand for DNA G‐quadruplex structures. Fluorescence titrations revealed selective binding to quadruplexes of different topologies including parallel, antiparallel, and (3+1) hybrid structures. The parallel c‐MYC sequence was found to constitute the preferred target with dissociation constants in the micromolar range. Binding of the benzothiazole‐based ligand to c‐MYC was structurally and thermodynamically characterized in detail by employing a comprehensive set of spectroscopic and calorimetric techniques. Job plot analyses and mass spectral data indicate noncooperative ligand binding to form complexes with 1:1 and 2:1 stoichiometries. Whereas stacking interactions are suggested by optical methods, NMR chemical shift perturbations also indicate significant rearrangements of both 5′‐ and 3′‐flanking sequences upon ligand binding. Additional isothermal calorimetry studies yield a thermodynamic profile of the ligand–quadruplex association and reveal enthalpic contributions to be the major driving force for binding. Structural and thermodynamic information obtained in the present work provides the basis for the rational development of benzothiazole derivatives as promising quadruplex binding agents.
Polyaniline‐Induced Arylation with Arenediazonium Salts Derived from Anilines
Authors: Hata Dai , Moriuchi Toshiyuki , Hirao Toshikazu , Amaya Toru
Published: March 2017

A catalytic amount of a reduced form of polyaniline (a redox‐active π‐conjugated polymer) was found to induce C−H direct arylation of (hetero)arenes with arenediazonium salts prepared from anilines with methanesulfonic acid (MeSO3H) and tert‐butyl nitrite (tBuONO). The difficult part of this method is the coexistence of an oxidant and a reductant in this sequential diazotization and arylation system; diazotization requires weak oxidants such as alkyl nitrites, whereas the arylation is induced by a reductant. This was achieved by the careful control of the amount of tBuONO (1.0 equivalent) for the diazotization step, and sequential arylation using 5 mol % of the polyaniline. The reaction took place under mild conditions without any metals or strong bases at room temperature, and the amino group is a formal leaving group. The scope of the substrates demonstrates the versatility in the combination of anilines with a variety of functional groups and several (hetero)arenes. Two‐directional arylation for the synthesis of an unsymmetrical 1,4‐diarylated (furyl and pyrrolyl groups) benzene was achieved, using mono‐Boc‐protected 1,4‐phenylenediamine as a substrate. This shows potential for the synthesis of more complicated oligoarene compounds.
Exploring the Influence of the Aromaticity on the Anticancer and Antivascular Activities of Organoplatinum(II) Complexes
Authors: Zamora Ana , Pérez Sergio A. , Rothemund Matthias , Rodríguez Venancio , Schobert Rainer , Janiak Christoph , Ruiz José
Published: March 2017

A series of new organometallic PtII complexes of the type [Pt(C^N)Cl(DMSO)] (C^N=N,N‐dimethyl‐1‐(2‐aryl)methanamine‐κ2C2,N; aryl=phenyl 2 a, biphenyl 2 b, p‐terphenyl 2 c, naphthyl 2 d, anthracenyl 2 e, or pyrenyl 2 f) have been synthesized to explore the influence of the aromaticity on their anticancer activity. The best performers, 2 b and d, are more active than cisplatin (CDDP) in epithelial ovarian carcinoma cells A2780, with 2 d having a higher selectivity factor than CDDP in all the tested cell lines. In addition, all the new compounds overcome the acquired resistance in A2780cisR cells and interestingly, show low micromolar IC50 values towards the triple negative breast cancer cell line MDA‐MB‐231 and the highly metastatic 518A2 melanoma cells. This study shows that the hydrophobicity, accumulation into cells, and metal levels on nuclear DNA for the complexes are consistent with their cytotoxicity. Complexes 2 b and d induce apoptosis in a caspase‐independent manner and suppress the intracellular ROS generation without modifying the mitochondria membrane potential. In addition, 2 a–f effectively inhibit angiogenesis in the endothelial cell line EA.hy926 at sub‐cytotoxic concentrations and 2 b and d show in vivo antivascular effects on the chorioallantoic membrane (CAM) of fertilized SPF‐eggs (SPF=specific‐pathogen‐free). Inhibition of tubulin polymerization and degeneration of cytoskeleton organization in 518A2 melanoma cells are presented as a preliminary mechanism of its antimetastatic activity.
Bifunctional Diaminoterephthalate Fluorescent Dye as Probe for Cross‐Linking Proteins
Authors: Wallisch Melanie , Sulmann Stefan , Koch Karl‐Wilhelm , Christoffers Jens
Published: March 2017

