bluuebunny/crossref_metadata_2025 huggingface dataset:
Acidity decline in Antarctic ice cores during the Little Ice Age linked to changes in atmospheric nitrate and sea salt concentrations
Authors: Pasteris Daniel , McConnell Joseph R. , Edwards Ross , Isaksson Elizabeth , Albert Mary R.
Published: April 2014

Acidity is an important chemical variable that impacts atmospheric and snowpack chemistry. Here we describe composite time series and the spatial pattern of acidity concentration (Acy = H+ − HCO3−) during the last 2000 years across the Dronning Maud Land region of the East Antarctic Plateau using measurements in seven ice cores. Coregistered measurements of the major ion species show that sulfuric acid (H2SO4), nitric acid (HNO3), and hydrochloric acid (HCl) determine greater than 98% of the acidity value. The latter, also described as excess chloride (ExCl−), is shown mostly to be derived from postdepositional diffusion of chloride with little net gain or loss from the snowpack. A strong inverse linear relationship between nitrate concentration and inverse accumulation rate provides evidence of spatially homogenous fresh snow concentrations and reemission rates of nitrate from the snowpack across the study area. A decline in acidity during the Little Ice Age (LIA, 1500–1900 Common Era) is observed and is linked to declines in HNO3 and ExCl− during that time. The nitrate decline is found to correlate well with published methane isotope data from Antarctica (δ13CH4), indicating that it is caused by a decline in biomass burning. The decrease in ExCl− concentration during the LIA is well correlated to published sea surface temperature reconstructions in the Atlantic Ocean, which suggests increased sea salt aerosol production associated with greater sea ice extent.
Impact of subgrid‐scale radiative heating variability on the stratocumulus‐to‐trade cumulus transition in climate models
Authors: Xiao Heng , Gustafson William I. , Wang Hailong
Published: April 2014

Subgrid‐scale interactions between turbulence and radiation are potentially important for accurately simulating marine low clouds in climate models. To better understand the impact of these interactions, the Weather Research and Forecasting model is configured for large eddy simulation to study the stratocumulus to trade cumulus (Sc‐to‐Cu) transition. Using the Global Energy and Water Cycle Experiment Atmospheric System Studies composite Lagrangian transition case and the Atlantic Trade Wind Experiment case, it is shown that the lack of subgrid‐scale turbulence‐radiation interaction, as is the case in current generation climate models, accelerates the Sc‐to‐Cu transition. Our analysis suggests that subgrid‐scale turbulence‐radiation interactions in cloud‐topped boundary layers contribute to stronger production of temperature variance, which in turn leads to stronger buoyancy production of turbulent kinetic energy and helps to maintain the Sc cover.
The asymmetry of the climate system's response to solar forcing changes and its implications for geoengineering scenarios
Authors: Schaller N. , Sedláček J. , Knutti R.
Published: April 2014

Motivated by proposals to compensate CO2‐induced warming with a decrease in solar radiation, this study investigates how single‐forcing simulations should be combined to best represent the spatial patterns of surface temperature and precipitation of idealized geoengineering scenarios. Using instantaneous and transient simulations with changing CO2 and solar forcings, we show that a geoengineering scenario, i.e., a scenario where the solar constant is reduced as CO2 concentrations are increased, is better represented by subtracting the response pattern of a solar forcing increase simulation from the response pattern of a CO2 forcing increase simulation, than by adding the response pattern of a solar forcing decrease simulation to a CO2 forcing increase simulation. The reason is a asymmetric response of the climate system to a forcing increase or decrease between both hemispheres. In particular, the Atlantic meridional overturning circulation responds faster to a solar forcing decrease compared to a solar forcing increase. Further, the climate feedbacks are state and region dependent, which is particularly apparent in the polar regions due to the sea ice‐albedo feedback. The importance of understanding the local response of the climate system to geoengineering and single‐forcing scenarios is highlighted, since these aspects are hardly discernible when only global mean values are considered.
Sensitivity of summer stream temperatures to climate variability in the Pacific Northwest
Authors: Luce Charles , Staab Brian , Kramer Marc , Wenger Seth , Isaak Dan , McConnell Callie
Published: April 2014

Estimating the thermal response of streams to a warming climate is important for prioritizing native fish conservation efforts. While there are plentiful estimates of air temperature responses to climate change, the sensitivity of streams, particularly small headwater streams, to warming temperatures is less well understood. A substantial body of literature correlates subannual scale temperature variations in air and stream temperatures driven by annual cycles in solar angle; however, these may be a low‐precision proxy for climate change driven changes in the stream energy balance. We analyzed summer stream temperature records from forested streams in the Pacific Northwest for interannual correlations to air temperature and standardized annual streamflow departures. A significant pattern emerged where cold streams always had lower sensitivities to air temperature variation, while warm streams could be insensitive or sensitive depending on geological or vegetation context. A pattern where cold streams are less sensitive to direct temperature increases is important for conservation planning, although substantial questions may yet remain for secondary effects related to flow or vegetation changes induced by climate change.
A vulnerability driven approach to identify adverse climate and land use change combinations for critical hydrologic indicator thresholds: Application to a watershed in Pennsylvania, USA
Authors: Singh R. , Wagener T. , Crane R. , Mann M. E. , Ning L.
Published: April 2014

