bluuebunny/crossref_metadata_2025 huggingface dataset:
Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent Synthesis
Authors: Potowski Marco , Merten Christian , Antonchick Andrey P. , Waldmann Herbert
Published: February 2015

An efficient multicomponent cascade transformation for the highly diastereo‐ and enantioselective synthesis of complex natural product inspired polycyclic products from simple starting materials is described. The cascade is initiated by copper‐catalyzed aerobic CH oxidation of cyclopentadiene to cyclopentadienone followed by double catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides. The cascade synthesis efficiently yields structurally complex 5,5,5‐tricyclic products with eight stereocenters with good yields and excellent diastereo‐ and enantiocontrol using one catalyst.
Bestandsaufnahme zu Aufkommen und Nutzung biogener Reststoffe in der deutschen Lebensmittel‐ und Biotechnikindustrie
Authors: Mahro Bernd , Gaida Bente , Schüttmann Ina , Zorn Holger
Published: February 2015

Die Intensivierung der Biomassenutzung als Energie‐ und Rohstoffträger führt zunehmend zu Nutzungskonflikten insbesondere im Hinblick auf die Sicherstellung einer ausreichenden Nahrungsmittelversorgung. Es ist deshalb wichtig, vor allem solche Biomasse‐Ressourcen möglichst effizient zu nutzen, die für eine unmittelbare Nahrungsmittelversorgung nicht in Frage kommen. Vor diesem Hintergrund wurden die pro Jahr in den verschiedenen Branchen der deutschen Lebensmittel‐ und Biotechnikindustrie anfallenden biogenen Reststoffe ermittelt. Diese biogenen Reststoffe beinhalten ein großes Potenzial für eine weitergehende stoffliche bzw. energetische Nutzung, werden derzeit aber primär im Bereich der Futtermittelherstellung verwertet.
Einfluss des Bindemittels und der Feuchtebeladung auf die Festigkeit von Zeolith 4A‐Granulaten
Authors: Müller Peter , Russell Alexander , Tomas Jürgen
Published: February 2015

In der vorliegenden Studie wurden das Materialverhalten und die Festigkeit eines bindemittelhaltigen und zweier bindemittelfreier zeolithischer Molekularsiebe in Granulatform untersucht. Die Proben wurden mittels einaxialem Druckversuch bei einer konstanten Beanspruchungsgeschwindigkeit bis zum Bruch untersucht. Die erhaltenen Kraft‐Weg‐Kurven wurden mit dem Modell nach Hertz bzw. nach Tomas ausgewertet. Zudem wurden die Bruchfestigkeits‐ und die spezifischen Bruchenergieverteilungen ermittelt. Der Einfluss des (temporären) Bindemittels bzw. des Bindemechanismus und unterschiedlicher Feuchtebeladungen auf die Produkteigenschaften der Granulate wird beschrieben.
Einflüsse der mechanischen Verfahrenstechnik auf die Herstellung von Elektroden für Lithium‐Ionen‐Batterien
Authors: Bitsch Boris , Willenbacher Norbert , Wenzel Valentin , Schmelzle Steffen , Nirschl Hermann
Published: February 2015

Mit der Intensivierung der Forschungsaktivitäten im Bereich der Energiespeicher hat die Lithium‐Ionen‐Batterie zunehmend an Bedeutung gewonnen. Im Herstellungsprozess spielt die Mechanische Verfahrenstechnik eine zentrale Rolle. Sowohl die Zusammensetzung der Elektrodenslurries als auch das Dispergierverfahren beeinflussen die Fließeigenschaften der Suspension und die Desagglomeration der feinskaligen Materialien maßgeblich. Wesentlicher Bestandteil der hier vorgestellten Experimente sind die rheologische Charakterisierung der prozessierten Slurries und die Beschreibung der Desagglomeration infolge variierender Spannungszustände während des Herstellungsprozesses. Es wird gezeigt, dass sich die Slurryqualität durch den Zusammenhang zwischen der Viskosität, der Prozessführung und der mechanischen Beanspruchung direkt beeinflussen lässt.
Mortality and Readmission Rates in Patients Hospitalized for Acute Decompensated Heart Failure: A Comparison Between Cardiology and General‐Medicine Service Outcomes in an Underserved Population
Authors: Selim Ahmed M. , Mazurek Jeremy A. , Iqbal Muhammad , Wang Dan , Negassa Abdissa , Zolty Ronald
Published: February 2015

Background

With recent legislation imposing penalties on hospitals for above‐average 30‐day all‐cause readmissions for patients with acute decompensated heart failure (ADHF), there is concern these penalties will more heavily impact hospitals serving socioeconomically vulnerable and underserved populations.

Hypothesis

Patients with ADHF and low socioeconomic status have better postdischarge mortality and readmission outcomes when cardiologists are involved in their in‐hospital care.

Methods

We retrospectively searched the electronic medical record for patients hospitalized for ADHF from 2001 to 2010 in 3 urban hospitals within a large university‐based health system. These patients were divided into 2 groups based on whether a cardiologist was involved in their care or not. Measured outcomes were 30‐ and 60‐day postdischarge mortality and readmission rates.

Results

Out of the 7516 ADHF patients, 1434 patients were seen by a cardiologist (19%). These patients had lower 60‐day mortality (5.4% vs 7.0%; hazard ratio [HR]: 0.70, 95% confidence interval [CI]: 0.52‐0.96, P = 0.034) and lower 30‐ and 60‐day readmission rates (16.7% vs 20.6%; HR: 0.76, 95% CI: 0.66‐0.89, P = 0.002, and 26.1% vs 30.2%; HR: 0.81, 95% CI: 0.72‐0.92, P = 0.003, respectively). There was no significant difference in the in‐hospital mortality between the 2 groups. Compared with other races, whites with systolic HF have marginally lower HF‐related readmission rates when treated by cardiologists.