Diaminoterephthalates are fluorescent dyes and define scaffolds, which can be orthogonally functionalized at their two carboxylate residues with functional residues bearing task specific reactive groups. The synthesis of monofunctionalized dyes with thiol groups for surface binding, an azide for click chemistry, and a biotinoylated congener for streptavidin binding is reported. Two bifunctionalized dyes were prepared: One with an azide for click chemistry and a biotin for streptavidin binding, the other with a maleimide for reaction with thiol and a cyclooctyne moiety for ligation with copper‐free click chemistry. In general, the compounds are red to orange, fluorescent materials with an absorption at about 450 nm and an emission at 560 nm with quantum yields between 2–41 %. Of particular interest is the maleimide‐functionalized compound, which shows low fluorescence quantum yield (2 %) by itself. After addition of a thiol, the fluorescence is “turned on”; quantum yield 41 %.
Investigations in Movement Behavior of Bulk Solids in Horizontal Ploughshare Mixers
Authors: Habermann Ralf
Published: March 2017

Beim Feststoffmischen in horizontalen Pflugscharmischern ist das durch die Mischwerkzeuge initiierte Bewegungsverhalten der Mischungskomponenten elementar für die erzielbare Mischgüte. Dabei wird zwischen Schub‐, Schleuder‐ und Ringschichtmischen unterschieden. Bislang beruhen die gewonnenen Erkenntnisse auf phänomenologischen Beobachtungen. In dieser Arbeit wurde der Übergangsbereich vom Schub‐ zum Schleudermischen in horizontalen Pflugscharmischern untersucht. Als Schüttgüter wurden Kalksteinmehl, Polystyrol‐Granulat, Kochsalzgranulat und Laktose verwendet. Ein deutlicher Einfluss des Füllgrads konnte nachgewiesen werden.
Simulation of Heat Exchange in Vessels with Helical Coils and Influence of Stirrer Position
Authors: Stefan Alexander , Hindges Sascha , Schultz Heyko J.
Published: March 2017

Agitated vessels are used for a wide range of applications, especially in chemical industry. This work is a pilot study on the influence of the stirrer installation height on the local as well as on the total heat flux with an immersed helical coil in an agitated vessel. A simplified geometrical model is used for observation of fundamental effects in contrast to a full mathematical model. The local heat flux, however, was observed to demonstrate the heat flux disparity along the coil. An optimum is proposed with the aim to maximize total heat flux and minimize tempering time.
Giant Radiolytic Dissolution Rates of Aqueous Ceria Observed in Situ by Liquid‐Cell TEM
Authors: Asghar Muhammad Sajid Ali , Inkson Beverley J. , Möbus Günter
Published: March 2017

The dynamics of cerium oxide nanoparticle aqueous corrosion are revealed in situ. We use innovative liquid‐cell transmission electron microscopy (TEM) combined with deliberate high‐intensity electron‐beam irradiation of nanoparticle suspensions. This enables life video‐recording of materials reactions in liquid, with nm resolution. We introduce image quantification to measure detailed rates of dissolution as a function of time and particle size to be compared with literature data. Giant dissolution rates, exceeding any previous reports for chemical dissolution rates at room temperature by many orders of magnitude, are discovered. The reasons for this accelerated dissolution are outlined, including the importance of the radiolysis of water preceding the ceria attack. Electron–water interaction generates radicals, ions, and hydrated electrons, which assist in hydration and reductive dissolution of oxide minerals. The presented methodology has the potential to become a novel accelerated testing procedure to compare multiple nanoscale materials for relative aqueous durability. The ceria–water system is of crucial importance for the fields of catalysis, abrasive polishing, environmental remediation, and as simulant for actinide oxide behaviour in contact with liquid for nuclear engineering.
Unveiling One‐Dimensional Supramolecular Structures Formed through π–π Stacking of Phenothiazines by Differential Pulse Voltammetry
Authors: Carvalho Fernando R. , Zampieri Eduardo H. , Caetano Wilker , Silva Rafael
Published: March 2017

