bluuebunny/crossref_metadata_2025 huggingface dataset:
Thermal drawdown and late‐stage seismic‐slip fault reactivation in enhanced geothermal reservoirs
Authors: Gan Quan , Elsworth Derek
Published: November 2014

Late‐stage seismic slip in geothermal reservoirs has been shown as a potential mechanism for inducing seismic events of magnitudes to ~2.6 as late as two decades into production. We investigate the propagation of fluid pressures and thermal stresses in a prototypical geothermal reservoir containing a centrally located critically stressed fault from a doublet injector and withdrawal well to define the likelihood, timing, and magnitude of events triggered by both fluid pressures and thermal stresses. We define two bounding modes of fluid production from the reservoir. For injection at a given temperature, these bounding modes relate to either low‐ or high‐relative flow rates. At low relative dimensionless flow rates the pressure pulse travels slowly, the pressure‐driven changes in effective stress are muted, but thermal drawdown propagates through the reservoir as a distinct front. This results in the lowest likelihood of pressure‐triggered events but the largest likelihood of late‐stage thermally triggered events. Conversely, at high relative non‐dimensional flow rates the propagating pressure pulse is larger and migrates more quickly through the reservoir but the thermal drawdown is uniform across the reservoir and without the presence of a distinct thermal front, and less capable of triggering late‐stage seismicity. We evaluate the uniformity of thermal drawdown as a function of a dimensionless flow rate QD that scales with fracture spacing s (m), injection rate q (kg/s), and the distance between the injector and the target point L∗ (QD ∝ qs2/L∗). This parameter enables the reservoir characteristics to be connected with the thermal drawdown response around the fault and from that the corresponding magnitude and timing of seismicity to be determined. These results illustrate that the dimensionless temperature gradient adjacent to the fault dTD/dxD is exclusively controlled by the factor QD. More significantly, this temperature gradient correlates directly with both the likelihood and severity of triggered events, enabling the direct scaling of likely magnitudes and timing to be determined a priori and directly related to the characteristics of the reservoir. This dimensionless scaling facilitates design for an optimum QD value to yield both significant heat recovery and longevity of geothermal reservoirs while minimizing associated induced seismicity.
Repositioning the Cobb human archive: The merger of a skeletal collection and its texts
Authors: Watkins Rachel , Muller Jennifer
Published: November 2014

The W. Montague Cobb skeletal collection, mainly comprised of African Americans living in Washington, DC, before 1969, is an important collection for human biological studies of the African Diaspora. This article outlines the process of constructing an improved study sample for biocultural analysis by merging skeletal remains from the collection with their associated texts. The merging allows for the inclusion of individuals from the original series for whom we no longer have skeletons. We argue that this step is necessary to construct a data set that reflects the demographic breadth (age, ethnicity, social class) of the original collection, taking into account a substantial number of skeletons lost during storage and disuse. The mechanics of this process were informed by a critical and humanistic orientation toward human biological study built upon the following premises: (1) scientific investigation is not an objective or passive practice, nor must it be; and, (2) relevant, publically accessible human biological research requires competence with social justice issues, as well as previous and current scholarship focused on addressing those issues. This approach to sample construction engages skeletal remains as biological and social products, and enhances the social and translational implications of our research practices. Am. J. Hum. Biol. 27:41–50, 2015. © 2014 Wiley Periodicals, Inc.
Designing mental health interventions informed by child development and human biology theory: A social ecology intervention for child soldiers inNepal
Authors: Kohrt Brandon A. , Jordans Mark J.D. , Koirala Suraj , Worthman Carol M.
Published: November 2014

The anthropological study of human biology, health, and child development provides a model with potential to address the gap in population‐wide mental health interventions. Four key concepts from human biology can inform public mental health interventions: life history theory and tradeoffs, redundancy and plurality of pathways, cascades and multiplier effects in biological systems, and proximate feedback systems. A public mental health intervention for former child soldiers in Nepal is used to illustrate the role of these concepts in intervention design and evaluation. Future directions and recommendations for applying human biology theory in pursuit of public mental health interventions are discussed. Am. J. Hum. Biol. 27:27–40, 2015. © 2014 Wiley Periodicals, Inc.
Applying the community partnership approach to human biology research
Authors: Ravenscroft Julia , Schell Lawrence M. , Cole Tewentahawih′tha′
Published: November 2014

Contemporary human biology research employs a unique skillset for biocultural analysis. This skillset is highly appropriate for the study of health disparities because disparities result from the interaction of social and biological factors over one or more generations. Health disparities research almost always involves disadvantaged communities owing to the relationship between social position and health in stratified societies. Successful research with disadvantaged communities involves a specific approach, the community partnership model, which creates a relationship beneficial for researcher and community. Paramount is the need for trust between partners. With trust established, partners share research goals, agree on research methods and produce results of interest and importance to all partners. Results are shared with the community as they are developed; community partners also provide input on analyses and interpretation of findings. This article describes a partnership‐based, 20 year relationship between community members of the Akwesasne Mohawk Nation and researchers at the University at Albany. As with many communities facing health disparity issues, research with Native Americans and indigenous peoples generally is inherently politicized. For Akwesasne, the contamination of their lands and waters is an environmental justice issue in which the community has faced unequal exposure to, and harm by environmental toxicants. As human biologists engage in more partnership‐type research, it is important to understand the long term goals of the community and what is at stake so the research circle can be closed and ‘helicopter’ style research avoided. Am. J. Hum. Biol. 27:6–15, 2015. © 2014 Wiley Periodicals, Inc.
Enantioselective Cycloadditions of Vinyl Cyclopropanes and Nitroolefins for Functionally and Optically Enriched Nitrocyclopentanes
Authors: Li Wen‐Ke , Liu Ze‐Shui , He Long , Kang Tai‐Ran , Liu Quan‐Zhong
Published: November 2014