Conclusions

In this cohort of ADHF patients from the Bronx, New York, involvement of a cardiologist resulted in improved short‐term mortality and readmission outcomes compared with treatment by general internal medicine.
Selective Inhibitors of Glutathione Transferase P1 with Trioxane Structure as Anticancer Agents
Authors: Bräutigam Maria , Teusch Nicole , Schenk Tobias , Sheikh Miriam , Aricioglu Rocky Z. , Borowski Swantje H. , Neudörfl Jörg‐Martin , Baumann Ulrich , Griesbeck Axel G. , Pietsch Markus
Published: February 2015

The response to chemotherapy in cancer patients is frequently compromised by drug resistance. Although chemoresistance is a multifactorial phenomenon, many studies have demonstrated that altered drug metabolism through the expression of phase II conjugating enzymes, including glutathione transferases (GSTs), in tumor cells can be directly correlated with resistance against a wide range of marketed anticancer drugs. In particular, overexpression of glutathione transferase P1 (GSTP1) appears to be a factor for poor prognosis during cancer therapy. Former and ongoing clinical trials have confirmed GSTP1 inhibition as a principle for antitumor therapy. A new series of 1,2,4‐trioxane GSTP1 inhibitors were designed via a type II photooxygenation route of allylic alcohols followed by acid‐catalyzed peroxyacetalization with aldehydes. A set of novel inhibitors exhibit low micromolar to high nanomolar inhibition of GSTP1, revealing preliminary SAR for further lead optimization. Importantly, high selectivity over another two human GST classes (GSTA1 and GSTM2) has been achieved. The trioxane GSTP1 inhibitors may therefore serve as a basis for the development of novel drug candidates in overcoming chemoresistance.
Cancer treatments and their side effects are associated with aggravation of insomnia: Results of a longitudinal study
Authors: Savard Josée , Ivers Hans , Savard Marie‐Hélène , Morin Charles M.
Published: February 2015

BACKGROUND

Insomnia affects between 30% to 60% of patients with cancer but to the authors' knowledge little is known regarding factors associated with its development. It has been postulated that adjuvant cancer treatments and their side effects could trigger sleep disturbances in this population but empirical evidence is lacking. The goal of the current study was to assess, separately in patients with breast and prostate cancer, the effect of adjuvant treatments on the evolution of insomnia symptoms and the mediating role of somatic symptoms.

METHODS

As part of a population‐based epidemiological study, patients with breast cancer (465 patients) and prostate cancer (263 patients) completed at baseline (perioperative period) and 2 months, 6 months, 10 months, 14 months, and 18 months later the Insomnia Severity Index (ISI) and a questionnaire assessing various somatic symptoms.

RESULTS

In patients with breast cancer, radiotherapy (overall effect) and chemotherapy (at 2 months), but not hormone therapy, were associated with increased insomnia severity, whereas androgen deprivation therapy was related to increased insomnia in patients with prostate cancer. In patients with breast cancer, the effect of chemotherapy and radiotherapy on insomnia was found to be significantly mediated by a variety of somatic symptoms, whereas night sweats had a particularly marked mediating role for hormone therapy, both in patients with breast and prostate cancer.

CONCLUSIONS

The findings of the current study indicate that cancer treatments and their side effects contribute to the aggravation of insomnia symptoms. Side effects of cancer treatments should be monitored more closely and managed as effectively as possible to prevent the occurrence or aggravation of insomnia. Cancer 2015;121:1703–1711. © 2015 American Cancer Society.
Environmentally Friendly Transistors and Circuits on Paper
Authors: Pettersson Fredrik , Remonen Tommi , Adekanye David , Zhang Yanxi , Wilén Carl‐Eric , Österbacka Ronald
Published: February 2015

We created environmentally friendly low‐voltage, ion‐modulated transistors (IMTs) that can be fabricated successfully on a paper substrate. A range of ionic liquids (ILs) based on choline chloride (ChoCl) were used as the electrolytic layer in the IMTs. Different organic compounds were mixed with ChoCl to create solution‐processable deep eutectic mixtures that are liquid or semiliquid at room temperature. In the final, solid version of the IMT, the ILs are also solidified by using a commercial binder to create printable transistor structures The semiconductor layer in the IMT is also substituted with a blend of the original semiconductor and a biodegradable polymer insulator. This reduces the amount of expensive and potentially harmful semiconductor used, and it also provides increased transistor performance, especially increasing the device switching speed. These environmentally friendly IMTs are then used to create ring oscillators, logic gates, and memories on paper.
Trial geography, pharmacogenetics, and global drug development
Authors: Schuck RN , Florian J , Charlab R , Pacanowski M
Published: February 2015

Drug development is increasingly global. The benefits of multiregional trials include worldwide evaluation of safety and efficacy. However, clinical practice, environmental, and genetic factors can vary across geographic regions, significantly influencing trial outcomes within a specific geographic region or the global population relative to the United States (US). Genomic technologies and research discoveries continue to advance at a remarkable pace, offering opportunities to explore intrinsic factors that could account for regional variability in drug pharmacokinetics or response.
Catalyzing the critical path initiative: FDA's progress in drug development activities
Authors: Parekh A , Buckman‐Garner S , McCune S , ONeill R , Geanacopoulos M , Amur S , Clingman C , Barratt R , Rocca M , Hills I , Woodcock J
Published: February 2015