Large uncertainties in streamflow projections derived from downscaled climate projections of precipitation and temperature can render such simulations of limited value for decision making in the context of water resources management. New approaches are being sought to provide decision makers with robust information in the face of such large uncertainties. We present an alternative approach that starts with the stakeholder's definition of vulnerable ranges for relevant hydrologic indicators. Then the modeled system is analyzed to assess under what conditions these thresholds are exceeded. The space of possible climates and land use combinations for a watershed is explored to isolate subspaces that lead to vulnerability, while considering model parameter uncertainty in the analysis. We implement this concept using classification and regression trees (CART) that separate the input space of climate and land use change into those combinations that lead to vulnerability and those that do not. We test our method in a Pennsylvania watershed for nine ecological and water resources related streamflow indicators for which an increase in temperature between 3°C and 6°C and change in precipitation between −17% and 19% is projected. Our approach provides several new insights, for example, we show that even small decreases in precipitation (∼5%) combined with temperature increases greater than 2.5°C can push the mean annual runoff into a slightly vulnerable regime. Using this impact and stakeholder driven strategy, we explore the decision‐relevant space more fully and provide information to the decision maker even if climate change projections are ambiguous.
Process‐dependent residual trapping of CO2 in sandstone
Authors: Zuo Lin , Benson Sally M.
Published: April 2014

This paper demonstrates that the nature and extent of residual CO2 trapping depend on the process by which the CO2 phase is introduced into the rock. We compare residual trapping of CO2 in Berea Sandstone by imbibing water into a core containing either exsolved CO2 or CO2 introduced by drainage. X‐ray computed tomography measurements are used to map the spatial distribution of CO2 preimbibition and postimbibition. Unlike during drainage where the CO2 distribution is strongly influenced by the heterogeneity of the rock, the distribution of exsolved CO2 is comparatively uniform. Postimbibition, the CO2 distribution retained the essential features for both the exsolved and drainage cases, but twice as much residual trapping is observed for exsolved CO2 even with similar preimbibition gas saturations. Residually trapped exsolved gas also disproportionately reduced water relative permeability. Development of process‐dependent parameterization will help better manage subsurface flow processes and unlock benefits from gas exsolution.
The Changing Structure of the Maize Seed Industry in Zambia: Prospects for Orange Maize
Authors: Smale Melinda , Simpungwe Eliab , Birol Ekin , Kassie Girma Tesfahun , de Groote Hugo , Mutale Raphael
Published: April 2014

Zambia's maize seed industry is currently one of the strongest and most competitive in Sub‐Saharan Africa. This paper describes the changing structure of the maize seed industry and seed supply chain in Zambia. The aim of the paper is to propose elements of a marketing strategy for seed production and delivery of recently released, provitamin A‐rich, orange maize varieties. Information sources include a thorough review of the literature, a statistical survey of farmers in the major maize‐producing areas of the country, and key informant interviews conducted with seed company representatives. We discuss the merits of two strategies: (1) liberalizing the provision of original orange maize planting material to all seed companies with the aim of maximizing the impact of this public health intervention, and (2) exclusive rights granted to companies with the goals of preserving differentiated products and ensuring standard seed quality to protect the brand. We find that, exclusive or not, risk‐sharing contracts with any company that takes up this product, as well as building and maintaining a unique brand for orange maize would be essential for the success of this product.
Computational screening of porous metal‐organic frameworks and zeolites for the removal of SO2 and NOx from flue gases
Authors: Sun Weizhen , Lin Li‐Chiang , Peng Xuan , Smit Berend
Published: April 2014

Sulfur oxides (SO2) and nitrogen oxides (NOx) are principal pollutants in the atmosphere due to their harmful impact on human health and environment. We use molecular simulations to study different adsorbents to remove SO2 and NOx from flue gases. Twelve representative porous materials were selected as possible candidates, including metal‐organic frameworks, zeolitic imidazolate frameworks, and all‐silica zeolites. Grand canonical Monte Carlo simulations were performed to predict the (mixture) adsorption isotherms to evaluate these selected materials. Both Cu‐BTC and MIL‐47 were identified to perform best for the removal of SO2 from the flue gases mixture. For the removal of NOx, Cu‐BTC was shown to be the best adsorbent. Additionally, concerning the simultaneous removal of SO2, NOx, and CO2, Mg‐MOF‐74 gave the best performance. The results and insights obtained may be helpful to the adsorbents selection in the separation of SO2 and NOx and carbon capture. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2314–2323, 2014
Thermal coupling links to liquid‐only transfer streams: A path for new dividing wall columns
Authors: Madenoor Ramapriya Gautham , Tawarmalani Mohit , Agrawal Rakesh
Published: April 2014

We propose new dividing wall columns (DWCs) that are equivalent to the fully thermally coupled (FTC) configurations. While our method can draw such configurations for any given n‐component mixture (n ≥ 3), we discuss in detail the DWCs for ternary and quaternary feed mixtures. A special feature of all the new DWCs is that during operation, they allow independent control of the vapor flow rate in each partitioned zone of the DWC by means that are external to the column. Because of this feature, we believe that the new arrangements presented in this work will enable the FTC configuration to be successfully implemented and optimally operated as a DWC in an industrial setting for any number of components. Also, interesting column arrangements result when a new DWC drawn for an n‐component mixture is adapted for the distillation of a mixture containing more than n components. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2949–2961, 2014
Cerebrospinal fluid JC virus antibody index for diagnosis of natalizumab‐associated progressive multifocal leukoencephalopathy
Authors: Warnke Clemens , von Geldern Gloria , Markwerth Philipp , Dehmel Thomas , Hoepner Robert , Gold Ralf , Pawlita Michael , Kümpfel Tania , Mäurer Mathias , Stangel Martin , Wegner Florian , Hohlfeld Reinhard , Straeten Vera , Limmroth Volker , Weber Thomas , Hermsen Derik , Kleinschnitz Christoph , Hartung Hans‐Peter , Wattjes Mike P. , Svenningson Anders , Major Eugene , Olsson Tomas , Kieseier Bernd C. , Adams Ortwin
Published: April 2014

Objective

Progressive multifocal leukoencephalopathy (PML), caused by JC virus (JCV), can occur in patients receiving natalizumab for multiple sclerosis (MS). JCV detection by quantitative polymerase chain reaction (qPCR) in cerebrospinal fluid (CSF), or brain biopsy, is required for probable or definite diagnosis of PML. However, in some patients only low levels of JCV DNA (<100 copies/ml) are present in CSF, making the diagnosis challenging. Our objective was to assess the complementary value of a CSF JCV antibody index (AIJCV) in the diagnosis of natalizumab‐associated PML.

