bluuebunny/crossref_metadata_2025 huggingface dataset:
RNA and Imidazoquinolines Are Sensed by Distinct TLR7/8 Ectodomain Sites Resulting in Functionally Disparate Signaling Events
Authors: Colak Elif , Leslie Alasdair , Zausmer Kieran , Khatamzas Elham , Kubarenko Andriy V. , Pichulik Tica , Klimosch Sascha N. , Mayer Alice , Siggs Owen , Hector Andreas , Fischer Roman , Klesser Benedikt , Rautanen Anna , Frank Martin , Hill Adrian V. S. , Manoury Bénédicte , Beutler Bruce , Hartl Dominik , Simmons Alison , Weber Alexander N. R.
Published: May 2014

TLRs 7 and 8 are pattern recognition receptors controlling antiviral host defense or autoimmune diseases. Apart from foreign and host RNA, synthetic RNA oligoribonucleotides (ORN) or small molecules of the imidazoquinoline family activate TLR7 and 8 and are being developed as therapeutic agonists. The structure-function relationships for RNA ORN and imidazoquinoline sensing and consequent downstream signaling by human TLR7 and TLR8 are unknown. Proteome- and genome-wide analyses in primary human monocyte-derived dendritic cells here showed that TLR8 sensing of RNA ORN versus imidazoquinoline translates to ligand-specific differential phosphorylation and transcriptional events. In addition, TLR7 and 8 ectodomains were found to discriminate between RNA ORN and imidazoquinolines by overlapping and nonoverlapping recognition sites to which murine loss-of-function mutations and human naturally occurring hyporesponsive polymorphisms map. Our data suggest TLR7 and TLR8 can signal in two different “modes” depending on the class of ligand. Considering RNA ORN and imidazoquinolines have been regarded as functionally interchangeable, our study highlights important functional incongruities whose understanding will be important for developing TLR7 or 8 therapeutics with desirable effector and safety profiles for in vivo application.
Effect of CDR3 Sequences and Distal V Gene Residues in Regulating TCR–MHC Contacts and Ligand Specificity
Authors: Stadinski Brian D. , Trenh Peter , Duke Brian , Huseby Priya G. , Li Guoqi , Stern Lawrence J. , Huseby Eric S.
Published: May 2014

The mature T cell repertoire has the ability to orchestrate immunity to a wide range of potential pathogen challenges. This ability stems from thymic development producing individual T cell clonotypes that express TCRs with unique patterns of Ag reactivity. The Ag specificity of TCRs is created from the combinatorial pairing of one of a set of germline encoded TCR Vα and Vβ gene segments with randomly created CDR3 sequences. How the amalgamation of germline encoded and randomly created TCR sequences results in Ag receptors with unique patterns of ligand specificity is not fully understood. Using cellular, biophysical, and structural analyses, we show that CDR3α residues can modulate the geometry in which TCRs bind peptide–MHC (pMHC), governing whether and how germline encoded TCR Vα and Vβ residues interact with MHC. In addition, a CDR1α residue that is positioned distal to the TCR–pMHC binding interface is shown to contribute to the peptide specificity of T cells. These findings demonstrate that the specificity of individual T cell clonotypes arises not only from TCR residues that create direct contacts with the pMHC, but also from a collection of indirect effects that modulate how TCR residues are used to bind pMHC.
TREX1 Deficiency Triggers Cell-Autonomous Immunity in a cGAS-Dependent Manner
Authors: Ablasser Andrea , Hemmerling Inga , Schmid-Burgk Jonathan L. , Behrendt Rayk , Roers Axel , Hornung Veit
Published: May 2014

Cytosolic detection of DNA is crucial for the initiation of antiviral immunity but can also cause autoimmunity in the context of endogenous nucleic acids being sensed. Mutations in the human 3′ repair exonuclease 1 (TREX1) have been linked to the type I IFN–associated autoimmune disease Aicardi–Goutières syndrome. The exact mechanisms driving unabated type I IFN responses in the absence of TREX1 are only partly understood, but it appears likely that accumulation of endogenous DNA species triggers a cell-autonomous immune response by activating a cytosolic DNA receptor. In this article, we demonstrate that knocking out the DNA sensor cyclic GMP–AMP synthase completely abrogates spontaneous induction of IFN-stimulated genes in TREX1-deficient cells. These findings indicate a key role of cyclic GMP–AMP synthase for the initiation of self-DNA–induced autoimmune disorders, thus providing important implications for novel therapeutic approaches.
European sea bass, Dicentrarchus labrax, in a changing ocean
Authors: Pope E. C. , Ellis R. P. , Scolamacchia M. , Scolding J. W. S. , Keay A. , Chingombe P. , Shields R. J. , Wilcox R. , Speirs D. C. , Wilson R. W. , Lewis C. , Flynn K. J.
Published: May 2014