Palladium‐catalyzed enantioselective cycloaddition of vinyl cyclopropane dicarbonitriles and nitroolefins was achieved to generate structurally and optically enriched nitrocyclopentanes with three consecutive chiral carbon centers in up to 96 % yield and with up to 92 % ee. The two diastereoisomers produced in each reaction are readily separable by simple chromatography. The present method allows the preparation of both diastereoisomers in optically enriched form.
Reproductive consequences of a matrilineal overthrow in rhesus monkeys
Authors: Dettmer Amanda M. , Woodward Ruth A. , Suomi Stephen J.
Published: November 2014

Matrilineal overthrows in macaque societies are rare but devastating events, often resulting in severe morbidity, mortality, and loss of individual and group fitness. The handful of documented macaque overthrows provides scant evidence to reveal the severity or longevity of reproductive consequences resulting from such violent events. We analyzed archival records from semi‐free ranging rhesus monkeys, Macaca mulatta, across 6 years (55 ≤ N ≤ 107, from 2007 to 2012) during which time a matrilineal overthrow occurred (in 2009) to test the hypothesis that extremely violent interactions such as a matrilineal overthrow would significantly reduce reproductive fitness for the involved matrilines and for the troop collectively. The matrilineal overthrow resulted in a significant increase in infant loss for the population from the previous year (χ2 = 8.117, df = 1, P = 0.004), as evidenced by the fact that in 2009, but not in other years, the proportion of infants lost was greater than the proportion of viable infants (χ2 = 4.55, df = 1, P = 0.03). Moreover, the deposed matriline suffered 100% infant loss in 2009, a significant change from the previous year (χ2 = 7.87, df = 1, P = 0.005) while the attacking matriline suffered 50% infant loss (also a significant change from the previous year; χ2 = 4.44, df = 1, P = 0.035), with the uninvolved, lowest‐ranking matriline showing no change in infant loss from the previous year (χ2 = 0.008, df = 1, P = 0.93). The deposed matriline did not produce viable offspring again until 3 years later. We further found that rates of severe fighting (as indicated by the number of fight wounds requiring medical treatment) were positively correlated with infant loss across the 6 years of the study (r[s] = 0.943, P = 0.005). Our data indicate that extreme periods of intra‐group conflict, such as the matrilineal overthrow, have marked short‐term consequences for individual fitness, and may be extreme examples of the long‐term influences that group violence exerts on the mean fitness within a primate troop. Am. J. Primatol. 77:346–352, 2015. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.
Targeting miR‐155 restores abnormal microglia and attenuates disease in SOD1 mice
Authors: Butovsky Oleg , Jedrychowski Mark P. , Cialic Ron , Krasemann Susanne , Murugaiyan Gopal , Fanek Zain , Greco David J. , Wu Pauline M. , Doykan Camille E. , Kiner Olga , Lawson Robert J. , Frosch Matthew P. , Pochet Nathalie , Fatimy Rachid El , Krichevsky Anna M. , Gygi Steven P. , Lassmann Hans , Berry James , Cudkowicz Merit E. , Weiner Howard L.
Published: November 2014

Objective

To investigate miR‐155 in the SOD1 mouse model and human sporadic and familial amyotrophic lateral sclerosis (ALS).

Methods

NanoString microRNA, microglia and immune gene profiles, protein mass spectrometry, and RNA‐seq analyses were measured in spinal cord microglia, splenic monocytes, and spinal cord tissue from SOD1 mice and in spinal cord tissue of familial and sporadic ALS. miR‐155 was targeted by genetic ablation or by peripheral or centrally administered anti–miR‐155 inhibitor in SOD1 mice.

Results

In SOD1 mice, we found loss of the molecular signature that characterizes homeostatic microglia and increased expression of miR‐155. There was loss of the microglial molecules P2ry12, Tmem119, Olfml3, transcription factors Egr1, Atf3, Jun, Fos, and Mafb, and the upstream regulators Csf1r, Tgfb1, and Tgfbr1, which are essential for microglial survival. Microglia biological functions were suppressed including phagocytosis. Genetic ablation of miR‐155 increased survival in SOD1 mice by 51 days in females and 27 days in males and restored the abnormal microglia and monocyte molecular signatures. Disease severity in SOD1 males was associated with early upregulation of inflammatory genes, including Apoe in microglia. Treatment of adult microglia with apolipoprotein E suppressed the M0‐homeostatic unique microglia signature and induced an M1‐like phenotype. miR‐155 expression was increased in the spinal cord of both familial and sporadic ALS. Dysregulated proteins that we identified in human ALS spinal cord were restored in SOD1G93A/miR‐155−/− mice. Intraventricular anti–miR‐155 treatment derepressed microglial miR‐155 targeted genes, and peripheral anti–miR‐155 treatment prolonged survival.