Organic‐based nanomaterials can be self‐assembled by strong and directional intermolecular forces such as π–π interactions. Experimental information about the stability, size, and geometry of the formed structures is very limited for species that easily aggregate, even at very low concentrations. Differential pulse voltammetry (DPV) can unveil the formation, growth, and also the stability window of ordered, one‐dimensional, lamellar self‐aggregates formed by supramolecular π stacking of phenothiazines at micromolar (10−6 mol L−1) concentrations. The self‐diffusion features of the species at different concentrations are determined by DPV and used to probe the π staking process through the concept of the frictional resistance. It is observed that toluidine blue and methylene blue start to self‐aggregate around 9 μmol L−1, and that the self‐aggregation process occurs by one‐dimensional growth as the concentration of the phenothiazines is increased up to around 170 μmol L−1 for toluidine blue and 200 μmol L−1 for methylene blue. At higher concentrations, the aggregation process leads to structures with lower anisometry.
An adolescent with large cell calcifying sertoli cell tumor of the testis and undiagnosed Carney Complex: A case report
Authors: Rosenblum Frida , Koenig Richard Gabriel , Mikhail Fady M. , Porterfield John R. , Nix Jeffrey W. , Eltoum Isam‐Eldin A.
Published: March 2017

Carney Complex (CNC) is a rare autosomal dominant condition with characteristic clinical presentation, tumor development, and unique genetic mutation. We present a unique case and literature review of CNC in which two neoplasms characteristic of this complex were initially diagnosed through cytological fine needle aspirate specimens, leading to the identification of CNC, with subsequent surgical and cytogenetic confirmation. Diagn. Cytopathol. 2017;45:634–639. © 2017 Wiley Periodicals, Inc.
The building of the neocortex with non‐hyperpolarizing neurotransmitters
Authors: Ascenzi Matteo , Bony Guillaume
Published: March 2017

The development of the neocortex requires the synergic action of several secreted molecules to achieve the right amount of proliferation, differentiation, and migration of neural cells. Neurons are well known to release neurotransmitters (NTs) in adult and a growing body of evidences describes the presence of NTs already in the embryonic brain, long before the generation of synapses. NTs are classified as inhibitory or excitatory based on the physiological responses of the target neuron. However, this view is challenged by the fact that glycine and GABA NTs are excitatory during development. Many reviews have described the role of nonhyperpolarizing GABA at this stage. Nevertheless, a global consideration of the inhibitory neurotransmitters and their downstream signaling during the embryonic cortical development is still needed. For example, taurine, the most abundant neurotransmitter during development is poorly studied regarding its role during cortical development. In the light of recent discoveries, we will discuss the functions of glycine, GABA, and taurine during embryonic cortical development with an emphasis on their downstream signaling. © 2017 Wiley Periodicals, Inc. Develop Neurobiol 77: 1023–1037, 2017
Worker brain development and colony organization in ants: Does division of labor influence neuroplasticity?
Authors: Kamhi J. Frances , Sandridge‐Gresko Aynsley , Walker Christina , Robson Simon K.A. , Traniello James F.A.
Published: March 2017

