bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of a β‐d‐Psicofuranosyl Sulfone and Inhibitory‐Activity Evaluation Against N‐Acetylglucosaminyltransferase I
Authors: Bella Maroš , Yan Shi , Šesták Sergej , Kozmon Stanislav , Lin Chun‐Hung , Mucha Ján , Koóš Miroslav
Published: September 2017

Alkyl or aryl 3‐acetamido‐3‐deoxy‐2‐thio‐β‐d‐psicofuranosides bearing a phosphate group at C‐1, which were originally designed as potential GnT‐I inhibitors (GnT = N‐acetylglucosaminyltransferase) by computational methods, were found to be unstable. Therefore their structure was slightly modified to stable 3‐acetamido‐3‐deoxy‐β‐d‐psicofuranosyl sulfones. A model inhibitor of GnT‐I, namely ethyl 3‐acetamido‐3‐deoxy‐1‐O‐phosphono‐β‐d‐psicofuranosyl sulfone, was synthesized based on the transformation of d‐mannose into 3‐azido‐3‐deoxy‐d‐psicofuranose as the key intermediate. Thioglycosylation of 1,2‐O‐diisopropylidene‐protected 3‐azido‐ or 3‐amino‐3‐deoxy‐d‐psicofuranose derivatives with thiols in the presence of BF3·OEt2 was found to be a crucial step in the synthesis of the predicted inhibitor. Biochemical evaluation of the proposed inhibitor revealed only a very weak inhibition of GnT‐I. Additional molecular modeling showed that further modifications of the UDP‐mimicking part of the synthesized inhibitor are necessary to improve its inhibitory activity against GnT‐I.
Tandem O–H Insertion/[3,3]‐Sigmatropic Rearrangement of Rhodium Carbenoids with 2‐Furfuryl Alcohols: A Strategy To Access Polysubstituted Furans
Authors: Mi Pengbing , Wang Hannan , Zhao Rui , Song Jinna
Published: September 2017

Polysubstituted furans are versatile building blocks in organic synthesis and are widely spread in a variety of natural products, pharmaceuticals, and functional materials. Herein, we report a convenient, facile, and economic approach for the synthesis of polysubstituted furans through a tandem O–H insertion/[3,3]‐sigmatropic rearrangement of rhodium carbenoids with easily available furfuryl alcohols. This protocol is characterized by its operational simplicity, high efficiency with excellent yields, broad substrate scope, and great functional‐group tolerance.
On gel electrophoresis of dielectric charged particles with hydrophobic surface: A combined theoretical and numerical study
Authors: Majee Partha Sarathi , Bhattacharyya Somnath , Gopmandal Partha Pratim , Ohshima Hiroyuki
Published: September 2017

A theoretical study on the gel electrophoresis of a charged particle incorporating the effects of dielectric polarization and surface hydrophobicity at the particle–liquid interface is made. A simplified model based on the weak applied field and low charge density assumption is also presented and compared with the full numerical model for a nonpolarizable particle to elucidate the nonlinear effects such as double layer polarization and relaxation as well as surface conduction. The main motivation of this study is to analyze the electrophoresis of the surface functionalized nanoparticle with tunable hydrophobicity or charged fluid drop in gel medium by considering the electrokinetic effects and hydrodynamic interactions between the particle and the gel medium. An effective medium approach, in which the transport in the electrolyte‐saturated hydrogel medium is governed by the Brinkman equation, is adopted in the present analysis. The governing electrokinetic equations based on the conservation principles are solved numerically. The Navier‐slip boundary condition along with the continuity condition of dielectric displacement are imposed on the surface of the hydrophobic polarizable particle. The impact of the slip length on the electrophoresis is profound for a thinner Debye layer, however, surface conduction effect also becomes significant for a hydrophobic particle. Impact of hydrophobicity and relaxation effects are higher for a larger particle. Dielectric polarization creates a reduction in its electrophoretic propulsion and has negligible impact at the thinner Debye length as well as lower gel screening length.
Thermodynamic modeling of the combined CLG–CLHG system for syngas and hydrogen generation
Authors: Wang Kun , Yu Qingbo , Qin Qin , Duan Wenjun
Published: September 2017

The combined CLG and CLHG is a novel technology for the co‐generation of syngas and H2‐riched gas. In CLG process, the reduction of oxygen carrier with biomass can produce syngas. In CLHG process, the oxidation of oxygen carrier with steam can produce H2‐riched gas. In this study, the Ce‐based oxygen carrier was selected as the candidate material based on the Gibbs free energy changes (ΔG) of the splitting water reactions. The redox mechanism of the Ce‐based oxygen carrier was discussed and thermodynamic analysis of syngas and hydrogen generation was performed by Gibbs free energy minimization method. The optimal O/C in the GR was determined as 0.6–0.8 and the total dry concentration of CO and H2 was higher than 95.0% under 850–1000°C. The optimal S/C in the SR was determined as 2–3 and the H2 fraction was higher than 70.0% under 850–1000°C. In the AR, all of the Ce oxides can be regenerated to CeO2 in the air flow of 0.5 kmol at 700°C. After one CLG–CLHG cycle, there was no carbon deposition on the surface of oxygen carrier. The redox mechanism of the Ce‐based oxygen carrier was defined as:
© 2017 American Institute of Chemical Engineers Environ Prog, 37: 1132–1139, 2018
A large‐scale medieval dam‐lake cascade in central Europe: Water level dynamics of the Havel River, Berlin–Brandenburg region, Germany
Authors: Kaiser Knut , Keller Nora , Brande Arthur , Dalitz Stefan , Hensel Nicola , Heußner Karl‐Uwe , Kappler Christoph , Michas Uwe , Müller Joachim , Schwalbe Grit , Weiße Roland , Bens Oliver
Published: September 2017

