bluuebunny/crossref_metadata_2025 huggingface dataset:
Colorectal Cancer Survival Disparities among Puerto Rican Hispanics: A Comparison to Racial/Ethnic Groups in the United States
Authors: Gonzalez-Pons Maria , Torres Mariela , Perez Javier , Velez Anneliese , Betancourt Jean Pierre , Marcano Lorena , Soto-Salgado Marievelisse , Cruz-Correa Marcia
Published: August 2016

Purpose: Ethnic/racial disparities in colorectal cancer (CRC) survival have been well documented. However, there is limited information regarding CRC survival among Hispanic subgroups. This study reports the 5-year relative survival and the relative risk of death of Puerto Rican Hispanic (PRH) CRC patients compared to other racial/ethnic groups in the US.

Methods: CRC incidence data from subjects >50 years was obtained from the Puerto Rico Central Cancer Registry and the Surveillance, Epidemiology and End Results (SEER) database from January 1, 2001 to December 31, 2003. Relative survival rates were calculated using the life tables from the population of Puerto Rico and SEER. A Poisson regression model was used to assess relative risk of death by stage, sex, and age.

Results: A total of 76,444 subjects with incident CRC were analyzed (non-Hispanic White (NHW) n=59,686; non-Hispanic black (NHB) n=7,700; US Hispanics (USH) n=5,699; PRH n=3,359). Overall and stage-specific 5-year survival rates differed by race/ethnicity. When comparing PRH to the other racial/ethnic groups, PRH had the lowest survival rates in regional cancers and were the only racial/ethnic group where a marked 5-year survival advantage was observed among females (66.0%) compared to males (60.3%). A comparable and significantly higher relative risk of death of CRC was observed for PRH and NHB compared to NHW.

Conclusions: Our findings establish baseline CRC survival data for PRH living in Puerto Rico. The gender and racial/ethnic disparities observed in PRH compared to US mainland racial/ethnic groups warrant further investigation of the risk factors affecting this Hispanic subgroup.
The Association between Audit Committee Members’ Multiple Directorship, Ownership and Earnings Management in Saudi Arabia
Authors: Alshetwi Mohammed
Published: August 2016

This study examines the association between the multiple directorship and stock ownership of audit committee members and companies’ earnings management. Based on a sample of 98 Saudi nonfinancial listed companies, this study finds that the multiple directorship of audit committee members is not statistically associated with a reduction in the level of earnings management; however, the stock ownership of audit committee members is significantly related to a reduction in the level of earnings management.

The results of this study add to the field of knowledge as they provide evidence on the alignment hypotheses from less developed countries (i.e. Saudi Arabia). Furthermore, these findings are useful to understand the current situation of the multiple directorship and stock ownership of audit committee members and their role in improving the monitoring system and reducing earnings management in countries with special characteristics like Saudi Arabia (i.e., with a less developed legal system and new corporate governance regulations).
Interrelated Factors Influencing the Adoption Decision of AIS Applications by SMEs in Jordan
Authors: Al-dmour Ahamed , Al-dmour Rand , Masa'deh Ra'ed
Published: August 2016

This study aims to identify the main factors that either facilitating (motivating) or inhabiting the adoption decision of AIS by small –medium sized companies in Jordan. In order to accomplish the research objectives, a conceptual framework was designed. The conceptual framework includes three major interrelated factors: organizational, technological and environmental factors. The data for this research were collected through email survey with 101 respondents. The target respondents were the small-medium sized companies in Jordan and the key respondent approach was used. A group of twenty factors, employed as variables from the previous studies and models of adoption were listed and examined in a neutral manner, without pre-classifying them as barriers or incentives, through email surveys sent to key respondent in the SMEs. Respondents were asked to indicate how these factors influence their AIS adoption decisions. Furthermore, a comparison analysis has conducted to show how these factors are perceived differently among those who have adopted as AIS, those that will not adopt it all and those that might adopt it in the near future. The finding showed that only twelve of these factors were found significant, eight labeled as incentives and four labeled as barriers. However, the set cost factor was the only shared one perceived as a barrier among all groups. The results showed the three groups adopt perceive factors differently. The research has finalized with some theoretical and practical implications and recommendations.
The Impact of Computerized Information Systems on the Compliance of Internal Control Requirements According to ISA (315) in Jordanian Companies from the Perspectives of Their Employees
Authors: Al-Rahamneh Loay S
Published: August 2016

This study aimed at identifying the impact of computerized information system in compliance to internal control requirements according to ISA (315) in the Jordanian Companies from the Perspectives of their Employees. The study was implemented during the year 2015/2016, with sample that was chosen randomly and consisted of 50 employees who work for the Jordanian computer system companies. The results showed impacts of computerized information system on compliance to internal control requirements according to ISA (315). The researcher recommended the need to enact laws and develop new regulations that contribute in improving the effective use of computerized information systems at the Jordanian computer system companies.
Impact of Environmental and Social Costs on Performance of Nigerian Manufacturing Companies
Authors: A. A. Agbiogwu , J. U. Ihendinihu , M. C. Okafor
Published: August 2016