Brain compartment size allometries may adaptively reflect cognitive needs associated with behavioral development and ecology. Ants provide an informative system to study the relationship of neural architecture and development because worker tasks and sensory inputs may change with age. Additionally, tasks may be divided among morphologically and behaviorally differentiated worker groups (subcastes), reducing repertoire size through specialization and aligning brain structure with task‐specific cognitive requirements. We hypothesized that division of labor may decrease developmental neuroplasticity in workers due to the apparently limited behavioral flexibility associated with task specialization. To test this hypothesis, we compared macroscopic and cellular neuroanatomy in two ant sister clades with striking contrasts in worker morphological differentiation and colony‐level social organization: Oecophylla smaragdina, a socially complex species with large colonies and behaviorally distinct dimorphic workers, and Formica subsericea, a socially basic species with small colonies containing monomorphic workers. We quantified volumes of functionally distinct brain compartments in newly eclosed and mature workers and measured the effects of visual experience on synaptic complex (microglomeruli) organization in the mushroom bodies—regions of higher‐order sensory integration—to determine the extent of experience‐dependent neuroplasticity. We demonstrate that, contrary to our hypothesis, O. smaragdina workers have significant age‐related volume increases and synaptic reorganization in the mushroom bodies, whereas F. subsericea workers have reduced age‐related neuroplasticity. We also found no visual experience‐dependent synaptic reorganization in either species. Our findings thus suggest that changes in the mushroom body with age are associated with division of labor, and therefore social complexity, in ants. © 2017 Wiley Periodicals, Inc. Develop Neurobiol 77: 1072–1085, 2017
Murine thymic NK cells are distinct from ILC1s and have unique transcription factor requirements
Authors: Gabrielli Sara , Sun Mengxi , Bell April , Zook Erin C. , de Pooter Renee F. , Zamai Loris , Kee Barbara L.
Published: March 2017

Group 1 innate lymphoid cells include natural killer (NK) cells and ILC1s, which mediate the response to intracellular pathogens. Thymic NK (tNK) cells were described with hybrid features of immature NK cells and ILC1 but whether these cells are related to NK cells or ILC1 has not been fully investigated. We report that murine tNK cells expressed the NK‐cell associated transcription factor EOMES and developed independent of the essential ILC1 factor TBET, confirming their placement within the NK lineage. Moreover, tNK cells resemble NK cells rather than ILC1 in their requirements for the E protein transcription factor inhibitor ID2. We provide further insight into the mechanisms governing tNK‐cell development by showing that the transcription factor ETS1 prevented tNK cell acquisition of the conventional NK‐cell maturation markers CD11b and KLRG1. Our data reveal few ILC1 in the thymus and clarify the identity and developmental requirements of tNK cells.
Effects of Multi‐Carborane Substitution on the Photophysical and Electron‐Accepting Properties of o‐Carboranylbenzene Compounds
Authors: You Dong Kyun , Lee Ji Hye , Choi Byung Hoon , Hwang Hyonseok , Lee Min Hyung , Lee Kang Mun , Park Myung Hwan
Published: March 2017

Multiple o‐carborane substituted compounds, mono‐, 1,3‐bis‐, and 1,3,5‐tris[2‐(4‐butylphenyl)‐o‐carboran‐1‐yl]benzene (1–3), were prepared and characterized by multinuclear NMR spectroscopy and elemental analysis. The solid‐state structures of 2 and 3 were also confirmed by single‐crystal X‐ray diffraction. While the mono‐carborane compound 1 was nonemissive in the solution state at 298 K, the photoluminescence (PL) spectra of 2 and 3 exhibited weak‐to‐moderate emission (λem = 352 nm for 2 and 363 nm for 3 in THF). Compounds 2 and 3 showed intriguing dual emission bands (λem = 361 and 537 nm for 2 and λem = 387 and 520 nm for 3) at 77 K, and in film, of which the low‐energy band was dominant in the solid state. TD‐DFT calculations on the S1 optimized structures suggested that the low‐energy fluorescence of 2 and 3 was attributed to the π(4‐butylphenyl) → π*(phenylene‐o‐carborane) intramolecular charge‐transfer transition. The low‐energy electronic transition of 2 and 3 was apparently associated with aggregation‐induced emission, and an enhanced emission intensity (λem = ca. 570 nm for 2 and λem = ca. 550 nm for 3) was observed upon increasing the water fraction (fw) in THF/water mixtures. Furthermore, the PL spectroscopic experiments of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) polymer films doped with 3 revealed the excellent electron‐accepting properties of 3.
Evaluation of an NIS‐Mediated Oxidative Cyclisation of Phenol‐Containing N‐Acyltryptamine Precursors towards Phalarine: Synthesis of 4′,5′‐Dihydrospiro[indole‐3,6′‐[1,3]oxazine]s
Authors: Tomakinian Terry , Hamdan Hussein Abou , Denizot Natacha , Guillot Régis , Baltaze Jean‐Pierre , Kouklovsky Cyrille , Vincent Guillaume
Published: March 2017