An interdisciplinary study was carried out to trace the hydrological changes of the Havel River in northeastern central Europe over the last ca. 2000 years. This research was driven by the hypothesis that the present‐day riverscape is to a large degree a result of medieval and modern human transformation of the drainage system. The river system forms a series of dammed lakes and river sections that were greatly altered through hydraulic engineering in the past. Along the middle course of the Havel, 16 sedimentary sequences available for geoarchaeological and paleoecological research were analyzed in order to reconstruct regional water level dynamics. Chronological control was ensured through a multitude of palynological, dendrochronological, archaeological, and radiocarbon data. The sections upriver from the Brandenburg/H. and Spandau weirs, representing sites with historic watermills, reveal substantial water level changes during the late Holocene. Generally, lower water levels before and higher levels during the medieval German colonization of that area (ca. A.D. 1180/1250) can be inferred. This water level increase, which is primarily attributed to dams constructed for watermills and secondarily due to a multitude of fish weirs, took place rapidly and amounted to a relative height of ca. 1.5 m. It enlarged the river's cross‐sections and increased the size of existing lakes or initiated secondary lakes that previously aggraded, and thus caused flooding of large parts of land. The rising water level even influenced the settlement topography to a large degree. Several medieval rural settlements were abandoned due to flooding. In total, a ca. 150‐km long dammed lake cascade was formed.
Altered white‐matter integrity in unaffected siblings of probands with autism spectrum disorders
Authors: Chien Yi‐Ling , Chen Yu‐Jen , Hsu Yung‐Chin , Tseng Wen‐Yih Isaac , Gau Susan Shur‐Fen
Published: September 2017

Despite the evidence of altered white‐matter tract property in individuals with autism spectrum disorder (ASD), little is known about their unaffected siblings. This study aimed to investigate white‐matter integrity in unaffected siblings of ASD probands. Thirty‐nine unaffected siblings (mean age 15.6 ± 6.0 years; 27 males, 69.2%) and 39 typically developing controls (TDC) (14.2 ± 5.6 years; 26 males, 66.7%) were assessed with diffusion spectrum images and neuropsychological tests. Using the tract‐based automatic analysis and the threshold‐free cluster weighted (TFCW) scores, we searched for the segments among 76 tracts with the largest difference over the entire brain compared to TDC. Tract integrity was quantified by calculating the mean generalized fractional anisotropy (mGFA) values of the segments with the largest difference in TFCW scores. Unaffected siblings showed reduced mGFA in the bilateral frontal aslant tracts, the right superior longitudinal fasciculus 2 (SLF2), the frontostriatal tracts from the right dorsolateral and left ventrolateral prefrontal cortices, the thalamic radiations of the left ventral and the right dorsal thalamus, the callosal fibers of the splenium, and the increased mGFA of the callosal fibers of the precuneus and the left inferior longitudinal fasciculus. Among these, reduced right SLF2 mGFA was associated with social awareness deficits; impaired frontostriatal tract was associated with internalizing problems, while right frontal aslant tract integrity was associated with visual memory deficits. In conclusion, unaffected siblings showed the aberrant integrity of several white‐matter tracts, which were correlated with clinical symptoms and neurocognitive dysfunction. The altered tract integrity could be further examined in the probands with ASD. Hum Brain Mapp 38:6053–6067, 2017. © 2017 Wiley Periodicals, Inc.
Gray matter volumes of early sensory regions are associated with individual differences in sensory processing
Authors: Yoshimura Sayaka , Sato Wataru , Kochiyama Takanori , Uono Shota , Sawada Reiko , Kubota Yasutaka , Toichi Motomi
Published: September 2017

Sensory processing (i.e., the manner in which the nervous system receives, modulates, integrates, and organizes sensory stimuli) is critical when humans are deciding how to react to environmental demands. Although behavioral studies have shown that there are stable individual differences in sensory processing, the neural substrates that implement such differences remain unknown. To investigate this issue, structural magnetic resonance imaging scans were acquired from 51 healthy adults and individual differences in sensory processing were assessed using the Sensory Profile questionnaire (Brown et al.: Am J Occup Ther 55 (2001) 75–82). There were positive relationships between the Sensory Profile modality‐specific subscales and gray matter volumes in the primary or secondary sensory areas for the visual, auditory, touch, and taste/smell modalities. Thus, the present results suggest that individual differences in sensory processing are implemented by the early sensory regions. Hum Brain Mapp 38:6206–6217, 2017. © 2017 Wiley Periodicals, Inc.
Do hospitals respond to rivals' quality and efficiency? A spatial panel econometric analysis
Authors: Longo Francesco , Siciliani Luigi , Gravelle Hugh , Santos Rita
Published: September 2017