Methods

AIJCV was assessed in 37 cases of natalizumab‐associated PML and 89 MS‐patients treated with natalizumab without PML. Sera and CSF were tested in a capture enzyme‐linked immunosorbent assay, using JCV‐VP1 fused to glutathione S‐transferase as antigen. Albumin levels and total immunoglobulin G concentration were determined by immunonephelometry, and the AIJCV was calculated as published.

Results

Twenty‐six of 37 (70%) patients with natalizumab‐associated PML exhibited an AIJCV > 1.5, whereas this was seen in none of the controls (p < 0.0001). At time of the first positive qPCR for JCV DNA, 11 of 20 (55%) patients with natalizumab‐associated PML had an AIJCV > 1.5. JCV DNA levels of <100 copies/ml were seen in 14 (70%) of these 20 patients, of whom 8 (57%) demonstrated an AIJCV > 1.5.

Interpretation

Determination of the AIJCV could be an added tool in the diagnostic workup for PML and should be included in the case definition of natalizumab‐associated PML. Ann Neurol 2014;76:792–801
Terminal Imido Rhodium Complexes
Authors: Geer Ana M. , Tejel Cristina , López José A. , Ciriano Miguel A.
Published: April 2014

Compounds of the late transition metals with MX multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second‐ and third‐row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity studies of the first rhodium complexes [Rh(PhBP3)(NR)] (PhBP3=PhB{CH2PPh2}3) with a multiple and terminal RhN bond. These imido compounds result from reactions of organic azides with the corresponding rhodium(I) complex having a labile ligand, and display a pseudo‐tetrahedral core geometry with an almost linear Rh‐N‐C arrangement [177.5(2)°] and a short RhN bond [1.780(2) Å]. We also show that the RhN bond undergoes protonation at the nitrogen atom or addition of H2, and also engages in nitrene‐group transfer and cycloaddition reactions.
Electron Transfer and Multi‐Electron Accumulation in ExBox4+
Authors: Dyar Scott M. , Barnes Jonathan C. , Juríček Michal , Stoddart J. Fraser , Co Dick T. , Young Ryan M. , Wasielewski Michael R.
Published: April 2014

Molecules capable of accepting and storing multiple electrons are crucial components of artificial photosynthetic systems designed to drive catalysts, such as those used to reduce protons to hydrogen. ExBox4+, a boxlike cyclophane comprising two π‐electron‐poor extended viologen units tethered at both ends by two p‐xylylene linkers, has been shown previously to accept an electron through space from a photoexcited guest. Herein is an investigation of an alternate, through‐bond intramolecular electron‐transfer pathway involving ExBox4+ using a combination of transient absorption and femtosecond stimulated Raman spectroscopy (FSRS). Upon photoexcitation of ExBox4+, an electron is transferred from one of the p‐xylylene linkers to one of the extended viologen units in ca. 240 ps and recombines in ca. 4 ns. A crystal structure of the doubly reduced species ExBox2+ was obtained.
Nanobiomolecular Multiprotein Clusters on Electrodes for the Formation of a Switchable Cascadic Reaction Scheme
Authors: Feifel Sven C. , Kapp Andreas , Ludwig Roland , Lisdat Fred
Published: April 2014

A supramolecular multicomponent protein architecture on electrodes is developed that allows the establishment of bidirectional electron transfer cascades based on interprotein electron exchange. The architecture is formed by embedding two different enzymes (laccase and cellobiose dehydrogenase) and a redox protein (cytochrome c) by means of carboxy‐modified silica nanoparticles in a multiple layer format. The construct is designed as a switchable dual analyte detection device allowing the measurement of lactose and oxygen, respectively. As the switching force we apply the electrode potential, which ensures control of the redox state of cytochrome c. The two signal chains are operating in a non‐separated matrix and are not disturbed by the other biocatalyst.
Surface decoration of electrospun scaffolds by microcontact printing
Authors: Giannitelli Sara M. , Abbruzzese Franca , Mozetic Pamela , De Ninno Adele , Businaro Luca , Gerardino Annamaria , Rainer Alberto
Published: April 2014

Microcontact printing has emerged as one of the most straightforward methods of surface patterning and has been successfully employed to obtain biologically instructive substrates for a wide range of tissue engineering applications. However, although a consolidated success has been gained in the patterning of smooth surfaces, limited popularity has been achieved in the modification of soft and/or textured substrates.