The US Food and Drug Administration (FDA) has directed considerable effort towards modernizing its regulatory processes over the past decade to address the challenges in the drug development sector. Through partnerships and input from stakeholders, multiple initiatives are under way, many projects have been launched, several have resulted in tangible results, and many are ongoing and under discussion. We are learning that collaborative efforts can better inform and leverage existing knowledge, that the challenges of data sharing and intellectual property can be overcome, and that there is wide interest in partnering to address key public health regulatory science issues. It is crucial that we continue to build on these initial efforts to facilitate drug development.
From adaptive licensing to adaptive pathways: Delivering a flexible life‐span approach to bring new drugs to patients
Authors: Eichler H‐G , Baird LG , Barker R , Bloechl‐Daum B , Børlum‐Kristensen F , Brown J , Chua R , Del Signore S , Dugan U , Ferguson J , Garner S , Goettsch W , Haigh J , Honig P , Hoos A , Huckle P , Kondo T , Le Cam Y , Leufkens H , Lim R , Longson C , Lumpkin M , Maraganore J , O'Rourke B , Oye K , Pezalla E , Pignatti F , Raine J , Rasi G , Salmonson T , Samaha D , Schneeweiss S , Siviero PD , Skinner M , Teagarden JR , Tominaga T , Trusheim MR , Tunis S , Unger TF , Vamvakas S , Hirsch G
Published: February 2015

The concept of adaptive licensing (AL) has met with considerable interest. Yet some remain skeptical about its feasibility. Others argue that the focus and name of AL should be broadened. Against this background of ongoing debate, we examine the environmental changes that will likely make adaptive pathways the preferred approach in the future. The key drivers include: growing patient demand for timely access to promising therapies, emerging science leading to fragmentation of treatment populations, rising payer influence on product accessibility, and pressure on pharma/investors to ensure sustainability of drug development. We also discuss a number of environmental changes that will enable an adaptive paradigm. A life‐span approach to bringing innovation to patients is expected to help address the perceived access vs. evidence trade‐off, help de‐risk drug development, and lead to better outcomes for patients.
Improving drug delivery to primary and metastatic brain tumors: Strategies to overcome the blood–brain barrier
Authors: Parrish KE , Sarkaria JN , Elmquist WF
Published: February 2015

Brain tumor diagnosis has an extremely poor prognosis, due in part to the blood–brain barrier (BBB) that prevents both early diagnosis and effective drug delivery. The infiltrative nature of primary brain tumors and the presence of micro‐metastases lead to tumor cells that reside behind an intact BBB. Recent genomic technologies have identified many genetic mutations present in glioma and other central nervous system (CNS) tumors, and this information has been instrumental in guiding the development of molecularly targeted therapies. However, the majority of these agents are unable to penetrate an intact BBB, leading to one mechanism by which the invasive brain tumor cells effectively escape treatment. The diagnosis and treatment of a brain tumor remains a serious challenge and new therapeutic agents that either penetrate the BBB or disrupt mechanisms that limit brain penetration, such as endothelial efflux transporters or tight junctions, are required in order to improve patient outcomes in this devastating disease.
Efficient production of hydrogen from formic acid using a Covalent Triazine Framework supported molecular catalyst
Authors: Bavykina A. V. , Goesten M. G. , Kapteijn F. , Makkee M. , Gascon J.
Published: February 2015

A heterogeneous molecular catalyst based on IrIIICp* (Cp*=pentamethylcyclopentadienyl) attached to a covalent triazine framework (CTF) is reported. It catalyses the production of hydrogen from formic acid with initial turnover frequencies (TOFs) up to 27 000 h−1 and turnover numbers (TONs) of more than one million in continuous operation. The CTF support, with a Brunauer–Emmett–Teller (BET) surface area of 1800 m2 g−1, was constructed from an optimal 2:1 ratio of biphenyl and pyridine carbonitrile building blocks. Biphenyl building blocks induce mesoporosity and, therefore, facilitate diffusion of reactants and products whereas free pyridinic sites activate formic acid towards β‐hydride elimination at the metal, rendering unprecedented rates in hydrogen production. The catalyst is air stable, produces CO‐free hydrogen, and is fully recyclable. Hydrogen production rates of more than 60 mol L−1 h−1 were obtained at high catalyst loadings of 16 wt % Ir, making it attractive towards process intensification.
Constructing hyperchaotic systems at will
Authors: Shen Chaowen , Yu Simin , Lü Jinhu , Chen Guanrong
Published: February 2015

Over the last two decades, chaotification has received increasing attention from various communities of science and engineering. This paper aims at developing a unified chaotification framework for generating desired higher‐dimensional dissipative hyperchaotic systems by using a single‐parameter controller. The main idea is to use a block diagonal matrix in the design of the nominal system, so as to construct a desired hyperchaotic system. Specifically, the proposed scheme is to assign desired closed‐loop poles to the controlled system, allocating the corresponding numbers of eigenvalues with positive real parts at two types of saddle‐focus equilibria. For the non‐degenerate case, the number of positive Lyapunov exponents of the controlled system is given by the largest number of positive Lyapunov exponents of the desired hyperchaotic system. Two representative examples are given to illustrate and verify the proposed design method. Finally, the digital signal processor is employed to implement the above 10‐dimensional hyperchaotic systems, and the experimental observation is also given. Copyright © 2015 John Wiley & Sons, Ltd.
SPREDs (Sprouty Related Proteins with EVH1 Domain) promote self‐renewal and inhibit mesodermal differentiation in murine embryonic stem cells
Authors: Mühl Bastian , Hägele Jasmin , Tasdogan Alpaslan , Loula Paraskevi , Schuh Kai , Bundschu Karin
Published: February 2015