Abstract. Ocean acidification, caused by rising concentrations of carbon dioxide (CO2), is widely considered to be a major global threat to marine ecosystems. To investigate the potential effects of ocean acidification on the early life stages of a commercially important fish species, European sea bass (Dicentrarchus labrax), 12 000 larvae were incubated from hatch through metamorphosis under a matrix of two temperatures (17 and 19 °C) and two seawater pCO2 levels (ambient and 1,000 μatm) and sampled regularly for 42 days. Calculated daily mortality was significantly affected by both temperature and pCO2, with both increased temperature and elevated pCO2 associated with lower daily mortality and a significant interaction between these two factors. There was no significant pCO2 effect noted on larval morphology during this period but larvae raised at 19 °C possessed significantly larger eyes and lower carbon:nitrogen ratios at the end of the study compared to those raised under 17 °C. Similarly, when the incubation was continued to post-metamorphic (juvenile) animals (day 67–69), fish raised under a combination of 19 °C and 1000 μatm pCO2 were significantly heavier. However, juvenile D. labrax raised under this combination of 19 °C and 1000 μatm pCO2 also exhibited lower aerobic scopes than those incubated at 19 °C and ambient pCO2. Most studies investigating the effects of near-future oceanic conditions on the early life stages of marine fish have used incubations of relatively short durations and suggested that these animals are resilient to ocean acidification. Whilst the increased survival and growth observed in this study supports this view, we conclude that more work is required to investigate whether the differences in juvenile physiology observed in this study manifest as negative impacts in adult fish.
Australian net (1950s–1990) soil organic carbon erosion: implications for CO2 emission and land–atmosphere modelling
Authors: Chappell A. , Webb N. P. , Viscarra Rossel R. A. , Bui E.
Published: May 2014

Abstract. The debate about soil erosion substantially offsetting fossil fuel emissions and acting as an important source or sink of CO2 remains unresolved. There is little historical land use and management context to this debate which is central to Australia's recent past of European settlement, agricultural expansion and agriculturally-induced soil erosion. We use "catchment" scale (∼25 km2) estimates of 137Cs-derived net (1950s–1990) soil redistribution of all processes (wind, water and tillage) to calculate the net soil organic carbon (SOC) redistribution across Australia. We approximate the selective removal of SOC at net eroding locations and SOC enrichment of transported sediment and net depositional locations. We map net (1950s–1990) SOC redistribtion across Australia and estimate erosion by all processes ∼4 Tg SOC yr−1 which represents a~loss of ∼2% of the total carbon stock (0–10 cm) of Australia. Assuming this net SOC loss is mineralised, the flux (∼15 Tg CO2-e yr−1) represents an omitted 12% of CO2-e emissions from all carbon pools in Australia. Although a small source of uncertainty in the Australian carbon budget, the mass flux interacts with energy and water fluxes and its omission from land surface models likely creates more uncertainty than has been previously recognised.
Radiative forcings for 28 potential Archean greenhouse gases
Authors: Byrne B. , Goldblatt C.
Published: May 2014

Abstract. Despite reduced insolation in the late Archean, evidence suggests a warm climate which was likely sustained by a stronger greenhouse effect, the so-called Faint Young Sun Problem (FYSP). CO2 and CH4 are generally thought to be the mainstays of this enhanced greenhouse, though many other gases have been proposed. We present high accuracy radiative forcings for CO2, CH4 and 26 other gases, performing the radiative transfer calculations at line-by-line resolution and using HITRAN 2012 line data for background pressures of 0.5, 1, and 2 bar. For CO2 to resolve the FYSP alone, 0.21 bar is needed with 0.5 bar of atmospheric pressure, 0.13 bar with 1 bar of atmospheric pressures, or 0.07 bar with 2 bar of atmospheric pressure. For CH4, we find that near-infrared absorption is much stronger than previously thought, arising from updates to the HITRAN database. CH4 radiative forcing peaks at 10.3, 9, or 8.3 W m−2 for background pressures of 0.5, 1 or 2 bar, likely limiting the utility of CH4 for warming the Archean. For the other 26 HITRAN gases, radiative forcings of up to a few to 10 W m−2 are obtained from concentrations of 0.1–1 ppmv for many gases. We further calculate the reduction of radiative forcing due to gas overlap for the 20 strongest gases. We recommend the forcings provided here be used both as a first reference for which gases are likely good greenhouse gases, and as a standard set of calculations for validation of radiative forcing calculations for the Archean.
Pliocene diatom and sponge spicule oxygen isotope ratios from the Bering Sea: isotopic offsets and future directions
Authors: Snelling A. M. , Swann G. E. A. , Pike J. , Leng M. J.
Published: May 2014

Abstract. Oxygen isotope analyses of different size fractions of Pliocene diatoms (δ18Odiatom) from the Bering Sea show no evidence of an isotope offset and support the use of bulk diatom species samples for palaeoceanographic reconstructions. Additional samples containing concentrations of sponge spicules produce δ18O values several per mille lower than δ18Odiatom with a calculated mean offset of 3.6‰ ± 0.7. This difference is significantly greater than modern day variations in water δ18O through the regional water column. Despite the potential for oxygen isotope disequilibrium within δ18Osponge, there appears to be some similarity between δ18Osponge and a global stacked benthic δ18Oforam record. This highlights the potential for δ18Osponge in palaeoenvironmental research at sites where carbonates are not readily preserved.
Simulating lightning into the RAMS model: implementation and preliminary results
Authors: Federico S. , Avolio E. , Petracca M. , Panegrossi G. , Sanò P. , Casella D. , Dietrich S.
Published: May 2014