Thus, aim of this study is to transfer protein patterns onto 3D electrospun matrices by a custom‐designed microcontact printing setup. The proposed approach has been successfully pursued for precise and gentle transfer of poly‐l‐lysine patterns from polydimethylsiloxane stamps onto sub‐micron‐sized poly(ε‐caprolactone) electrospun fibers without loss of biological activity. In vitro performance of the patterned substrates has been preliminary evaluated in combination with human mesenchymal stem cells. Copyright © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Solid‐state NMR study of spin finish of thermally treated PAN and PAN/CNT precursor fibers
Authors: Ghoshal Sushanta , Liu Yaodong , Gulgunje Prabhakar , Gupta Kishor , Chae Han Gi , Leisen Johannes , Kumar Satish
Published: April 2014

Dry‐jet wet‐spun polyacrylonitrile (PAN) and PAN/carbon nanotubes (CNTs) precursor fibers coated by spin finishes were characterized using the solid‐state 1H nuclear magnetic resonance technique. Series of fiber samples were prepared upon thermal treatment at different temperatures (room temperature to 180°C). Using the Hahn echo sequence, relatively mobile components were identified and the effect of the heat treatment on those components was studied. It was observed that the mobile components are mainly the spin finishes. Heat treatment caused loss of one of the spin finishes (Type B) to a great extent (∼80%), whereas the other two spin finishes (Type A and Type C) were more stable. Additional information regarding the change in molecular mobility due to heat treatment was obtained by the spin‐lattice relaxation time (T1) analysis. It was found that the presence of CNT affects the T1 relaxation time of the polymer in the composite fiber, however, that of relatively mobile components remains unaffected. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40734.
Stone use and avoidance on Easter Island: Red scoria from the topknot quarry at Puna Pau and other sources
Authors: Seager Thomas Mike
Published: April 2014

The paper presents new observations on the use and avoidance of different red scoria rocks on Easter Island (Rapa Nui), made during fieldwork. It describes the different facies of the rock, their origins, their nature and their context of quarrying and use. From the latter, it is inferred that, for the prehistoric Rapanui, the meaning of red scoria transcended practical utility. A combination of stone context and ethnographic analogy suggests what this meaning or these meanings might be. Stone use on the Island is presented as a model against which the stone use of other prehistoric cultures might be measured.
Racial and Ethnic Differences in Older Adults With Knee Osteoarthritis
Authors: Cruz‐Almeida Yenisel , Sibille Kimberly T. , Goodin Burel R. , Petrov Megan E. , Bartley Emily J. , Riley Joseph L. , King Christopher D. , Glover Toni L. , Sotolongo Adriana , Herbert Matthew S. , Schmidt Jessica K. , Fessler Barri J. , Staud Roland , Redden David , Bradley Laurence A. , Fillingim Roger B.
Published: April 2014

Objective

Knee osteoarthritis (OA) contributes significantly to disability in older individuals, and racial/ethnic minorities are disproportionately affected. The present study aimed to characterize differences in clinical and experimental pain, including pain inhibition, among older African American (AA) and non‐Hispanic white (NHW) subjects with knee OA.

Methods

AA and NHW subjects with knee OA (n = 267) completed clinical and functional pain assessments, including quantitative sensory testing (QST). We hypothesized that, when compared to NHW subjects, AA subjects would display 1) lower pain tolerance and higher ratings of heat‐, mechanical‐, and cold‐induced pain, 2) greater temporal summation of pain, 3) reduced pain inhibition, and 4) greater clinical pain and poorer function. In addition, we hypothesized that the findings from QST would significantly predict the severity of clinical pain within each race/ethnicity.

Results

AA subjects with knee OA displayed increased pain sensitivity, greater temporal summation, and reduced pain inhibition when compared to NHW subjects with knee OA. Moreover, AA subjects reported greater clinical pain and poorer function. Racial/ethnic differences in clinical pain became nonsignificant when the analyses were controlled for education and annual income, whereas differences in QST findings remained highly significant. Although the extent of pain inhibition predicted the severity of clinical pain in both groups, different QST measures were additionally predictive of clinical pain within each group.

Conclusion

The results of this study establish that there are racial/ethnic differences in experimental and clinical pain and function in older individuals with knee OA. Our findings indicating that different QST measures were associated with clinical pain within the 2 racial/ethnic groups, whereas reduced pain inhibition was important in all participants, warrant further study in order to elucidate the common and group‐specific pathophysiologic mechanisms contributing to clinical pain in OA.
Low‐Dose Irinotecan Improves Advanced Lupus Nephritis in Mice Potentially by Changing DNA Relaxation and Anti–Double‐Stranded DNA Binding
Authors: Frese‐Schaper Manuela , Keil Andreas , Steiner Selina K. , Gugger Mathias , Körner Meike , Kocher Gregor J. , Schiffer Lena , Anders Hans‐Joachim , Huynh‐Do Uyen , Schmid Ralph A. , Frese Steffen
Published: April 2014

Objective

Despite clear advances in the treatment of systemic lupus erythematosus (SLE), many patients still present with refractory lupus nephritis, requiring new treatment strategies for this disease. This study was undertaken to determine whether reduced doses of the topoisomerase I (topo I) inhibitor irinotecan, which is known as a chemotherapeutic agent, suppress SLE in (NZB × NZW)F1 (NZB/NZW) mice, and to evaluate the potential mechanism by which irinotecan influences the course of SLE.

Methods

NZB/NZW mice were treated with low‐dose irinotecan beginning at either 24 weeks of age or established glomerulonephritis, defined as proteinuria of grade ≥3+. Binding of anti–double‐stranded DNA (anti‐dsDNA) antibodies was measured by enzyme‐linked immunosorbent assay (ELISA), and DNA relaxation was visualized by gel electrophoresis.

Results

Significantly reduced irinotecan doses improved lupus nephritis and prolonged survival in NZB/NZW mice. The lowest dose successfully used for the treatment of established murine lupus nephritis was >50 times lower than the dose usually used for chemotherapy in humans. As a mechanism, low‐dose irinotecan reduced B cell activity. However, the levels of B cell activity in irinotecan‐treated mice were similar to those in BALB/c mice of the same age, suggesting that irinotecan did not induce clear immunosuppression. In addition, incubation of dsDNA with topo I increased binding of murine and human anti‐dsDNA antibodies, showing for the first time that relaxed DNA is more susceptible to anti‐dsDNA antibody binding. This effect was reversed by addition of the topo I inhibitor camptothecin.