Background: Pluripotency, self‐renewal, and differentiation are special features of embryonic stem (ES) cells, thereby providing valuable perspectives in regenerative medicine. Developmental processes require a fine‐tuned organization, mainly regulated by the well‐known JAK/STAT, PI3K/AKT, and ERK/MAPK pathways. SPREDs (Sprouty related proteins with EVH1 domain) were discovered as inhibitors of the ERK/MAPK signaling pathway, whereas nothing was known about their functions in ES cells and during early differentiation, so far. Results: We generated SPRED1 and SPRED2 overexpressing and SPRED2 knockout murine ES cells to analyze the functions of SPRED proteins in ES cells and during early differentiation. Overexpression of SPREDs increases significantly the self‐renewal and clonogenicity of murine ES cells, whereas lack of SPRED2 reduces proliferation and increases apoptosis. During early differentiation in embryoid bodies, SPREDs promote the pluripotent state and inhibit differentiation whereby mesodermal differentiation into cardiomyocytes is considerably delayed and inhibited. LIF‐ and growth factor‐stimulation revealed that SPREDs inhibit ERK/MAPK activation in murine ES cells. However, no effects were detectable on LIF‐induced activation of the JAK/STAT3, or PI3K/AKT signaling pathway by SPRED proteins. Conclusions: We show that SPREDs promote self‐renewal and inhibit mesodermal differentiation of murine ES cells by selective suppression of the ERK/MAPK signaling pathway in pluripotent cells. Developmental Dynamics 244:591–606, 2015. © 2015 Wiley Periodicals, Inc.
Behavioural Difficulties That Co‐occur With Specific Word Reading Difficulties: A UK Population‐ Based Cohort Study
Authors: Russell Ginny , Ryder Denise , Norwich Brahm , Ford Tamsin
Published: February 2015

This study aimed to examine the association between specific word reading difficulties (SWRD) identified at age 7 years using a discrepancy approach and subsequent dimensional measures of behavioural difficulties reported by teachers and parents at age 11 years. Behavioural problems were assessed using the Strengths and Difficulties Questionnaire. Secondary analysis of a UK representative population‐based sample of children (n = 12 631) was conducted using linear regression models.

There were 284 children (2.2%) identified with SWRD at age 7 years. Children with SWRD had significantly higher scores on all measures of behavioural difficulties in unadjusted analysis. SWRD was associated with elevated behavioural difficulties at age 11 years according to parent report, and with greater emotional problems, hyperactivity and conduct issues according to teachers, even after having controlled for baseline difficulties. These results were replicated for children with low reading attainment, but no cognitive ability discrepancy. Categories of special educational need into which children with SWRD were classed at school were varied.

Given high rates of co‐occurring behavioural difficulties, assessment that identifies each individual child's specific functional, rather than categorical, difficulties is likely to be the most effective way of providing classroom support. © 2015 The Authors. Dyslexia published by John Wiley & Sons Ltd.
The effect of developmental nutrition on life span and fecundity depends on the adult reproductive environment in Drosophila melanogaster
Authors: May Christina M. , Doroszuk Agnieszka , Zwaan Bas J.
Published: February 2015

Both developmental nutrition and adult nutrition affect life‐history traits; however, little is known about whether the effect of developmental nutrition depends on the adult environment experienced. We used the fruit fly to determine whether life‐history traits, particularly life span and fecundity, are affected by developmental nutrition, and whether this depends on the extent to which the adult environment allows females to realize their full reproductive potential. We raised flies on three different developmental food levels containing increasing amounts of yeast and sugar: poor, control, and rich. We found that development on poor or rich larval food resulted in several life‐history phenotypes indicative of suboptimal conditions, including increased developmental time, and, for poor food, decreased adult weight. However, development on poor larval food actually increased adult virgin life span. In addition, we manipulated the reproductive potential of the adult environment by adding yeast or yeast and a male. This manipulation interacted with larval food to determine adult fecundity. Specifically, under two adult conditions, flies raised on poor larval food had higher reproduction at certain ages – when singly mated this occurred early in life and when continuously mated with yeast this occurred during midlife. We show that poor larval food is not necessarily detrimental to key adult life‐history traits, but does exert an adult environment‐dependent effect, especially by affecting virgin life span and altering adult patterns of reproductive investment. Our findings are relevant because (1) they may explain differences between published studies on nutritional effects on life‐history traits; (2) they indicate that optimal nutritional conditions are likely to be different for larvae and adults, potentially reflecting evolutionary history; and (3) they urge for the incorporation of developmental nutritional conditions into the central life‐history concept of resource acquisition and allocation.
Calculation of the Characteristics of Salient‐Pole Synchronous Machines Assisted by Permanent Magnets on the Basis of the Operating Principle
Authors: Yamazaki Katsumi , Tamiya Shuichi , Shima Kazuo , Fukami Tadashi
Published: February 2015

In this study we investigate a method for accurately calculating the characteristics of salient‐pole synchronous machines assisted by permanent magnets. First, the operating principle of the machines is investigated by using both finite element analysis and a simple magnetic circuit. Then, a theoretical representation of the assist effect on the permanent magnets is derived based on the magnetic circuit. Finally, the measured and calculated results are compared in order to confirm the validity of the proposed calculation method. We show that the load characteristics of the proposed machine can be accurately estimated from the no‐load and short‐circuit characteristics of the conventional machine without permanent magnets, and the size and magnetization of the inserted permanent magnets.
The RNA‐binding protein HuR/ELAVL1 regulates IFN‐β mRNA abundance and the type I IFN response
Authors: Herdy Barbara , Karonitsch Thomas , Vladimer Gregory I. , Tan Chris S.H. , Stukalov Alexey , Trefzer Claudia , Bigenzahn Johannes W. , Theil Tamara , Holinka Johannes , Kiener Hans P. , Colinge Jacques , Bennett Keiryn L , Superti‐Furga Giulio
Published: February 2015

Secretion of type I interferon (IFN) is the first cellular reaction to invading pathogens. Despite the protective function of these cytokines, an excessive response to their action can contribute to serious pathologies, such as autoimmune diseases. Transcripts of most cytokines contain adenylate‐uridylate (A/U)‐rich elements (AREs) that make them highly unstable. RNA‐binding proteins (RBPs) are mediators of the regulatory mechanisms that determine the fate of mRNAs containing AREs. Here, we applied an affinity proteomic approach and identified lethal, abnormal vision, drosophila‐like 1 (ELAVL1)/Hu antigen R (HuR) as the predominant RBP of the IFN‐β mRNA ARE. Reduced expression or chemical inhibition of HuR severely hampered the type I IFN response in various cell lines and fibroblast‐like synoviocytes isolated from joints of rheumatoid arthritis patients. These results define a role for HuR as a potent modulator of the type I IFN response. Taken together, HuR could be used as therapeutic target for diseases where type I IFN production is exaggerated.
Development of thymic Foxp3+ regulatory T cells: TGF‐β matters
Authors: Chen WanJun , Konkel Joanne E.
Published: February 2015

CD4+ regulatory T cells expressing the transcription factor Foxp3 can be generated in the thymus (tTreg cells), but the cellular and molecular pathways driving their development remain incompletely understood. TGF‐β is essential for the generation of Foxp3+ Treg cells converted from peripheral naïve CD4+ T cells (pTreg cells), yet a role for TGF‐β in tTreg‐cell development was initially refuted. Nevertheless, recent studies have unmasked a requirement for TGF‐β in the generation of tTreg cells. Experimental evidence reveals that TGF‐β in the context of TCR stimulation induces Foxp3 gene transcription in thymic Treg precursors, CD4+CD8–CD25– semimature and mature single‐positive thymocytes. Intriguingly, thymic apoptosis was found to be intrinsically linked to the generation of tTreg cells, as apoptosis induced expression of TGF‐β intrathymically. In this short review, we will highlight key data, discuss the experimental evidence and propose a modified model of tTreg‐cell development involving TGF‐β. We will also outline the remaining unresolved questions concerning generation of thymic Foxp3+ Treg cells and provide our personal perspectives on the mechanisms controlling tTreg‐cell development.
Dinuclear DOTA‐Based GdIII Chelates – Revisiting a Straightforward Strategy for Relaxivity Improvement
Authors: Fontes André , Karimi Shima , Helm Lothar , Yulikov Maxim , Ferreira Paula M. , André João P.
Published: February 2015

The need for magnetic resonance imaging (MRI) contrast agents with improved relaxivity maintains the development of new GdIII chelates as an intensive and demanding field of research. In this work, we introduce the new dimeric chelators bis{1,4,7,10‐tetraazacyclododecane‐1‐[(6‐amino)hexanoic]‐4,7,10‐triacetic acid}adipate [L2, bis(DOTA‐AHA)adipate] and bis{1,4,7,10‐tetraazacyclododecane‐1‐[(6‐amino)hexanoic]‐4,7,10‐triacetic acid}1,3‐phenyldiacetate [L3, bis(DOTA‐AHA)1,3‐phenyldiacetate], which are based on the bifunctional ligand 1,4,7,10‐tetraazacyclododecane‐1‐[(6‐amino)hexanoic]‐4,7,10‐triacetic acid (L1, DOTA‐AHA). Their GdIII chelates were studied by variable‐temperature 1H nuclear magnetic relaxation dispersion (NMRD) and 17O NMR spectroscopy to measure their relaxivities and the parameters that govern them. The rates of exchange of inner‐sphere water from the monomer GdL1 and from the two dinuclear chelates Gd2L2 and Gd2L3 are very similar (298kex ≈ 6.5 × 106 s–1) and slightly faster than that for [Gd(DOTA)H2O]– (298kex = 4.1 × 106 s–1). All three compounds form weakly bound aggregates with equilibrium constants 298K of 2.9, 15.6, and 14.6 for GdL1, Gd2L2, and Gd2L3, respectively. Even though the aggregates contain only 10 to 15 % of the total amount of GdIII ions, a marked increase in relaxivity between 30 and 100 MHz is observed. Furthermore, the distance between the two GdIII centers in the dinuclear compounds has been determined by double electron–electron resonance (DEER) spectroscopy experiments and by molecular modeling studies, which afforded comparable distances. The linkers between the chelating moieties allow GdIII–GdIII distances of ca. 3.0 nm for the completely stretched linker conformation and less than 1.9 nm for the conformation with the metal centers at a closer distance. These metal‐to‐metal distances by themselves cannot explain the considerably long tumbling times of the chelates in solution. Only a model consistent with some level of aggregation for the dinuclear chelates in aqueous solution could satisfactorily explain our results.
Customized Buchwald‐Type Phosphines Bearing an “Inverted” Pyrimidinium Betaine as an Aryl Group Surrogate – Synthesis and Coordination Chemistry with Gold(I)
Authors: Noël‐Duchesneau Ludovik , Lugan Noël , Lavigne Guy , Labande Agnès , César Vincent
Published: February 2015

