bluuebunny/crossref_metadata_2025_split huggingface dataset:
Assessing the relative effectiveness of statistical downscaling and distribution mapping in reproducing rainfall statistics based on climate model results
Authors: Langousis Andreas , Mamalakis Antonios , Deidda Roberto , Marrocu Marino 
Published: December 2015

AbstractTo improve the level skill of climate models (CMs) in reproducing the statistics of daily rainfall at a basin level, two types of statistical approaches have been suggested. One is statistical correction of CM rainfall outputs based on historical series of precipitation. The other, usually referred to as statistical rainfall downscaling, is the use of stochastic models to conditionally simulate rainfall series, based on large‐scale atmospheric forcing from CMs. While promising, the latter approach attracted reduced attention in recent years, since the developed downscaling schemes involved complex weather identification procedures, while demonstrating limited success in reproducing several statistical features of rainfall. In a recent effort, Langousis and Kaleris () developed a statistical framework for simulation of daily rainfall intensities conditional on upper‐air variables, which is simpler to implement and more accurately reproduces several statistical properties of actual rainfall records. Here we study the relative performance of: (a) direct statistical correction of CM rainfall outputs using nonparametric distribution mapping, and (b) the statistical downscaling scheme of Langousis and Kaleris (), in reproducing the historical rainfall statistics, including rainfall extremes, at a regional level. This is done for an intermediate‐sized catchment in Italy, i.e., the Flumendosa catchment, using rainfall and atmospheric data from four CMs of the ENSEMBLES project. The obtained results are promising, since the proposed downscaling scheme is more accurate and robust in reproducing a number of historical rainfall statistics, independent of the CM used and the characteristics of the calibration period. This is particularly the case for yearly rainfall maxima.
Hedging the financial risk from water scarcity for Great Lakes shipping
Authors: Meyer Eliot S. , Characklis Gregory W. , Brown Casey , Moody Paul 
Published: December 2015

AbstractLow water levels in the Great Lakes have recently had significant financial impacts on the region's commercial shipping, which transports hundreds of millions of dollars' worth of bulk goods each year. Cargo capacity is a function of a ship's draft, the distance between water level and the ship's bottom, and lower water levels force ships to reduce cargo loads to prevent running aground in shallow harbors and locks. Financial risk transfer instruments, such as index‐based insurance contracts, may provide an adaptable method for managing these financial risks. In this work, a relationship between water levels and shipping revenues is developed and used in an actuarial analysis of the frequency and magnitude of revenue losses. This analysis is used to develop a standardized suite of binary financial contracts, which are indexed to water levels and priced according to predefined thresholds. These contracts are then combined to form hedging portfolios with different objectives for the shippers. Results suggest that binary contracts could substantially reduce the risk of financial losses during low lake level periods and at a relatively low cost of only one to three percent of total revenues, depending on coverage level.
Die “anderen” Inositole und ihre Phosphate: Synthese, Biologie und Medizin (sowie jüngste Fortschritte in dermyo‐Inositolchemie)
Authors: Thomas Mark P. , Mills Stephen J. , Potter Barry V. L. 
Published: December 2015

AbstractZelluläre Signalkaskaden über Inositolphosphate, insbesondere über den sekundären Botenstoffmyo‐Inositol‐1,4,5‐trisphosphat und über die Phosphoinositide, umfassen ein riesiges Gebiet der Zellbiologie. Unter den neun 1,2,3,4,5,6‐Cyclohexanhexolisomeren istmyo‐Inositol vorherrschend, während die “anderen” Inositole (cis‐,epi‐,allo‐,muco‐,neo‐,l‐chiro‐,d‐chiro‐ undscyllo‐) und ihre Derivate seltener sind oder nicht in der Natur vermutet wurden. Vor kurzem wurden jedochneo‐ undd‐chiro‐Inositolhexakisphosphate in terrestrischen und aquatischen Ökosystemen entdeckt, was zeigt, wie lückenhaft unser Wissen über die Herkunft und möglichen biologischen Funktionen solcher Stereoisomere, einer vorherrschenden Gruppe in der Natur vorkommender organischer Phosphate, und der Inositole als Ausgangsverbindungen ist. Einige “andere” Inositole sind medizinisch bedeutsam, wiescyllo‐Inositol (bei neurodegenerativen Erkrankungen) undd‐chiro‐Inositol (bei Diabetes). Es ist an der Zeit, Funktionen und Anwendungsmöglichkeiten der “anderen” Isomere und ihrer Derivate zu erforschen, vor allem mit Methoden, die für diemyo‐Inositole inzwischen gut etabliert sind.
Spontaneous Resolution of an Electron‐Deficient Tetrahedral Fe4L4 cage
Authors: Bonakdarzadeh Pia , Pan Fangfang , Kalenius Elina , Jurček Ondřej , Rissanen Kari 
Published: December 2015

AbstractA highly electron‐deficient C3‐symmetric tris(bipyridyl) ligand was prepared in four steps and used for the coordination of Fe(OTf)2, thereby resulting in the homochiral assembly of a new family of robust tetrahedral M4L4 cages. This homochiral T‐symmetric cage containing a relatively large cavity of 330 Å3 is capable of encapsulating an anionic guest, as was determined by mass spectrometry, 19F NMR spectroscopy, and finally shown from its crystal structure. Moreover, crystallization of the cage from CH3CN led to crystals containing both (ΔΔΔΔ and ΛΛΛΛ) enantiomers, while crystallization from CH3OH resulted in crystals containing only the right‐handed (ΔΔΔΔ) cage. The difference in the crystal packing of the two crystal structures is discussed and a feasible explanation for the unique phenomenon among supramolecular cages—spontaneous resolution—is given.
Sequential 1,4‐/1,2‐Addition of Lithium(trimethylsilyl)diazomethane onto Cyclic Enones to Induce C−C Fragmentation and N−Li Insertion
Authors: O'Connor Matthew J. , Sun Chunrui , Guan Xinyu , Sabbasani Venkata R. , Lee Daesung 
Published: December 2015

Abstractα,β‐Unsaturated ketones generally undergo addition reactions with nucleophiles with a preference for either 1,2‐ or 1,4‐addition, but rarely both. However, the right combination of reagents allows for consecutive 1,4‐ and 1,2‐additions to occur: Cyclic α,β‐unsaturated ketones undergo double additions with lithium(trimethylsilyl)diazomethane, effectively generating various molecular frameworks with complexity and diversity. Owing to the sequential generation of several intermediates of multifaceted reactivity, including diazoalkane derivatives and alkylidene carbenes, it is possible to induce novel Grob‐type C−C fragmentations, alkylidene carbene mediated Li−N insertions, and dipolar cycloadditions by controlling the reaction parameters.
A novel screening system based on VanX‐mediated autolysis—Application to Gaussia luciferase
Authors: Wu Nan , Kamioka Tetsuya , Kuroda Yutaka 
Published: December 2015

ABSTRACTWe report a novel bacterial screening protocol based on co‐expressing the target protein with VanX, an enzyme which mediates Escherichia coli's autolysis and the release of the target protein into the culture medium, thereby facilitating activity measurement and screening from crude medium. This protocol as assessed with 19 Gaussia luciferase (GLuc) expressing colonies, was able to detect bioluminescence wavelength shift as small as 1.5 nm. We demonstrate the performance and versatility of this protocol by applying it to a semi‐rational search for GLuc variants with red‐shifted bioluminescence. Six GLuc's sites, F113, I114, W143, L144, A149, and F151, were randomly mutated, and for each site, 50 colonies were cultivated in 3 mL samples, from which bioluminescence was measured without purification. We identified two GLuc single mutation red‐shifted variants: W143V and L144A. Their red shifted bioluminescence and biophysical/biochemical properties were confirmed using HPLC purified variants. Biotechnol. Bioeng. 2016;113: 1413–1420. © 2015 Wiley Periodicals, Inc.
Pooled long-term outcomes from two randomized trials of axillary node sampling with axillary radiotherapy versus axillary node clearance in patients with operable node-positive breast cancer
Authors: Bing A U , Kerr G R , Jack W , Chetty U , Williams L J , Rodger A , Dixon J M 
Published: December 2015

Abstract

Background
The aim was to determine long-term overall, breast cancer-specific and metastasis-free survival as well as axillary relapse rate from a pooled analysis of two randomized trials in women with operable breast cancer. These trials compared axillary node sampling (ANS), combined with axillary radiotherapy (AXRT) if the sampled nodes were involved, with axillary node clearance (ANC).

Methods
Data from two clinical trials at the Edinburgh Breast Unit that randomized patients between 1980 and 1995 were pooled. Long-term survival was analysed using Kaplan–Meier curves and Cox regression, with separate analyses for patients with node-positive (ANS + AXRT versus ANC) and node-negative (ANS versus ANC) disease.

Results
Of 855 women randomized, 799 were included in the present analysis after a median follow-up of 19·4 years. Some 301 patients (37·7 per cent) had node-positive disease. There was no evidence of a breast cancer survival advantage for ANS versus ANC in patients with node-negative disease (hazard ratio (HR) 0·88, 95 per cent c.i. 0·58 to 1·34; P = 0·557), or for ANS + AXRT versus ANC in those with node-positive breast cancer (HR 1·07, 0·77 to 1·50; P = 0·688). There was no metastasis-free survival advantage for ANS versus ANC in patients with node-negative tumours (HR 1·03, 0·70 to 1·51; P = 0·877), or ANS + AXRT versus ANC in those with node-positive disease (HR 1·03, 0·75 to 1·43; P = 0·847). Node-negative patients who underwent ANS had a higher risk of axillary recurrence than those who had ANC (HR 3·53, 1·29 to 9·63; P = 0·014). Similarly, among women with node-positive tumours, the risk of axillary recurrence was greater after ANS + AXRT than ANC (HR 2·64, 1·00 to 6·95; P = 0·049).

Conclusion
Despite a higher rate of axillary recurrence with ANS combined with radiotherapy to the axilla, ANC did not improve overall, breast cancer-specific or metastasis-free survival. Axillary recurrence is thus not a satisfactory endpoint when comparing axillary treatments.
Mutating a Highly Conserved Residue in Diverse Cytochrome P450s Facilitates Diastereoselective Olefin Cyclopropanation
Authors: Gober Joshua G. , Rydeen Amy E. , Gibson‐O'Grady Evan J. , Leuthaeuser Janelle B. , Fetrow Jacquelyn S. , Brustad Eric M. 
Published: December 2015

AbstractCytochrome P450s and other heme‐containing proteins have recently been shown to have promiscuous activity for the cyclopropanation of olefins using diazoacetate reagents. Despite the progress made thus far, engineering selective catalysts for all possible stereoisomers for the cyclopropanation reaction remains a considerable challenge. Previous investigations of a model P450 (P450BM3) revealed that mutation of a conserved active site threonine (Thr268) to alanine transformed the enzyme into a highly active and selective cyclopropanation catalyst. By incorporating this mutation into a diverse panel of P450 scaffolds, we were able to quickly identify enantioselective catalysts for all possible diastereomers in the model reaction of styrene with ethyl diazoacetate. Some alanine variants exhibited selectivities that were markedly different from the wild‐type enzyme, with a few possessing moderate to high diastereoselectivity and enantioselectivities up to 97 % for synthetically challenging cis‐cyclopropane diastereomers.
Electrocatalytic Water Oxidation by a Highly Active and Robust α‐Mn2O3 Thin Film Sintered on a Fluorine‐Doped Tin Oxide Electrode
Authors: Zahran Zaki N. , Mohamed Eman A. , Ohta Takehiro , Naruta Yoshinori 
Published: December 2015

AbstractAs a water oxidation catalyst, α‐Mn2O3 has higher activity than other manganese oxides. However, the robustness of the catalyst supported on conducting electrodes has only been tested for a short time (1 h) and it shows a gradual decrease in activity. Furthermore, the turnover number (TON) and turnover frequency (TOF) have not been reported. Herein, we optimized the preparation of transparent nanocrystalline α‐Mn2O3 on a fluorine‐doped tin oxide (FTO) electrode, and this resulting catalyst shows, in neutral aqueous 0.1 m potassium phosphate buffer solution, a high electrocatalytic water oxidation activity with a TON of 230, a TOF of 5.3×10−3 s−1 based on the all‐Mn content, and a TOF of 2.1 s−1 based on the amount of surface‐active Mn with a Faradic efficiency of 96.7 % at an overpotential of 470 mV. The robustness of the α‐Mn2O3/FTO electrocatalyst was tested for a long time (80 h) without a decrease in activity.
A Three‐Component Assembly Promoted by Boronic Acids Delivers a Modular Fluorophore Platform (BASHY Dyes)
Authors: Santos Fábio M. F. , Rosa João N. , Candeias Nuno R. , Carvalho Cátia Parente , Matos Ana I. , Ventura Ana E. , Florindo Helena F. , Silva Liana C. , Pischel Uwe , Gois Pedro M. P. 
Published: December 2015