Abstract. This paper shows the results of a tailored version of a previously published methodology, designed to simulate lightning activity, implemented into the Regional Atmospheric Modeling System (RAMS). The method gives the flash density at the resolution of the RAMS grid-scale allowing for a detailed analysis of the evolution of simulated lightning activity. The system is applied in detail to two case studies occurred over the Lazio Region, in Central Italy. Simulations are compared with the lightning activity detected by the LINET network. The cases refer to two thunderstorms of different intensity. Results show that the model predicts reasonably well both cases and that the lightning activity is well reproduced especially for the most intense case. However, there are errors in timing and positioning of the convection, whose magnitude depends on the case study, which mirrors in timing and positioning errors of the lightning distribution. To assess objectively the performance of the methodology, standard scores are presented for four additional case studies. Scores show the ability of the methodology to simulate the daily lightning activity for different spatial scales and for two different minimum thresholds of flash number density. The performance decreases at finer spatial scales and for higher thresholds. The comparison of simulated and observed lighting activity is an immediate and powerful tool to assess the model ability to reproduce the intensity and the evolution of the convection. This shows the importance of the use of computationally efficient lightning schemes, such as the one described in this paper, in forecast models.
Parameterization of atmosphere–surface exchange of CO2 over sea ice
Authors: Sørensen L. L. , Jensen B. , Glud R. N. , McGinnis D. F. , Sejr M. K. , Sievers J. , Søgaard D. H. , Tison J.-L. , Rysgaard S.
Published: May 2014

Abstract. We suggest the application of a flux parameterization commonly used over terrestrial areas for calculation of CO2 fluxes over sea ice surfaces. The parameterization is based on resistance analogy. We present a concept for parameterization of the CO2 fluxes over sea ice suggesting to use properties of the atmosphere and sea ice surface that can be measured or calculated on a routine basis. Parameters, which can be used in the conceptual model, are analysed based on data sampled from a seasonal fast-ice area, and the different variables influencing the exchange of CO2 between the atmosphere and ice are discussed. We found the flux to be small during the late winter with fluxes in both directions. Not surprisingly we find that the resistance across the surface controls the fluxes and detailed knowledge of the brine volume and carbon chemistry within the brines as well as knowledge of snow cover and carbon chemistry in the ice are essential to estimate the partial pressure of pCO2 and CO2 flux. Further investigations of surface structure and snow cover and driving parameters such as heat flux, radiation, ice temperature and brine processes are required to adequately parameterize the surface resistance.
The Federal Reserve, the Global Monetary Regime, and Real-World Economic Justice
Authors: Feldmann John
Published: May 2014

There are debates going on right now on global economic justice in two separate disciplines—political philosophy and monetary economics. Both concern the same fundamental issue: whether, and how much, the institutions and peoples of one country should be responsible for and take account of the consequences of their actions on other countries. The debate in political philosophy involves whether there even exists a working standard of global economic justice. This debate is being carried on between the “statists,” who see justice as a political standard, and the “cosmopolitans,” who argue that global justice has universal applicability. The debate in monetary economics involves whether the monetary policies of the dominant reserve central bank(s) should be concerned with and take into account the harmful consequences of their polices on the peoples and institutions of the periphery countries. The developing countries advance the view that the reserve currency central banks should design their monetary policies to avoid any harm they may be causing around the globe—basically representing the cosmopolitan view. The position of the U.S. Federal Reserve, the dominant central bank and the focus of criticism, is that any harm caused are not necessarily their responsibility—basically the statist view. In examining the monetary economics debate I present the claims of the harmful externalities of U.S. monetary policy and consider the defenses of the Federal Reserve to these charges. I argue that the U.S. Federal Reserve has a special obligation as the dominant reserve currency bank to evaluate policy consequences by justice standards and that the failure to do so puts its legitimacy at risk.
Compartmentalization and contextual issues: The neglected aspects of engineering education
Authors: Pervez Tasneem , Al-Harthy Ali S.
Published: May 2014

The existing engineering programs in the Gulf region, to some extent, over emphasize or underemphasize the two important aspects namely compartmentalization and contextual issues. Both topics are important, intertwined and need to be adequately and properly addressed by the engineering educators to produce globally competent engineers. There is a growing need for engineers who recognize the complexities of global and societal issues and respond to those complex issues with the solutions they develop. This paper presents authors' thought to explain the compartmentalization and contextual issues in regional engineering curriculum and its delivery and how it can be improved to attain global competitiveness.
Industrial engineers articulate their critical thinking for problem solving via the D.R.I.V.E.S. model
Authors: Sawhney Rupy , de Anda Enrique Macias
Published: May 2014

Industrial engineers face a challenge to develop sustainable continuous improvement implementations, to help businesses change and adapt to continual survival challenges. Recent industrial engineering graduates face difficulties in structuring their acquired knowledge from an open-ended problem solving perspective. Leadership at Boeing is determined by the ability to define knowledge, model and mentor/teach others that knowledge. By this definition, industrial engineers fall short on their ability to teach others their problem solving process. This paper first provides a framework for a set of attributes, defined to establish the core elements of what industrial engineers must learn, practice and develop for sustainable solutions, to later introduce the D.R.I.V.E.S. model as a structured methodology for continuous improvement, using different industrial engineering tools to narrow down open-ended problems into a sequence of steps to propose the right set of solutions and ensure sustainable improvement implementations.
The significance of industry experience in civil engineering education
Authors: Shaaban Khaled Salah
Published: May 2014