We investigate whether hospitals in the English National Health Service change their quality or efficiency in response to changes in quality or efficiency of neighbouring hospitals. We first provide a theoretical model that predicts that a hospital will not respond to changes in the efficiency of its rivals but may change its quality or efficiency in response to changes in the quality of rivals, though the direction of the response is ambiguous. We use data on eight quality measures (including mortality, emergency readmissions, patient reported outcome, and patient satisfaction) and six efficiency measures (including bed occupancy, cancelled operations, and costs) for public hospitals between 2010/11 and 2013/14 to estimate both spatial cross‐sectional and spatial fixed‐ and random‐effects panel data models. We find that although quality and efficiency measures are unconditionally spatially correlated, the spatial regression models suggest that a hospital's quality or efficiency does not respond to its rivals' quality or efficiency, except for a hospital's overall mortality that is positively associated with that of its rivals. The results are robust to allowing for spatially correlated covariates and errors and to instrumenting rivals' quality and efficiency.
The Affordable Care Act's insurance market regulations' effect on coverage
Authors: Wettstein Gal
Published: September 2017

Much of the debate surrounding reform of the Patient Protection and Affordable Care Act (ACA) revolves around its insurance market regulation. This paper studies the impact on health insurance coverage of those provisions. Using data from the American Community Survey, years 2008–2015, I focus on individuals, ages 26 to 64, who are ineligible for the subsidies or Medicaid expansions included in the ACA to isolate the effect of its market regulation. To account for time trends, I utilize a differences‐in‐differences approach with a control group of residents of Massachusetts who were already subject to a similarly regulated health insurance market. I find that the ACA's regulations caused an increase of 0.95 percentage points in health insurance coverage for my sample in 2014. This increase was concentrated among younger individuals, suggesting that the law's regulations ameliorated adverse selection in the individual health insurance market.
Challenges facing community health workers inBrazil's Family Health Strategy:Aqualitative study
Authors: Grossman‐Kahn Rebecca , Schoen Julia , Mallett John William , Brentani Alexandra , Kaselitz Elizabeth , Heisler Michele
Published: September 2017

Community health worker (CHW) programs are implemented in many low‐ and middle‐income countries such as Brazil to increase access to and quality of care for underserved populations; CHW programs have been found to improve certain indicators of health, but few studies have investigated the daily work of CHWs, their perspectives on what both helps and hinders them from fulfilling their roles, and ways that their effectiveness and job satisfaction could be increased. To examine these questions, we observed clinic visits, CHW home visits, and conducted semistructured interviews with CHWs in 7 primary care centers in Brazil—2 in Salvador, Bahia, and 5 in São Paulo, SP—in which CHWs are incorporated into the work of all primary care health teams. In addition to enhancing communication between the medical system and the community, CHWs consider their key roles to be helping persuade community members to seek medical care and increasing health professionals' awareness of the social conditions affecting their patients' health. Key obstacles that CHWs face include failure to be fully integrated into the primary care team, inability to follow‐up on identified health needs due to limited resources, as well as community members' lack of understanding of their work and undervaluing of preventative medicine. Increased training, better incorporation of CHWs into clinic flow and decision making, and establishing a clear community awareness of the roles and value of CHWs will help increase the motivation and effectiveness of CHWs in Brazil.
A DFT Survey of the Effects of d‐Electron Count and Metal Identity on the Activation and Functionalization of C−H Bonds for Mid to Late Transition Metals
Authors: Moulder Catherine A. , Cundari Thomas R.
Published: September 2017

The contribution of metal identity to the activation and functionalization of methane by a series of three‐coordinate imide complexes is evaluated in silico for a 3‐by‐3 block of metals from Fe to Pt. Three mechanisms were studied: oxidative addition (OA) to the metal; hydrogen atom abstraction (HAA) by the imide nitrogen; and, [2+2] addition across the metal‐imide bond. In no studied case, was a [2+2] mechanism preferred, perhaps suggesting this mechanism is largely (entirely?) the domain of d0 imides. There is a diagonal relationship within the nonet of metals studied in that OA is preferred for earlier, heavier (5d) members of the series, transitioning to an HAA mechanism for later, lighter (3d) imides. DFT indicates that important parameters in partitioning between HAA and OA mechanisms include the strength of the metal‐imide π‐bond, the ability of larger metals to accommodate increases in formal oxidation state and coordination number, and the soft acid/base compatibility of larger transition metals with soft hydride and methyl ligands
A method to establish stimulus control and compliance with instructions
Authors: Borgen John G. , Charles Mace F. , Cavanaugh Brenna M. , Shamlian Kenneth , Lit Keith R. , Wilson Jillian B. , Trauschke Stephanie L.
Published: September 2017

We evaluated a unique procedure to establish compliance with instructions in four young children diagnosed with autism spectrum disorder (ASD) who had low levels of compliance. Our procedure included methods to establish a novel therapist as a source of positive reinforcement, reliably evoke orienting responses to the therapist, increase the number of exposures to instruction–compliance–reinforcer contingencies, and minimize the number of exposures to instruction–noncompliance–no reinforcer contingencies. We further alternated between instructions with a high probability of compliance (high‐p instructions) with instructions that had a prior low probability of compliance (low‐p instructions) as soon as low‐p instructions lost stimulus control. The intervention is discussed in relation to the conditions necessary for the development of stimulus control and as an example of a variation of translational research.
Cr(VI) and lindane removal by Streptomyces M7 is improved by maize root exudates
Authors: Simon Sola María Z. , Pérez Visñuk Daiana , Benimeli Claudia S. , Polti Marta Alejandra , Alvarez Analia
Published: September 2017

