bluuebunny/crossref_metadata_2025_split huggingface dataset:
Testing the two‐layer model for correcting near‐cloud reflectance enhancement using LES/SHDOM‐simulated radiances
Authors: Wen Guoyong , Marshak Alexander , Várnai Tamás , Levy Robert 
Published: August 2016

AbstractA transition zone exists between cloudy skies and clear sky; such that, clouds scatter solar radiation into clear‐sky regions. From a satellite perspective, it appears that clouds enhance the radiation nearby. We seek a simple method to estimate this enhancement, since it is so computationally expensive to account for all three‐dimensional (3‐D) scattering processes. In previous studies, we developed a simple two‐layer model (2LM) that estimated the radiation scattered via cloud‐molecular interactions. Here we have developed a new model to account for cloud‐surface interaction (CSI). We test the models by comparing to calculations provided by full 3‐D radiative transfer simulations of realistic cloud scenes. For these scenes, the Moderate Resolution Imaging Spectroradiometer (MODIS)‐like radiance fields were computed from the Spherical Harmonic Discrete Ordinate Method (SHDOM), based on a large number of cumulus fields simulated by the University of California, Los Angeles (UCLA) large eddy simulation (LES) model. We find that the original 2LM model that estimates cloud‐air molecule interactions accounts for 64% of the total reflectance enhancement and the new model (2LM + CSI) that also includes cloud‐surface interactions accounts for nearly 80%. We discuss the possibility of accounting for cloud‐aerosol radiative interactions in 3‐D cloud‐induced reflectance enhancement, which may explain the remaining 20% of enhancements. Because these are simple models, these corrections can be applied to global satellite observations (e.g., MODIS) and help to reduce biases in aerosol and other clear‐sky retrievals.
The May 1967 great storm and radio disruption event: Extreme space weather and extraordinary responses
Authors: Knipp D. J. , Ramsay A. C. , Beard E. D. , Boright A. L. , Cade W. B. , Hewins I. M. , McFadden R. H. , Denig W. F. , Kilcommons L. M. , Shea M. A. , Smart D. F. 
Published: August 2016

AbstractAlthough listed as one of the most significant events of the last 80 years, the space weather storm of late May 1967 has been of mostly fading academic interest. The storm made its initial mark with a colossal solar radio burst causing radio interference at frequencies between 0.01 and 9.0 GHz and near‐simultaneous disruptions of dayside radio communication by intense fluxes of ionizing solar X‐rays. Aspects of military control and communication were immediately challenged. Within hours a solar energetic particle event disrupted high‐frequency communication in the polar cap. Subsequently, record‐setting geomagnetic and ionospheric storms compounded the disruptions. We explain how the May 1967 storm was nearly one with ultimate societal impact, were it not for the nascent efforts of the United States Air Force in expanding its terrestrial weather monitoring‐analysis‐warning‐prediction efforts into the realm of space weather forecasting. An important and long‐lasting outcome of this storm was more formal Department of Defense‐support for current‐day space weather forecasting. This story develops during the rapid rise of solar cycle 20 and the intense Cold War in the latter half of the twentieth century. We detail the events of late May 1967 in the intersecting categories of solar‐terrestrial interactions and the political‐military backdrop of the Cold War. This was one of the “Great Storms” of the twentieth century, despite the apparent lack of large geomagnetically induced currents. Radio disruptions like those discussed here warrant the attention of today's radio‐reliant, cellular‐phone and satellite‐navigation enabled world.
Kinetically Controlled α‐Selective O‐Glycosylation of Phenol Derivatives Using 2‐Nitroglycals by a Bifunctional Chiral Thiourea Catalyst
Authors: Yoshida Keisuke , Kanoko Yohei , Takao Kenichi 
Published: August 2016

AbstractThe highly α‐selective organocatalytic glycosylation of phenol derivatives using 2‐nitroglycals has been developed. The stereoselectivity of this reaction was kinetically controlled by a bifunctional thiourea catalyst, the chirality of which was crucial for obtaining the high α‐selectivity. A variety of phenol derivatives were added to 2‐nitrogalactal with excellent stereoselectivity. The reaction of 2‐nitroglucal also achieved highly stereoselective glycosylation. The reaction was applied to the synthesis of glycopeptides.
Die Enzymologie organischer Umwandlungen: Namensreaktionen in biologischen Systemen
Authors: Lin Chia‐I. , McCarty Reid M. , Liu Hung‐wen 
Published: August 2016

AbstractChemische Reaktionen, die zu Ehren ihrer wahren oder zumindest wahrgenommenen Entdecker benannt sind, werden als “Namensreaktionen” bezeichnet. Dieser Aufsatz ist eine Zusammenstellung von biologischen Beispielen für benannte chemische Reaktionen. Der Schwerpunkt liegt dabei auf Reaktionsarten und Katalysemechanismen, die die chemische Diversität in der Biosynthese von Naturstoffen wie auch Parallelen zur organischen Synthesechemie veranschaulichen. Enzymatische Katalysemechanismen werden soweit möglich im Kontext mit den entsprechenden Mechanismen in der Synthese beschrieben, und für derzeit noch untersuchte Reaktionen werden mechanistische Hypothesen diskutiert. Der Aufsatz ist nach Reaktionsarten gegliedert, z. B. Kondensation, Reduktion und Oxidation, Substitution, Carboxylierung, Radikal‐vermittelte Reaktionen und Umlagerungen, und diese sind anhand der Namensreaktionen weiter unterteilt.
C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands
Authors: Jacquet Jérémy , Chaumont Pauline , Gontard Geoffrey , Orio Maylis , Vezin Hervé , Blanchard Sébastien , Desage‐El Murr Marine , Fensterbank Louis 
Published: August 2016

AbstractThe reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low‐valent counterpart bearing reduced ligands, this complex performs high‐yielding C−N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high‐valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high‐valent metallic species.
The Enzymology of Organic Transformations: A Survey of Name Reactions in Biological Systems
Authors: Lin Chia‐I. , McCarty Reid M. , Liu Hung‐wen 
Published: August 2016

AbstractChemical reactions that are named in honor of their true, or at least perceived, discoverers are known as “name reactions”. This Review is a collection of biological representatives of named chemical reactions. Emphasis is placed on reaction types and catalytic mechanisms that showcase both the chemical diversity in natural product biosynthesis as well as the parallels with synthetic organic chemistry. An attempt has been made, whenever possible, to describe the enzymatic mechanisms of catalysis within the context of their synthetic counterparts and to discuss the mechanistic hypotheses for those reactions that are currently active areas of investigation. This Review has been categorized by reaction type, for example condensation, nucleophilic addition, reduction and oxidation, substitution, carboxylation, radical‐mediated, and rearrangements, which are subdivided by name reactions.
Stabilization of Charge Carriers in Picket‐Fence Polythiophenes Using Dielectric Side Chains
Authors: Zhao Chunhui , Sakurai Tsuneaki , Yoneda Satoru , Seki Shu , Sugimoto Manabu , Oki Choji , Takeuchi Masayuki , Sugiyasu Kazunori 
Published: August 2016

AbstractInsulated molecular wires (IMWs) are π‐conjugated polymers that are molecularly sheathed with an insulating layer and are structurally analogous to electric power cords at the nanoscale. Such unique architectures are expected in molecular electronics and organic devices. Herein, we propose a new molecular design concept of IMWs, in which the sheaths can be customized, thereby enabling the modulation of the electronic properties of the interior π‐conjugated systems. To this end, we focused our attention on the dielectric constant of the sheaths, as it governs the electrostatic interaction between charges. Upon doping, charge carriers, such as polaron and bipolaron, were generated regardless of the dielectric properties of the sheaths. Flash‐photolysis time‐resolved microwave conductivity measurements revealed that intrawire charge carrier mobility was independent of the sheaths. However, we found that the charge carriers could be stabilized by the sheaths with a high dielectric constant owing to the charge screening effect. We expect that IMWs designed in this way will be useful in a variety of applications, where the nature of charge carriers plays an important role, and particularly when redox switching is required (e.g., electrochromic, magnetic, and memory applications).
Fe‐Catalyzed Cross‐Coupling Reaction of Vinylic Ethers with Aryl Grignard Reagents
Authors: Iwasaki Takanori , Akimoto Ryo , Kuniyasu Hitoshi , Kambe Nobuaki 
Published: August 2016

AbstractIron‐catalyzed cross‐coupling reaction of vinylic ethers with aryl Grignard reagents is described. The reaction proceeded at room temperature with catalytic amounts of an iron salt without the aid of costly ligands and additives. In this catalytic system, vinylic C−O bonds were preferentially cleaved over aromatic C−O bonds of aryl ethers or aryl sulfonates.
Patterns of disease relapse in primary extremity soft-tissue sarcoma
Authors: Smith H G , Memos N , Thomas J M , Smith M J F , Strauss D C , Hayes A J 
Published: August 2016

Abstract

Background
Extremity soft-tissue sarcomas comprise a range of distinct histological subtypes. This study aimed to characterize the patterns of disease relapse in patients undergoing resection of primary extremity soft-tissue sarcoma.