This study examines the impact of environmental and social costs on performance of Nigerian manufacturing companies. With the use of secondary data, sourced from ten (10) randomly selected firms’ annual report and financial summary 2014. The study makes use of t- test of Spss version 20 for the analysis of collected data. Finding from the analysis shows that the sample companies environmental and social cost significantly affect Net profit margin, Earnings per share and Return on capital employed of manufacturing companies. The researchers recommended that government should ensure complete adherence of environmental laws by manufacturing companies in Nigeria.
Is Abnormally Large Volume a Clue?
Authors: Lu Tsung-Hsun , Lee Jun-De
Published: August 2016

This paper investigates whether abnormal trading volume provides information about future movements in stock prices. Utilizing data from the Taiwan 50 Index from October 29, 2002 to December 31, 2013, the researchers employ trading volume rather than stock price to test the principles of resistance and support level employed by technical analysis. The empirical results suggest that abnormal trading volume provides profitable information for investors in the Taiwan stock market. An out-of-sample test and a sensitive analysis are conducted for the robustness of the results.
An Empirical Analysis of the Impact of Energy Consumption on the Financial Development of the Emerging Economies: A Moderating Role of Oil Prices
Authors: Mahmood Faisal , Saleem Maria
Published: August 2016

This research empirically analyzes the relationship between energy consumption and financial development by making use of secondary data for 22 emerging economies over the period of 1999-2012. Moreover, this paper also spotlights the moderating role of oil prices. Furthermore, financial development is measured by utilizing of various proxies relevant to banking sector and stock market as well. Hence, the findings of the research reveals that oil prices negatively moderates the relationship between energy consumption and financial development. Moreover, results highlight that measures used to calculate financial development are also of key concern to explore the relationship between energy consumption and financial development.
A Barycentric Interpolation Collocation Method for Linear Nonlocal Boundary Value Problems
Authors: Tian Dan , Li Weiya , Wang Cec Yulan
Published: August 2016

This paper is devoted to the numerical treatment of a class of higher-order multi-point boundary value problem-s(BVPs). The method is proposed based on the Lagrange interpolation collocation method, but it avoids thenumerical instability of Lagrange interpolation. Numerical results obtained by present method compare with othermethods show that the present method is simple and accurate for higher-order multi-point BVPs, and it is eectivefor solving six order or higher order multi-point BVPs.
Planning and Development: Social Capital and Promoting Mental Health
Authors: Yaghoubi Nour Mohammad , Kaseb Masoumeh Zare , Sayedalhosseini Sayed Moslem , Moloudi Jamshid , Nori Homayoon
Published: August 2016

During the planning and development of a country, social capital along with natural, human and physical capitals is considered as input and output of development. In underdeveloped countries, social capital is called as missing link development. According to the impact of this factor on varicose aspects of human life and more importantly on Mental Health, the present study attempted to identify the main factor of Mental Health and how to increase it by Social Capital and its dimensions (Cognitive, Relative and Structural Capitals). Present study researchers have used the Social capital and Mental Health theories, application survey and questionnaire. In present research the sample size consists of 264 employees (59 women and 205 men) that were selected at random from 243 small and medium enterprises located in Science and Technology Park. Data analysis was carried out by using the statistical program packages SPSS 17.0, AMOS SPSS 16.0.1 and LISREL 8.54. Results of the present study were illustrated that there is significant relationship between Social capital and its dimensions and Mental health in the present companies (p<0/01). The results of Enter Regression showed that predictor variables significantly (cognitive, relative and structural capital) have determined 47.7 % of the variance of Mental Health together. Also the result of LISREL statistical software was illustrated that the data of present study involve significant goodness of fit. Also the interesting results were obtained from Regression analysis and Factor Analysis to predict Social capital and its dimensions on the mental health that will watch in the present study.
Desalination Versus Duct Tape: (Dis)Incentives to Securing Water Supplies
Authors: Glennon Robert , Taylor Clark
Published: August 2016

Utilities can address diminishing supplies by investing in innovative infrastructure; current utility regulations, however, provide little incentive to do so.
Using Utility Management Standards to Optimize Operations
Authors: Nieminski Eva , Oberoi Kan , Sham Chi Ho , Yates Gerard
Published: August 2016

As shown in three case studies, AWWA's utility management standards provide guidance for utilities to achieve peak management performance.
Committee Report: Ripples From the San Juan Capistrano Decision
Authors: Zieburtz William , Gaur Sanjay , Kiger Miles H. , Giardina Giardina
Published: August 2016

The capistrano decision implies that all U.S. utility managers should prepare for potential requests for rate structure justification.
System and Surroundings
Authors: Mercer Kenneth L.
Published: August 2016

Early on, engineering students are typically taught some version of the following approach to tackling problems. The professor draws a small circle on the chalkboard and writes a single word inside: SYSTEM. The professor then writes a single word outside the circle: SURROUNDINGS, explaining that in problem‐solving one must focus entirely on the system and ignore the rest of the universe except at the boundaries where system and surroundings interface.
Behind the Numbers
Authors: LaFrance David B.
Published: August 2016

In the July 2016 issue of Journal AWWA, Editor‐in‐Chief Kenneth Mercer provided critical insights into the current state of the water industry (“2016 State of the Water Industry: The Cornerstone Needs Support”). Mercer provided key demographic information before summarizing the overall results, which helps us understand who is taking the voluntary survey; as a result, we can speculate as to how the survey pool demographics influence the results.
The Expanding Role of the Utility
Authors: Tracy Mehan G. , Carpenter Adam T. , Via Steve
Published: August 2016

In addition to managing the most vital public works of a developed society, a water utility must also function as a dynamic business with limited budget and increasing expectations. Customer needs are evolving, new and enhanced services like potable reuse and improved water loss control have been coming on‐line, and the regulatory landscape is in a constant state of change. However, four trends spreading across the sector warrant particular attention: planning for sustainability, investing in source water protection, thinking beyond the meter, and using new funding sources for infrastructure renewal and replacement. Although only a part of the expanding roles of the utility, these four developments frame the increasing complexity utilities face moving forward.
Encouraging Greater Compliance Requires a Change in the Status Quo
Authors: Fewell Brent
Published: August 2016

In the March 2016 issue of Journal AWWA, I wrote “The Failure of Cooperative Federalism in Flint, Michigan,” a Law and Water column that reflected upon the important role of the US Environmental Protection Agency (USEPA) and the states, as co‐regulators, in implementing and enforcing our nation's environmental laws. The fallout from Flint continues, as numerous state and local officials were criminally indicted in April and July 2016 by Michigan's Attorney General.
Mesenchymal Stem Cells Yield Transient Improvements in Motor Function in an Infant Rhesus Macaque with Severe Early-Onset Krabbe Disease
Authors: Isakova Irina A. , Baker Kate C. , Dufour Jason , Phinney Donald G.
Published: August 2016

Krabbe disease, or globoid cell leukodystrophy, is a rare disorder caused by deficient galactosylceramidase activity and loss of myelin-forming oligodendrocytes, resulting in progressive demyelination and severely impaired motor function. Disease symptoms in humans appear within 3–6 months of age (early infantile) and manifest as marked irritability, spasticity, and seizures. The disease is often fatal by the second year of life, with few effective treatment options. Herein we evaluated the therapeutic potential of mesenchymal stem cells (MSCs) administered intracranially to a 1-month-old rhesus macaque diagnosed with severe early-onset Krabbe disease that displayed neurologic and behavioral symptoms similar to those of human patients. The infant was subjected to physical and neurological behavior examinations and nerve conduction velocity tests to assess efficacy, and outcomes were compared with age-matched normal infants and Krabbe-affected rhesus monkeys with late-onset disease. Changes in major blood lymphocyte populations were also monitored to assess host immune cell responses. MSC administration resulted in transient improvements in coordination, ambulation, cognition, and large motor skills, which correlated with increased peripheral nerve conduction velocities and decreased latencies. Improvements also corresponded to transient increases in peripheral blood lymphocyte counts, but secondary challenge failed to elicit allo-antibody production. Nevertheless, white cell and neutrophil counts showed dramatic increases, and CD20+ B cell counts underwent a precipitous decline at late stages of disease progression. Correlative data linking MSC administration to transient improvements in motor function suggest that MSCs should be evaluated further as an experimental therapy for rare neurodegenerative diseases.
Directing Differentiation of Pluripotent Stem Cells Toward Retinal Pigment Epithelium Lineage
Authors: Choudhary Parul , Booth Heather , Gutteridge Alex , Surmacz Beata , Louca Irene , Steer Juliette , Kerby Julie , Whiting Paul John
Published: August 2016

Development of efficient and reproducible conditions for directed differentiation of pluripotent stem cells into specific cell types is important not only to understand early human development but also to enable more practical applications, such as in vitro disease modeling, drug discovery, and cell therapies. The differentiation of stem cells to retinal pigment epithelium (RPE) in particular holds promise as a source of cells for therapeutic replacement in age-related macular degeneration. Here we show development of an efficient method for deriving homogeneous RPE populations in a period of 45 days using an adherent, monolayer system and defined xeno-free media and matrices. The method utilizes sequential inhibition and activation of the Activin and bone morphogenetic protein signaling pathways and can be applied to both human embryonic stem cells and induced pluripotent stem cells as the starting population. In addition, we use whole genome transcript analysis to characterize cells at different stages of differentiation that provides further understanding of the developmental dynamics and fate specification of RPE. We show that with the described method, RPE develop through stages consistent with their formation during embryonic development. This characterization— together with the absence of steps involving embryoid bodies, three-dimensional culture, or manual dissections, which are common features of other protocols—makes this process very attractive for use in research as well as for clinical applications.
Énoncés visuels des mobilisations
Authors: Bertho Alain
Published: August 2016

La production et le partage en ligne d’images et de vidéos fait aujourd’hui partie du répertoire des mobilisations partout dans le monde. Cette pratique individuelle alimente un nouveau discours collectif visuel. L’analyse de ces images comme langage vernaculaire des mobilisations nous documente de façon originale sur la subjectivité collective qui les constitue. Celles des mobilisations brésilienne, turque et ukrainienne de 2013-2014 dessinent des « autoportraits des peuples » complexes et contrastés. La crise de la représentation politique signe-t-elle l’avènement du spectacle comme nouvel espace de confrontation ?
La mise en images de soi des jeunes montréalaises d’origine haïtienne
Authors: Boukala Mouloud
Published: August 2016

