bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multidimensional SuFEx Click Chemistry: Sequential Sulfur(VI) Fluoride Exchange Connections of Diverse Modules Launched From An SOF4 Hub
Authors: Li Suhua , Wu Peng , Moses John E. , Sharpless K. Barry 
Published: February 2017

AbstractSulfur(VI) fluoride exchange (SuFEx) is a new family of click chemistry based transformations that enable the synthesis of covalently linked modules via SVI hubs. Here we report thionyl tetrafluoride (SOF4) as the first multidimensional SuFEx connector. SOF4 sits between the commercially mass‐produced gases SF6 and SO2F2, and like them, is readily synthesized on scale. Under SuFEx catalysis conditions, SOF4 reliably seeks out primary amino groups [R‐NH2] and becomes permanently anchored via a tetrahedral iminosulfur(VI) link: R−N=(O=)S(F)2. The pendant, prochiral difluoride groups R−N=(O=)SF2, in turn, offer two further SuFExable handles, which can be sequentially exchanged to create 3‐dimensional covalent departure vectors from the tetrahedral sulfur(VI) hub.
Catalytic Dearomatization of N‐Heteroarenes with Silicon and Boron Compounds
Authors: Park Sehoon , Chang Sukbok 
Published: February 2017

AbstractDearomatized N‐heterocycles are an important class of structural motifs for organic synthesis and chemical biology. The catalytic dearomative reduction of unactivated N‐heteroarenes using silicon and/or boron‐containing compounds as a reductant is one of the most straightforward alternatives to hydrogenation. However, thus far, there are few reported examples on the catalytic reduction of N‐heteroaromatic compounds with silane or borane reducing agents. This Review presents recent advances in the catalytic reduction of unactivated N‐heteroarenes by hydrosilanes, hydroboranes, silaboranes, and diboranes. The focus is on the chemical reactivity and selectivity of transition‐metal or metal‐free organocatalyst systems. In addition, the working modes of these catalysis will be described primarily on the basis of experimental mechanistic insight.
Effects of microstructure design on aluminum surface hydrophobic and ice‐retarding properties
Authors: Chen K. , Sun T. 
Published: February 2017

AbstractThe poor mechanical strength of superhydrophobic surface limits its use in civil aviation. In this work, superhydrophobic surfaces with open and closed microstructure design were prepared, and their hydrophobicity and icephobicity over icing/de‐icing cycles were thoroughly studied. For all samples, contact angle decreased and contact angle hysteresis increased over time. However, surface with interconnected hollow honeycomb microstructure design kept its Cassie–Baxter state even after 20 times icing/de‐icing cycles, while surface with repeated individual post microscopic unit lost its superhydrophobicity only after six times icing/de‐icing cycles. The interconnected hollow honeycomb microstructure design strengthened surface mechanical strength by lowering the damage to microscopic unit. The freezing time for water droplet on surface with interconnected hollow honeycomb microstructure design was only slightly shortened over time. The difference in water/ice‐solid contact area for surfaces with different nano‐microscale design also led to the difference in wetting and ice‐retarding ability. Surface with interconnected hollow honeycomb microstructure design showed the strongest ice‐retarding ability followed by surface with interconnected hollow brick, ladder type, and triangle shape microstructure design. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
A preliminary redating of the Holocene Roonka burials, south‐eastern Australia
Authors: LITTLETON JUDITH , PETCHEY FIONA , WALSHE KERYN , PATE F. DONALD 
Published: February 2017