Students pursuing their civil engineering degree usually learn the theory part in class but may struggle relating theory to practice if the instructor have no industry experience. Engineering graduates can benefit more when civil engineering courses are taught by instructors that have both academic and practical experience. An instructor with industry experience can motivate students, enable them to relate what was learned in the class with the real world, and allow them to start developing their own engineering judgment, which is essential for the successful practice of civil engineering. The paper discusses the importance of practical experience in civil engineering education, problems facing practical teaching, and successful practices in practical teaching.
Research Note: Who is the Charter Passenger? Characteristics and Attitudes of the Least-Known Passenger
Authors: Castillo-Manzano José I. , López-Valpuesta Lourdes
Published: May 2014

Despite the fact that charter flights have become a hybrid model between the low-cost carriers and the network carriers, the charter passenger's profile presents important differences from those of the passengers of the other two types of airline. This article analyses those differences. The authors use a multinomial logit model and a broad database of almost 40,000 passengers. Their results break with certain stereotypical assumptions, such as that charter passengers are low-income, that they use the services of travel agencies to a greater degree, or that they show a clear bias for travel for vacation purposes. Their profile is of infrequent flyers with a longer waiting time before boarding, although this does not mean that they make more purchases at the airport. Furthermore, they look to travel to more remote destinations, with no intermediate stopovers, which are not usually served by the low-cost carriers, as a result of which they have a greater presence at hub airports.
The dispersal of Allan Cunningham's botanical collections
Authors: Orchard Anthony
Published: May 2014

Allan Cunningham’s herbarium collections are known to be distributed in at least 26 institutions world-wide. Many passed through several hands before being lodged in an official herbarium. The history of their collection, Cunningham’s numbering practices, and the intricate web of distribution of specimens through the hands of friends, colleagues and dealers is traced from letters, published accounts and the multifarious labels appearing on the herbarium sheets themselves. Particular attention is paid to Cunningham’s Asteraceae used by Candolle in the Prodromus, as these bear different numbers in Geneva (G, G-DC), Kew (K) and the Natural History Museum (BM) herbaria, and in some others. For many of these collections it has been possible to reconcile these differences, leading to the identification of hitherto unrecognised Type material. Many of the different kinds of labels attached to Cunningham specimens are illustrated, and interpreted. A brief synopsis is provided of the distribution of some of his other collections, of mammals, birds, reptiles, insects and artefacts. Two Appendices are provided: one listing Cunningham's Asteraceae donation to Candolle, with details of surviving holdings in various herbaria, and the other a list of specimens given by Cunningham to the captain of the ship L’Héroine for the French government.
Eruptive timing and 200 year episodicity at 92°W on the hot spot‐influenced Galapagos Spreading Center derived from geomagnetic paleointensity
Authors: Bowles Julie A. , Colman Alice , McClinton J. Timothy , Sinton John M. , White Scott M. , Rubin Kenneth H.
Published: May 2014

Eruptive timing in mid‐ocean ridge systems is relatively poorly constrained, despite being an important variable in our understanding of many mid‐ocean ridge processes, including volcanic construction; magma recharge, flux, and storage; and the stability of hydrothermal systems and biological communities. Only a handful of absolute eruption chronologies exist, yet they are essential in understanding how eruptive timing varies with important controlling variables. To construct an eruptive history at one location on the Galapagos Spreading Center, we present age determinations derived from geomagnetic paleointensity. To aid interpretation of the paleointensity data, we also present results from on‐bottom magnetic anomaly measurements and forward modeling of topographic‐induced magnetic anomalies. Anomalies may lead to a 1–2 µT bias in flow‐mean paleointensities, which does not significantly affect the overall interpretation. Paleointensity results for the three youngest sampled units are indistinguishable, consistent with the flows being emplaced in relatively rapid succession. Comparisons with models of geomagnetic field behavior suggest these flows were erupted sometime in the past 100–200 years. The fourth sampled unit has a significantly higher paleointensity, consistent with an age of roughly 400 years. The possible bias in paleointensity data allows for ages as young as ∼50 years for the youngest three flows and 200–400 years for the oldest flow. This age distribution demonstrates an episodicity in the emplacement of the largest flows at this location, with a 200–300 year period of relative quiescence between emplacement of the oldest unit and the three youngest units.
Early Eocene carbon isotope excursions: Evidence from the terrestrial coal seam in the Fushun Basin, Northeast China
Authors: Chen Zuoling , Ding Zhongli , Tang Zihua , Wang Xu , Yang Shiling
Published: May 2014

A series of transient global warming events between 56 and 50 Ma are characterized by a pronounced negative carbon isotope excursion (CIE). However, the documents of these hyperthermals, such as Eocene Thermal Maximum 2 and H2 events, have come chiefly from marine sediments, and their expression in terrestrial organic carbon is still poorly constrained. Here we yield a high‐resolution carbon isotope record of terrestrial organic material from the Fushun Basin, which displays four prominent CIEs with magnitudes larger than 2.5‰. Based on age constraint and comparisons with deep‐sea records, our data provide the first evidence of the four hyperthermals in coal seams and suggest a global significance of these events. Moreover, the difference of CIE magnitudes between marine and terrestrial records shows a significant linear correlation with the marine carbonate CIE, implying that these events are likely attributable to recurring injections of 13C‐depleted carbon from submarine methane hydrates and/or permafrost.
Ionospheric response to the shock and acoustic waves excited by the launch of the Shenzhou 10 spacecraft
Authors: Ding Feng , Wan Weixing , Mao Tian , Wang Min , Ning Baiqi , Zhao Biqiang , Xiong Bo
Published: May 2014

We used a dense GPS network in China to track the ionospheric response to waves excited by the launch of the rocket that carried Shenzhou 10 spacecraft on 11 June 2013. The long‐distance propagation of shock and acoustic waves were observed on both sides of the rocket's trajectory. On the southern side, the wave structures (characterized by a horizontal extension of ~1400 km and initial amplitudes of 0.3 total electron content unit (TECU) and 0.1 TECU for the shock and acoustic waves, respectively), traveled southwestward a distance of ~1500 km at mean velocities of 1011 m s−1 and 709 m s−1, respectively. On the northern side, northward propagating waves were seen to travel a distance of ~600 km with much smaller amplitudes of less than 0.05 TECU. Subsequent waves with amplitudes of less than 0.02 TECU could also be seen. Clear wave structures were found at a distance of ~600–2000 km from launch site.
Logarithmic radiative effect of water vapor and spectral kernels
Authors: Bani Shahabadi Maziar , Huang Yi
Published: May 2014

Radiative kernels have become a useful tool in climate analysis. A set of spectral kernels is calculated using a moderate resolution atmospheric transmission code MODTRAN and implemented in diagnosing spectrally decomposed global outgoing longwave radiation (OLR) changes. It is found that the effect of water vapor on the OLR is in proportion to the logarithm of its concentration. Spectral analysis discloses that this logarithmic dependency mainly results from water vapor absorption bands (0–560 cm−1 and 1250–1850 cm−1), while in the window region (800–1250 cm−1), the effect scales more linearly to its concentration. The logarithmic and linear effects in the respective spectral regions are validated by the calculations of a benchmark line‐by‐line radiative transfer model LBLRTM. The analysis based on LBLRTM‐calculated second‐order kernels shows that the nonlinear (logarithmic) effect results from the damping of the OLR sensitivity to layer‐wise water vapor perturbation by both intra‐ and inter‐layer effects. Given that different scaling approaches suit different spectral regions, it is advisable to apply the kernels in a hybrid manner in diagnosing the water vapor radiative effect. Applying logarithmic scaling in the water vapor absorption bands where absorption is strong and linear scaling in the window region where absorption is weak can generally constrain the error to within 10% of the overall OLR change for up to eightfold water vapor perturbations.
Ensemble downscaling in coupled solar wind‐magnetosphere modeling for space weather forecasting
Authors: Owens M. J. , Horbury T. S. , Wicks R. T. , McGregor S. L. , Savani N. P. , Xiong M.
Published: May 2014

Advanced forecasting of space weather requires simulation of the whole Sun‐to‐Earth system, which necessitates driving magnetospheric models with the outputs from solar wind models. This presents a fundamental difficulty, as the magnetosphere is sensitive to both large‐scale solar wind structures, which can be captured by solar wind models, and small‐scale solar wind “noise,” which is far below typical solar wind model resolution and results primarily from stochastic processes. Following similar approaches in terrestrial climate modeling, we propose statistical “downscaling” of solar wind model results prior to their use as input to a magnetospheric model. As magnetospheric response can be highly nonlinear, this is preferable to downscaling the results of magnetospheric modeling. To demonstrate the benefit of this approach, we first approximate solar wind model output by smoothing solar wind observations with an 8 h filter, then add small‐scale structure back in through the addition of random noise with the observed spectral characteristics. Here we use a very simple parameterization of noise based upon the observed probability distribution functions of solar wind parameters, but more sophisticated methods will be developed in the future. An ensemble of results from the simple downscaling scheme are tested using a model‐independent method and shown to add value to the magnetospheric forecast, both improving the best estimate and quantifying the uncertainty. We suggest a number of features desirable in an operational solar wind downscaling scheme.
Mass Spectrometry and Gas‐phase Ion Chemistry of Metal–phenolate and Metal–phenol complexes
Authors: P. Palii Sergiu , M. Indricean Constantin , D. Revenco Mihail
Published: May 2014

The current chapter summarizes 276 references to offer an up‐to‐date survey of literature on the mass spectrometry and gas‐phase ion chemistry of phenolate‐ or phenol‐containing metal complexes and their chalcogenide thio‐ and seleno‐analogs. Analytical applications of MS techniques to the characterization of these metal–ligand systems are discussed. The latter include more than 400 species such as mixed‐ligand metal complexes, bifunctional compounds containing organometallic and classical Werner‐type coordination sites, nanoclusters, species with metal–metal bonds, mixed‐metal complexes, etc. Some of them are isomers. The reviewed data provides the reader with a solid foundation for selecting the adequate MS instrumentation in related future studies. Data on gas‐phase ion structure, energetics and reactivity are summarized as well. Circa 150 examples of ion/molecule reactions with the participation of metal‐containing ions and phenol or thiophenol derivatives are examined. Additionally, the review addresses the 3D structural features of several model complexes between metal ions and phenol‐ or thiophenol‐related species as determined from theoretical calculations and IRMPD spectroscopic measurements, as well as their use for elucidation of the nature of metal cation–π interaction or σ‐binding, which mimic the active centers of biomolecular systems.
Physical Activity and Experience of Total Knee Replacement in Patients One to Four Years Postsurgery in the Dominican Republic: A Qualitative Study
Authors: Stenquist Derek S. , Elman Scott A. , Davis Aileen M. , Bogart Laura M. , Brownlee Sarah A. , Sanchez Edward S. , Santiago Adianez , Ghazinouri Roya , Katz Jeffrey N.
Published: May 2014

Objective

Musculoskeletal disorders are the second leading cause of years lived with disability globally. Total knee replacement (TKR) offers patients with advanced arthritis relief from pain and the opportunity to return to physical activity. We investigated the impact of TKR on physical activity for patients in a developing nation.