Interpretation

We found overexpression of miR‐155 in the SOD1 mouse and in both sporadic and familial human ALS. Targeting miR‐155 in SOD1 mice restores dysfunctional microglia and ameliorates disease. These findings identify miR‐155 as a therapeutic target for the treatment of ALS. ANN NEUROL 2015;77:75–99
Coding mutations in SORL1 and Alzheimer disease
Authors: Vardarajan Badri N. , Zhang Yalun , Lee Joseph H. , Cheng Rong , Bohm Christopher , Ghani Mahdi , Reitz Christiane , Reyes‐Dumeyer Dolly , Shen Yufeng , Rogaeva Ekaterina , St George‐Hyslop Peter , Mayeux Richard
Published: November 2014

Objective

Common single nucleotide polymorphisms in the SORL1 gene have been associated with late onset Alzheimer disease (LOAD), but causal variants have not been fully characterized nor has the mechanism been established. The study was undertaken to identify functional SORL1 mutations in patients with LOAD.

Methods

This was a family‐ and cohort‐based genetic association study. Caribbean Hispanics with familial and sporadic LOAD and similarly aged controls were recruited from the United States and the Dominican Republic, and patients with sporadic disease of Northern European origin were recruited from Canada. Prioritized coding variants in SORL1 were detected by targeted resequencing and validated by genotyping in additional family members and unrelated healthy controls. Variants transfected into human embryonic kidney 293 cell lines were tested for Aβ40 and Aβ42 secretion, and the amount of the amyloid precursor protein (APP) secreted at the cell surface was determined.

Results

Seventeen coding exonic variants were significantly associated with disease. Two rare variants (rs117260922‐E270K and rs143571823‐T947M) with minor allele frequency (MAF) < 1% and 1 common variant (rs2298813‐A528T) with MAF = 14.9% segregated within families and were deemed deleterious to the coding protein. Transfected cell lines showed increased Aβ40 and Aβ42 secretion for the rare variants (E270K and T947M) and increased Aβ42 secretion for the common variant (A528T). All mutants increased the amount of APP at the cell surface, although in slightly different ways, thereby failing to direct full‐length APP into the retromer‐recycling endosome pathway.

Interpretation

Common and rare variants in SORL1 elevate the risk of LOAD by directly affecting APP processing, which in turn can result in increased Aβ40 and Aβ42 secretion. Ann Neurol 2015;77:215–227
C‐H‐Aktivierung mit Komplexen der f‐Block‐Elemente
Authors: Arnold Polly L. , McMullon Max W. , Rieb Julia , Kühn Fritz E.
Published: November 2014

Homogene Katalyse hängt zu erheblichen Teilen von der Synthese von Metallkomplexen ab, die in der Lage sind, (niedermolekulare) Substrate zu binden und zu wertvolleren Produkten umzusetzen. Einen ersten Vorgeschmack der katalytischen C‐H‐Aktivierung mit metallorganischen Lanthanoidkomplexen gab es vor etwa 25 Jahren, als es gelang, mit Bis(pentamethylcyclopentadenyl)lanthanoid‐Methylkomplexen [(η5‐(C5Me5)2Ln(CH3)] eine C‐H‐Bindung von Methan zu spalten. In der Zwischenzeit wurden zahlreiche Metallkomplexe aus dem ganzen Periodensystem gefunden, die selektiv C‐H‐Bindungen aktivieren können, aber die Herausforderung, einen geschlossenen Katalysezyklus zu etablieren, bleibt bestehen. Viele f‐Block‐Komplexe scheinen aber über großes Potenzial auf diesem wichtigen Gebiet zu verfügen.
An Aqueous Rechargeable Formate‐Based Hydrogen Battery Driven by Heterogeneous Pd Catalysis
Authors: Bi Qing‐Yuan , Lin Jian‐Dong , Liu Yong‐Mei , Du Xian‐Long , Wang Jian‐Qiang , He He‐Yong , Cao Yong
Published: November 2014

The formate‐based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H2 storage used in fuel cell applications. Described herein is an additive‐free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H2 handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner. Up to six repeated discharging/charging cycles can be performed without noticeable degradation in the storage capacity.
Polyaniline‐anchored palladium catalyst‐mediated Mizoroki–Heck and Suzuki–Miyaura reactions and one‐pot Wittig–Heck and Wittig–Suzuki reactions
Authors: Patel Heta A. , Patel Arun L. , Bedekar Ashutosh V.
Published: November 2014

A polyaniline‐anchored palladium catalyst was prepared and screened for coupling reactions of aryl halides. The robust and recyclable catalyst was effective in Mizoroki–Heck and Suzuki–Miyaura reactions of aryl bromides and aryl iodides. The catalyst system was further employed for one‐pot Wittig–Heck and Wittig–Suzuki combinations to build conjugated compounds in good conversions. Copyright © 2014 John Wiley & Sons, Ltd.
GM‐PHD Filter With Signal Features Of Emitter
Authors: Zhu Youqing , Zhou Shilin
Published: November 2014

A new GM‐PHD filter for multiple emitter targets tracking is proposed in this paper. It integrates the signal features of emitter into the process of weights update. In the case of unknowing the distribution of signal features, the FCM algorithm is used for reference to calculate the correlation coefficients between the measurements and candidate targets in place of the likelihoods. Simulation results show that the proposed method can effectively improve the tracking performance in the scenarios with different clutter densities.
Fault Detection for Linear Discrete Time‐varying Systems with Intermittent Observations and Quantization Errors
Authors: Li Yueyang , Liu Shuai , Wang Zhonghua
Published: November 2014