Conclusion

Our findings indicate that topo I inhibition may be a novel and targeted therapy for SLE.
Query‐performance prediction for effective query routing in domain‐specific repositories
Authors: Sarnikar Surendra , Zhang Zhu , Zhao J. Leon
Published: April 2014

The effective use of corporate memory is becoming increasingly important because every aspect of e‐business requires access to information repositories. Unfortunately, less‐than‐satisfying effectiveness in state‐of‐the‐art information‐retrieval techniques is well known, even for some of the best search engines such as Google. In this study, the authors resolve this retrieval ineffectiveness problem by developing a new framework for predicting query performance, which is the first step toward better retrieval effectiveness. Specifically, they examine the relationship between query performance and query context. A query context consists of the query itself, the document collection, and the interaction between the two. The authors first analyze the characteristics of query context and develop various features for predicting query performance. Then, they propose a context‐sensitive model for predicting query performance based on the characteristics of the query and the document collection. Finally, they validate this model with respect to five real‐world collections of documents and demonstrate its utility in routing queries to the correct repository with high accuracy.
SnS2 Nanoplatelet@Graphene Nanocomposites as High‐Capacity Anode Materials for Sodium‐Ion Batteries
Authors: Xie Xiuqiang , Su Dawei , Chen Shuangqiang , Zhang Jinqiang , Dou Shixue , Wang Guoxiu
Published: April 2014

Na‐ion batteries have been attracting intensive investigations as a possible alternative to Li‐ion batteries. Herein, we report the synthesis of SnS2 nanoplatelet@graphene nanocomposites by using a morphology‐controlled hydrothermal method. The as‐prepared SnS2/graphene nanocomposites present a unique two‐dimensional platelet‐on‐sheet nanoarchitecture, which has been identified by scanning and transmission electron microscopy. When applied as the anode material for Na‐ion batteries, the SnS2/graphene nanosheets achieved a high reversible specific sodium‐ion storage capacity of 725 mA h g−1, stable cyclability, and an enhanced high‐rate capability. The improved electrochemical performance for reversible sodium‐ion storage could be ascribed to the synergistic effects of the SnS2 nanoplatelet/graphene nanosheets as an integrated hybrid nanoarchitecture, in which the graphene nanosheets provide electronic conductivity and cushion for the active SnS2 nanoplatelets during Na‐ion insertion and extraction processes.
FDI Design for Uncertain Nonlinear Systems with Both Actuator and Sensor Faults
Authors: Yang Junqi , Zhu Fanglai
Published: April 2014

This paper considers the problems of simultaneous actuator and sensor fault detection and isolation (FDI) for a class of uncertain Lipschitz nonlinear systems when the observer matching condition is not satisfied. An augmented vector is proposed to construct an augmented system that contains a fault vector consisting of both the actuator and sensor faults of the original system. An auxiliary output vector is constructed to satisfy the observer matching condition, and a high‐gain sliding mode observer is designed to approximately estimate the auxiliary output vector. An adaptive robust sliding mode observer is developed as a fault detector to detect the actuator and sensor faults simultaneously. Then, multi‐observers are designed to attain the actuator and sensor fault isolation purpose. Finally, a numerical simulation is given to show the effectiveness of the proposed methods.
Strong subsurface soil temperature feedbacks on summer climate variability over the arid/semi‐arid regions of East Asia
Authors: Wu Lingyun , Zhang Jingyong
Published: April 2014

Two long‐term regional climate model simulations with and without subsurface soil temperature feedbacks are performed to investigate the role of soil temperature–atmosphere coupling in influencing interannual variability of summer climate over East Asia. Results indicate that soil temperature–atmosphere coupling depends on climate regimes, mainly affecting summer climate variability over the arid/semi‐arid regions. Over these areas, subsurface soil temperature feedbacks play an important role in amplifying summer surface air temperature variability, accounting for about 30–70% of total variance. The feedbacks on precipitation variability are weaker than those on surface air temperature variability over the arid/semi‐arid regions, but are still significant over many areas of western part.
Epidemiology of multiple congenital anomalies in Europe: A EUROCAT population‐based registry study
Authors: Calzolari Elisa , Barisic Ingeborg , Loane Maria , Morris Joan , Wellesley Diana , Dolk Helen , Addor Marie‐Claude , Arriola Larraitz , Bianchi Fabrizio , Neville Amanda J. , Budd Judith L.S. , Klungsoyr Kari , Khoshnood Babak , McDonnell Bob , Nelen Vera , Queisser‐Luft Annette , Rankin Judith , Rissmann Anke , Rounding Catherine , Tucker David , Verellen‐Dumoulin Christine , de Walle Hermien , Garne Ester
Published: April 2014

Background

This study describes the prevalence, associated anomalies, and demographic characteristics of cases of multiple congenital anomalies (MCA) in 19 population‐based European registries (EUROCAT) covering 959,446 births in 2004 and 2010.

Methods

EUROCAT implemented a computer algorithm for classification of congenital anomaly cases followed by manual review of potential MCA cases by geneticists. MCA cases are defined as cases with two or more major anomalies of different organ systems, excluding sequences, chromosomal and monogenic syndromes.