Environmental mixed pollution by both organic and inorganic compounds are detected worldwide. Phytoremediation techniques have been proposed as ecofriendly methods for cleaning up polluted sites. Several studies have demonstrated enhanced dissipation of contaminants at the root‐soil interface through an increase in microbial activity caused by the release of plant root exudates (REs). The aim of this study was to evaluate the effectiveness for Cr(VI) and lindane removal by Streptomyces M7 cultured in a co‐contaminated system in presence of maize REs. Our results showed when REs were added to the contaminated minimal medium (MM) as the only carbon source, microbial removal of Cr(VI) and lindane increased significantly in comparison to contaminant removal obtained in MM with glucose 1 g L−1. The maximum removal of 91% of lindane and 49.5% of Cr(VI) were obtained in the co‐contaminated system. Moreover, Streptomyces M7 showed plant growth promoting traits which could improve plant performance in contaminated soils. The results presented in this study provide evidence that maize REs improved growth of Streptomyces M7 when REs were used as a carbon source in comparison to glucose. Consequently, lindane and Cr(VI) removal was considerably enhanced making evident the phytoremediation potential of the actinobacteria‐plant partnership.
Exploring the rise of blockchain technology: Towards distributed collaborative organizations
Authors: Scott Brett , Loonam John , Kumar Vikas
Published: September 2017

Cryptocurrencies and blockchain technology are playing an increasingly important role for organizations that seek to build social and solidarity‐based finance. Blockchain technology has emerged as a potential disruptor for the financial industry. However, cryptocurrencies and blockchain technology may help develop organizations that seek to build social and solidarity‐based finance.
Blockchain for good?
Authors: Kewell Beth , Adams Richard , Parry Glenn
Published: September 2017

The blockchain innovation appears to represent viable catalysts for achieving global sustainable development targets. Projects and initiatives seeking to extend the reach of distributed ledger technologies (DLTs) seem mostly intended for the benefit of for‐profit businesses, governments, and consumers. DLT projects devised for the public good could aim, in theory, to fulfill the United Nation’s current sustainable development goals. Blockchain technology is being applied in ways that could transform this ambition for good into a practical reality.
The networked record industry: How blockchain technology could transform the record industry
Authors: O’Dair Marcus , Beaven Zuleika
Published: September 2017

Blockchain technology may have transformational potential for those music industries associated with recorded music, and for the sustainability of music careers. While predictions of widespread disintermediation may have been premature, blockchain technology does appear to have the potential to transform the role of third parties and to make musicians’ careers more sustainable. Blockchains could improve the accuracy and availability of copyright data, facilitate near‐instant micropayments for royalties, and significantly improve the transparency of the value chain.
Hemocompatibility of Ca2+‐Crosslinked Nanocellulose Hydrogels: Toward Efficient Management of Hemostasis
Authors: Basu Alex , Hong Jaan , Ferraz Natalia
Published: September 2017

The present work investigates Ca2+‐crosslinked nanofibrillated cellulose hydrogels as potential hemostatic wound dressings by studying core interactions between the materials and a central component of wounds and wound healing—the blood. Hydrogels of wood‐derived anionic nanofibrillated cellulose (NFC) and NFC hydrogels that incorporate kaolin or collagen are studied in an in vitro whole blood model and with platelet‐free plasma assays. The evaluation of thrombin and factor XIIa formation, platelet reduction, and the release of activated complement system proteins, shows that the NFC hydrogel efficiently triggered blood coagulation, with a rapid onset of clot formation, while displaying basal complement system activation. By using the NFC hydrogel as a carrier of kaolin, the onset of hemostasis is further boosted, while the NFC hydrogel containing collagen exhibits blood activating properties comparable to the anionic NFC hydrogel. The herein studied NFC hydrogels demonstrate great potential for being part of advanced wound healing dressings that can be tuned to target certain wounds (e.g., strongly hemorrhaging ones) or specific phases of the wound healing process for optimal wound management.
Synthesis and Characterization of Functional Triphenylphosphine‐Containing Microporous Organic Polymers for Gas Storage and Separation
Authors: Xu Jiawei , Zhang Chong , Qiu Zexiong , Lei Zhenyu , Chen Bing , Jiang Jia‐Xing , Wang Feng
Published: September 2017

Two kinds of novel triphenylphosphine‐containing microporous organic polymers are designed and synthesized via palladium‐catalyzed Sonogashira−Hagihara coupling condensation reaction of triphenylphosphine oxide‐ and sulfide‐based monomers with different arylethynylene linkers. The gas adsorption isotherms reveal that these polymers have strong binding affinity for CO2 with high CO2 adsorption capacity, although they have moderate Brunauer−Emmett−Teller surface area ranging from 684 to 883 m2 g−1. Among the resulting polymers, triphenylphosphine oxide–tris(4‐ethynylphenyl)amine exhibits the highest CO2 uptake capacity of 2.61 mmol g−1 at 273 K and 1.13 bar with relatively high gas selectivity of 60.2 for CO2 over N2 at 273 K.
Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting
Authors: Ramakers Gijs , Krivcov Alexander , Trouillet Vanessa , Welle Alexander , Möbius Hildegard , Junkers Tanja
Published: September 2017