This paper deals with the fault detection (FD) problem for linear discrete time‐varying (LDTV) systems subject to multiple intermittent observations and quantization errors. A set of independent identical distributed random variables are introduced as the indicators of the observation sequences to describe the multiple intermittent measurements. The measured observation is quantized by a logarithmic type quantizer. Our focus is to construct an observer‐based fault detection filter (FDF) to recognize the fault in spite of multiple measurement packet dropouts and quantization inaccuracy. By defining generalized input‐to‐output operators, the FD problem is formulated into a two‐objective optimization framework such that stochastic H∞/H∞ or H−/H∞ performance index is maximized. Probability/indicators‐dependent and probability‐dependent analytical solutions are respectively derived by virtue of an adjoint operator based optimization approach for two cases. One is that the indicators are on‐line known while the other one is that the indicators are not available at each time instant. An illustrative example is employed to demonstrate the effectiveness and applicability of the proposed approach.
A New Model of Networked Control Systems in Robust Control Framework
Authors: Wen Kai , Geng Zhiyong , Zhang Zhenyong , Zhang Lijia
Published: November 2014

In this paper, a new model is proposed to describe networked control systems (NCS) with delays and quantization errors. Firstly, the non‐idealizations are unified in the classic robust control framework and the entire system is modeled as a discrete system closed via a block uncertainty. Then, the stability criteria are derived using small gain theorem, μ tool and integral quadratic constraint (IQC) method, respectively. Finally, a simulation and a numerical example are provided to demonstrate the effectiveness of the proposed methods. This work is supported by the Science Foundation of China University of Petroleum, Beijing (No.YJRC‐2013‐11) and National Natural Science Foundation (NNSF) of China under Grant 61374033.
Trajectory Linearization Control Based Output Tracking Method for Nonlinear Uncertain System Using Linear Extended State Observer
Authors: Xingling Shao , Honglun Wang
Published: November 2014

In this paper, a trajectory linearization control based control law using a linear extended state observer (LESO) is proposed for the output tracking problem of a nonlinear system with uncertainties. First, based on the tracking error dynamics derived by Taylor expansion for the original nonlinear system along the desired trajectory, a feedback linearization (FL) based control law is designed to stabilize a linear time‐varying (LTV) system. To reduce the controller performance sensitive to uncertainties, with partial model information, LESO is constructed to estimate the tracking error vector, as well as the uncertainties in an integrated manner. The closed‐loop stability of the system under the proposed compound scheme is established. Also, simulation results on affine and non‐affine nonlinear uncertain systems are provided to demonstrate the effectiveness of the control strategy. Finally, the issues of sensitivity to sensor noise and the guidelines of tuning parameters are discussed.
Developmental Changes in Brain Function Underlying Inhibitory Control in Autism Spectrum Disorders
Authors: Padmanabhan Aarthi , Garver Krista , O'Hearn Kirsten , Nawarawong Natalie , Liu Ran , Minshew Nancy , Sweeney John , Luna Beatriz
Published: November 2014

The development of inhibitory control—the ability to suppress inappropriate actions in order to make goal‐directed responses—is often impaired in autism spectrum disorders (ASD). In the present study, we examined whether the impairments in inhibitory control evident in ASD reflect—in part—differences in the development of the neural substrates of inhibitory control from adolescence into adulthood. We conducted a functional magnetic resonance imaging (fMRI) study on the anti‐saccade task, a probe of inhibitory control, in high‐functioning adolescents and adults with ASD compared to a matched group of typically developing (TD) individuals. The ASD group did not show the age‐related improvements in behavioral performance from adolescence to adulthood evident in the typical group, consistent with previous behavioral work. The fMRI results indicated that much of the circuitry recruited by the ASD group was similar to the TD group. However, the ASD group demonstrated some unique patterns, including: (a) a failure to recruit the frontal eye field during response preparation in adolescence but comparable recruitment in adulthood; (b) greater recruitment of putamen in adolescence and precuneus in adolescence and adulthood than the TD group; and (c) decreased recruitment in the inferior parietal lobule relative to TD groups. Taken together, these results suggest that brain circuitry underlying inhibitory control develops differently from adolescence to adulthood in ASD. Specifically, there may be relative underdevelopment of brain processes underlying inhibitory control in ASD, which may lead to engagement of subcortical compensatory processes. Autism Res 2015, 8: 123–135. © 2014 International Society for Autism Research, Wiley Periodicals, Inc.
Impact of a Stereocentre Inversion in Cyclic Lipodepsipeptides from the Viscosin Group: A Comparative Study of the Viscosinamide and Pseudodesmin Conformation and Self‐Assembly
Authors: Geudens Niels , De Vleeschouwer Matthias , Fehér Krisztina , Rokni‐Zadeh Hassan , Ghequire Maarten G. K. , Madder Annemieke , De Mot René , Martins José C. , Sinnaeve Davy
Published: November 2014

The viscosin group covers a series of cyclic lipodepsipeptides (CLPs) produced by Pseudomonas bacteria, with a range of biological functions and antimicrobial activities. Their oligopeptide moieties are composed of both L‐ and D‐amino acids. Remarkably, the Leu5 amino acid—centrally located in the nonapeptide sequence—is the sole residue found to possess either an L or D configuration, depending on the producing strain. The impact of this D/L switch on the solution conformation was investigated by NMR‐restrained molecular modelling of the epimers pseudodesmin A and viscosinamide A. Although the backbone fold remained unaffected, the D/L switch adjusted the segregation between hydrophobic and hydrophilic residues, and thus the amphipathicity. It also influenced the self‐assembly capacity in organic solvents. Additionally, several new minor variants of viscosinamide A from Pseudomonas fluorescens DR54 were identified, and an NMR assay is proposed to assess the presence of either an L‐ or D‐Leu5.
Pulmonary valvotomy with echocardiographic guidance in neonates with pulmonary atresia and intact ventricular septum
Authors: Hyang Kim Yeo
Published: November 2014

Background

Percutaneous transcatheter valvotomy of the atretic pulmonary valve (PV) carries a risk of perforation of the right ventricle (RV) and requires standby of the cardiac surgical team for potential emergent cardiac management. The objective of this study was to introduce a successful and safe transcatheter wire perforation of the atretic PV using echocardiographic guidance in neonates with pulmonary atresia and an intact ventricular septum.

Methods

In addition to fluoroscopic guidance, echocardiography was used throughout the procedure. For positioning the Judkins right (JR) catheter at the point of ‘tenting’ indicating center of the PV, the morphology and position of the PV were confirmed using a left‐tilted parasternal long axis view and a slight counterclockwise‐rotated parasternal short axis view. After the JR catheter was positioned at the point of tenting of the atretic PV, the stiff end of the 0.014 mm PTCA wire was advanced through the PV toward the main pulmonary artery using echocardiographic guidance. During the first portion of the procedure, accurate perforation using echocardiographic imaging was confirmed. After then, pulmonary valvuloplasty with increasingly larger balloons, beginning with an initial 2.5 × 20 mm2 PTCA balloon and finishing with a final 8 × 20 mm2 PTA balloon was performed.

Results

In all patients, successful valve perforation and balloon valvuloplasty were achieved. There were no significant cardiac complications, including perforation of the RV.

Conclusions

Pulmonary valvotomy using transthoracic echocardiographic guidance can reduce the risk of perforation of the RV and be more successful compared with that using only fluoroscopic guidance. © 2014 Wiley Periodicals, Inc.
Synthesis of New Porphyrin–Fullerene Dyads Capable of Forming Charge‐Separated States on a Microsecond Lifetime Scale
Authors: Konev Alexander S. , Khlebnikov Alexander F. , Prolubnikov Pavel I. , Mereshchenko Andrey S. , Povolotskiy Alexey V. , Levin Oleg V. , Hirsch Andreas
Published: November 2014

A series of covalently linked axially symmetric porphyrin–fullerene dyads with a rigid pyrrolo[3,4‐c]pyrrolic linker enabling a fixed and orthogonal arrangement of the chromophores has been synthesized and studied by means of transient absorption spectroscopy and cyclic voltammetry. The lifetime of the charge‐separated state has been found to depend on the substituents on the porphyrin core, reaching up to 4 μs for a species with meso‐(p‐MeOC6H4) substituents. The ground and excited electronic states of model compounds have been calculated at the DFT and TD‐DFT B3LYP(6‐31G(d)) levels of theory and analyzed with regard to the effect of the substituent on the stabilization of the charge‐separated state in the porphyrin–fullerene ensemble with a view to explaining the observed dependence.
Synthesis of Phosphorus‐Doped Graphene and its Wide Potential Window in Aqueous Supercapacitors
Authors: Wen Yangyang , Wang Bei , Huang Congcong , Wang Lianzhou , Hulicova‐Jurcakova Denisa
Published: November 2014

Phosphorus‐doped (P‐doped) graphene with the P doping level of 1.30 at % was synthesized by annealing the mixture of graphene and phosphoric acid. The presence of P was confirmed by elemental mapping and X‐ray photoelectron spectroscopy, while the morphology of P‐doped graphene was revealed by using scanning electron microscopy and transmission electron microscopy. To investigate the effect of P doping, the electrochemical properties of P‐doped graphene were tested as a supercapacitor electrode in an aqueous electrolyte of 1 M H2SO4. The results showed that doping of P in graphene exhibited significant improvement in terms of specific capacitance and cycling stability, compared with undoped graphene electrode. More interestingly, the P‐doped graphene electrode can survive at a wide voltage window of 1.7 V with only 3 % performance degradation after 5000 cycles at a current density of 5 A g−1, providing a high energy density of 11.64 Wh kg−1 and a high power density of 831 W kg−1.
Stereo‐ and Regioselective Phyllobilane Oxidation in Leaf Homogenates of the Peace Lily (Spathiphyllum wallisii): Hypothetical Endogenous Path to Yellow Chlorophyll Catabolites
Authors: Vergeiner Clemens , Ulrich Markus , Li Chengjie , Liu Xiujun , Müller Thomas , Kräutler Bernhard
Published: November 2014