Results

The combination of an epidemiological and clinical approach for classification of cases has improved the quality and accuracy of the MCA data. Total prevalence of MCA cases was 15.8 per 10,000 births. Fetal deaths and termination of pregnancy were significantly more frequent in MCA cases compared with isolated cases (p < 0.001) and MCA cases were more frequently prenatally diagnosed (p < 0.001). Live born infants with MCA were more often born preterm (p < 0.01) and with birth weight < 2500 grams (p < 0.01). Respiratory and ear, face, and neck anomalies were the most likely to occur with other anomalies (34% and 32%) and congenital heart defects and limb anomalies were the least likely to occur with other anomalies (13%) (p < 0.01). However, due to their high prevalence, congenital heart defects were present in half of all MCA cases. Among males with MCA, the frequency of genital anomalies was significantly greater than the frequency of genital anomalies among females with MCA (p < 0.001).

Conclusion

Although rare, MCA cases are an important public health issue, because of their severity. The EUROCAT database of MCA cases will allow future investigation on the epidemiology of these conditions and related clinical and diagnostic problems. Birth Defects Research (Part A) 100:270–276, 2014. © 2014 Wiley Periodicals, Inc.
Rapid communication capturing the destabilizing effect of dihydrouridine through molecular simulations
Authors: Deb Indrajit , Sarzynska Joanna , Nilsson Lennart , Lahiri Ansuman
Published: April 2014

The structural effects of the commonly occurring modified nucleoside dihydrouridine (D) observed experimentally in model oligonucleotides include a strong destabilization of the C3′‐endo sugar conformation of D, the disruption of stacking interactions of neighboring residues with D and a possible destabilization of the C3′‐endo sugar pucker of the 5′‐neighboring nucleoside. Our simulations with a combination of a set of parameters for modified RNA residues with the recently developed AMBER FF99χ force field having reoptimized glycosidic torsion angle parameters for standard nucleosides was found to reproduce the destabilizing effect of dihydrouridine better than with the AMBER FF99 force field for nucleic acids for which the parameters for the modified residues were originally developed. © 2014 Wiley Periodicals, Inc. Biopolymers 101: 985–991, 2014.
Relative stability of G‐quadruplex structures: Interactions between the human Bcl2 promoter region and derivatives of carbazole and diphenylamine
Authors: Sheu Sheh‐Yi , Huang Chao‐Hsien , Zhou Jia‐Kai , Yang Dah‐Yen
Published: April 2014

The bcl2 promoter region forms a G‐quadruplex structure, which is a crucial target for anticancer drug development. In this study, we provide theoretical predictions of the stability of different G‐quadruplex folds of the 23‐mer bcl2 promoter region and G‐quadruplex ligand. We take into account the whole G‐quadruplex structure, including bound‐cations and solvent effects, in order to compute the ligand binding free energy using molecular dynamics simulation. Two series of the carbazole and diphenylamine derivatives are used to screen for the most potent drug in terms of stabilization. The energy analysis identifies the predominant energy components affecting the stability of the various different G‐quadruplex folds. The energy associated with the stability of the G‐quadruplex‐K+ structures obtained displays good correlation with experimental Tm measurements. We found that loop orientation has an intrinsic influence on G‐quadruplex stability and that the basket structure is the most stable. Furthermore, parallel loops are the most effective drug binding site. Our studies also demonstrate that rigidity and planarity are the key structural elements of a drug that stabilizes the G‐quadruplex structure. BMVC‐4 is the most potential G‐quadruplex ligand. This approach demonstrates significant promise and should benefit drug design. © 2014 Wiley Periodicals, Inc. Biopolymers 101: 1038–1050, 2014.
Stability and degradation patterns of chemically modified analogs of apelin‐13 in plasma and cerebrospinal fluid
Authors: Murza Alexandre , Belleville Karine , Longpré Jean‐Michel , Sarret Philippe , Marsault Éric
Published: April 2014

Apelin is the endogenous ligand of APJ, which belongs to the superfamily of G protein‐coupled receptors. In recent years, the apelin/APJ system has been detected in many tissues and emerges as a promising target for the treatment of various pathophysiological conditions. Pyr1‐apelin‐13 is the major isoform of apelin in human plasma; however its stability and proteolytic degradation pattern remain poorly understood. The aim of the present study was first to identify the cleavage sites of Pyr1‐apelin‐13 in mouse, rat and human plasma and rat cerebrospinal fluid, then to determine its stability to proteolytic degradation following intravenous administration in rats. Secondly, key residues were substituted by natural and unnatural amino acids in order to examine the impact onin vitrostability and degradation pattern. The kinetics of degradation revealed that the Leu5‐Ser6 peptide bond of Pyr1‐apelin‐13 is the first cleavage observed in plasma, independently of the species. Replacement of Phe13 by unnatural amino acids showed a 10‐fold increase in plasma stability although the hydrolysis of Pro12‐Phe13 bond, previously described as a site of cleavage by ACE‐2, was not observed.In vivo, this Pro12‐Phe13 bond was cleaved yet appears as a minor product compared to hydrolysis of the Pro10‐Met11 bond. This study pinpoints the most critical amino acids targeted by proteases and will be instrumental for the design of Pyr1‐apelin‐13 analogs possessing increased stability. © 2014 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 102: 297–303, 2014.
Gender‐Intrusive Questioning: A Survey of Expert Witnesses
Authors: Daftary‐Kapur Tarika , O'Connor Maureen , Mechanic Mindy
Published: April 2014

This paper reports the results of a survey of male and female psychologists with expert witness experience. The survey explored the roles of both expert witness gender and valence of the testimony to provide preliminary empirical data on whether gender in combination with the valence of testimony leads to perceived bias targeted towards female experts. The presence of such bias might diminish the credibility of the expert and subsequently the proffered testimony and, thus, undermine the legal system as effective fact‐finder by leading to decision‐making based on extra‐legal factors. Copyright © 2014 John Wiley & Sons, Ltd.
Does a parental history of cancer moderate the associations between impaired health status in parents and psychosocial problems in teenagers: a HUNT study
Authors: Jeppesen Elisabeth , Bjelland Ingvar , Fosså Sophie D. , Loge Jon H. , Sørebø Øystein , Dahl Alv A.
Published: April 2014