Methods
All patients who had resection of primary extremity soft-tissue sarcoma at the Royal Marsden Hospital between January 2004 and January 2014 were identified from an institutional database.

Results
In the period examined, 556 patients underwent resection. The most common histological subtypes were undifferentiated pleomorphic sarcoma (169 patients, 30·4 per cent), well differentiated liposarcoma (63, 11·3 per cent), myxoid liposarcoma (62, 11·2 per cent), myxofibrosarcoma (54, 9·7 per cent) and leiomyosarcoma (39, 7·0 per cent). Local recurrence-free survival (LRFS) did not differ significantly between histological subtypes (P = 0·222). Distant metastasis-free survival (DMFS) and disease-specific survival (DSS) were found to differ significantly between subtypes (P &lt; 0·001 for both DMFS and DSS), with the worst outcomes in patients with undifferentiated pleomorphic sarcoma (5-year survival rate: 56·8 (95 per cent c.i. 52·5 to 61·1) per cent for DMFS; 60·1 (55·6 to 64·6) per cent for DSS). However, on multivariable analysis, histological subtype was not found to be independently prognostic for LRFS, DMFS or DSS. Metastatic disease developed in 149 patients, with the lungs being the most common site of first metastasis (120 patients, 80·5 per cent). The site of first metastasis differed between subtypes, with extrapulmonary metastases predominant in myxoid liposarcoma (11 of 13 patients; P &lt; 0·001).

Conclusion
Although histological subtype was not found to be an independent prognostic factor for oncological outcomes, the site of first metastasis differed significantly between subtypes.
Chemoselective Preparation of Clickable Aryl Sulfonyl Fluoride Monomers: A Toolbox of Highly Functionalized Intermediates for Chemical Biology Probe Synthesis
Authors: Fadeyi Olugbeminiyi , Parikh Mihir D. , Chen Ming Z. , Kyne Robert E. , Taylor Alexandria P. , O'Doherty Inish , Kaiser Stephen E. , Barbas Sabrina , Niessen Sherry , Shi Manli , Weinrich Scott L. , Kath John C. , Jones Lyn H. , Robinson Ralph P. 
Published: August 2016

AbstractSulfonyl fluoride (SF)‐based activity probes have become important tools in chemical biology. Herein, exploiting the relative chemical stability of SF to carry out a number of unprecedented SF‐sparing functional group manipulations, we report the chemoselective synthesis of a toolbox of highly functionalized aryl SF monomers that we used to quickly prepare SF chemical biology probes. In addition to SF, the monomers bear an embedded click handle (a terminal alkyne that can perform copper(I)‐mediated azide–alkyne cycloaddition). The monomers can be used either as fragments to prepare clickable SF analogues of drugs (biologically active compounds) bearing an aryl ring or, alternatively, attached to drugs as minimalist clickable aryl SF substituents.
A Catalytic Nanoreactor Based on in Vivo Encapsulation of Multiple Enzymes in an Engineered Protein Nanocompartment
Authors: Giessen Tobias W. , Silver Pamela A. 
Published: August 2016

AbstractBacterial protein compartments concentrate and sequester enzymes, thereby regulating biochemical reactions. Here, we generated a new functional nanocompartment in Escherichia coli by engineering the MS2 phage capsid protein to encapsulate multiple cargo proteins. Sequestration of multiple proteins in MS2‐based capsids was achieved by SpyTag/SpyCatcher protein fusions that covalently crosslinked with the interior surface of the capsid. Further, the functional two‐enzyme indigo biosynthetic pathway could be targeted to the engineered capsids, leading to a 60 % increase in indigo production in vivo. The enzyme‐loaded particles could be purified in their active form and showed enhanced long‐term stability in vitro (about 95 % activity after seven days) compared with free enzymes (about 5 % activity after seven days). In summary, this engineered in vivo encapsulation system provides a simple and versatile way for generating highly stable multi‐enzyme nanoreactors for in vivo and in vitro applications.
A Lamellar Coordination Polymer with Remarkable Catalytic Activity
Authors: Mendes Ricardo F. , Antunes Margarida M. , Silva Patrícia , Barbosa Paula , Figueiredo Filipe , Linden Anthony , Rocha João , Valente Anabela A. , Almeida Paz Filipe A. 
Published: August 2016

AbstractA positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4nmp)(H2O)2]Cl⋅2 H2O (1) [H6nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one‐pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone. For all reaction systems, very high conversions were reached (92–97 %) in only 15–30 min under mild conditions (35 °C, atmospheric pressure). The coordination polymer exhibits a protonic conductivity of 1.23×10−5 S cm−1 at 98 % relative humidity and 40 °C.
Structure Determination of an AgI‐Mediated Cytosine–Cytosine Base Pair within DNA Duplex in Solution with 1H/15N/109Ag NMR Spectroscopy
Authors: Dairaku Takenori , Furuita Kyoko , Sato Hajime , Šebera Jakub , Nakashima Katsuyuki , Kondo Jiro , Yamanaka Daichi , Kondo Yoshinori , Okamoto Itaru , Ono Akira , Sychrovský Vladimír , Kojima Chojiro , Tanaka Yoshiyuki 
Published: August 2016

AbstractThe structure of an AgI‐mediated cytosine–cytosine base pair, C–AgI–C, was determined with NMR spectroscopy in solution. The observation of 1‐bond 15N‐109Ag J‐coupling (1J(15N,109Ag): 83 and 84 Hz) recorded within the C–AgI–C base pair evidenced the N3–AgI–N3 linkage in C–AgI–C. The triplet resonances of the N4 atoms in C–AgI–C demonstrated that each exocyclic N4 atom exists as an amino group (−NH2), and any isomerization and/or N4–AgI bonding can be excluded. The 3D structure of AgI–DNA complex determined with NOEs was classified as a B‐form conformation with a notable propeller twist of C–AgI–C (−18.3±3.0°). The 109Ag NMR chemical shift of C‐AgI‐C was recorded for cytidine/AgI complex (δ(109Ag): 442 ppm) to completed full NMR characterization of the metal linkage. The structural interpretation of NMR data with quantum mechanical calculations corroborated the structure of the C–AgI–C base pair.
Chemoenzymatic Total Synthesis of (+)‐Galanthamine and (+)‐Narwedine from Phenethyl Acetate
Authors: Endoma‐Arias Mary A. A. , Hudlicky Tomas 
Published: August 2016

AbstractThe stereoselective total synthesis of unnatural (+)‐galanthamine starting from phenethyl acetate is described. Chirality was introduced via microbial dihydroxylation of phenethyl acetate with the recombinant strain JM109 (pDTG601A) to the corresponding cis‐cyclohexadi–enediol, configuration of which provided the absolute stereochemistry of the ring C of (+)‐galanthamine. Intramolecular Heck cyclization was used to form the quaternary carbon and dibenzofuran functionality. The synthesis of (+)‐galanthamine was completed in a total of ten steps and an overall yield of 5.5 %. Experimental and spectral data are provided for all new compounds.
Steady‐State, Scalable Production of Mesoporous Rutile and Brookite Particles and Their Use in Energy Conversion and Storage Cells
Authors: Yasin Amrita , Guo Fuqiang , Sussman Micah J. , Gauvin Raynald , Demopoulos George P. 
Published: August 2016

AbstractMesoporous TiO2 rutile particles with a cauliflower‐like morphology and an internal structure of self‐assembled nanoneedles were synthesized in a novel TiIV chloride aqueous‐solution hydrolysis process. In an effort to make nanostructured rutile synthesis cost‐effective and green, the process was conducted at steady‐state in a continuously stirred tank reactor (CSTR) below 100 °C. High TiCl4 concentration 0.5–1 m yielded rutile, while lowering the concentration to 0.1 m led to the crystallization of brookite nanoplatelets. Apart from phase control, specific surface area of rutile may be tuned via TiCl4 concentration regulation from 85 to 500 m2 g−1. Investigation revealed that low pH/high TiIV concentration conditions favored direct nucleation of rutile nuclei during steady state that grow radially outward into nanoneedle structured cauliflower particles with nanoscale edgy surface. The unique steady‐state produced mesoporous rutile particles were shown to have excellent light scattering properties in a bi‐layer photoanode structure resulting in 42.5 % increase in photovoltaic efficiency. Brookite nanoplatelets were shown, in addition to their scattering properties, to exhibit stable Li‐ion intercalation functionality.
A similarity‐based cross‐language comparison of basicness and demarcation of “blue” terms
Authors: Bimler David , Uusküla Mari 
Published: August 2016