To access the benzofuro[3,2‐b]indoline scaffold of the natural product phalarine, we planned an NIS‐mediated oxidative coupling of an N‐acetyltryptamine derivative and a phenol. To control the regioselectivity of benzofuroindoline formation, the phenol was appended, before the cyclisation, at the 2‐position of the indole ring through an optimised gram‐scale C–H arylation. The indole nucleus was indeed oxidised at its 3‐position, however, the cyclisation did not occur through the phenol but through the acetamide and a 4′,5′‐dihydrospiro[indole‐3,6′‐[1,3]oxazine] was obtained instead of the benzofuro[3,2‐b]indoline scaffold of the natural product.
Radical Cyclizations in the Synthesis of 3‐Methyl‐cis‐octahydroindol‐5‐ones
Authors: Jansana Sergi , Coussanes Guilhem , Diaba Faïza , Bonjoch Josep
Published: March 2017

Three approaches to the stereoselective synthesis of 3‐methyl‐cis‐octahydroindoles through a 5‐endo‐trig radical cyclization are described. First, starting from an N‐vinyl‐α‐chloroacetamide, the cyclization was followed by lactam methylenation and hydrogenation. Second, starting from an alkyne‐tethered enamide, the cyclization was promoted by Bu3SnH, and this was followed by protonolysis of the vinylstannane and hydrogenation of the exocyclic alkene. Third, through a 2,2‐dichloropropanamide cyclization onto an alkenyl bond, and hydrogenation of the resulting endocyclic double bond; this represents the most efficient sequence to form the target compounds. 1,5‐Enyne cyclizations through a 5‐endo‐trig process are reported. Here, a remote functional group (ketal or ketone), allowed the diastereoselectivity of the octahydroindole ring formation to be reversed through steric control of the facial selectivity in the hydrogen radical delivery step.
Ruthenium‐Catalyzed Cross‐Metathesis of Allyl Acetate and Styrenes: A Practical Approach to the Synthesis of Tripolinolate A and Its Analogs
Authors: Araki Yasuhiro , Topolovčan Nikola , Kotora Martin
Published: March 2017

The scope of the Ru‐catalyzed cross‐metathesis of allyl acetates and styrenes was explored. A variety of electronically and structurally divergent styrenes were tolerated, and the resultant products were obtained in reasonable yields. The reported method was utilized in the synthesis of inhibitors of the proliferation of glioma and colorectal cancer cells, tripolinolate A and its diacetate analog.
Towards Sustainable Amino Acid Derived Organocatalysts for Asymmetric syn‐Aldol Reactions
Authors: Gerasimchuk Vasiliy V. , Kucherenko Alexandr S. , Fakhrutdinov Artem N. , Medvedev Michael G. , Nelyubina Yulia V. , Zlotin Sergei G.
Published: March 2017

The undesirable side‐processes responsible for the fast deactivation of primary amino acid derived organocatalysts in asymmetric aldol reactions are identified. A new ionic‐liquid‐supported (S)‐valine‐/(S)‐α,α‐diphenylserinol‐derived catalyst (9) is designed on the basis of these results and exhibits much better recyclability in asymmetric syn‐aldol reactions between hydroxyacetone and aldehydes. Furthermore, this catalyst appeared to be useful for the stereoselective synthesis of the naturally occurring 1(3H)‐isobenzofuran‐1‐one scaffold through an asymmetric syn‐aldol/lactonization cascade reaction.
Implementation of a Simple Nanostructured Bio‐electrode with Immobilized Rhus Vernicifera Laccase for Oxygen Sensing Applications
Authors: Torrinha Álvaro , Montenegro Maria C. B. S. M. , Araújo Alberto N.
Published: March 2017

In this work a simple nanostructured direct‐electron transfer bio‐electrode based on tree laccase from Rhus vernicifera is described. The electrode was implemented on a 2 mm diameter graphite mine casted with a reduced graphene surface presenting the specific capacitance of 195.8 F g−1. About 10 μl of mixture between 25 mg mL−1 laccase suspension and 5 mg mL−1 single‐walled carbon nanotubes in 2 % SDS is dropped over the surface followed by 5 μl of the biological friendly tetrakis(2,3‐dihydroxypropyl)‐silane monomer sol to provide physical entrapment in a silica matrix after gelation. The rigidity of enzyme encapsulation allowed to obtain a constant enzyme turnover of about 16 min−1 in the extended pH range of 6.0‐7.5, being the activity almost proportional to the temperature used in the interval between 25 and 40 °C. The graphite‐graphene/SWCNT‐laccase/sol‐gel electrode enabled a proportional response to molecular oxygen up to the concentration of 0.45 mmol L−1 and is capable to generate the maximum power of 4.5 μW cm−2 at 0.250 V vs the AgCl/Ag reference electrode in quiescent oxygen saturated solution.
Reproductive and Appetite Hormones and Bulimic Symptoms during Midlife
Authors: Baker Jessica H. , Peterson Claire M. , Thornton Laura M. , Brownley Kimberly A. , Bulik Cynthia M. , Girdler Susan S. , Marcus Marsha D. , Bromberger Joyce T.
Published: March 2017

Eating disorders and related symptoms occur during midlife; however, little is known about their aetiology. It has been hypothesised that perimenopause represents a window of vulnerability for the development or exacerbation of eating disorder symptomatology because, like puberty, perimenopause is a period of reproductive hormone change. We compared symptoms of bulimia nervosa (bulimic symptomatology) assessed via mean scores on a self‐report questionnaire in premenopausal and perimenopausal women. We also examined the association between hormone concentrations (reproductive/appetite) and bulimic symptomatology. No mean differences in bulimic symptomatology were observed between premenopause and perimenopause. However, there was a significant positive association between leptin and binge eating. Although no significant associations between reproductive hormones and bulimic symptomatology were observed, additional research is needed to provide definitive information. It is essential to learn more about the aetiology of eating disorders and related symptomatology across the lifespan in order to develop age‐relevant treatment and prevention programs. Copyright © 2017 John Wiley & Sons, Ltd and Eating Disorders Association.
Subaerial gravel size measurement using topographic data derived from a UAV‐SfM approach
Authors: Woodget Amy S. , Austrums Robbie
Published: March 2017

Accurate and reliable methods for quantifying grain size are important for river science, management and in various other sedimentological settings. Remote sensing offers methods of quantifying grain size, typically providing; (a) coarse outputs (c. 1 m) at the catchment scale where individual grains are at subpixel level, or; (b) fine resolution outputs (c. 1 mm) at the patch scale. Recently, approaches using unmanned aerial vehicles (UAVs) have started to fill the gap between these scales, providing hyperspatial resolution data (< 10 cm) over reaches a few hundred metres in length, where individual grains are at suprapixel level. This ‘mesoscale’ is critical to habitat assessments. Most existing UAV‐based approaches use two‐dimensional (2D) textural variables to predict grain size. Validation of results is largely absent however, despite significant differences in platform stability and image quality obtained by manned aircraft versus UAVs. Here, we provide the first quantitative assessment of the accuracy and precision of grain size estimates produced from a 2D image texture approach. Furthermore, we present a new method which predicts subaerial gravel size using three‐dimensional (3D) topographic data derived from UAV imagery. Data is collected from a small gravel‐bed river in Cumbria, UK. Results indicate that our new topographic method gives more accurate measures of grain size (mean residual error ‐0.0001 m). Better results for the image texture method may be precluded by our choice of texture measure, the scale of analysis or the effects of image blur resulting from an inadequate camera gimbal. We suggest that at our scale of assessment, grain size is more strongly related to 3D variation in elevation than to the 2D textural patterns expressed within the imagery. With on‐going improvements, our novel method has potential as the first grain size quantification approach where a trade‐off between coverage and resolution is not necessary or inherent. Copyright © 2017 John Wiley & Sons, Ltd.
Impact of rainfall pattern on interrill erosion process
Authors: Wang Bin , Steiner Jean , Zheng Fenli , Gowda Prasanna
Published: March 2017

The impact of rainfall pattern on the interrill erosion process is not fully understood despite its importance. Systematic rainfall simulation experiments involving various rainfall intensities, stages, intensity sequences, and surface cover conditions were conducted in this study to investigate their effects on the interrill erosion process. Five rainfall patterns designed with the same total kinetic energy/precipitation (increasing, decreasing, rising–falling, falling–rising and constant patterns) were randomly delivered to a pre‐wet clay loam soil surface at a 10° slope gradient. Significant differences in soil losses were observed among the different rainfall patterns and stages, but there was no obvious difference in runoff. Kinetic energy flux (KEr) was a governing factor for interrill erosion, and constant rainfall pattern (CST) produced nine times greater soil loss than runs with no KEr. Varied‐intensity patterns had a profound effect on raindrop‐induced sediment transport processes; path analysis results indicated that said effect was complex, interactive and intensity‐dependent. Low hydraulic parameter thresholds further indicated that KErwas the dominant factor in detaching soil particles, while overland flow mainly contributed to transporting the pre‐detached particles. This study not only sheds light on the mechanism of interrill sediment transport capacity and detachability, but also may provide a useful database for developing event‐based interrill erosion prediction models. Copyright © 2017 John Wiley & Sons, Ltd.
Architecture of relict charcoal hearths in northwestern Connecticut, USA
Authors: Raab Thomas , Hirsch Florian , Ouimet William , Johnson Katharine M. , Dethier David , Raab Alexandra
Published: March 2017

Relict charcoal hearths are round or elliptical earthen platforms up to 11 m in diameter and a widespread feature of historical industry that supplied charcoal used in the production of iron in furnaces or smelters. The iron industry dominated Litchfield County, Connecticut, and surrounding areas in the northeast United States throughout the 19th century, peaking in ∼1850. The large number of charcoal hearths in this region is a relic of >150 years of widespread iron production. In this study, we describe the architecture and soil stratigraphy of 26 charcoal hearths in Litchfield County. This contribution aims to (1) compare soils that comprise the charcoal hearths with “natural” adjacent soils, (2) measure the thickness of topsoil developed upon the hearths, and (3) characterize the stratigraphy associated with these features. Results indicate that the black topsoils overlying the charcoal hearths contain residual charcoal and are on average 2.6 times thicker than adjacent Cambisols. Charcoal hearths display two or more black, charcoal‐rich strata separated by layers of reddish‐brown soil low in charcoal content indicating multiple episodes of use. We also find that many charcoal hearths have been stabilized with boulders on the downslope side during construction and repeated use. Overall, the results presented here provide significant information regarding the construction, use, and associated impacts of earthen platforms for charcoal production in the northeast United States, with further relevance to other areas where historical charcoal production occurred.
This Is Who I Want to Be! Exploring Possible Selves by Interviewing Women in Science
Authors: Early Jessica Singer
Published: March 2017

This article shares a study of an interview/writing project for adolescent girls, which was a component of the Girls Writing Science Project at a diverse urban high school in the Southwestern United States. The group of high school girls planned, initiated, conducted, and wrote interview profiles of women scientists from their local community. This study of adolescent writers represents a model for teachers across disciplines to use the teaching of writing as a pathway for students to access, explore, and articulate possibilities for their future selves in connection to science. More specifically, this project offers a means of narrowing the gender divide in the sciences by supporting students in studying high‐achieving women working in science‐related careers and by practicing writing as a real‐world, transferable skill with meaningful purpose.
Preference and reinforcer efficacy of high‐ and low‐tech items: A comparison of item type and duration of access
Authors: Hoffmann Audrey N. , Samaha Andrew L. , Bloom Sarah E. , Boyle Megan A.
Published: March 2017

This study examined the interactions of stimulus type (high‐ vs. low‐tech) and magnitude (duration of access) on preference and reinforcer efficacy. Two preference assessments were conducted to identify highly preferred high‐tech and low‐tech items for each participant. A subsequent assessment examined preference for those items when provided at 30‐s and 600‐s durations. We then evaluated reinforcer efficacy for those same items when provided for a range of durations using progressive‐ratio schedules. Results suggested item type and access duration interacted to influence preference and reinforcer efficacy. Participants preferred high‐tech items at longer durations of access and engaged in more responding when the high‐tech item was provided for long durations, but these patterns were reversed for the low‐tech item. In addition, participants engaged in less responding when the high‐tech item was provided for short durations and when the low‐tech item was provided for long durations.