A new ligand scaffold inspired by Buchwald‐type phosphines is disclosed. Its design consists of the formal replacement of the distal aryl group of the original archetype by a pyrimidinium betaine connected to the o‐phosphinophenyl moiety through the C‐5 position of its malonate subunit. A productive synthetic pathway towards this phosphine is described along with its ability to coordinate to a gold(I) center. A weak bonding interaction between the metal center and the malonate group is observed in the solid state.
Triphenylguanidine‐Promoted ortho‐Metalation Reaction in a Triply Bonded Dirhenium System – Spectroscopic, Structural, and Computational Studies
Authors: Mallick Suman , Ghosh Mrinal Kanti , Chattopadhyay Swarup
Published: February 2015

Triphenylguanidine‐promoted ortho‐metalation reactions have been observed in reactions between the triply bonded dirhenium(II) complex Re2Cl4(μ‐Ph2PCH2PPh2)2 (1) and different para‐substituted triphenylguanidine ligands (HTPGR) in ethanol under reflux. The products are of the type Re2Cl2(μ‐dppm)(μ‐dppm°)(TPGR) [2(R), dppm = Ph2PCH2PPh2, μ‐dppm° represents the ortho‐metalated dppm ligand and R = H, 2(H); Me, 2(Me), and OMe, 2(OMe)]. These are the first examples of ortho‐metalated dirhenium complexes with bridging dppm ligands. These complexes have very similar spectral (UV/Vis, IR, and NMR) and electrochemical properties, which are also reported. The solid‐state structure of 2(H) has been established by single‐crystal X‐ray diffraction [Re–Re distance 2.2741(6) Å]. In the solid state, the molecules are linked by π···π and C–H···π intermolecular interactions and form infinite supramolecular chains. Anion···π interactions have also been revealed in the solid state. The electronic structures of the complexes are also scrutinized by density functional theory (DFT) calculations.
Toward Better Sodium–Oxygen batteries: A Study on the Performance of Engineered Oxygen Electrodes based on Carbon Nanotubes
Authors: Bender Conrad L. , Bartuli Waldemar , Schwab Matthias Georg , Adelhelm Philipp , Janek Jürgen
Published: February 2015

Sodium–oxygen cells with NaO2 as discharge product show very low overvoltages during discharge and charge, and their energy efficiency can be higher than 90 %. In this study the electrochemical behavior of three different free‐standing gas diffusion layers (GDL) is discussed, with each prepared by using a straightforward process from commercial starting materials: A pure carbon nanotube (CNT) electrode, a CNT electrode mixed with carbon fibers (CF) and a CNT electrode mixed with carbon black (CB). A solvent‐free method was applied to the fabrication of these electrodes, which may help to overcome limitations of common slurry‐based processes. NaO2 formed as the sole discharge product for all electrodes tested. The pure CNT electrode performs best in terms of capacity (1530 mAh g−1, 4.2 mAh cm−2) and cycle life (more than 140 cycles), and the results are superior in comparison to previous studies.
Restricted spatial regression in practice: geostatistical models, confounding, and robustness under model misspecification
Authors: Hanks Ephraim M. , Schliep Erin M. , Hooten Mevin B. , Hoeting Jennifer A.
Published: February 2015

In spatial generalized linear mixed models (SGLMMs), covariates that are spatially smooth are often collinear with spatially smooth random effects. This phenomenon is known as spatial confounding and has been studied primarily in the case where the spatial support of the process being studied is discrete (e.g., areal spatial data). In this case, the most common approach suggested is restricted spatial regression (RSR) in which the spatial random effects are constrained to be orthogonal to the fixed effects. We consider spatial confounding and RSR in the geostatistical (continuous spatial support) setting. We show that RSR provides computational benefits relative to the confounded SGLMM, but that Bayesian credible intervals under RSR can be inappropriately narrow under model misspecification. We propose a posterior predictive approach to alleviating this potential problem and discuss the appropriateness of RSR in a variety of situations. We illustrate RSR and SGLMM approaches through simulation studies and an analysis of malaria frequencies in The Gambia, Africa. Copyright © 2015 John Wiley & Sons, Ltd.
Quantification, characterization, and anaerobic digestion of sheep manure: The influence of diet and addition of crude glycerin
Authors: Orrico Junior Marco Antonio Previdelli , Orrico Ana Carolina Amorim
Published: February 2015

The objective of this study was to evaluate the influence of roughage‐to‐concentrate ratio on quantification and characterization of sheep manure, and to verify whether the addition of crude glycerin improves the efficiency of the anaerobic digestion process. The characterization study was carried out with two treatments (diet 1 with 40% roughage and 60% concentrate and diet 2 with 60% roughage and 40% concentrate) and 12 replicates per treatment. Parameters evaluated were as follows: production of manure, total solids (TS), volatile solids (VS), most probable number (MPN) of total (TC) and thermotolerant coliforms (TTC), chemical oxygen demand (COD), and residue coefficient. The digestion test was performed in batch digesters that were loaded with sheep manure with the doses of crude glycerin: 0, 3, 6, 9, 12, and 15% in the substrate. The process efficiency was measured by the reduction of TS, VS, and COD as well as the production of biogas. No differences were observed for the production of TS and manure among the diets. The contents of VS, COD, and MPN of TC and TTC were greater in manure from animals fed with higher concentrate ratio. Multiple linear models were generated according to the reductions of VS, TS, COD and production and potential of biogas and methane production and hence, both the additions of concentrate in the diet and crude glycerin in the codigestion influenced, in a positive way, the removal organic load in digesters. © 2015 American Institute of Chemical Engineers Environ Prog, 34: 1038–1043, 2015
Damage response of multistorey r/c buildings with different structural systems subjected to seismic motion of arbitrary orientation
Authors: Kostinakis Konstantinos , Morfidis Konstantinos , Xenidis Hariton
Published: February 2015