AbstractTo investigate linguistic and perceptual boundaries within the “blue” region of the color gamut, we analyzed sorting data from speakers of six languages who sorted color stimuli by similarity. Two of these languages, Russian and Italian, are thought to have a separate basic color term and category for “light blue,” distinguishing it from “blue,” and the third was English, which lacks this distinction. There has been less study of the possible basicness of “light blue” terms in the other three languages: Lithuanian and Estonian (both spoken in Baltic states) and Udmurt (a linguistic enclave in North Russia). Sorting data from each sample of speakers were analyzed with principal component analysis and multidimensional scaling, reducing them to a pattern of interstimulus similarities. In addition, color‐naming data were collected for five of the languages and confirmed that sorting responses were not simply a reflection of the words used by subjects to label the stimuli. A “clustering index” was created, quantifying the extent of light/dark blue separation and the strength of any category boundary between them; this was low for English‐language participants but high for Russian and Italian. Udmurt and Lithuanian values were also high, whereas Estonian responses were closer to English. Thus, when clustering of blue stimuli is used as an additional indicator of basicness, the results are compatible with earlier evidence that “light blue” is a separate basic color category in Russian and Italian, and further indicate that light blue terms are basic in Udmurt and Lithuanian, but not Estonian. It may be that “blue” categories are especially susceptible to splitting into two under the influence of linguistic contact. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 362–377, 2017
Encapsulation of Perovskite Solar Cells for High Humidity Conditions
Authors: Dong Qi , Liu Fangzhou , Wong Man Kwong , Tam Ho Won , Djurišić Aleksandra B. , Ng Annie , Surya Charles , Chan Wai Kin , Ng Alan Man Ching 
Published: August 2016

AbstractWe examined different encapsulation strategies for perovskite solar cells by testing the device stability under continuous illumination, elevated temperature (85 °C) and ambient humidity of 65 %. The effects of the use of different epoxies, protective layers and the presence of desiccant were investigated. The best stability (retention of ∼80 % of initial efficiency on average after 48 h) was obtained for devices protected by a SiO2 film and encapsulated with a UV‐curable epoxy including a desiccant sheet. However, the stability of ZnO‐based cells encapsulated by the same method was found to be inferior to that of TiO2‐based cells. Finally, outdoor performance tests were performed for TiO2‐based cells (30–90 % ambient humidity). All the stability tests were performed following the established international summit on organic photovoltaic stability (ISOS) protocols for organic solar cell testing (ISOS‐L2 and ISOS‐O1).
Energy Consumption for CO2 Capture by means of the Calcium Looping Process: A Comparative Analysis using Limestone, Dolomite, and Steel Slag
Authors: Ortiz Carlos , Valverde José M. , Chacartegui Ricardo 
Published: August 2016

AbstractThe calcium looping (CaL) process, based upon the dry carbonation/calcination of CaO/CaCO3, is at the center of a potentially low‐cost, second‐generation technology for CO2 capture. This manuscript analyzes the energy penalty that arises from the integration of the CaL process into a coal‐fired power plant using cheap and abundantly available CaO precursors such as natural limestone, dolomite, and steel slag. Experimental results on their multicycle capture capacity behavior obtained from thermogravimetric analysis (TGA) at realistic CaL conditions for CO2 capture are used to this end. This work shows that the specific energy consumption for CO2 avoided (SPECCA) is reduced by using either dolomite or steel slag, whose carbonation kinetics in the diffusive phase are accelerated as compared to limestone. Thus, the use of dolomite as CaO precursor would yield a low SPECCA value of approximately 2 MJ kg−1 CO2 for a residence time of the solids in the carbonator of approximately 10 minutes, which is clearly below the SPECCA value usually reported for conventional amine‐based CO2 capture systems.