Severe disease in a parent is associated with increased psychosocial problems in their children. However, moderating factors of such associations are less studied. In this cross‐sectional population‐based controlled study we examined the moderating effects of a history of parental cancer on the association between impaired health status in parents and psychosocial problems among their teenagers. Among families with both parents responding to the adult Health Survey of Nord‐Trøndelag County of Norway (the HUNT‐2 study) 71 couples were identified with primary invasive cancer in one parent. Their 81 teenage children took part in the Young‐HUNT study. These families were compared to 322 cancer‐free families with 328 teenagers. Based on self‐report data the relations between three variables of parental impaired health and six psychosocial problems in teenagers were analyzed family wise by structural equation modeling. Significant associations between parental and teenagers' variables were observed in eight of 18 models. A history of parental cancer was a significant moderator which decreased four of eight significant associations. Such a history significantly weakened the associations between parental poor self‐rated health and teenagers' anxiety/depression and school problems. A similar association of a history of parental cancer was found between psychological distress in parents and teenagers' feelings of loneliness and poor self‐rated health. This study confirmed strong associations between impaired parental health and psychosocial problems in their teenagers. A history of parental cancer weakened several of the significant associations between parental impaired health variables and psychosocial problems in their teenagers.
A Salen–Co3+ Catalyst for the Hydration of Terminal Alkynes and in Tandem Catalysis with Ru–TsDPEN for the One‐Pot Transformation of Alkynes into Chiral Alcohols
Authors: Wang Shoufeng , Miao Chengxia , Wang Wenfang , Lei Ziqiang , Sun Wei
Published: April 2014

The cobalt–salen complex (C1:[(salen)Co3+(OAc)]; salen= N,N′‐bis(salicylidene)ethylenediamine, OAc=acetate) was found to efficiently promote the hydration of terminal alkynes to give methyl ketones in the presence of the H2SO4 cocatalyst. In addition, the one‐pot transformation of alkynes into chiral alcohols through tandem catalysis by catalyst C1 coupled with a ruthenium–TsDPEN complex (C3: [(R,R‐TsDPEN)Ru2+(cymene)]; TsDPEN=(1R,2R)‐N‐(p‐toluenesulfonyl)‐1,2‐diphenylethylenediamine, cymene=1‐methyl‐4‐(1‐methylethyl)benzene) catalyst was realized with excellent yields and enantioselectivities.
Whole‐Cell One‐Pot Biosynthesis of Azelaic Acid
Authors: Otte Konrad B. , Kittelberger Jens , Kirtz Marko , Nestl Bettina M. , Hauer Bernhard
Published: April 2014

The front cover artwork for Issue 04/2014 is provided by the Institute of Technical Biochemistry, University of Stuttgart. The image shows the depiction of an­ Escherichia coli­ whole cell factory, which converts linoleic acid directly into azelaic acid. The three reaction steps are indicated in blue, green, and orange in the zoom‐in. See the Full Paper itself at http://dx.doi.org/10.1002/cctc.201300787.
Integrating 31P DOSY NMR Spectroscopy and Molecular Mechanics as a Powerful Tool for Unraveling the Chemical Structures of Polyoxomolybdate‐Based Amphiphilic Nanohybrids in Aqueous Solution
Authors: Shestakova Pavletta , Absillis Gregory , Martin‐Martinez Francisco J. , De Proft Frank , Willem Rudolph , Parac‐Vogt Tatjana N.
Published: April 2014

Novel organic–inorganic hybrids of various sizes were generated by reaction of 1,8‐octanediphosphonic acid (ODP) and (NH4)6Mo7O24 in aqueous solution. The formation of rodlike hybrids with variable numbers of covalently bound ODP and polyoxomolybdate (POM) units can be tuned as a function of increasing (NH4)6Mo7O24 concentration at fixed ODP concentration. The chemical structure of the ODP/POM hybrids was characterized by 1H, 31P, and 95Mo NMR spectroscopy. Heteronuclear 31P DOSY (diffusion‐ ordered NMR spectroscopy) and molecular mechanics (MM) calculations were applied to determine the size and shape of the nanosized hybrids generated at various ODP/POM ratios. For this purpose, the structures of ODP/POM hybrids with variable numbers of ODP and POM units were optimized by MM and then approximated as cylinder‐shaped objects by using a recently described mathematical algorithm. The thus‐obtained cylinder length and diameter were further used to calculate the expected diffusion coefficients of the ODP/POM hybrids. Comparison of the calculated and experimentally determined diffusion coefficients led to the most probable ODP/POM hybrid length for each sample composition. The 31P DOSY results show that the length of the hybrids increases with increasing POM concentration and reaches a maximum corresponding to an average of 8 ODP/7 POM units per chain at a sample composition of 20 mM ODP and 14 mM POM. With excess POM, above the latter concentration, the formation of shorter‐chain hybrids terminated by Mo7 clusters at one or both ends was evidenced on further increasing the POM concentration. The results demonstrate that the combination of 31P DOSY and MM, although virtually unexplored in POM chemistry, is a powerful innovative strategy for the detailed characterization of nanosized organic–inorganic POM‐based hybrids in solution.
ChemInform Abstract: The Isotypic Hydrogen Phosphate and Arsenate Dihydrates M2HXO4·2H2O (M: Rb, Cs; X: P, As).
Authors: Stoeger Berthold , Weil Matthias
Published: April 2014