Methods

As part of the Operation Walk Boston surgical mission program, we interviewed 18 Dominican patients (78% women) who received TKR about their level of physical activity after surgery. Qualitative interviews were conducted in Spanish, and English transcripts were analyzed using content analysis.

Results

Most patients found that TKR increased their participation in physical activities in several life domains, such as occupational or social pursuits. Some patients limited their own physical activities due to uncertainty about medically appropriate levels of joint use and postoperative physical activity. Many patients noted positive effects of TKR on mood and mental health. For most patients in the study, religion offered a framework for understanding their receipt of and experience with TKR.

Conclusion

Our findings underscore the potential of TKR to permit patients in the developing world to return to physical activities. This research also demonstrates the influence of patients' education, culture, and religion on patients' return to physical activity. As the global burden of musculoskeletal disease increases, it is important to characterize the impact of activity limitation on patients' lives in diverse settings and the potential for surgical intervention to ease the burden of chronic arthritis.
Hybrid Interface States and Spin Polarization at Ferromagnetic Metal–Organic Heterojunctions: Interface Engineering for Efficient Spin Injection in Organic Spintronics
Authors: Shi Shengwei , Sun Zhengyi , Bedoya‐Pinto Amilcar , Graziosi Patrizio , Li Xin , Liu Xianjie , Hueso Luis , Dediu Valentin A. , Luo Yi , Fahlman Mats
Published: May 2014

Ferromagnetic metal–organic semiconductor (FM‐OSC) hybrid interfaces have been shown to play an important role for spin injection in organic spintronics. Here, 11,11,12,12‐tetracyanonaptho‐2,6‐quinodimethane (TNAP) is introduced as an interfacial layer in Co‐OSCs heterojunctions with an aim to tune the spin injection. The Co/TNAP interface is investigated by use of X‐ray and ultraviolet photoelectron spectroscopy (XPS/UPS), near edge X‐ray absorption fine structure (NEXAFS) and X‐ray magnetic circular dichroism (XMCD). Hybrid interface states (HIS) are observed at Co/TNAP interfaces, resulting from chemical interactions between Co and TNAP. The energy level alignment at the Co/TNAP/OSCs interface is also obtained, and a reduction of the hole injection barrier is demonstrated. XMCD results confirm sizeable spin polarization at the Co/TNAP hybrid interface.
Behavioral and physiological responses to fruit availability of spider monkeys ranging in a small forest fragment
Authors: Rimbach Rebecca , Link Andrés , Montes‐Rojas Andrés , Di Fiore Anthony , Heistermann Michael , Heymann Eckhard W.
Published: May 2014

Numerous animal species currently experience habitat loss and fragmentation. This might result in behavioral and dietary adjustments, especially because fruit availability is frequently reduced in fragments. Food scarcity can result in elevated physiological stress levels, and chronic stress often has detrimental effects on individuals. Some animal species exhibit a high degree of fission–fusion dynamics, and theory predicts that these species reduce intragroup feeding competition by modifying their subgroup size according to resource availability. Until now, however, there have been few studies on how species with such fission–fission dynamics adjust their grouping patterns and social behavior in small fragments or on how food availability influences their stress levels. We collected data on fruit availability, feeding behavior, stress hormone levels (measured through fecal glucocorticoid metabolites (FGCM)), subgroup size, and aggression for two groups of brown spider monkeys (Ateles hybridus) in a small forest fragment in Colombia and examined whether fruit availability influences these variables. Contrary to our predictions, spider monkeys ranged in smaller subgroups, had higher FGCM levels and higher aggression rates when fruit availability was high compared to when it was low. The atypical grouping pattern of the study groups seems to be less effective at mitigating contest competition over food resources than more typical fission–fusion patterns. Overall, our findings illustrate that the relationship between resource availability, grouping patterns, aggression rates, and stress levels can be more complex than assumed thus far. Additional studies are needed to investigate the long‐term consequences on the health and persistence of spider monkeys in fragmented habitats. Am. J. Primatol. 76:1049–1061, 2014. © 2014 The Authors.American Journal of PrimatologyPublished by Wiley Periodicals, Inc.
Pericellular Hydrogel/Nanonets Inhibit Cancer Cells
Authors: Kuang Yi , Shi Junfeng , Li Jie , Yuan Dan , Alberti Kyle A. , Xu Qiaobing , Xu Bing
Published: May 2014