Cet article prend pour objet d’étude les autoreprésentations des jeunes Montréalaises d’origine haïtienne (15-24 ans) nées au Québec et vise à documenter, puis analyser leurs propres perceptions et les modes d’énonciation (vidéos, dessins, photographies, etc.) qu’elles emploient pour se représenter. En nous intéressant à leur autoreprésentation, nous explorerons le rôle et les impacts de ces images dans le contexte des dynamiques d’inclusion et d’exclusion sociale et culturelle qui marquent la société cosmopolite montréalaise : ces « techniques de soi » (Foucault 1985) constituent-elles des alternatives à « une violence envers le sujet de la représentation » (Saïd 2014 : 13) ? Leurs productions médiatiques les enferment-elles (production et alimentation d’une stéréotypie déjà existante) ou bien les désenclavent-elles (« les libèrent en les exposant à comparaître, les gratifiant ainsi d’une puissance propre d’apparition », Didi-Huberman 2012 : 144) ? Quelle est la variété de ces expressions de soi ? Comment s’élaborent des identités virtuelles ? Ces identités virtuelles contribuent-elles à des schémas d’action ?
Photographie, un objet du pouvoir
Authors: Jewsiewicki Bogumil
Published: August 2016

Ce texte examine les effets sociaux des usages congolais de la photographie comme medium de production et de circulation de l’identité et du corps modernes. Au cours du XXe siècle, la représentation photographique témoigne de la nouvelle identité mise en circulation dans l’univers moderne. L’image « mécaniquement reproduite » constitue un artefact tenant lieu et place d’une personne moderne. Pour ce numéro spécial, l’intérêt du texte proposé ici est surtout comparatif. L’analyse d’un processus de représentation de soi par la photographie éclaire ce que fait à la représentation de soi la circulation sur Internet des images autoproduites. Certes, les deux situations sont opposées : dans le cas congolais l’image fixe est bidimensionnelle, sa production par un tiers et sa circulation sont commodifiées ; sur Internet l’image animée est autoproduite pour la circulation dans l’espace non commodifié. Néanmoins, dans un cas comme dans l’autre, il y a coïncidence entre le changement de médium et la volonté du sujet de mettre en circulation une autre représentation de soi, de contrôler l’image de son corps. Au Congo, l’identité moderne est en construction permanente, elle semble graviter autour de la personne plutôt que faire partie du corps. Socialement acceptée, la représentation du corps noir féminin « moderne » s’inscrit dans la mémoire culturelle de la domination, y compris au plan de l’érotisme. Par contre, lorsque des femmes s’emparent de l’image de leur corps pour défier le système social, le corps nu est représenté en tant que bien commodifié. Il est alors inscrit dans un mode de jouissance « moderne » et dans l’offre de satisfaction du désir masculin individuel contre l’accès aux réseaux de pouvoir. Faut-il y voir un désir de pouvoir ou une tentative de libération de la domination masculine ? La distinction est difficile à opérer. En effet, sur le sexe féminin exposé plane la mémoire d’une autre conception selon laquelle ce sexe est autant le lieu d’où vient la vie que le siège d’une puissance sorcière. Exposer/regarder le sexe féminin est ainsi un acte de pouvoir.
L’institutionnalisation des fat studies : l’impensé des « corps gros » comme modes de subjectivation politique et scientifique
Authors: Rousseau Audrey
Published: August 2016

Cet article discute de l’institutionnalisation croissante du champ de recherche desfat studies. Entremêlant savoirs militants et connaissances universitaires, ce courant interdisciplinaire et intersectionnel veut dénoncer la discrimination basée sur le poids dans les sociétés occidentales en mettant en avant le vécu des personnesfat. Puisque ces théories et ces pratiques sont peu connues des communautés féministes francophones, en raison d’un déficit de traduction, l’auteure a choisi de présenter certains enjeux liés à la construction sociale des discours sur la « corpulence » et la reconnaissance des « corps gros » comme sujets épistémiques.
Entre science et politique : la question épistémologique dans l’histoire de la psychologie féministe
Authors: Pache Stéphanie
Published: August 2016

L’expertise psychologique a acquis durant leXXe siècle un statut social qui en a fait la cible des critiques des féministes de la deuxième vague. Cet article présente l’histoire de la façon dont cette critique politique et épistémologique se développe en une approche féministe de la psychologie. Il discute également le processus qui fait de la psychologie féministe une nouvelle expertise.
Récolter et préserver la mémoire des femmes : réflexions méthodologiques sur le recours à l’histoire orale auprès des femmes âgées
Authors: Labrie Christine
Published: August 2016

S’inspirant d’une enquête menée auprès de femmes âgées qui n’ont pas eu d’enfants, l’auteure propose une réflexion sur l’intérêt de l’histoire orale pour redonner de l’importance aux femmes en tant qu’actrices de l’histoire. Elle aborde notamment les particularités de cette approche méthodologique lorsque les participantes sont âgées, ce qui a une incidence sur le recrutement, le choix du médium d’enregistrement et le déroulement de l’entrevue. Finalement, l’auteure présente la réflexion ayant mené au dépôt des enregistrements dans un centre d’archives, afin de rendre accessible au public ainsi qu’aux chercheurs et aux chercheuses la mémoire de ces femmes.
Pour une pédagogie féministe de l’enseignement des méthodologies (féministes)
Authors: Lampron Ève-Marie
Published: August 2016

Cette note d’action, écrite par une enseignante des méthodologies féministes en contexte universitaire, trace un portrait sommaire des multiples rôles assumés par les personnes étudiantes dans la coconstruction des connaissances à caractère plus précisément méthodologique. Que ce soit par des pédagogies interactives qui nécessitent leur participation, par les travaux d’équipe ou par le partage d’expériences pertinentes relativement à l’apprentissage du plus grand nombre, ces personnes se livrent, dans une certaine mesure, au coenseignement. En filigrane, le texte insiste également sur la nécessaire cohérence entre les principes féministes enseignés en classe et leur application concrète, notamment au coeur de la relation enseignante-étudiante ou étudiant.
Rapid induction of GFP expression by the nitrate reductase promoter in the diatomPhaeodactylum tricornutum
Authors: Chu Lili , Ewe Daniela , Río Bártulos Carolina , Kroth Peter G. , Gruber Ansgar
Published: August 2016

An essential prerequisite for a controlled transgene expression is the choice of a suitable promoter. In the model diatomPhaeodactylum tricornutum, the most commonly used promoters for trans-gene expression are the light dependent lhcf1 promoters (derived from two endogenous genes encoding fucoxanthin chlorophyll a/c binding proteins) and the nitrate dependent nr promoter (derived from the endogenous nitrate reductase gene). In this study, we investigated the time dependent expression of the green fluorescent protein (GFP) reporter under control of the nitrate reductase promoter in independently genetically transformedP. tricornutumcell lines following induction of expression by change of the nitrogen source in the medium via flow cytometry, microscopy and western blotting. In all investigated cell lines, GFP fluorescence started to increase 1 h after change of the medium, the fastest increase rates were observed between 2 and 3 h. Fluorescence continued to increase slightly for up to 7 h even after transfer of the cells to ammonium medium. The subsequent decrease of GFP fluorescence was much slower than the increase, probably due to the stability of GFP. The investigation of several cell lines transformed with nr based constructs revealed that, also in the absence of nitrate, the promoter may show residual activity. Furthermore, we observed a strong variation of gene expression between independent cell lines, emphasising the importance of a thorough characterisation of genetically modified cell lines and their individual expression patterns.
Thermal treatment and leaching of biochar alleviates plant growth inhibition from mobile organic compounds
Authors: Gale Nigel V. , Sackett Tara E. , Thomas Sean C.
Published: August 2016

Recent meta-analyses of plant responses to biochar boast positive average effects of between 10 and 40%. Plant responses, however, vary greatly across systems, and null or negative biochar effects are increasingly reported. The mechanisms responsible for such responses remain unclear. In a glasshouse experiment we tested the effects of three forestry residue wood biochars, applied at five dosages (0, 5, 10, 20, and 50 t/ha) to a temperate forest drystic cambisol as direct surface applications and as complete soil mixes on the herbaceous pioneersLolium multiflorumandTrifolium repens. Null and negative effects of biochar on growth were found in most cases. One potential cause for null and negative plant responses to biochar is plant exposure to mobile compounds produced during pyrolysis that leach or evolve following additions of biochars to soil. In a second glasshouse experiment we examined the effects of simple leaching and heating techniques to ameliorate potentially phytotoxic effects of volatile and leachable compounds released from biochar. We used Solid Phase Microextraction (SPME)–gas chromatography–mass spectrometry (GC-MS) to qualitatively describe organic compounds in both biochar (through headspace extraction), and in the water leachates (through direct injection). Convection heating and water leaching of biochar prior to application alleviated growth inhibition. Additionally, growth was inhibited when filtrate from water-leached biochar was applied following germination. SPME-GC-MS detected primarily short-chained carboxylic acids and phenolics in both the leachates and solid chars, with relatively high concentrations of several known phytotoxic compounds including acetic acid, butyric acid, 2,4-di-tert-butylphenol and benzoic acid. We speculate that variable plant responses to phytotoxic organic compounds leached from biochars may largely explain negative plant growth responses and also account for strongly species-specific patterns of plant responses to biochar amendments in short-term experiments.
Propagation of rating curve uncertainty in design flood estimation
Authors: Steinbakk G. H. , Thorarinsdottir T. L. , Reitan T. , Schlichting L. , Hølleland S. , Engeland K.
Published: August 2016

Statistical flood frequency analysis is commonly performed based on a set of annual maximum discharge values which are derived from stage measurements via a stage‐discharge rating curve model. Such design flood estimation techniques often ignore the uncertainty in the underlying rating curve model. Using data from eight gauging stations in Norway, we investigate the effect of curve and sample uncertainty on design flood estimation by combining results from a Bayesian multisegment rating curve model and a Bayesian flood frequency analysis. We find that sample uncertainty is the main contributor to the design flood estimation uncertainty. However, under extrapolation of the rating curve, the uncertainty bounds for both the rating curve model and the flood frequency analysis are highly skewed and ignoring these features may underestimate the potential risk of flooding. We expect this effect to be even more pronounced in arid and semiarid climates with a higher variability in floods.
The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the 15N Haber‐Bosch effect
Authors: Yang Simon , Gruber Nicolas
Published: August 2016

Over the last 100 years, anthropogenic emissions have led to a strong increase of atmospheric nitrogen deposition over the ocean, yet the resulting impacts and feedbacks are neither well understood nor quantified. To this end, we run a suite of simulations with the ocean component of the Community Earth System Model v1.2 forced with five scenarios of nitrogen deposition over the period from 1850 through 2100, while keeping all other forcings unchanged. Even though global oceanic net primary production increases little in response to this fertilization, the higher export and the resulting expansion of the oxygen minimum zones cause an increase in pelagic and benthic denitrification and burial by about 5%. In addition, the enhanced availability of fixed nitrogen in the surface ocean reduces global ocean N2 fixation by more than 10%. Despite the compensating effects through these negative feedbacks that eliminate by the year 2000 about 60% of the deposited nitrogen, the anthropogenic nitrogen input forced the upper ocean N budget into an imbalance of between 9 and 22 Tg N yr−1 depending on the deposition scenario. The excess nitrogen accumulates to highly detectable levels and causes in most areas a distinct negative trend in the δ15N of the oceanic fixed nitrogen pools—a trend we refer to as the 15N Haber‐Bosch effect. Changes in surface nitrate utilization and the nitrogen feedbacks induce further changes in the δ15N of
, making it a good but complex recorder of the overall impact of the changes in atmospheric deposition.
Iron‐Based Imidazolium Salts as Versatile Catalysts for the Synthesis of Quinolines and 2‐ and 4‐Allylanilines by Allylic Substitution of Alcohols
Authors: Trillo Paz , Pastor Isidro M.
Published: August 2016

Readily available iron(III)‐based imidazolium salts have proven to be very versatile catalysts for the allylic substitution reaction of alcohols with anilines, allowing the synthesis of quinolines, 2‐allylanilines and 4‐allylanilines just by modulating the reaction conditions. Noteworthy, the formation of quinoline derivatives proceeds by ortho‐allylation of the corresponding aniline and subsequent oxidative cyclization mediated by atmospheric oxygen. The reaction using anilines as nucleophiles is selective to the C‐alkylation versus the N‐alkylation, under any reaction conditions studied.

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Efficient Biosynthesis of (R)‐ or (S)‐2‐Hydroxybutyrate from l‐Threonine through a Synthetic Biology Approach
Authors: Yao Peiyuan , Cui Yunfeng , Yu Shanshan , Du Yuncheng , Feng Jinhui , Wu Qiaqing , Zhu Dunming
Published: August 2016

An efficient multi‐enzyme cascade reaction for the synthesis of (R)‐ or (S)‐2‐hydroxybutyric acid [(R)‐ or (S)‐2‐HB] from l‐threonine was developed by using recombinant Escherichia coli cells expressing separately or co‐expressing l‐threonine deaminase from Escherichia coli K‐12 (ilvA), formate dehydrogenase (FDH) from Candida boidinii and l‐lactate dehydrogenase (l‐LDH) from Oryctolagus cuniculus or d‐lactate dehydrogenase (d‐LDH) from Staphylococcus epidermidis ATCC 12228. Up to 750 mM of l‐threonine were completely transformed to (R)‐ or (S)‐2‐HB in optically pure form (>99% ee) with high isolated yields. This one‐pot multi‐enzyme transformation provides a new practical method for the synthesis of these important optically pure compounds.

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Aerobic Copper Catalysis for Tandem Oxy‐N‐alkenylation of [1,2,3]Triazolo[1,5‐a]pyridines
Authors: Pankajakshan Sreekumar , Ang Wei Li , Sreejith Sivarampanicker , Stuparu Mihaiela Corina , Loh Teck‐Peng
Published: August 2016

N‐Alkenylated triazolinone ylides were generated through copper‐catalyzed oxy‐N‐alkenylation of triazolopyridines. The mechanistic course of this aerobic tandem reaction has been experimentally elucidated and primary photophysical data of the ylide products are also given.

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Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether‐Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure–Reactivity Relationship and Mechanistic DFT Study
Authors: Della Monica Francesco , Vummaleti Sai V. C. , Buonerba Antonio , Nisi Assunta De , Monari Magda , Milione Stefano , Grassi Alfonso , Cavallo Luigi , Capacchione Carmine
Published: August 2016

A series of dinuclear iron(III)I complexes supported by thioether‐triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron‐based catalysts (5200 h−1; 120 °C, 2 MPa, 1 h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle.

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Access to Polycyclic Alkaloid‐Like Structures by Coupling the Passerini and Ugi Reactions with Two Sequential Metal‐Catalyzed Cyclizations
Authors: Spallarossa Martina , Banfi Luca , Basso Andrea , Moni Lisa , Riva Renata
Published: August 2016

Complex polycyclic compounds resembling some natural alkaloids have been prepared in only three high yielding steps by combining the Ugi or Passerini multicomponent reactions with two metal‐catalyzed cyclizations: an intramolecular Tsuji–Trost reaction of the isocyanide‐derived amide followed by a ring‐closing metathesis. Scaffold diversity may be explored by the appropriate choice of starting unsaturated isocyanides. The Tsuji–Trost cyclization proceeds with moderate to good diastereoselectivity, and the major diastereomer was in most cases isolated in the pure form.

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Prediction of the originating site of sinonasal inverted papilloma by preoperative magnetic resonance imaging and computed tomography
Authors: Fang Gaoli , Lou Hongfei , Yu Wenling , Wang Xiangdong , Yang Bentao , Xian Junfang , Song Xiaohong , Fan Erzhong , Li Ying , Wang Chengshuo , Zhang Luo
Published: August 2016

Background

Precise localization and excision of the originating site of a sinonasal inverted papilloma (SNIP) is essential for decreasing tumor recurrence. In this study we evaluated the use of preoperative computed tomography (CT) and magnetic resonance imaging (MRI) to pinpoint the attachment/originating sites of SNIPs in 143 patients.

Methods

Osteitis signs in CTs and convoluted cerebriform pattern (CCP)–based reverse tracings from MRIs of 143 SNIP patients were analyzed preoperatively to predict the originating site of SNIPs. The predicted sites were compared with actual SNIP attachment sites determined by surgery, and patients were followed‐up for evaluation of SNIP recurrence rates over a mean period of about 4 years.

Results

Osteitis signs in CT accurately predicted the actual tumor attachment site in 49.7% of all patients. In comparison, convoluted cerebriform pattern (CCP)–based reverse tracings in MRI and combination CT plus MRI accurately predicted the SNIP originating sites in 84.1% and 86% of the patients, respectively. Sensitivity and specificity in predicting the SNIP originating site were: CT, 54.6% and 69.2%; MRI, 93.1% and 76.9%; and CT+MRI, 94.6% and 92.3%, respectively. A single postoperative recurrence occurred in 4.2% of the patients.

Conclusions

Preoperative combination of MRI and CT provides a better option to accurately predict the SNIP originating site, and thus may facilitate accurate and complete excision of the SNIP.
{[CuSn5Sb3]2−}2: Ein Dimer inhomogener Superatome
Authors: Wilson Robert J. , Broeckaert Lies , Spitzer Fabian , Weigend Florian , Dehnen Stefanie
Published: August 2016

Die Reaktion des binären Zintl‐Anions (Sn2Sb2)2− mit dem β‐Diketiminato‐Komplex [LCu(NCMe)] (L=nacnac=[(N(C6H3iPr2‐2,6)C(Me))2CH]−) in Ethylendiamin oder DMF führt zur Bildung des ternären Cluster‐Dimers {[CuSn5Sb3]2−}2 (1) in Form seines [K(crypt‐222)]+‐Salzes. Die Elementzusammensetzung von 1 wurde mithilfe energiedispersiver Röntgenspektroskopie (EDX) und quantenchemischer Rechnungen verifiziert. Das Dimer besteht aus monomeren, trimetallischen Einheiten “[CuSn5Sb3]2−”, deren Struktur zwischen der des dreifach überdachten trigonalen Prismas und der des einfach überdachten quadratischen Antiprismas angesiedelt ist. Das Cluster‐Monomer lässt sich infolge der Anwesenheit von Sb‐Atomen und insbesondere der eines Cu‐Atoms (anstelle von ausschließlich Sn‐Atomen) als inhomogenes Superatom beschreiben, das – wie quantenchemische Rechnungen zeigen – durch Dimerisierung stabilisiert wird. Dabei resultiert ein relativ kleiner Cu⋅⋅⋅Cu‐Abstand, allerdings ohne signifikante bindende Wechselwirkung.
Biomimetic Hybrid Nanocontainers with Selective Permeability
Authors: Messager Lea , Burns Jonathan R. , Kim Jungyeon , Cecchin Denis , Hindley James , Pyne Alice L. B. , Gaitzsch Jens , Battaglia Giuseppe , Howorka Stefan
Published: August 2016

Chemistry plays a crucial role in creating synthetic analogues of biomacromolecular structures. Of particular scientific and technological interest are biomimetic vesicles that are inspired by natural membrane compartments and organelles but avoid their drawbacks, such as membrane instability and limited control over cargo transport across the boundaries. In this study, completely synthetic vesicles were developed from stable polymeric walls and easy‐to‐engineer membrane DNA nanopores. The hybrid nanocontainers feature selective permeability and permit the transport of organic molecules of 1.5 nm size. Larger enzymes (ca. 5 nm) can be encapsulated and retained within the vesicles yet remain catalytically active. The hybrid structures constitute a new type of enzymatic nanoreactor. The high tunability of the polymeric vesicles and DNA pores will be key in tailoring the nanocontainers for applications in drug delivery, bioimaging, biocatalysis, and cell mimicry.
Decarbonylative Silylation of Esters by Combined Nickel and Copper Catalysis for the Synthesis of Arylsilanes and Heteroarylsilanes
Authors: Guo Lin , Chatupheeraphat Adisak , Rueping Magnus
Published: August 2016

An efficient nickel/copper‐catalyzed decarbonylative silylation reaction of carboxylic acid esters with silylboranes is described. This reaction provides access to structurally diverse silanes with high efficiency and excellent functional‐group tolerance starting from readily available esters.
Prediction of Protein Structure Using Surface Accessibility Data
Authors: Hartlmüller Christoph , Göbl Christoph , Madl Tobias
Published: August 2016

An approach to the de novo structure prediction of proteins is described that relies on surface accessibility data from NMR paramagnetic relaxation enhancements by a soluble paramagnetic compound (sPRE). This method exploits the distance‐to‐surface information encoded in the sPRE data in the chemical shift‐based CS‐Rosetta de novo structure prediction framework to generate reliable structural models. For several proteins, it is demonstrated that surface accessibility data is an excellent measure of the correct protein fold in the early stages of the computational folding algorithm and significantly improves accuracy and convergence of the standard Rosetta structure prediction approach.
A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}8–10
Authors: Chalkley Matthew J. , Peters Jonas C.
Published: August 2016

Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO}8, {FeNO}9, and {FeNO}10. These {FeNO}8–10 compounds are each low‐spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}8–10 are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers.
From 0 to II in One‐Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2
Authors: Yang Xiuxiu , Gianetti Thomas L. , Harbort Joshua , Wörle Michael D. , Tan Lilin , Su Cheng‐Yong , Jurt Pascal , Harmer Jeffrey R. , Grützmacher Hansjörg
Published: August 2016

We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2 (trop=5‐H‐dibenzo‐[a,d]cyclohepten‐5‐yl) in the oxidation states 0, +I, and +II, formed via successive one‐electron oxidization steps from Ru0(tropPPh2)2. The bidentate character of the tropPPh2 ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X‐ray diffraction analysis. EPR data of the mononuclear RuI complex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the RuI center.
5‐Formylcytosin ist vermutlich eine semipermanente Base an definierten Genompositionen
Authors: Su Meng , Kirchner Angie , Stazzoni Samuele , Müller Markus , Wagner Mirko , Schröder Arne , Carell Thomas
Published: August 2016

Die epigenetische Base 5‐Formyl‐2′‐desoxycytosin (fdC) wurde kürzlich im Genom von Stammzellen entdeckt. Ihre Funktion ist bisher jedoch unbekannt. Daten aus Genomsequenzierungen zeigen eine Anreicherung in CpG‐Inseln von Promotoren, weshalb eine Beteiligung an der Regulation der Transkription während der zellulären Differenzierung angenommen wird. Auch ist fdC dafür bekannt, von dem Enzym Thymin‐DNA‐Glykosylase (Tdg) erkannt und ausgeschnitten zu werden. Folglich wird angenommen, dass fdC als Intermediat während der aktiven Demethylierung auftritt. Um die Funktion von fdC zu verstehen, ist es von großer Bedeutung, seine Bildung und Entfernung an definierten genomischen Positionen analysieren zu können. Im Folgenden beschreiben wir eine neue derartige Methode, die sequenzspezifische chemische Derivatisierung von fdC mit Droplet Digital PCR kombiniert. Erste Ergebnisse zeigen, dass das Reparaturprotein Tdg nur 50 % der fdCs an einer bestimmten Position im Genom entfernt, was auf semipermanente Eigenschaften dieser Base hinweist.
Ruthenium(II)‐Catalyzed C−H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate‐Controlled Synthesis of Indoles and 3H‐Indoles
Authors: Li Yunyun , Qi Zisong , Wang He , Yang Xifa , Li Xingwei
Published: August 2016

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor–acceptor diazo compounds were developed that afforded NH indoles and 3H‐indoles under ruthenium catalysis. The coupling of α‐diazoketoesters afforded NH indoles by cleavage of the C(N2)−C(acyl) bond whereas α‐diazomalonates gave 3H‐indoles by C−N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium‐catalyzed C−H activation.
Hydrogen Peroxide Coordination to Cobalt(II) Facilitated by Second‐Sphere Hydrogen Bonding
Authors: Wallen Christian M. , Palatinus Lukáš , Bacsa John , Scarborough Christopher C.
Published: August 2016

M(H2O2) adducts have been postulated as intermediates in biological and industrial processes; however, only one observable M(H2O2) adduct has been reported, where M is redox‐inactive zinc. Herein, direct solution‐phase detection of an M(H2O2) adduct with a redox‐active metal, cobalt(II), is described. This CoII(H2O2) compound is made observable by incorporating second‐sphere hydrogen‐bonding interactions between bound H2O2 and the supporting ligand, a trianionic trisulfonamido ligand. Thermodynamics of H2O2 binding and decay kinetics of the CoII(H2O2) species are described, as well as the reaction of this CoII(H2O2) species with Group 2 cations.
{[CuSn5Sb3]2−}2: A Dimer of Inhomogeneous Superatoms
Authors: Wilson Robert J. , Broeckaert Lies , Spitzer Fabian , Weigend Florian , Dehnen Stefanie
Published: August 2016

Reaction of the binary Zintl anion (Sn2Sb2)2− with the β‐diketiminato complex [LCu(NCMe)] (L=nacnac=[(N(C6H3iPr2‐2,6)C(Me))2CH]−) in ethylenediamine or DMF affords the ternary cluster dimer {[CuSn5Sb3]2−}2 (1) as its [K(crypt‐222)]+ salt. The chemical formulation of 1 is supported by energy‐dispersive X‐ray spectroscopy (EDX) and quantum chemical calculations. Each monomeric part of the dimer represents a trimetallic “[CuSn5Sb3]2−” cluster, with an architecture in between a tricapped trigonal prism and a capped square antiprism. As shown by quantum chemical investigations, the presence of Sb atoms and, in particular, of Cu atoms in the cluster skeleton makes the monomeric unit behave like an inhomogeneous superatom, which clearly prefers to dimerize, thereby producing a relatively short, yet virtually non‐bonding Cu⋅⋅⋅Cu distance.