The organocatalyzed photo‐atom transfer radical polymerization (photoATRP) using 10‐phenylphenothiazine as catalyst is studied toward its use in methacrylic acid (MAA) polymerization and surface grafting. The organocatalyzed photoATRP of methyl methacrylate (MMA) is first optimized for continuous flow synthesis in order to assess the livingness of the polymerization. MMA can be polymerized in batch and in flow; however, conversions are limited by the loss of bromine functionality and hence high conversions have to be traded in with increasing dispersities. Also, MAA is polymerized successfully in continuous flow with similar limitations. Flow conditions are transferred to surface grafting from silanized silicon wafers. The presence of ATRP initiators after silanization is confirmed by secondary ion mass spectrometry and X‐ray photoelectron spectroscopy. Dense polymethacrylic acid brush films are successfully produced, which is not directly accessible via classical copper‐mediated ATRP techniques.
ITIH5 induces a shift in TGF‐β superfamily signaling involving Endoglin and reduces risk for breast cancer metastasis and tumor death
Authors: Rose Michael , Meurer Steffen K. , Kloten Vera , Weiskirchen Ralf , Denecke Bernd , Antonopoulos Wiebke , Deckert Martina , Knüchel Ruth , Dahl Edgar
Published: September 2017

ITIH5 has been proposed being a novel tumor suppressor in various tumor entities including breast cancer. Recently, ITIH5 was furthermore identified as metastasis suppressor gene in pancreatic carcinoma. In this study we aimed to specify the impact of ITIH5 on metastasis in breast cancer. Therefore, DNA methylation of ITIH5 promoter regions was assessed in breast cancer metastases using the TCGA portal and methylation‐specific PCR (MSP). We reveal that the ITIH5 upstream promoter region is particularly responsible for ITIH5 gene inactivation predicting shorter survival of patients. Notably, methylation of this upstream ITIH5 promoter region was associated with disease progression, for example, abundantly found in distant metastases. In vitro, stably ITIH5‐overexpressing MDA‐MB‐231 breast cancer clones were used to analyze cell invasion and to identify novel ITIH5‐downstream targets. Indeed, ITIH5 re‐expression suppresses invasive growth of MDA‐MB‐231 breast cancer cells while modulating expression of genes involved in metastasis including Endoglin (ENG), an accessory TGF‐β receptor, which was furthermore co‐expressed with ITIH5 in primary breast tumors. By performing in vitro stimulation of TGF‐β signaling using TGF‐β1 and BMP‐2 we show that ITIH5 triggered a TGF‐β superfamily signaling switch contributing to downregulation of targets like Id1, known to endorse metastasis. Moreover, ITIH5 predicts longer overall survival (OS) only in those breast tumors that feature high ENG expression or inversely regulated ID1 suggesting a clinical and functional impact of an ITIH5‐ENG axis for breast cancer progression. Hence, we provide evidence that ITIH5 may represent a novel modulator of TGF‐β superfamily signaling involved in suppressing breast cancer metastasis.
How well do Met Office post‐processed site‐specific probabilistic forecasts predict relative‐extreme events?
Authors: Sharpe Michael A. , Bysouth Clare E. , Stretton Rebecca L.
Published: September 2017

The Met Office routinely generates post‐processed forecasts at sites throughout the United Kingdom; both deterministic and probabilistic products exist and deterministic data populate the publicly available website. In recent years, providers of weather information have focused upon the impact of events; impact is often related to the frequency of occurrence of an event at a site which is determined by its climatology. The ability with which a site‐specific forecast predicts relative‐extremes may be investigated by examining the skill with which these events (defined in terms of a percentile chosen from the climatology at each site) are predicted. The blended, deterministic, website forecast is less likely to forecast extreme events; therefore, the probabilistic forecast product (which does not currently appear on the Met Office website) was evaluated for its ability to predict heavy rainfall (RF24), maximum summer day time temperature (Tmax), minimum winter night time temperature (Tmin) and strong winds (WShrly) over a 21 month period between December 2013 and August 2015. To this end, four methods of verification are considered: the Symmetric Extremal Dependency Index (SEDI), a threshold weighted version of the continuous ranked probability skill score (CRPSS) and a conditioned version of the CRPSS together with an analysis of the discrimination and reliability. Each method indicates forecast skill, with Tmax and RF24 identified as the most and least skilful respectively and WShrly identified as the most reliable. Site‐specific values of both versions of the CRPSS appear relatively well correlated and these scores also show correlation with SEDI for WShrly.
Model evaluation using ballistic trajectories and preliminary mesoscale model accuracies with age of global model initialization data
Authors: Cogan J.
Published: September 2017

The evaluation of vertical profiles derived from model output normally consists of comparisons with meteorological observations at prescribed levels. Simulated ballistic trajectories with their major dependence on meteorological conditions is suggested as an additional means to evaluate the accuracy of a model over the vertical extent of the trajectory, and is demonstrated with a preliminary model evaluation. Normally, initialization and adjustment of lateral boundary conditions employs the most recent output available from a larger scale regional or global model. However, some applications such as for civilian or military responders in areas with minimal or no connectivity to data centres may require the use of older large‐scale model data. This paper demonstrates the alternative method in a preliminary investigation on the effect of using older large‐scale data on mesoscale model accuracy. Initial results for trajectories and comparisons with meteorological observations showed wide variation among individual cases and a general tendency towards poorer accuracy with age of the large‐scale data. As the age of the large‐scale model increased from 3 to 4 days, trajectory outcomes showed slight improvements, and wind and, to a lesser extent, temperature appeared to improve slightly at several heights. Model profile and coincident radiosonde‐based trajectories differed by about 89 m for the mesoscale model forecast using the most recent (0 day) large‐scale input to 276 m for the oldest (4 days). While a far more complete dataset is required for conclusive results, these outcomes help point the way to further research.
Luminescent Capillary‐Based Whispering Gallery Mode Sensors: Crossing the Lasing Threshold
Authors: Meldrum A. , Morrish William , Lane Stephen , Wu Wanjie , Monro Tanya M. , François Alexandre
Published: September 2017

Silicon nanocrystals (Si NCs) present many advantages for sensor applications, including relatively bright and stable luminescence, low‐to‐negligible toxicity, and high physical and chemical robustness. In this work, the efforts in creating capillary‐based sensors from smooth films of oxide‐embedded SiNCs are summarized, and their responses to dye‐doped polymer films are compared. The main method is to form sub‐micrometer luminescent coatings on microcapillary channel walls. The coating must have a high index of refraction so that it can support the luminescence whispering gallery modes (WGMs) which propagate through the film and extend into the channel medium. Using Si NCs, a general refractometric sensing and the detection of layer‐by‐layer polyelectrolyte deposition on the capillary channel are demonstrated. The Si NC sensors are exceptionally robust and can be cleaned and re‐used multiple times. The main limitation of the method currently involves the relatively slow detection (requiring typically more than 20 s per collected luminescence spectrum) due to the low light levels associated with the Si NC luminescence. Finally, our most recent work is discussed, which aims to extend the luminescent capillary sensor into the lasing regime.
Reliability analysis for electronic devices using beta‐Weibull distribution
Authors: Méndez‐González Luis Carlos , Rodríguez‐Picón Luis Alberto , Valles‐Rosales Delia Julieta , Romero‐López Roberto , Quezada‐Carreón Abel Eduardo
Published: September 2017

Today, in reliability analysis, the most used distribution to describe the behavior of electronic products under voltage profiles is the Weibull distribution. Nevertheless, the Weibull distribution does not provide a good fit to lifetime datasets that exhibit bathtub‐shaped or upside‐down bathtub–shaped (unimodal) failure rates, which are often encountered in the reliability analysis of electronic devices. In this paper, a reliability model based on the beta‐Weibull distribution and the inverse power law is proposed. This new model provides a better approach to model the performance and fit of the lifetimes of electronic devices. To estimate the parameters of the proposed model, a Bayesian analysis is used. A case study based on the lifetime of a surface mounted electrolytic capacitor is presented, the results showed that the estimation of the proposed model differs from the inverse power law–Weibull and that it affects directly the mean time to failure, the failure rate, the behavior, and the performance of the capacitor under analysis.
Catalytic activation of nitrobenzene on PVP passivated silver cluster: A DFT investigation
Authors: Shukla Madhulata , Sinha Indrajit
Published: September 2017

Poly(N‐vinyl‐2‐pyrrolidone) (PVP) has been used extensively to stabilize the surface of noble metal nanoparticles against aggregation and also to produce anisotropic nanostructures. Naturally, it is very important to understand the effect of such surface stabilization by PVP on the catalytic activity of these nanoparticles. This communication investigates through DFT calculations the electronic properties of PVP stabilized 13‐atom Ag cluster for catalytic activation of nitrobenzene (NB). These computations suggest that poly(N‐vinyl‐2‐pyrrolidone) (PVP) interact with silver (Ag) cluster mainly through oxygen atom and acts not only as a stabilizer to prevent the aggregation of Ag clusters but also as an electron donor to activate the Ag clusters for further reaction. Natural Bonding Orbital (NBO) calculations show that catalytic activation of NB by PVP passivated Ag cluster occurs due to interaction of the oxygen of the nitro group with the Ag cluster. Weak back donation of electrons from M(dπ) orbital of Ag to antibonding σ* of one of the NO bond, facilitates the formation of the nitroso intermediate. To understand the extent and the nature of this interaction better, vibrational frequency calculation of nitrobenzene association with Ag13‐2PVP cluster is carried out. Red shift in the frequencies is consequence of strong interaction with that of silver cluster present in Ag13‐2PVP‐NB model.
A closer look into the nitrogen blank in elemental analyser/isotope ratio mass spectrometry measurements
Authors: Langel Reinhard , Dyckmans Jens
Published: September 2017

Rationale

One important limitation for the precise measurement of minute amounts of nitrogen (N) in solid samples by elemental analyser/isotope ratio mass spectrometry (EA/IRMS) is the accurate determination of the analyser blank value. This study was performed to identify different sources, amounts and isotopic composition of N blanks in EA/IRMS in order to identify measures for minimising the effect of the N blank on N isotopic data quality.

Methods

Different types of autosamplers, with and without zero‐blank functionality, were tested by analysing different amounts of substances of varying isotopic composition by EA/IRMS.

Results

Using zero‐blank autosamplers reduces the atmospheric N2 blank from 60 nmol to between 4 and 5 nmol depending on the autosampler type. This blank is derived from atmospheric N2 leaking into the elemental analyser, trapped in the sample tin capsules or contained in the oxygen added for combustion. Another source of blank is the reaction tube. As the sources of the blank differ, the isotopic composition of the blank is very variable. In addition, cross‐contamination from previous samples may contribute up to 3.3 nmol N.

Conclusions

For precise measurements of minute amounts of N in solid samples, reduction of the N blank is the most promising strategy. Correcting for the remaining N blank is only meaningful if the sample isotopic composition is very different from that of the N blank, because the precise determination of the isotopic composition of the N blank is not possible.
Does Fairtrade Certification Meet Producers' Expectations Related to Participating in Mainstream Markets? An Analysis of Advertised Benefits and Perceived Impact
Authors: Mook Anne , Overdevest Christine
Published: September 2017

In this paper, we identify three literature‐based hypotheses about how and whether Fairtrade labeling delivers its advertised benefits: a market mechanism that provides producers in developing countries advantaged access to consumer markets; a sustainable agriculture mechanism that improves the sustainability of Fairtrade products and a social justice mechanism that protects the rights and livelihoods of farmers and workers. We surveyed a broad cross‐section of Fairtrade‐certified producer organizations and compared their expectations with their satisfactions using an importance–performance analysis (IPA), principal component analysis (PCA) and ordered logit regression analyses. According to our results, Fairtrade producers report both high importance and high performance in terms of metrics such as empowering women, democratic decision‐making and reduction of child labor, suggesting that farmers are most satisfied with Fairtrade as a social justice mechanism. Fairtrade producers report high importance but lower performance of Fairtrade as a market mechanism and least satisfaction as a sustainable agriculture mechanism. We explore the drivers and implications of these findings for Fairtrade and provide recommendations to increase producer satisfaction.
Catalyst‐Free Synthesis for Pyrazole‐Fused Isocoumarins in Recyclable and Biodegradable Reaction Medium
Authors: Yadav Vijay B. , Rai Pragati , Sagir Hozeyfa , Kumar Akhilesh , Siddiqui Ibadur R.
Published: September 2017

An efficient and facile protocol for the synthesis of pyrazole‐fused isocoumarins via reactions of readily available ninhydrin and arylhydrazone is disclosed. This approach illustrate operational simplicity, offering a modified and expedient methodology for the direct construction of synthetically useful pyrazole‐fused isocoumarins compounds in good to excellent yields. This documented strategy, provide a cost effective and environmentally benign alternative to the other existing method.
Electrochemical Study of Self‐Assembled Aminothiol Substituted Phthalonitrile Layers for Corrosion Protection of Copper
Authors: Arslan Ece , Gürten Ali A. , Gök Halil Z. , Farsak Murat
Published: September 2017

Self‐assembled layers were formed using the compound of 4‐(2‐aminophenylthio)‐5‐(5‐mercaptopentylthio) phthalo‐nitrile (AMPN) to protect the copper surface from chloride corrosion. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) techniques were used to examine the interaction of self‐assembled layers with the copper surface. Electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and linear polarization resistance methods were used in 3.5% NaCl solution to investigate the effect of self‐assembled layers on copper corrosion. The results show that the optimum waiting time for the layer formed on the copper surface is 8 hours and the AMPN concentration is 15 mM. The AMPN‐self assembled film on the copper surface exhibited a maximum of 98.7% inhibition.
A New Approach to Chiral Enrichment by Exposure of Racemates of Amino Acids to Sonochemically‐Prepared BSA Microspheres
Authors: Kumar Vijay Bhooshan , Steinberg Yael , Porat Ze'ev , Nassir Molhm , Saady Abed , Hassner Alfred , Gedanken Aharon
Published: September 2017

This preliminary study describes a one‐step sonochemical formation of Bovine Serum Albumin (BSA) microspheres and theirchiralinteraction with several amino acids. Partial separation between enantiomers of various amino acids was accomplished by the interaction of these microspheres with solutions of racemic amino acids. The highest rate of enantiomeric enrichment was attained for D,L‐cysteine, where 59% enantiomeric excess (ee) of the L‐cysteine was measured. This indicates the preferrential interaction of theBSAmicrospheres with the D‐enantiomer of cystein. Nochiralactivity was observed for unsonicatedBSAmolecules. All other D,L‐amino acids that were examined provided enrichment of the D‐enantiomer albeit in lower ee values. D,L‐cysteine interacted with theBSAmicrospheres leading to L‐enantioselective enrichment up to 59 % ee at room tempertaure and 72% at 5 °C.Chiralenrichment was also carried out succesfully with other protein microspheres such as Avidin microspheres. In this case up to 41 % ee was acheived on interaction with DL‐phenylalanine. Our simple and facile method opens a new window for enantiomeric separation of racemic compounds.
Highly Efficient Synthesis of 4,3‐Fused 1,2,4‐Triazoles via One‐Pot Multicomponent Domino Reaction Catalyzed by KI/TBHP
Authors: Inturi Surendra Babu , Kalita Biswajit , Ahamed Abdul Gafoor Jafar
Published: September 2017

An unprecedented and highly efficient multicomponent domino reaction for construction of various 4,3‐fused 1,2,4‐triazoles from readily available starting materials such as aldehydes, p‐toluenesulfonhydrazide and aromatic N‐heterocycles catalyzed by KI/TBHP system has been developed. The method is transition metal free, operationally simple, eco‐friendly and inexpensive with broad functional group tolerance. This unique methodology was further expanded toward a new concept of multicomponent diversity oriented synthesis (DOS) to generate various 4,3‐fused 1,2,4‐triazoles using a combination of multiple N‐heterocycles and aldehydes, all in one‐pot, to give the corresponding products.
Preparation of Mesoporous Biomass Carbon Derived from Corn Stalks and Formation Mechanism
Authors: Yu Kaifeng , Zhu He , Li Mingyu , Zhang Hanxiang , Liang Ce
Published: September 2017

Different formational process could lead to diverse morphologies and properties. Therefore, the study on formation mechanism was very important to figure out the influence of formational process. The corn stalk core (CSC), as a kind of renewable biological resource, could be used as raw materials to prepare activated carbon materials (ACs) via carbonizing and activating. The transformational mechanisms on the every step and the variation of various components in the CSC were studied, which was supposed the feasible methods to enhance the performance. In addition, the process of cellulose transforming into the carbon and the carbon structure were deduced. The carbon materials prepared were characterized through a series of equipments, such as scanning electron microscopy (SEM) and nitrogen adsorption‐desorption measurements (BET), the obtained results showed that the ACs with more pores and higher specific surface area than the materials unactivated. In the end, the ACs was applied as anode in the lithium ion batteries (LIBs) to test their electrochemical performances. Comparing the carbon materials unactivated, the role of activated process was revealed.
[Bmim]BF4: A Versatile Ionic Liquid for the Synthesis of Diverse Bioactive Heterocycles
Authors: Banerjee Bubun
Published: September 2017

Last decade has seen a tremendous applications of [bmim]BF4 (1‐butyl‐3‐methyl imidazolium tetrafluoroborate) as an efficient, cheap, commercially available, less toxic ionic liquid for the various organic transformations. On the other hand heterocycles are the privileged structural subunit of many marketed drug molecules. The present review deals with the recent applications of [bmim]BF4 as an efficient reaction medium for the synthesis of diverse biologically relevant heterocycles reported so far.
Slowly Digestible‐ and Non‐Digestible α‐Glucans: An Enzymatic Approach to Starch Modification and Nutritional Effects
Authors: Sorndech Waraporn , Tongta Sunanta , Blennow Andreas
Published: September 2017

Escalating diabetes, obesity, cardiovascular disease, and bowel syndrome have increased consumer awareness of nutrition and energy values of starch products. Slowly digestible starch (SDS), slowly digestible maltooligosaccharides (SDM), and highly branched maltooligosaccharides, so called isomaltooligosaccharides (IMOs), generated by enzyme modification of starch, provide a new concept to meet consumer demands and solve urgent health‐associated problems. The combination of starch‐active enzymes in the glucanotransferase and glucanohydrolase families to produce slowly digestible‐ and non‐digestible α‐glucans has been widely studied, mainly focusing on the activities of branching enzyme (BE), amylomaltase (AM), and α‐transglucosidase (TGase). Products obtained from the action of these enzymes have resulted in completely novel types of maltooligosaccharides that are slowly degraded and therefore digested in the small intestine to maintain regulated blood glucose levels and suppressed glycemic‐index response. Some IMOs can even escape the small intestine and become fermented by micro‐organisms in the large intestine to produce health‐promoting short‐chain fatty acids such as butyric acid. Such slowly digested α‐glucans can regulate and trigger health‐promoting gut hormone release. Different novel production strategies of health‐promoting α‐glucans, their structures and nutritional effects are discussed here.
Zahedan climate and January–March composite analysis forecasts
Authors: Mirafzal Lily
Published: September 2017

This study shows that the mean monthly temperature and precipitation for Zahedan from January to March are predictable. They have oscillatory behavior in relation to El Niño–Southern Oscillation (ENSO) phases. The 200hPa vector wind composite mean maps from January to March show that a jet streak oscillates between 27°N and 30°N, to the west of Iran. These oscillations result in strong contour gradients of 1000hPa geopotential height during strong La Niña events; by contrast, they result in weak contour gradients during El Niño events in the southeast of the country. The composite forecasts for Zahedan based on El Niño/La Niña seem to be skillful for the strong events and show some skill for neutral events. The applicability of the forecasts in water management, agriculture, health, and other fields is considerable.
Sterol synthesis and cell size distribution under oscillatory growth conditions in Saccharomyces cerevisiae scale‐down cultivations
Authors: Marbà‐Ardébol Anna‐Maria , Bockisch Anika , Neubauer Peter , Junne Stefan
Published: September 2017

Physiological responses of yeast to oscillatory environments as they appear in the liquid phase in large‐scale bioreactors have been the subject of past studies. So far, however, the impact on the sterol content and intracellular regulation remains to be investigated. Since oxygen is a cofactor in several reaction steps within sterol metabolism, changes in oxygen availability, as occurs in production‐scale aerated bioreactors, might have an influence on the regulation and incorporation of free sterols into the cell lipid layer. Therefore, sterol and fatty acid synthesis in two‐ and three‐compartment scale‐down Saccharomyces cerevisiae cultivation were studied and compared with typical values obtained in homogeneous lab‐scale cultivations. While cells were exposed to oscillating substrate and oxygen availability in the scale‐down cultivations, growth was reduced and accumulation of carboxylic acids was increased. Sterol synthesis was elevated to ergosterol at the same time. The higher fluxes led to increased concentrations of esterified sterols. The cells thus seem to utilize the increased availability of precursors to fill their sterol reservoirs; however, this seems to be limited in the three‐compartment reactor cultivation due to a prolonged exposure to oxygen limitation. Besides, a larger heterogeneity within the single‐cell size distribution was observed under oscillatory growth conditions with three‐dimensional holographic microscopy. Hence the impact of gradients is also observable at the morphological level. The consideration of such a single‐cell‐based analysis provides useful information about the homogeneity of responses among the population.