AbstractThe modular assembly of boronic acids with Schiff‐base ligands enabled the construction of innovative fluorescent dyes [boronic acid salicylidenehydrazone (BASHY)] with suitable structural and photophysical properties for live cell bioimaging applications. This reaction enabled the straightforward synthesis (yields up to 99 %) of structurally diverse and photostable dyes that exhibit a polarity‐sensitive green‐to‐yellow emission with high quantum yields of up to 0.6 in nonpolar environments. These dyes displayed a high brightness (up to 54 000 m−1 cm−1). The promising structural and fluorescence properties of BASHY dyes fostered the preparation of non‐cytotoxic, stable, and highly fluorescent poly(lactide‐co‐glycolide) nanoparticles that were effectively internalized by dendritic cells. The dyes were also shown to selectively stain lipid droplets in HeLa cells, without inducing any appreciable cytotoxicity or competing plasma membrane labeling; this confirmed their potential as fluorescent stains.
High‐Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide
Authors: Guan Guijian , Cai Yongqing , Liu Shuhua , Yu Haidong , Bai Shiqiang , Cheng Yuan , Tang Tao , Bharathi M. S. , Zhang Yong‐Wei , Han Ming‐Yong 
Published: December 2015

AbstractHigh‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag+ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag28Au10‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag28Au10 NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag28Au10 NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.
In Situ Synthesis and Characterization of Poly(aryleneethynylene)‐Grafted Reduced Graphene Oxide
Authors: Sun Sai , Zhuang Xiaodong , Liu Bo , Wang Luxing , Gu Linfeng , Song Sannian , Zhang Bin , Chen Yu 
Published: December 2015

AbstractUsing highly soluble bromo‐functionalized reduced graphene oxide (RGBr) as a key graphene template for surface‐directing Sonogashira–Hagihara polymerization, a novel soluble poly(arylene‐ethynylene)‐grafted reduced graphene oxide, hereafter abbreviated as PAE‐g‐RGO, was prepared in situ. The entirely different electron distribution of LUMO and HOMO of PAE‐g‐RGO suggested the existence of a charge‐transfer (CT) state (PAE.−–RGO.+). The negative ΔGCS value (−2.57 eV) indicates that the occurrence of the charge separation via 1RGO* in o‐DCB is exothermic and favorable. Upon irradiation with 365 nm light, the light‐induced electron paramagnetic resonance (LEPR) spectrum of PAE‐g‐RGO showed a decrease in the spin‐state density owing to photoinduced intramolecular electron transfer events in this system. A sandwich‐type Al/PAE‐g‐RGO/ITO device showed representative bistable electrical switching behavior. The nonvolatile memory performance was attributed to the CT‐induced conductance changes, which was supported by molecular computation results and conductive atomic force microscopy (C‐AFM) images.
Impact of a Developing Velocity Profile on Heat and Mass Transfer in Absorbing Laminar Falling Films
Authors: Mittermaier Martin , Ziegler Felix 
Published: December 2015

AbstractThis study describes a developing laminar falling film over a vertical plate while heat and mass transfer occurs. The model accounts for a developing film thickness and uni‐directional diffusion. The fluid properties are assumed to be constant, and latent heat, which is relatively large in comparison to the sensible heat, is set free at the liquid‐vapor interface. Temperature and concentration profiles in the film, the development of the interface velocity, as well as the absorbed mass fluxes are presented and two different boundary conditions have been applied to the inlet of the film.
Unresectable intrahepatic cholangiocarcinoma: Systemic plus hepatic arterial infusion chemotherapy is associated with longer survival in comparison with systemic chemotherapy alone
Authors: Konstantinidis Ioannis T. , Koerkamp Bas Groot , Do Richard K. G. , Gönen Mithat , Fong Yuman , Allen Peter J. , D'Angelica Michael I. , Kingham T. Peter , DeMatteo Ronald P. , Klimstra David S. , Kemeny Nancy E. , Jarnagin William R. 
Published: December 2015

BACKGROUNDIntrahepatic cholangiocarcinoma (ICC) is associated with poor survival. This study compared the outcomes of patients with unresectable ICC treated with hepatic arterial infusion (HAI) plus systemic chemotherapy (SYS) with the outcomes of patients treated with SYS alone.METHODSConsecutive patients with ICC were retrospectively reviewed. Clinicopathologic data were reviewed. Survival rates were compared by Kaplan‐Meier analysis and log‐rank testing.RESULTSBetween January 2000 and August 2012, 525 patients with ICC were evaluated at Memorial Sloan Kettering Cancer Center, and 236 patients with unresectable tumors (locally advanced or metastatic) were analyzed. Disease was confined to the liver in 104 patients, who underwent treatment with combined HAI and SYS (n = 78 or 75%) or SYS alone (n = 26 or 25%). The response rate in the combined group was better than the rate in the group receiving SYS alone, although this did not reach statistical significance (59% vs 39%, P = .11). Overall survival for the combined group was longer than overall survival for the patients who received SYS alone (30.8 vs 18.4 months, P < .001), and this difference was maintained when patients with portal lymph node disease were included in the survival analysis (29.6 months with HAI and SYS [n = 93] vs 15.9 months with SYS [n = 74], P < .001). Eight patients who initially presented with unresectable tumors responded enough to undergo complete resection and had a median overall survival of 37 months (range, 10.4‐92.3 months).CONCLUSIONSIn patients with unresectable ICC confined to the liver or with limited regional nodal disease, a combination of SYS and HAI chemotherapy is associated with greater survival than SYS alone. Cancer 2016;122:758–765. © 2015 American Cancer Society.
Performance of fixed‐gain amplify‐and‐forward nonlinear relaying with hardware impairments
Authors: Maletić N. , Čabarkapa M. , Nešković N. 
Published: December 2015

SummaryIn this paper, a fixed‐gain amplify‐and‐forward relaying under non‐ideal hardware is analyzed. The relaying system is impaired because of relay's power amplifier (PA) nonlinearity and in‐phase and quadrature‐phase (IQ) imbalance at a destination. Closed‐form expressions for outage probability as well as ergodic capacity approximation and its upper bound are derived. Also, the outage probability and the ergodic capacity asymptotic expressions in the high signal‐to‐noise ratio are deduced. For the first time, the joint influence of PA nonlinearity and IQ imbalance on the system in terms of outage probability, symbol error rate, and ergodic capacity is investigated. The results are compared with the respect to soft envelope limiter and traveling‐wave tube amplifier at the relay. Based on the analytical and the numerical results, important insights into the impact of IQ imbalance and nonlinearity of the aforementioned PA models on the system performance are gained as well as valuable information on the performance of practically deployed fixed‐gain amplify‐and‐forward relaying system. Copyright © 2015 John Wiley & Sons, Ltd.
Synthesis of a novel cross‐linked organophosphorus‐nitrogen containing polymer and its application in flame retardant epoxy resins
Authors: Xu Miaojun , Li Xu , Li Bin 
Published: December 2015

SummaryA novel cross‐linked organophosphorus–nitrogen polymetric flame retardant additive poly(urea tetramethylene phosphonium sulfate) defined as PUTMPS was synthesized by the condensation polymerization between urea and tetrahydroxymethyl phosphonium sulfate. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, 13C and 31P solid‐state nuclear magnetic resonance. The synthesized PUTMPS and curing agent m‐phenylenediamine were blended into epoxy resins to prepare flame retardant epoxy resin thermosets. The effects of PUTMPS on fire retardancy and thermal degradation behavior of EP/PUTMPS thermosets were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter measurement, and thermalgravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS), respectively. Water resistant properties of epoxy resin thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the EP/12 wt% PUTMPS thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value reached 31.3%. The TGA results indicated that the incorporation of PUTMPS promoted epoxy resin matrix decomposed and char forming ahead of time, which led to a higher char yield and thermal stability for epoxy resin thermosets at high temperature. The morphological structures and analysis of XPS for the char residues of the epoxy resin thermosets shown that PUTMPS benefited to the formation of a sufficient, more compact, and homogeneous char layer with rich flame retardant elements on the materials surface during burning, which prevented the heat transmission and diffusion, limited the production of combustible gases, inhibited the emission of smoke, and then led to the reduction of the heat release rate and smoke produce rate. After water resistance tests, EP/12 wt% PUTMPS thermosets still remained excellent flame retardancy. Copyright © 2015 John Wiley & Sons, Ltd.