ABSTRACTRoonka is one of the most complete excavations of an Aboriginal burial ground in south‐eastern Australia. The chronology of the site and the nature of its use have proven difficult to interpret. Previous dating and chronological interpretations of the site have emphasised a chronology of changing use and burial practices, but the nature of the site and the dates obtained do not clearly support these interpretations. We report on the direct dating of human bone from a further ten burials from the main excavation. In order to further investigate the cultural chronology set out by Pretty (1977), samples were selected to cover a range of burial types and preservation states. Comparison of these dates with the previous conventional dates and early AMS dates not only shows the impact of improving technology but demonstrates that multiple burial styles were in use contemporaneously. Moreover, the results suggest that use of the site may have been discontinuous. Consequently, interpretations that assume a chronological sequence for Roonka based on burial practice are not supported, while analyses based on a synchronic interpretation may ignore significant temporal change.
Molecular Oligogermanes and Related Compounds: Structure, Optical and Semiconductor Properties
Authors: Zaitsev Kirill V. , Tafeenko Viktor A. , Oprunenko Yuri F. , Kharcheva Anastasia V. , Zhanabil Zhaisan , Suleimen Yerlan , Lam Kevin , Zaitsev Vladimir B. , Zaitseva Anna V. , Zaitseva Galina S. , Karlov Sergey S. 
Published: February 2017

AbstractThe optical (UV/Vis absorbance, fluorescence in the solid state and in solution) and semiconducting properties of a number of di‐ and trigermanes as well as related silicon‐ and tin‐containing germanes, 1–6 ((p‐Tol)3GeGeMe3 (1), Ph3SnGe(SiMe3)3 (2), (C6F5)3GeGePh3 (3), (p‐Tol)3GeSiMe2SiMe3 (4), (p‐Tol)3GeGeMe2Ge(p‐Tol)3 (5), (p‐Tol)3GeSiMe2SiMe2Ge(p‐Tol)3 (6)) were investigated. Molecular structures of 5 and 6 were studied by X‐ray diffraction analysis. All compounds displayed luminescence properties. In addition, a band gap (of about 3.3 eV) was measured for compounds 1–6 showing that those molecules display semiconductor properties.
Severity of pedestrian injuries due to traffic crashes at signalized intersections in Hong Kong: a Bayesian spatial logit model
Authors: Xu Xuecai , Xie Siqi , Wong Sze Chun , Xu Pengpeng , Huang Helai , Pei Xin 
Published: February 2017

SummaryThe present study intended to (1) investigate the injury risk of pedestrian casualties involved in traffic crashes at signalized intersections in Hong Kong; (2) determine the effect of pedestrian volumes on the severity levels of pedestrian injuries; and (3) explore the role of spatial correlation in econometric crash‐severity models. The data from 1889 pedestrian‐related crashes at 318 signalized intersections between 2008 and 2012 were elaborately collected from the Traffic Accident Database System maintained by the Hong Kong Transport Department. To account for the cross‐intersection heterogeneity, a Bayesian hierarchical logit model with uncorrelated and spatially correlated random effects was developed. An intrinsic conditional autoregressive prior was specified for the spatial correlation term. Results revealed that (1) signalized intersections with greater pedestrian volumes generally exhibited a lower injury risk; (2) ignoring the spatial correlation potentially results in reduced model goodness‐of‐fit, an underestimation of variability and standard error of parameter estimates, as well as inconsistent, biased, and erroneous inference; (3) special attention should be paid to the following factors, which led to a significantly higher probability of pedestrians being killed or sustaining severe injury: pedestrian age greater than 65 years, casualties with head injuries, crashes that occurred on footpaths that were not obstructed/overcrowded, heedless or inattentive crossing, crashes on the two‐way carriageway, and those that occurred near tram or light‐rail transit stops. Copyright © 2017 John Wiley & Sons, Ltd.
Planning the optimal site, size, and feed of biogas plants in agricultural districts
Authors: Zema Demetrio Antonio 
Published: February 2017

AbstractIn agricultural districts, biogas production through anaerobic co‐digestion of residual biomasses is a sustainable way to valorize agro‐industry and livestock residues and integrate farm profits. Size and location of a biogas plant as well as co‐digestion substrate composition strictly depend on the substrate properties and availability within the rural district. The logistical substrate chain should be optimized to assure the right size and the maximum profitability of the planned biogas plant. A simple method is proposed to site a digester and choose its power output as well as to identify the optimal substrate blend, reducing the complexity of design and management operations. The method, requiring a reduced number of easy‐to‐survey input parameters, has been verified by its application to an agricultural district of southern Italy. If the planned plant is fed by a prevalent substrate from a single farm, the most economical power output is 300 kW. This size depends also on the Italian subsidy system to renewable energy. However, in the case of a centralized plant, supplied by a blend of substrates, the method gives the optimal plant location, based on the district barycenter, weighed by the biogas potential production of each farm. Secondly, the method suggests the annual amounts of the different substrates in the digester blend, maximizing the plant's annual profit and complying with technical‐economic constraints. Thirdly, the most economical power output of the plant is 480 kW. Finally, it indicates the related annual revenues, costs, and profits. The method can also be applied to other agricultural biomasses, such as ensiled crops or energy species available at a competitive cost, as are found in northern Europe. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Quantifizierung der Beanspruchung infolge der Temperatur und des Erddrucks bei Integralbrücken bis 30 m Länge
Authors: della Pietra Regina , Tue N. V. 
Published: February 2017