Fibrils formed by proteins are vital components for cells. However, selective formation of xenogenous nanofibrils of small molecules on mammalian cells has yet to be observed. Here we report an unexpected observation of hydrogel/nanonets of a small D‐peptide derivative in pericellular space. Surface and secretory phosphatases dephosphorylate a precursor of a hydrogelator to trigger the self‐assembly of the hydrogelator and to result in pericellular hydrogel/nanonets selectively around the cancer cells that overexpress phosphatases. Cell‐based assays confirm that the pericellular hydrogel/nanonets block cellular mass exchange to induce apoptosis of cancer cells, including multidrug‐resistance (MDR) cancer cells, MES‐SA/Dx5. Pericellular hydrogel/nanonets of small molecules to exhibit distinct functions illustrates a fundamentally new way to engineer molecular assemblies spatiotemporally in cellular microenvironment for inhibiting cancer cell growth and even metastasis.
A Series of Potent CREBBP Bromodomain Ligands Reveals an Induced‐Fit Pocket Stabilized by a Cation–π Interaction
Authors: Rooney Timothy P. C. , Filippakopoulos Panagis , Fedorov Oleg , Picaud Sarah , Cortopassi Wilian A. , Hay Duncan A. , Martin Sarah , Tumber Anthony , Rogers Catherine M. , Philpott Martin , Wang Minghua , Thompson Amber L. , Heightman Tom D. , Pryde David C. , Cook Andrew , Paton Robert S. , Müller Susanne , Knapp Stefan , Brennan Paul E. , Conway Stuart J.
Published: May 2014

The benzoxazinone and dihydroquinoxalinone fragments were employed as novel acetyl lysine mimics in the development of CREBBP bromodomain ligands. While the benzoxazinone series showed low affinity for the CREBBP bromodomain, expansion of the dihydroquinoxalinone series resulted in the first potent inhibitors of a bromodomain outside the BET family. Structural and computational studies reveal that an internal hydrogen bond stabilizes the protein‐bound conformation of the dihydroquinoxalinone series. The side chain of this series binds in an induced‐fit pocket forming a cation–π interaction with R1173 of CREBBP. The most potent compound inhibits binding of CREBBP to chromatin in U2OS cells.
A Natural‐Product Switch for a Dynamic Protein Interface
Authors: Scheepstra Marcel , Nieto Lidia , Hirsch Anna K. H. , Fuchs Sascha , Leysen Seppe , Lam Chan Vinh , in het Panhuis Leslie , van Boeckel Constant A. A. , Wienk Hans , Boelens Rolf , Ottmann Christian , Milroy Lech‐Gustav , Brunsveld Luc
Published: May 2014

Small ligands are a powerful way to control the function of protein complexes via dynamic binding interfaces. The classic example is found in gene transcription where small ligands regulate nuclear receptor binding to coactivator proteins via the dynamic activation function 2 (AF2) interface. Current ligands target the ligand‐binding pocket side of the AF2. Few ligands are known, which selectively target the coactivator side of the AF2, or which can be selectively switched from one side of the interface to the other. We use NMR spectroscopy and modeling to identify a natural product, which targets the retinoid X receptor (RXR) at both sides of the AF2. We then use chemical synthesis, cellular screening and X‐ray co‐crystallography to split this dual activity, leading to a potent and molecularly efficient RXR agonist, and a first‐of‐kind inhibitor selective for the RXR/coactivator interaction. Our findings justify future exploration of natural products at dynamic protein interfaces.
Total Synthesis of the Biphenyl Alkaloid (−)‐Lythranidine
Authors: Gebauer Konrad , Fürstner Alois
Published: May 2014

A sequence comprising a ring‐closing alkyne metathesis of a propargyl alcohol derivative, followed by a ruthenium‐catalyzed redox isomerization of the derived cycloalkyne and a transannular aza‐Michael addition allowed the formation of the distinguishing piperidine‐metacyclophane framework of the Lythraceum alkaloid lythanidine in a few high‐yielding steps. This application attests to the excellent functional‐group tolerance of a molybdenum alkylidyne complex endowed with triphenylsilanolate ligands, which enabled the macrocyclization even in the presence of protic functionalities, and thus illustrates the power of contemporary catalytic acetylene chemistry for target‐oriented synthesis.
Be2C Monolayer with Quasi‐Planar Hexacoordinate Carbons: A Global Minimum Structure
Authors: Li Yafei , Liao Yunlong , Chen Zhongfang
Published: May 2014

The design of new materials is an important subject in order to attain new properties and applications, and it is of particular interest when some peculiar topological properties such as reduced dimensionality and rule‐breaking chemical bonding are involved. In this work, we designed a novel two‐dimensional (2D) inorganic material, namely Be2C monolayer, by comprehensive density functional theory (DFT) computations. In Be2C monolayer, each carbon atom binds to six Be atoms in an almost planar fashion, forming a quasi‐planar hexacoordinate carbon (phC) moiety. Be2C monolayer has good stability and is the lowest‐energy structure in 2D space confirmed by a global minima search based on the particle‐swarm optimization (PSO) method. As a semiconductor with a direct medium band gap, Be2C monolayer is promising for applications in electronics and optoelectronics.
New nickel(II) diimine complexes bearing phenyl and sec‐phenethyl groups: synthesis, characterization and ethylene polymerization behaviour
Authors: Wang Fuzhou , Yuan Jianchao , Li Qingshan , Tanaka Ryo , Nakayama Yuushou , Shiono Takeshi
Published: May 2014

A series of nickel(II) catalysts containing phenyl and chiral sec‐phenethyl groups, {[(4‐R1‐2‐R2C6H2NC)2Nap]NiBr2} (Nap: 1,8‐naphthdiyl, R1 = Me, R2 = Ph (3a); R1 = Me, R2 = sec‐phenethyl (3b); R1 = Cl, R2 = sec‐phenethyl (3c); R1 = Me, R2 = Me (3d) were synthesized and characterized. All organic compounds were fully characterized by FT‐IR and NMR spectroscopy and elemental analysis. The single crystal for X‐ray crystallography was isolated from 3a in CH2Cl2/n‐hexane under air; the crystal structure showed a binuclear complex 3a′, in which each nickel atom was six‐coordinate. The two nickel atoms together with two bromine atoms form a planar four‐membered ring, with a bromine and H2O axial ligands. These complexes, activated by diethylaluminum chloride and chiral nickel pre‐catalysts rac‐3c, exhibited good activities (up to 2.85 × 106 g PE (mol Ni h bar)−1) for ethylene polymerization, and produced polyethylene products with a high degree of branching (up to 117 branched per 1000 carbons) at high temperature. The type and amount of branches of the polyethylenes obtained were determined by 1H and 13C NMR spectroscopy. Copyright © 2014 John Wiley & Sons, Ltd.
Profiling social networks to provide useful and privacy‐preserving web search
Authors: Viejo Alexandre , Sánchez David
Published: May 2014

Web search engines (WSEs) use search queries to profile users and to provide personalized services like query disambiguation or refinement. These services are valuable because users get an enhanced search experience. However, the compiled user profiles may contain sensitive information that might represent a privacy threat. This issue should be addressed in a way that it also preserves the utility of the profile with regard to search services. State‐of‐the‐art approaches tackle these issues by generating and submitting fake queries that are related to the interests of the user. This technique allows the WSE to only know general (and useful) data while the detailed (and potentially private) data are obfuscated. To build fake queries, these proposals rely on past queries to obtain user interests. However, we argue that this is not always the best strategy and, in this article, we study the use of social networks to gather more accurate user profiles that enable better personalized service while offering a similar, or even better, level of practical privacy. These hypotheses are empirically supported by evaluations using real profiles gathered from Twitter and a set of AOL search queries.
The value of user feedback: Healthcare professionals' comments to the health information provider
Authors: Tang David Li , Bouthillier France , Pluye Pierre , Grad Roland , Repchinsky Carol
Published: May 2014

The construct of value is highly relevant to information. For research on the value of information, Saracevic and Kantor (1997) proposed a framework from a value perspective in philosophy. In this report, we substantiate the framework with an updated review of the literature and demonstrate its applicability to understanding the value of user feedback as one type of information. Our field study, in the setting of a health information provider whose information products serve thousands of Canadian healthcare professionals, provides an example of how this value‐of‐information framework can be operationalized for an organization. In addition to the theoretical and methodological contributions, this research adds to the literature by documenting the way that textual feedback data were used to optimize the content of an information resource. This contrasts with published studies that only dealt with the use of quantitative feedback by information providers not involved in content production.
Towards a framework for untangling complexity: The interprofessional decision‐making model for the complex patient
Authors: Weinberger Hadas , Cohen Jonathan , Tadmor Boaz , Singer Pierre
Published: May 2014

Decision making for the complex patient is challenging for doctors because of increased complexity, such as multiple co‐morbidities and interprofessionality for which evidence‐based literature and guidelines are currently lacking. The consequent uncertainty causes vagueness, threatening patient safety and the quality of care. This article is motivated by the design science paradigm and describes the interprofessional decision‐making model for the complex patient, namely, INDECO along with an example instantiation. Drawing on our experience in an intensive care unit of a tertiary hospital in Israel, the bi‐dimensional view of this model includes the medical‐ and the interprofessional perspective. Retrospective assessment of 3 case studies of complex patients is used for assessing the usefulness of INDECO in decision making. The study reported here draws support from relevant literature, including the information science, information systems, and the medical domains. The findings resonate with emerging research developments focusing on healthcare decision making.
Applications of Chiral Phosphine‐Based Organocatalysts in Catalytic Asymmetric Reactions
Authors: Wei Yin , Shi Min
Published: May 2014

Chiral phosphines are versatile Lewis basic catalysts that are capable of promoting a wide range of asymmetric reactions. In particular, recently designed chiral phosphines based on the concept of bi‐/multifunctionality have been demonstrated to be effective catalysts for many types of asymmetric reactions, such as (aza)‐MBH reactions, cycloaddition reactions, and nucleophilic addition reactions. This short overview summarizes the recent advances in this field and highlights the most‐significant achievements.
Differential Mode Modeling of PMSM for High Frequencies and Harmonic Pulses Calculation
Authors: Adam Ali Ahmed , Gulez Kayhan
Published: May 2014

This work proposes and analyses a model for a cable and permanent magnet synchronous motor to deal with high frequency differential mode components due to IGBT inverter systems. The model permits the study of the differential mode effects separately in the rotor reference frame. The experimental measurements show that the motor differential mode stray capacitances are functions of rotor position. The simulation results of the proposed differential mode circuits, together with the experimental results, show that the level of the differential mode noise currents is of significant value that cannot be ignored. The flow of some differential mode currents in the motor stator windings may contribute to torque pulsations which, require EMI noise filters to be used.