Cs2HAsO4·2H2O, Cs2HPO4·2H2O, Rb2HAsO4·2H2O, and Rb2HPO4·2H2O are precipitated from aqueous H3XO4 (X: As, P) solutions with one equivalent of aqueous M2CO3 (M: Cs,Rb) followed by slow drying.
ChemInform Abstract: Na3[BN2] and Na2K[BN2]: A Known and a Novel Alkali Metal Dinitridoborate Obtained via Mild Thermal Dehydrogenation.
Authors: Koz Cevriye , Acar Selcuk , Prots Yurii , Hoehn Peter , Somer Mehmet
Published: April 2014

Na3[BN2] (I) and Na2K[BN2] (II) are obtained from the reaction of the respective binary mixtures NaNH2:NaBH4 and NaNH2:KBH4 in a molar ratio of 2:1 via thermal dehydrogenation (873 K and 683 K, resp., under Ar).
ChemInform Abstract: Synthesis, Structure, and Magnetic Properties of the Novel Sodium Cobalt Tellurate Na5Co15.5Te6O36.
Authors: Shan Yue Jin , Yoshioka Yuta , Wakeshima Makoto , Tezuka Keitaro , Imoto Hideo
Published: April 2014

Single crystals of the new title compound are synthesized by solid state reaction of Na2CO3, Co3O4, and TeO2 (alumina boat, 1273 K, 4 h).
ChemInform Abstract: Ferromagnetic Ordering in the Layer‐Structured Pd(HS2O7)2.
Authors: Bruns Joern , Niehaus Oliver , Poettgen Rainer , Wickleder Mathias S.
Published: April 2014

Violet single crystals of Pd(HS2O7)2 are prepared by reaction of elemental Pd and (NO2)OTf in oleum (65% SO3) in a thick‐walled glass ampule (90 °C, 24 h).
ChemInform Abstract: Enantioselective Monofluoromethylation of Aldehydes with 2‐Fluoro‐1,3‐benzodithiole‐1,1,3,3‐tetraoxide Catalyzed by a Bifunctional Cinchona Alkaloid‐Derived Thiourea‐Titanium Complex.
Authors: Ma Hai , Matsuzaki Kohei , Yang Yu‐Dong , Tokunaga Etsuko , Nakane Daisuke , Ozawa Tomohiro , Masuda Hideki , Shibata Norio
Published: April 2014

The first enantioselective monofluorination of aldehydes with the title fluorodithiole (I) is described using a cinchono‐derived thiourea complex as catalyst.
ChemInform Abstract: 3‐Methyl‐4‐oxa‐5‐azahomoadamantane: Alkoxyamine‐Type Organocatalyst for Alcohol Oxidation.
Authors: Sasano Yusuke , Murakami Keiichi , Nishiyama Tomohiro , Kwon Eunsang , Iwabuchi Yoshiharu
Published: April 2014

The title organocatalyst exhibits unexpected high catalytic activity in the presence of NaOCl and KBr to oxidize primary and secondary alcohols to their corresponding carbonyl compounds.
ChemInform Abstract: Chemoselective Hydrogenation Catalyzed by Pd on Spherical Carbon.
Authors: Sajiki Hironao , et al. et al.
Published: April 2014

The reduction of azides, nitro compounds, alkynes, and alkenes is achieved in the presence of benzyl esters, benzyl ethers, nitriles, aromatic ketones, N‐carbobenzyloxy protecting groups, and aromatic O‐TBS ethers using the new heterogeneous palladium catalyst supported on spherical carbon.
ChemInform Abstract: Iodine‐Catalyzed Cycloalkenylation of Dihydroquinolines and Arylamines Through a Reaction with Cyclic Ketones under Neat Conditions.
Authors: Fotie Jean , Ayer Suraj K. , Poudel Binit S. , Reid Carolyn S.
Published: April 2014

The title reaction offers an easy and metal‐free method for the regioselective direct cycloalkenylation of arylamines.
ChemInform Abstract: A Rhodium‐Catalyzed Tandem Alkyne Dimerization/1,4‐Addition Reaction.
Authors: Lerum Ronald V. , Russo Christopher M. , Marquez Jocellie E. , Chisholm John D.
Published: April 2014

The rhodium‐catalyzed tandem alkyne dimerization/1,4‐addition reaction of different alkynes with vinyl ketones is studied.
ChemInform Abstract: Synthesis of Highly‐Substituted Enantiomerically Pure Allylboronic Esters and Investigation of Their Stereoselective Addition to Aldehydes.
Authors: Vahabi Roza , Frey Wolfgang , Pietruszka Joerg
Published: April 2014

A highly stereoselective addition of preformed enantiomerically pure allyl boranes is applicable to a broad variety of aldehydes bearing different functional groups in good to high yields.
ChemInform Abstract: C2‐Symmetric Hemiaminal Ethers and Diamines: New Ligands for Copper‐Catalyzed Desymmetrization of meso‐1,2‐Diols and Asymmetric Henry Reactions.
Authors: Kaluza Zbigniew , Bielawski Krzysztof , Cwiek Rafal , Niedziejko Piotr , Kaliski Przemyslaw
Published: April 2014

The new C2‐symmetric hemiacetal ligand (CSH) gives generally good results for the asymmetric benzoylation of meso‐diols as well as for the Henry nitro aldol reaction.
ChemInform Abstract: Reactivity of α‐Trifluoromethanesulfonyl Esters, Amides and Ketones: Decarboxylative Allylation, Methylation, and Enol Formation.
Authors: Kong Han Il , Gill Monica A. , Hrdina Amy H. , Crichton Jennifer E. , Manthorpe Jeffrey M.
Published: April 2014

The influence of the α‐trifluoromethanesulfonyl group on the reactivity of carbonyl compounds is studied.