AbstractBei Integralbrücken ist die realistische Erfassung der Zwangbeanspruchungen und der Boden‐Bauwerks‐Interaktion von entscheidender Bedeutung für eine gelungene Bauwerksplanung. Im vorliegenden Beitrag werden wesentliche Ergebnisse zum Einfluss des Baugrunds auf die Schnittgrößen infolge von Temperaturänderung und des Erddrucks für Bauwerkslängen bis zu 30 m dargestellt und diskutiert. Damit werden mehr als 80 % der Brücken im Straßennetz von Österreich und Deutschland behandelt. Weiterhin wird der Frage nach dem Abbau der Zwangkraft im ULS und SLS nachgegangen. Auf diesen Ergebnissen basierend, werden Empfehlungen für die Planung und Bemessung von Integralbrücken bis zu 30 m Länge vorgeschlagen.
Exosome separation using microfluidic systems: size‐based, immunoaffinity‐based and dynamic methodologies
Authors: Yang Fang , Liao Xiangzhi , Tian Yuan , Li Guiying 
Published: February 2017

AbstractExosomes, nanovesicles secreted by most types of cells, exist in virtually all bodily fluids. Their rich nucleic acid and protein content make them potentially valuable biomarkers for noninvasive molecular diagnostics. They also show promise, after further development, to serve as a drug delivery system. Unfortunately, existing exosome separation technologies, such as ultracentrifugation and methods incorporating magnetic beads, are time‐consuming, laborious and separate only exosomes of low purity. Thus, a more effective separation method is highly desirable. Microfluidic platforms are ideal tools for exosome separation, since they enable fast, cost‐efficient, portable and precise processing of nanoparticles and small volumes of liquid samples. Recently, several microfluidic‐based exosome separation technologies have been studied. In this article, the advantages of the most recent technologies, as well as their limitations, challenges and potential uses in novel microfluidic exosome separation and collection applications is reviewed. This review outlines the uses of new powerful microfluidic exosome detection tools for biologists and clinicians, as well as exosome separation tools for microfluidic engineers. Current challenges of exosome separation methodologies are also described, in order to highlight areas for future research and development.
Light dilution via wavelength management for efficient high‐density photobioreactors
Authors: Ooms Matthew D. , Graham Percival J. , Nguyen Brian , Sargent Edward H. , Sinton David 
Published: February 2017

ABSTRACTThe spectral distribution of light influences microalgae productivity; however, development of photobioreactors has proceeded largely without regard to spectral optimization. Here, we use monochromatic light to quantify the joint influence of path length, culture density, light intensity, and wavelength on productivity and efficiency in Synechococcus elongatus. The productivity of green light was ∼4× that of red at the highest levels of culture density, depth, and light intensity. This performance is attributed to the combination of increased dilution and penetration of this weakly absorbed wavelength over a larger volume fraction of the reactor. In contrast, red light outperformed other wavelengths in low‐density cultures with low light intensities. Low‐density cultures also adapted more rapidly to reduce absorption of longer wavelengths, allowing for prolonged cultivation. Taken together, these results indicate that, particularly for artificially lit photobioreactors, wavelength needs to be included as a critical operational parameter to maintain optimal performance. Biotechnol. Bioeng. 2017;114: 1160–1169. © 2017 Wiley Periodicals, Inc.
Memory Errors in Alibi Generation: How an Alibi Can Turn Against Us
Authors: Crozier William E. , Strange Deryn , Loftus Elizabeth F. 
Published: February 2017