In the present study the combined influence of seismic orientation and a number of parameters characterizing the structural system of Reinforced Concrete (R/C) buildings on the level of expected damages are examined. For the purposes of the above investigation eight medium‐rise buildings are designed on the basis of the current seismic codes. The structural characteristics examined are the ratio of the base shear received by the structural walls, the ratio of horizontal stiffness in two orthogonal directions and the structural eccentricity. Then, the buildings are analyzed by nonlinear time response analysis using 100 bidirectional earthquake ground motions. The two horizontal accelerograms of each ground motion are applied along horizontal orthogonal axes, forming 72 different angles with the structural axes. The structural damage is expressed in terms of the Park and Ang damage index. The results of the analyses revealed that the damage level of the buildings is strongly affected by the incident angle of the ground motion. The extent at which the orientation of the seismic records influences the damage response depends on the structural system and the distance of the record to the fault rupture. As a consequence, the common practice of applying the earthquake records along the structural axes can lead to significant underestimation of structural damage. Also, it was shown that the structural eccentricity can significantly differentiate the seismic damage level, as well as the impact of the earthquake orientation on the structural damage. Copyright © 2015 John Wiley & Sons, Ltd.
The evolution of gully headcut morphology: a case study using terrestrial laser scanning and hydrological monitoring
Authors: Rengers Francis K. , Tucker Greg E.
Published: February 2015

We present observations and analysis of gully headcut erosion, which differ from previous headcut studies in both spatial and temporal detail. Using ten terrestrial laser scanning (TLS) surveys conducted over a period of 3 years, we mapped headcut erosion with centimeter‐scale detail on a sub‐annual basis. Erosional change is observed through point cloud differencing, which expands on previous studies of headcut retreat rate by revealing the evolution of the headcut morphology. Headcut retreat observations are combined with hydrological measurements to explore the controlling factors of erosional retreat. We find that (i) mass failure due to wetting, (ii) saturation weakening of shale bedrock in plunge pools, and (iii) direct wash over the headcut face all appear to contribute to headcut retreat; however, mass failure via wetting appears to be the dominant process. Soil moisture was monitored near the study headcut at 0.4 m depth, and time‐lapse photos show that soil wetting tends to be concentrated along the headcut apex after rainfall and snowmelt runoff events. We find that moisture concentration at the headcut apex leads to more rapid erosion at that location than along the headcut sidewalls, resulting in a semi‐ellipsoidal plan view morphology that is maintained as the headcut migrates up‐valley. Copyright © 2015 John Wiley & Sons, Ltd.
Arsenite stress variably stimulates pro-oxidant enzymes, anatomical deformities, photosynthetic pigment reduction, and antioxidants in arsenic-tolerant and sensitive rice seedlings
Authors: Tripathi Preeti , Singh Rana Pratap , Sharma Yogesh Kumar , Tripathi Rudra Deo
Published: February 2015

Contamination of arsenic (As) in rice (Oryza sativa L.) paddies and subsequent uptake by rice plants is a serious concern, because rice is a staple crop for millions of people. Identification of As toxicity and detoxification mechanisms in paddy rice cultivars would help to reduce As-associated risk. Arsenic tolerance and susceptibility mechanisms were investigated in 2 differential As-accumulating rice genotypes, Triguna and IET-4786, selected from initial screening of 52 rice cultivars as an As-tolerant and an As-sensitive cultivar, respectively, on the basis of root and shoot length during various arsenite (AsIII) exposures (0–50 μM). Indicators of oxidative stress, such as pro-oxidant enzymes (reduced nicotinamide adenine dinucleotide phosphate [NADPH] oxidase and ascorbate oxidase) and nitric oxide, were more numerous in the sensitive cultivar than in the tolerant cultivar. Arsenic-induced anatomical deformities were frequent in the sensitive cultivar, showing more distorted and flaccid root cells than the tolerant cultivar. Chlorophyll and carotenoid synthesis were inhibited in both cultivars, although the decline was more prominent in the sensitive cultivar at higher doses of As. Furthermore, the tolerant cultivar tolerated As stress by producing more antioxidants, such as proline, sustaining the ratio of ascorbate, dehydroascorbate, and glutathione peroxidase (GPX) activity as well as As detoxifying enzymes arsenate reductase, whereas these respective metabolic activities declined in sensitive cultivar, resulting in greater susceptibility to As toxicity. Environ Toxicol Chem 2015;34:1562–1571. © 2015 SETAC
An evaluation of the residual toxicity and chemistry of a sodium hydroxide-based ballast water treatment system for freshwater ships
Authors: Elskus Adria A. , Ingersoll Christopher G. , Kemble Nile E. , Echols Kathy R. , Brumbaugh William G. , Henquinet Jeffrey W. , Watten Barnaby J.
Published: February 2015

Nonnative organisms in the ballast water of freshwater ships must be killed to prevent the spread of invasive species. The ideal ballast water treatment system (BWTS) would kill 100% of ballast water organisms with minimal residual toxicity to organisms in receiving waters. In the present study, the residual toxicity and chemistry of a BWTS was evaluated. Sodium hydroxide was added to elevate pH to >11.5 to kill ballast water organisms, then reduced to pH <9 by sparging with wet-scrubbed diesel exhaust (the source of CO2). Cladocerans (Ceriodaphnia dubia), amphipods (Hyalella azteca), and fathead minnows (Pimephales promelas) were exposed for 2 d to BWTS water under an air atmosphere (pH drifted to ≥9) or a 2.5% CO2 atmosphere (pH 7.5–8.2), then transferred to control water for 5 d to assess potential delayed toxicity. Chemical concentrations in the BWTS water met vessel discharge guidelines with the exception of concentrations of copper. There was little to no residual toxicity to cladocerans or fish, but the BWTS water was toxic to amphipods. Maintaining a neutral pH and diluting BWTS water by 50% eliminated toxicity to the amphipods. The toxicity of BWTS water would likely be minimal because of rapid dilution in the receiving water, with subsurface release likely preventing pH rise. This BWTS has the potential to become a viable method for treating ballast water released into freshwater systems. Environ Toxicol Chem 2015;34:1405–1416. © 2015 SETAC
Aquatic environmental risk assessment for human use of the old antibiotic sulfamethoxazole in Europe
Authors: Straub Jürg Oliver
Published: February 2015

Sulfamethoxazole (SMX) is an old sulfonamide antibiotic that was launched first in combination with trimethoprim in 1969 by F.Hoffmann-La Roche. Although sales figures for SMX have been declining over the past 20 yr, the compound is still widely used; moreover, many measured environmental concentrations (MECs) are available from Europe, the United States, Asia, Australia, and Africa. To assess aquatic risks of SMX in Europe, the exposure of European surface waters was predicted based on actual sales figures from IMS Health, incorporating environmental fate data on one side, and based on collated MECs representing more than 5500 single measurements in Europe on the other. Environmental effects were assessed using chronic and subchronic ecotoxicity data for 16 groups of aquatic organisms, from periphyton communities to cyanobacteria, algae, higher plants, various invertebrates, and vertebrates. Predicted no-effect concentrations (PNECs) were derived using both deterministic and probabilistic methodology. The predicted environmental concentration (PEC)/PNEC and MEC/PNEC comparisons overall showed no appreciable risk, except in a low incidence (<0.55%) of cases in which exceptionally high MECs led to MEC/PNEC risk characterization ratios greater than 1. The PNECs derived in the present study can be used to extend aquatic environmental risk assessment for SMX to other continents. No risk appears for indirect human exposure to SMX via the environment. Environ Toxicol Chem 2016;35:767–779. © 2015 SETAC
Synthesis, odour evaluation and antimicrobial activity of some geranyl acetone and nerolidol analogues
Authors: Bonikowski Radosław , Świtakowska Paulina , Kula Józef
Published: February 2015

Geranyl acetone and nerolidol have a broad spectrum of bioactivity, they exhibit, inter alia, olfactory, germicidal and antimicrobial properties. Twelve E/Z‐mixtures of analogues of geranyl acetone and nerolidol were examined for their odour and antimicrobial activity. Mixtures of analogues of geranyl acetone generally have a scent that is similar to the parent terpenoid, with interesting notes (violet, rose, fruity), while the odour of similar mixtures of nerolidol analogues was rather weak, floral, fresh and fruity. The odour thresholds and relative volatility factors were determined. The antimicrobial activity of products described in this paper, in comparison with nerolidol and geranyl acetone, was similar. Copyright © 2015 John Wiley & Sons, Ltd.
Mechanical Response of a Large Fuel Cell Stack to Impact: A Numerical Analysis
Authors: Wu C.‐W. , Liu B. , Wei M.‐Y. , Zhang W.
Published: February 2015

Large fuel cell stacks usually undergo dynamic load (vibration and impact) during packing, transportation, and serving time, in particular for those used in the automobiles. This may cause the decay in the performance, and even structure damage of the stack. We numerically analyze the mechanical response of a large fuel cell stack clamped by steel belts to a violent impact in the present paper. It is found that the location of the clamping belts has a great effect on the anti‐impact performance of the stack. The results also indicate that the cells near the endplates have a worse anti‐impact performance than those far from the endplates. When subjected to a large impact in the direction parallel with the cells, the stack may give rise to interface slippage between cells, showing a downward bowing phenomenon. The relative slippage between cells is affected by the clamping force, impact acceleration and the friction coefficient between cells. A large interface friction coefficient and a reasonable high clamping force are expected in order to increase the anti‐impact performance.
Astrocyte‐targeted production of IL‐10 induces changes in microglial reactivity and reduces motor neuron death after facial nerve axotomy
Authors: Villacampa Nàdia , Almolda Beatriz , Vilella Antonietta , Campbell Iain L. , González Berta , Castellano Bernardo
Published: February 2015

Interleukin‐10 (IL‐10) is a cytokine that plays a crucial role in regulating the inflammatory response and immune reactions. In the central nervous system (CNS), IL‐10 is mainly produced by astrocytes and microglia and it is upregulated after various insults, such as experimental autoimmune encephalomyelitis, middle cerebral artery occlusion, excitotoxicity and traumatic brain injury. To better understand the effects of IL‐10 in the normal and injured CNS, we generated transgenic mice (termed GFAP‐IL‐10Tg) that expressed the murine IL‐10 gene under the transcriptional control of the glial fibrillary acidic protein (GFAP) promoter. Previous studies demonstrated marked changes in the microglial phenotype in these mice under basal conditions. The objective of the present study was to investigate the effects of local astrocyte‐targeted IL‐10 production on glial activation, neuronal degeneration and leukocyte recruitment after axotomy. GFAP‐IL‐10Tg mice had marked changes in the phenotype of activated microglial cells, as well as in the number of microglial clusters and in microglial cell density. These microglial changes are accompanied by a twofold increase in lymphocyte infiltration in GFAP‐IL‐10Tg mice and around twofold decrease in neuronal cell death at 21 dpi. Altogether, our findings suggested that astrocyte‐targeted production of IL‐10 impacted the microglial response and lymphocyte recruitment and culminated in a beneficial effect on neuronal survival. GLIA 2015;63:1166–1184