In senescent leaves, chlorophyll typically is broken down to colorless and essentially photo‐inactive phyllobilanes, which are linear tetrapyrroles classified as “nonfluorescent” chlorophyll catabolites (NCCs) and dioxobilane‐type NCCs (DNCCs). In homogenates of senescent leaves of the tropical evergreen Spathiphyllum wallisii, when left at room temperature and extracted with methanol, the major endogenous, naturally formed NCC was regio‐ and stereoselectively oxidized (in part) to a mixture of its 15‐hydroxy and 15‐methoxy derivative. In the absence of methanol in the extract, only the 15‐OH‐NCC was observed. The endogenous oxidation process depended upon molecular oxygen. It was inhibited by carbon monoxide, as well as by keeping the leaf homogenate and extract at low temperatures. The remarkable “oxidative activity” was inactivated by heating the homogenate for 10 min at 70 °C. Upon addition of a natural epimeric NCC (epiNCC) to the homogenate of senescent or green Sp. wallisii leaves at room temperature, the exogenous epiNCC was oxidized regio‐ and stereoselectively to 15‐OH‐epiNCC and 15‐OMe‐epiNCC. The identical two oxidized epiNCCs were also obtained as products of the oxidation of epiNCC with dicyanodichlorobenzoquinone (DDQ). Water elimination from 15‐OH‐epiNCC occurred readily and gave a known “yellow” chlorophyll catabolite (YCC). The endogenous oxidation process, described here, may represent the elusive natural path from the colorless NCCs to yellow and pink coloured phyllobilins, which were found in (extracts of) some senescent leaves.
Mononuclear Iridium Dinitrogen Complexes Bonded to Zeolite HY
Authors: Yang Dong , Chen Mingyang , Martinez‐Macias Claudia , Dixon David A. , Gates Bruce C.
Published: November 2014

The adsorption of N2 on structurally well‐defined dealuminated HY zeolite‐supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273–373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.
Proton‐Induced Generation of Remote N‐Heterocyclic Carbene–Ru Complexes
Authors: Fukushima Takashi , Fukuda Ryoichi , Kobayashi Katsuaki , Caramori Giovanni F. , Frenking Gernot , Ehara Masahiro , Tanaka Koji
Published: November 2014

The proton‐induced RuC bond variation, which was previously found to be relevant in the water oxidation, has been investigated by using cyclometalated ruthenium complexes with three phenanthroline (phen) isomers. The designed complexes, [Ru(bpy)2(1,5‐phen)]+ ([2]+), [Ru(bpy)2(1,6‐phen)]+ ([3]+), and [Ru(bpy)2(1,7‐phen)]+ ([4]+) were newly synthesized and their structural and electronic properties were analyzed by various spectroscopy and theoretical protocols. Protonation of [4]+ triggered profound electronic structural change to form remote N‐heterocyclic carbene (rNHC), whereas protonation of [2]+ and [3]+ did not affect their structures. It was found that changes in the electronic structure of phen beyond classical resonance forms control the rNHC behavior. The present study provides new insights into the ligand design of related ruthenium catalysts.
Aggregation‐Induced Emission Rotors: Rational Design and Tunable Stimuli Response
Authors: Li Jie , Zhang Yang , Mei Ju , Lam Jacky W. Y. , Hao Jianhua , Tang Ben Zhong
Published: November 2014

A novel molecular design strategy is provided to rationally tune the stimuli response of luminescent materials with aggregation‐induced emission (AIE) characteristics. A series of new AIE‐active molecules (AIE rotors) are prepared by covalently linking different numbers of tetraphenylethene moieties together. Upon gradually increasing the number of rotatable phenyl rings, the sensitivity of the response of the AIE rotors to viscosity and temperature is significantly enhanced. Although the molecular size is further enlarged, the performance is only slightly improved due to slightly increased effective rotors, but with largely increased rotational barriers. Such molecular engineering and experimental results offer more in‐depth insight into the AIE mechanism, namely, restriction of intramolecular rotations. Notably, through this rational design, the AIE rotor with the largest molecular size turns out to be the most viscosensitive luminogen with a viscosity factor of up to 0.98.
Selective and Scalable Synthesis of Trifluoromethanesulfenamides and Fluorinated Unsymmetrical Disulfides using a Shelf‐Stable Electrophilic SCF3 Reagent
Authors: Pluta Roman , Rueping Magnus
Published: November 2014

The chemoselective trifluoromethylthiolation of nitrogen nucleophiles and thiols using N‐(trifluoromethylthio)phthalimide under mild, metal‐free conditions is described. A series of trifluoromethanesulfenamides and unsymmetrical disulfides is prepared from the corresponding aliphatic and aromatic amines and thiols in good yields. The reactions are operationally simple and tolerate a wide variety of functional groups. Trifluoromethanesulfenamides and disulfides belong to interesting classes of organic molecules which possess remarkable properties for medicinal and agrochemical applications.
Regioselective Synthesis of Aurone Derivatives via PBu3‐Catalyzed Cyclization of 2‐Alkynoylphenols
Authors: Liu Changqing , Zhang Zhannan , Zhang Jitan , Liu Xing , Xie Meihua
Published: November 2014

Aurone derivatives were synthesized in good to high yields by PBu3‐catalyzed intramolecular 5‐exo cyclization of 2‐alkynoylphenols. The reaction proceeds in high regioselectivity without forming 6‐endo cyclization products.
Hydrocyanation of Unsaturated Imines Using Potassium Hexacyanoferrate(II) as a Cyanide Source
Authors: Li Zheng , Wen Fei , Yang Jingya
Published: November 2014

An efficient method for the hydrocyanation of unsaturated imines to synthesize β,γ‐unsaturated α‐aminonitriles by a one‐pot two‐step procedure using potassium hexacyanoferrate(II) as a cyanide source and benzoyl chloride as a promoter under catalyst‐free condition is described. The advantages of this protocol are the use of a nontoxic, nonvolatile and inexpensive cyanating agent, no use of transition metal catalysts, high yield and simple work‐up procedure.
Copper‐Catalyzed Cyanations of Aromatic Bromides with Benzoyl Cyanide
Authors: Wang Liang , Pan Liang , Chen Qun , He Mingyang
Published: November 2014

Aromatic nitriles were synthesized through copper‐catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source. A series of functional groups were tolerated under the reaction conditions to provide the products in good yields. Moreover, this protocol avoids using of highly toxic alkali cyanides and expensive palladium catalysts.
Neuroarchitecture and neuroanatomy of the Drosophila central complex: A GAL4‐based dissection of protocerebral bridge neurons and circuits
Authors: Wolff Tanya , Iyer Nirmala A. , Rubin Gerald M.
Published: November 2014

Insects exhibit an elaborate repertoire of behaviors in response to environmental stimuli. The central complex plays a key role in combining various modalities of sensory information with an insect's internal state and past experience to select appropriate responses. Progress has been made in understanding the broad spectrum of outputs from the central complex neuropils and circuits involved in numerous behaviors. Many resident neurons have also been identified. However, the specific roles of these intricate structures and the functional connections between them remain largely obscure. Significant gains rely on obtaining a comprehensive catalog of the neurons and associated GAL4 lines that arborize within these brain regions, and on mapping neuronal pathways connecting these structures. To this end, small populations of neurons in the Drosophila melanogaster central complex were stochastically labeled using the multicolor flip‐out technique and a catalog was created of the neurons, their morphologies, trajectories, relative arrangements, and corresponding GAL4 lines. This report focuses on one structure of the central complex, the protocerebral bridge, and identifies just 17 morphologically distinct cell types that arborize in this structure. This work also provides new insights into the anatomical structure of the four components of the central complex and its accessory neuropils. Most strikingly, we found that the protocerebral bridge contains 18 glomeruli, not 16, as previously believed. Revised wiring diagrams that take into account this updated architectural design are presented. This updated map of the Drosophila central complex will facilitate a deeper behavioral and physiological dissection of this sophisticated set of structures. J. Comp. Neurol. 523:997–1037, 2015. © 2014 Wiley Periodicals, Inc.
Semantic client‐side approach for web personalization of SaaS‐based cloud services
Authors: Fan Haolong , Hussain Farookh Khadeer , Hussain Omar Khadeer
Published: November 2014

The demand of software as a service (SaaS)‐based services delivering computing resources as on‐demand software is on the rise in the IT industry. However, one of the drawbacks of the existing SaaS services is that they offer limited or no personalization of the services provided according to the users profile. Personalization as mentioned in the literature has been a key driver in the adoption and usage of various applications and in providing better service experience to the users. However, overwhelming majority of such personalized services rely extensively on the server side, without embracing fast‐developing client‐side technologies. In SaaS‐based cloud services, utilizing this technology is necessary considering their limited processing specifications. Approaches have been proposed in the literature that focus on cloud‐based personalization using client‐side technologies but none of them actually address all the different components that are required for a scalable and holistic personalization framework for SaaS‐based cloud services. In this paper, we address this drawback by proposing a user‐focussed personalization framework. Our proposed framework takes advantage of powerful client side browsers to reduce server overheads, ameliorate performance, establish high intelligence and enrich data processing. To validate and demonstrate the applicability of our framework, we build a prototype model and compare its performance against existing approaches using different metrics. Copyright © 2014 John Wiley & Sons, Ltd.
Toward memory scalability of GYSELA code for extreme scale computers
Authors: Rozar Fabien , Latu Guillaume , Roman Jean , Grandgirard Virginie
Published: November 2014

Gyrokinetic simulations lead to huge computational needs. Up to now, the Semi‐Lagrangian code GYSELA performed large simulations using up to 65k cores. To understand more accurately the nature of plasma turbulence, finer resolutions are necessary, which make GYSELA a good candidate to exploit the computational power of future extreme scale machines. Among the Exascale challenges, the less memory per core is one of the most critical issues. This paper deals with memory management in order to reduce the memory peak and presents a general method to understand the memory behavior of an application when dealing with very large meshes. This enables us to extrapolate the behavior of GYSELA for expected capabilities of extreme scale machines. Copyright © 2014 John Wiley & Sons, Ltd.
Linear Free‐Energy Relationships between a Single Gas‐Phase Ab Initio Equilibrium Bond Length and Experimental pKaValues in Aqueous Solution
Authors: Alkorta Ibon , Popelier Paul L. A.
Published: November 2014

Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKavalues in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups,meta/parasubstitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKavalues can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKaunits for 5 drug molecules.
Mechanistic Insights into Phenol Oxidation by a Copper(II) Complex of a Pyridine‐ and Amide‐Containing Copolymer in an Aqueous Medium
Authors: Lykourinou Vasiliki , Ming Li‐June
Published: November 2014

A CuII complex of a pyridine‐ and amide‐containing copolymer (Cu‐P1) exhibits effective activity toward phenol hydroxylation in 50 % aqueous methanol solution at apparent pH 8.0 and 25 °C. The complex shows significant first‐order rate accelerations of 4.2 × 105 and 1.4 × 105 relative to phenol autoxidation in air and in the presence of 20 mM H2O2, respectively. The reaction mechanisms with H2O2 and air are different on the basis of (a) the different activity profiles for Cu binding, (b) the different deuterium kinetic isotope effects (2.8 in 20 mM H2O2 and 1.2 aerobically), and (c) the formation of a dinuclear substrate–(Cu‐P1) complex with H2O2 but a mononuclear one aerobically. The mechanism in the presence of H2O2 is consistent with that of the type‐3 dicopper tyrosinase. Although oxidized di‐CuII tyrosinase can only use H2O2 for phenol hydroxylation, CuII‐P1 can use either air or H2O2 for this process. The studies herein introduce a versatile chemical system for the further exploration of Cu–oxygen chemistry and other types of metal‐centered chemistry and for the aerobic degradation of aromatic compounds in environmental and green chemistry.
3d Metal Complexes Supported by a Bis(imidazolin‐2‐imino)pyridine Pincer Ligand – Synthesis, Structural Characterisation, and Magnetic Properties
Authors: Filimon Sabina‐Alexandra , Petrovic Dejan , Volbeda Jeroen , Bannenberg Thomas , Jones Peter G. , Freiherr von Richthofen Carl‐Georg , Glaser Thorsten , Tamm Matthias
Published: November 2014

The coordination chemistry of the tridentate pincer ligand TLtBu, which contains two electron‐rich imidazolin‐2‐imine moieties, has been explored. The reaction of TLtBu with metal dihalides gave complexes of the general formula [(TLtBu)MX2] (M = Mn, Fe, Co, Ni; X = Cl, Br). These complexes were characterized by X‐ray diffraction analysis, which showed them to have different geometries in the solid state. Although [(TLtBu)MnCl2] (1) is best described as distorted square‐pyramidal, the complexes [(TLtBu)FeCl2] (2) and [(TLtBu)CoCl2] (3) show distorted tetrahedral geometries with the TLtBu ligand bound in a κ2 fashion and one of its imidazolin‐2‐imine fragments not coordinated to the metal atom. [(TLtBu)NiBr]Br (4) crystallizes with a slightly distorted square‐planar cation. The reaction of the triflate (OTf) salts [M(OTf)2·nMeCN] (M = Mn, n = 1; M = Fe, Co, n = 2; OTf = CF3SO3) with TLtBu resulted in [(TLtBu)M(OTf)][OTf] (M = Mn, 5; M = Fe, 6) and [(TLtBu)Co(NCMe)][OTf]2 (7). Complexes 6 and 7 were characterized by X‐ray diffraction analysis, and both showed distorted square‐planar geometries. Magnetic measurements of 5, 6 and 7 showed them to possess a S = 5/2, 2 and 1/2 ground states, respectively. The bromide ions in complex 4 were exchanged by reaction with AgBF4 to afford [(TLtBu)Ni(NCMe)][BF4]2 (8), which showed a distorted square‐planar geometry in the solid state. The reactions of 1 and 6 with AgOTf resulted in the oxidation of the complexes and the formation of [(TLtBu)MnCl(OTf)][OTf] (9) and [(TLtBu)Fe(OTf)2][OTf] (10), respectively. Complexes 9 and 10 both display distorted square‐pyramidal geometries in the solid state. The ground state of 10 was found to be S = 5/2 by superconducting quantum interference device (SQUID) magnetometry measurements. The oxidation of 5, 6 and 7 with the iodosobenzene derivative (tBuSO2)C6H4IO was investigated. Although the reactions of 6 and 7 gave no evidence for the formation of transient oxo species, crystals were obtained from the reaction of 5. These crystals showed the formation of [TLtBu*Mn(OH)](OTf)2 (11), in which one of the tBu groups of the TLtBu ligand has undergone a C–H activation by a putative MnIV=O bond. The complex shows a distorted square‐pyramidal geometry in the solid state, and the carbon atom of the CH‐activated tBu group occupies the apical position.
Synthesis and Characterization of Diaminobisfuroxane
Authors: Fischer Dennis , Klapötke Thomas M. , Stierstorfer Jörg
Published: November 2014

The synthesis of 3,3′‐diamino‐4,4′‐bisfuroxane and its isomer 4,4′‐diamino‐3,3′‐bisfuroxane was explored for the first time. In addition, the structure of highly dense (2.007 g cm–3 at 100 K) and energetic 4,4′‐dinitro‐3,3′‐bisfuroxane was determined. The energetic properties of the compounds, including their thermal behavior and sensitivities, were determined, and their heat of formation and explosive properties were calculated.
No effects of hydrocortisone and dexamethasone on pain sensitivity in healthy individuals
Authors: Wingenfeld K. , Wolf S. , Kunz M. , Krieg J.‐C. , Lautenbacher S.
Published: November 2014

Background

There is some evidence that stress‐induced cortisol increase leads to a decrease in pain, while lowering cortisol levels enhances pain sensitivity, but no study has yet investigated both pharmacological enhancement and reduction of cortisol levels in the same individuals.

Methods

Firstly, we tested in 16 healthy individuals whether the treatment with hydrocortisone and dexamethasone, respectively, results in altered pain thresholds. Secondly, we aimed to test whether hormone effects are different across the pain range by using ratings for pain stimuli with varying intensity; and thirdly, we tested whether cortisol levels influence the discrimination ability for painful stimuli.

Results

Despite substantial effects of dexamethasone and hydrocortisone administration on cortisol levels, no effect of these drugs was seen in terms of pain sensitivity (pain threshold, pain rating, pain discrimination ability), although comprehensively examined. However, in the placebo condition, a significant negative correlation between cortisol and pain thresholds was seen. Similarly, there were also strong negative associations between cortisol levels in the placebo condition and pain thresholds after drug treatment (especially after hydrocortisone).

Conclusion

These findings suggest that short‐term variations of cortisol do not influence pain sensitivity whereas, in general, high levels of cortisol are associated with increased pain sensitivity, at least for weak to moderate stimuli.