AbstractAlibis play a critical role in the criminal justice system. Yet research on the process of alibi generation and evaluation is still nascent. Indeed, similar to other widely investigated psychological phenomena in the legal system – such as false confessions, historical claims of abuse, and eyewitness memory – the basic assumptions underlying alibi generation and evaluation require closer empirical scrutiny. To date, the majority of alibi research investigates the social psychological aspects of the process. We argue that applying our understanding of basic human memory is critical to a complete understanding of the alibi process. Specifically, we challenge the use of alibi inconsistency as an indication of guilt by outlining the “cascading effects” that can put innocents at risk for conviction. We discuss how normal encoding and storage processes can pose problems at retrieval, particularly for innocent suspects that can result in alibi inconsistencies over time. Those inconsistencies are typically misunderstood as intentional deception, first by law enforcement, affecting the investigation, then by prosecutors affecting prosecution decisions, and finally by juries, ultimately affecting guilt judgments. Put differently, despite the universal nature of memory inconsistencies, a single error can produce a cascading effect, rendering an innocent individual's alibi, ironically, proof of guilt. Copyright © 2017 John Wiley & Sons, Ltd.
Needle Terpenes as Chemotaxonomic Markers in Pinus: Subsections Pinus and Pinaster
Authors: Mitić Zorica S. , Jovanović Snežana Č. , Zlatković Bojan K. , Nikolić Biljana M. , Stojanović Gordana S. , Marin Petar D. 
Published: February 2017

Chemical compositions of needle essential oils of 27 taxa from the section Pinus, including 20 and 7 taxa of the subsections Pinus and Pinaster, respectively, were compared in order to determine chemotaxonomic significance of terpenes at infrageneric level. According to analysis of variance, six out of 31 studied terpene characters were characterized by a high level of significance, indicating statistically significant difference between the examined subsections. Agglomerative hierarchical cluster analysis has shown separation of eight groups, where representatives of subsect. Pinaster were distributed within the first seven groups on the dendrogram together with P. nigra subsp. laricio and P. merkusii from the subsect. Pinus. On the other hand, the eighth group included the majority of the members of subsect. Pinus. Our findings, based on terpene characters, complement those obtained from morphological, biochemical, and molecular parameters studied over the past two decades. In addition, results presented in this article confirmed that terpenes are good markers at infrageneric level.
Insights from NMR Spectroscopy into the Conformational Properties of Man‐9 and Its Recognition by Two HIV Binding Proteins
Authors: Shahzad‐ul‐Hussan Syed , Sastry Mallika , Lemmin Thomas , Soto Cinque , Loesgen Sandra , Scott Danielle A. , Davison Jack R. , Lohith Katheryn , O'Connor Robert , Kwong Peter D. , Bewley Carole A. 
Published: February 2017

AbstractMan9GlcNAc2 (Man‐9) present at the surface of HIV makes up the binding sites of several HIV‐neutralizing agents and the mammalian lectin DC‐SIGN, which is involved in cellular immunity and trans‐infections. We describe the conformational properties of Man‐9 in its free state and when bound by the HIV entry‐inhibitor protein microvirin (MVN), and define the minimum epitopes of both MVN and DC‐SIGN by using NMR spectroscopy. To facilitate the implementation of 3D 13C‐edited spectra to deconvolute spectral overlap and to determine the solution structure of Man‐9, we developed a robust expression system for the production of 13C,15N‐labeled glycans in mammalian cells. The studies reveal that Man‐9 interacts with HIV‐binding proteins through distinct epitopes and adopts diverse conformations in the bound state. In combination with molecular dynamics simulations we observed receptor‐bound conformations to be sampled by Man‐9 in the free state, thus suggesting a conformational selection mechanism for diverse recognition.
Lactosamine‐Based Derivatives as Tools to Delineate the Biological Functions of Galectins: Application to Skin Tissue Repair
Authors: Dion Johann , Deshayes Frédérique , Storozhylova Nataliya , Advedissian Tamara , Lambert Annie , Viguier Mireille , Tellier Charles , Dussouy Christophe , Poirier Françoise , Grandjean Cyrille 
Published: February 2017

AbstractGalectins have been recognized as potential novel therapeutic targets for the numerous fundamental biological processes in which they are involved. Galectins are key players in homeostasis, and as such their expression and function are finely tuned in vivo. Thus, their modes of action are complex and remain largely unexplored, partly because of the lack of dedicated tools. We thus designed galectin inhibitors from a lactosamine core, functionalized at key C2 and C3′ positions by aromatic substituents to ensure both high affinity and selectivity, and equipped with a spacer that can be modified on demand to further modulate their physico‐chemical properties. As a proof‐of‐concept, galectin‐3 was selectively targeted. The efficacy of the synthesized di‐aromatic lactosamine tools was shown in cellular assays to modulate collective epithelial cell migration and to interfere with actin/cortactin localization.
Reversible dementia: subclinical seizure in early‐onset dementia
Authors: Tjong Elysia , McHugh William , Peng Yen‐Yi 
Published: February 2017

Key Clinical MessageWe report a case of early‐onset dementia with subclinical seizures. Aggressive seizure control improved the patient's cognition. Commonly, an EEG is only performed following overt behavioral seizures. Therefore, subclinical seizures tend to be underdiagnosed. Serial or extended EEG should be seriously considered in patients with early‐onset dementia.
Aerobic Oxidation of Alkynes to 1,2‐Diketones by Organic Photoredox Catalysis
Authors: Qin Hai‐Tao , Xu Xiao , Liu Feng 
Published: February 2017

AbstractA method for the synthesis of 1,2‐diketones through the mild and metal‐free catalytic photooxygenation of alkynes is described. This reaction, using 9,10‐dicyanoanthracene as a catalytic sensitizer with/without biphenyl as a co‐sensitizer, readily furnished a variety of desired products upon visible‐light irradiation. Mechanistic studies indicated that a radical cation process might have been involved. This report provides the first examples of the transformation of alkynes via acetenyl radical cation intermediates, which have thus far not been explored in organic synthesis.
Mysterious Decomposition of Alkoxyphosphonium Chlorides: Postulated Involvement of the HCl2 Anion and Its Capture in the Solid State
Authors: Nikitin Kirill , Müller‐Bunz Helge , Muldoon Jimmy , Gilheany Declan G. 
Published: February 2017

AbstractP‐Alkoxyphosphonium (AP) chlorides were generated by reacting P‐chlorophosphonium chlorides with alcohols. Their well‐known spontaneous Arbuzov‐type collapse leading to phosphine oxides was studied and its rate found to be dependent on a number of factors in an unexpected fashion: it is inversely proportional to the initial concentration and it shows strong dependence on the acidity of the media but is not very sensitive to the presence of base. To explain these observations, we evoke a self‐inhibition model with the formation of the less nucleophilic hydrodichloride anion HCl2 in solution. Detailed analysis of the kinetic data yields the association constant (K=3×102 m−1) of the putative HCl2 species in chloroform. Experimental observations for the collapse of highly enriched diastereomeric alkoxyphosphonium (DAP) chlorides are fully analogous to the achiral AP also implying the involvement of HCl2 anions. Moreover, crystallisation of a highly enriched DAP salt derived from (−)‐menthol furnished, for the first time, crystals of individual (RP)‐DAP hydrodichloride as confirmed by X‐ray diffractometry. Importantly, the P‐configuration and detailed conformation of the DAP moiety is in good agreement with DFT‐level computational results. The thermal collapse of (RP)‐DAP⋅HCl2 proceeds with complete retention of the P‐configuration furnishing the phosphine oxide of exceptional enantiomeric purity.
Cyclic Phosphopeptides to Rationalize the Role of Phosphoamino Acids in Uranyl Binding to Biological Targets
Authors: Starck Matthieu , Laporte Fanny A. , Oros Stephane , Sisommay Nathalie , Gathu Vicky , Solari Pier Lorenzo , Creff Gaëlle , Roques Jérôme , Den Auwer Christophe , Lebrun Colette , Delangle Pascale 
Published: February 2017

AbstractThe specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high‐affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X‐ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo.