bluuebunny/crossref_metadata_2025_split huggingface dataset:
2‐[(Neopentyl glycolato)boryl]phenyl Triflates and Halides for Fluoride Ion‐Mediated Generation of Functionalized Benzynes
Authors: Ikawa Takashi , Yamamoto Rika , Takagi Akira , Ito Toyohiro , Shimizu Kazunori , Goto Masahiko , Hamashima Yoshitaka , Akai Shuji 
Published: July 2015

Abstract2‐[(Neopentyl glycolato)boryl]phenyl trifluoromethanesulfonates (triflates) and halides have been developed as new benzyne precursors, which generate benzynes at 120 °C in the presence of a fluoride ion. There are two major features of these types of precursors. First, they generate benzynes bearing various reactive functional groups, such as carbonyl, cyano, bromo, and primary amino groups. Second, these precursors were directly synthesized through either the palladium‐catalyzed Miyaura borylation of 2‐iodophenol derivatives or ortho‐selective iodination of the corresponding boronic acids as key steps without using any protecting groups. The in‐situ‐generated benzynes underwent [4+2], (3+2), and [2+2] cycloadditions to give the benzo‐fused multicyclic compounds while maintaining such functional groups. In particular, 4‐aminobenzyne was generated for the first time and underwent the Diels–Alder reaction with the free primary amino group remaining intact.magnified image
Synthesis of Allenes Bearing Phosphine Oxide Groups and Investigation of Their Reactivity toward Gold Complexes
Authors: Vanitcha Avassaya , Gontard Geoffrey , Vanthuyne Nicolas , Derat Etienne , Mouriès‐Mansuy Virginie , Fensterbank Louis 
Published: July 2015

AbstractA collection of phosphine oxide allenes has been prepared. Their coordination to gold(I) has been studied giving new coordination complexes when a pendant pyridine moiety was present. Alternatively, their gold(I)‐catalyzed cycloisomerization has proven to be quite efficient. An almost complete axial‐to‐central chirality transfer in the cyclization process was observed, opening the potential access to valuable enantiopure phosphorus derivatives.magnified image
Body mass estimation from knee breadth, with application to early hominins
Authors: Squyres Nicole , Ruff Christopher B. 
Published: July 2015

AbstractObjectivesThe estimation of living body mass from skeletal dimensions is an important component of many studies of early hominins and more recent human archaeological remains. Most previous investigations have concentrated on weight‐bearing elements of the lower limb, in particular the femoral head. In this study, we develop new body mass estimation equations derived from measurements of the knee in a modern sample of known body mass, and use them to estimate body mass in 11 fossil hominin specimens (including Au. africanus, Au. afarensis, and early Homo).Materials and MethodsThe reference sample consisted of 100 living subjects who participated in the Baltimore Longitudinal Study of Aging. Mediolateral breadth measurements were taken from radiographs of the knee, and regressed against recorded body weight to generate body mass estimation equations.ResultsKnee dimensions were generally found to be good predictors of body mass in the modern human sample, with median absolute percent prediction errors of 7 to 9% (comparable to or better than previously reported equations derived from the femoral head). Taxon‐average estimated body masses were 46.1 kg for Au. afarensis, 38.4 kg for Au. africanus, and 53.6 kg for early Homo.DiscussionEstimates for early Homo were similar to or smaller than those generated previously from the femoral head. Estimates for australopiths, however, were larger than those generated from femoral head equations. This result is consistent with other evidence that the femoral head was relatively unloaded in australopiths compared with Homo, possibly due to subtle differences in gait. Am J Phys Anthropol 158:198–208, 2015. © 2015 Wiley Periodicals, Inc.
Electrocardiographic left atrial abnormality and stroke subtype in the atherosclerosis risk in communities study
Authors: Kamel Hooman , O'Neal Wesley T. , Okin Peter M. , Loehr Laura R. , Alonso Alvaro , Soliman Elsayed Z. 
Published: July 2015

ObjectiveThe aim of this study was to assess the relationship between abnormally increased P‐wave terminal force in lead V1, an electrocardiographic (ECG) marker of left atrial abnormality, and incident ischemic stroke subtypes. We hypothesized that associations would be stronger with nonlacunar stroke, given that we expected left atrial abnormality to reflect the risk of thromboembolism rather than in situ cerebral small‐vessel occlusion.MethodsOur cohort comprised 14,542 participants 45 to 64 years of age prospectively enrolled in the Atherosclerosis Risk in Communities study and free of clinically apparent atrial fibrillation (AF) at baseline. Left atrial abnormality was defined as PTFV1 >4,000μV*ms. Outcomes were adjudicated ischemic stroke, nonlacunar (including cardioembolic) ischemic stroke, and lacunar stroke.ResultsDuring a median follow‐up period of 22 years (interquartile range, 19–23 years), 904 participants (6.2%) experienced a definite or probable ischemic stroke. A higher incidence of stroke occurred in those with baseline left atrial abnormality (incidence rate per 1,000 person‐years, 6.3; 95% confidence interval [CI]: 5.4–7.4) than in those without (incidence rate per 1,000 person‐years, 2.9; 95% CI: 2.7–3.1; p < 0.001). In Cox regression models adjusted for potential confounders and incident AF, left atrial abnormality was associated with incident ischemic stroke (hazard ratio [HR]: 1.33; 95% CI: 1.11–1.59). This association was limited to nonlacunar stroke (HR, 1.49; 95% CI: 1.07–2.07) as opposed to lacunar stroke (HR, 0.89; 95% CI: 0.57–1.40).InterpretationWe found an association between ECG‐defined left atrial abnormality and subsequent nonlacunar ischemic stroke. Our findings suggest that an underlying atrial cardiopathy may cause left atrial thromboembolism in the absence of recognized AF. Ann Neurol 2015;78:Ann Neurol 2015;78:679–696
Ein katalytischer SEAr‐Zugang zu Dibenzosilolen mit Funktionalisierung an beiden Benzolkernen
Authors: Omann Lukas , Oestreich Martin 
Published: July 2015

AbstractEs wird über eine allgemeine Reaktionsvorschrift zur katalytischen Synthese von an einem oder beiden Benzolringen funktionalisierten Dibenzosilolen berichtet, die von leicht verfügbaren ortho‐silylierten Biphenylen ausgeht. Diese Methode ermöglicht einen schnellen Zugang zu Silolbausteinen mit Chloratomen an beiden Phenylengruppen und beschreibt somit einen katalytischen Weg zu direkt polymerisierbaren Dibenzosilolen. Es wird außerdem gezeigt, dass trotz hochgradig elektrophiler Zwischenstufen eine beachtliche Breite an Lewis‐basischen, beispielsweise sauerstoff‐ und stickstoffhaltigen, funktionellen Gruppen toleriert wird. Der Mechanismus dieser intramolekularen elektrophilen aromatischen Substitution (SEAr) durchläuft ein schwefelstabilisiertes Siliciumkation, das katalytisch aus der Hydrosilanvorstufe generiert wird.
Probing Invisible, Excited Protein States by Non‐Uniformly Sampled Pseudo‐4D CEST Spectroscopy
Authors: Long Dong , Delaglio Frank , Sekhar Ashok , Kay Lewis E. 
Published: July 2015

AbstractChemical exchange saturation transfer (CEST) NMR spectroscopy is a powerful tool for studies of slow timescale protein dynamics. Typical experiments are based on recording a large number of 2D data sets and quantifying peak intensities in each of the resulting planes. A weakness of the method is that peaks must be resolved in 2D spectra, limiting applications to relatively small proteins. Resolution is significantly improved in 3D spectra but recording uniformly sampled data is time‐prohibitive. Here we describe non‐uniformly sampled HNCO‐based pseudo‐4D CEST that provides excellent resolution in reasonable measurement times. Data analysis is done through fitting in the time domain, without the need of reconstructing the frequency dimensions, exploiting previously measured accurate peak positions in reference spectra. The methodology is demonstrated on several protein systems, including a nascent form of superoxide dismutase that is implicated in neurodegenerative disease.
Organometallic Antitumor Compounds: Ferrocifens as Precursors to Quinone Methides
Authors: Wang Yong , Pigeon Pascal , Top Siden , McGlinchey Michael J. , Jaouen Gérard 
Published: July 2015

AbstractThe synthesis and chemical oxidation profile of a new generation of ferrocifen derivatives with strong antiproliferative behavior in vitro is reported. In particular, the hydroxypropyl derivative HO(CH2)3C(Fc)=C(C6H4OH)2 (3 b) exhibited exceptional antiproliferative activity against the cancer cell lines HepG2 and MDA‐MB‐231 TNBC, with IC50 values of 0.07 and 0.11 μM, respectively. Chemical oxidation of 3 b yielded an unprecedented tetrahydrofuran‐substituted quinone methide (QM) via internal cyclization of the hydroxyalkyl chain, whereas the corresponding alkyl analogue CH3CH2‐C(Fc)=C(C6H4OH)2 merely formed a vinyl QM. The ferrocenyl group in 3 b plays a key role, not only as an intramolecular reversible redox “antenna”, but also as a stabilized carbenium ion “modulator”. The presence of the oxygen heterocycle in 3 b‐QM enhances its stability and leads to a unique chemical oxidation profile, thus revealing crucial clues for deciphering its mechanism of action in vivo.
Superior Na‐Storage Performance of Low‐Temperature‐Synthesized Na3(VO1−xPO4)2F1+2x (0≤x≤1) Nanoparticles for Na‐Ion Batteries
Authors: Qi Yuruo , Mu Linqin , Zhao Junmei , Hu Yong‐Sheng , Liu Huizhou , Dai Sheng 
Published: July 2015

AbstractNa‐ion batteries are becoming comparable to Li‐ion batteries because of their similar chemical characteristics and abundant sources of sodium. However, the materials production should be cost‐effective in order to meet the demand for large‐scale application. Here, a series of nanosized high‐performance cathode materials, Na3(VO1−xPO4)2F1+2x (0≤x≤1), has been synthesized by a solvothermal low‐temperature (60–120 °C) strategy without the use of organic ligands or surfactants. The as‐synthesized Na3(VOPO4)2F nanoparticles show the best Na‐storage performance reported so far in terms of both high rate capability (up to 10 C rate) and long cycle stability over 1200 cycles. To the best of our knowledge, the current developed synthetic strategy for Na3(VO1−xPO4)2F1+2x is by far one of the least expensive and energy‐consuming methods, much superior to the conventional high‐temperature solid‐state method.
Hematite‐Based Solar Water Splitting in Acidic Solutions: Functionalization by Mono‐ and Multilayers of Iridium Oxygen‐Evolution Catalysts
Authors: Li Wei , Sheehan Stafford W. , He Da , He Yumin , Yao Xiahui , Grimm Ronald L. , Brudvig Gary W. , Wang Dunwei 
Published: July 2015

AbstractSolar water splitting in acidic solutions has important technological implications, but has not been demonstrated to date in a dual absorber photoelectrochemical cell. The lack of functionally stable water‐oxidation catalysts (WOCs) in acids is a key reason for this slow development. The only WOCs that are stable at low pH are Ir‐based systems, which are typically too expensive to be implemented broadly. It is now shown that this deficiency may be corrected by applying an ultra‐thin monolayer of a molecular Ir WOC to hematite for solar water splitting in acidic solutions. The turn‐on voltage is observed to shift cathodically by 250 mV upon the application of a monolayer of the molecular Ir WOC. When the molecular WOC is replaced by a heterogeneous multilayer derivative, stable solar water splitting for over 5 h is achieved with near‐unity Faradaic efficiency.
The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2− (M=Mo, W)
Authors: Haiges Ralf , Skotnitzki Juri , Fang Zongtang , Dixon David A. , Christe Karl O. 
Published: July 2015

AbstractMolybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2− were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X‐ray crystal structures.
Palladium‐Catalyzed Direct Cyclopropylation of Heterocycles
Authors: Wu Xiaojin , Lei Chuanhu , Yue Guizhou , Zhou Jianrong (Steve) 
Published: July 2015

AbstractMany 1,3‐azoles and thiophenes are directly cyclopropylated in the presence of a simple palladium catalyst. The relative configuration on the three‐membered rings is retained in the products. Thus, the cyclopropyl–halide bond undergoes concerted oxidative addition to palladium(0) and cyclopropyl radicals are not involved in the productive pathway.
Bioactive Seed Layer for Surface‐Confined Self‐Assembly of Peptides
Authors: Vigier‐Carrière Cécile , Garnier Tony , Wagner Déborah , Lavalle Philippe , Rabineau Morgane , Hemmerlé Joseph , Senger Bernard , Schaaf Pierre , Boulmedais Fouzia , Jierry Loïc 
Published: July 2015

AbstractThe design and control of molecular systems that self‐assemble spontaneously and exclusively at or near an interface represents a real scientific challenge. We present here a new concept, an active seed layer that allows to overcome this challenge. It is based on enzyme‐assisted self‐assembly. An enzyme, alkaline phosphatase, which transforms an original peptide, Fmoc‐FFY(PO42−), into an efficient gelation agent by dephosphorylation, is embedded in a polyelectrolyte multilayer and constitutes the “reaction motor”. A seed layer composed of a polyelectrolyte covalently modified by anchoring hydrogelator peptides constitutes the top of the multilayer. This layer is the nucleation site for the Fmoc‐FFY peptide self‐assembly. When such a film is brought in contact with a Fmoc‐FFY(PO42−) solution, a nanofiber network starts to form almost instantaneously which extents up to several micrometers into the solution after several hours. We demonstrate that the active seed layer allows convenient control over the self‐assembly kinetics and the geometric features of the fiber network simply by changing its peptide density.
Cobalt(II)‐Catalyzed CH Alkynylation/Annulation with Terminal Alkynes: Selective Access to 3‐Methyleneisoindolin‐1‐one
Authors: Zhang Lin‐Bao , Hao Xin‐Qi , Liu Zhan‐Jiang , Zheng Xin‐Xiang , Zhang Shou‐Kun , Niu Jun‐Long , Song Mao‐Ping 
Published: July 2015

AbstractA highly efficient cobalt(II)‐catalyzed alkynylation/annulation of terminal alkynes assisted by an N,O‐bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts, and offers a new approach to 3‐methyleneisoindolin‐1‐one, which can be converted into an oxadiazine salt in one step. Moreover, the directing group could be removed in three steps.
Development of novel polar thermoplastic vulcanizates based on ethylene acrylic elastomer and polyamide 12 with special reference to heat and oil aging
Authors: Reffai Syed Ismail Syed Mohammed , Chatterjee Tuhin , Naskar Kinsuk 
Published: July 2015

ABSTRACTThermoplastic vulcanizates (TPVs) based on ethylene acrylic elastomer (AEM) and polyamide 12 (PA12) have been developed by the dynamic vulcanization process, in which selective cross‐linking of the elastomer phase (AEM) during melt mixing with the thermoplastic phase (PA12) has been carried out simultaneously. TPVs at varied blend ratios (50 : 50, 60 : 40, 70 : 30) of AEM/PA12 were prepared at 185°C at a rotor speed of 80 rpm up to 5 min of mixing. Di‐(2‐tert‐butyl peroxy isopropyl) benzene (DTBPIB) was chosen as the suitable cross‐linking peroxide to carry out the dynamic vulcanization. Morphology study reveals the development of continuous agglomerate of rubber network in case of all the TPVs took place and the average dimension of the rubber particles are in the range of 30–40 nm. TPV based on 50 : 50 AEM/PA12 shows better physicomechanical properties, thermal stability, and dynamic mechanical behavior among all the TPVs. For aging test, TPVs were exposed to air, ASTM oil 2 and 3. Air aging tests were carried out in hot air oven for 72 h at 125°C, while the oil aging tests were carried out after immersion of the samples into the oils in an aging oven. After aging, there are only slight deterioration of physicomechanical properties of the TPVs. Particularly in case of 50 : 50 blend of AEM/PA12, the retention of the properties even after aging was found excellent. The recyclability of these new TPVs is also found to be excellent leading to find potential application in automotives. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42655.
Composition‐Dependent Reaction Pathways and Hydrogen Storage Properties of LiBH4/Mg(AlH4)2 Composites
Authors: Pang Yuepeng , Liu Yongfeng , Zhang Xin , Li Qian , Gao Mingxia , Pan Hongge 
Published: July 2015

AbstractHerein, an initial attempt to understand the relationships between hydrogen storage properties, reaction pathways, and material compositions in LiBH4–x Mg(AlH4)2 composites is demonstrated. The hydrogen storage properties and the reaction pathways for hydrogen release from LiBH4–x Mg(AlH4)2 composites with x=1/6, 1/4, and 1/2 were systematically investigated. All of the composites exhibit a four‐step dehydrogenation event upon heating, but the pathways for hydrogen desorption/absorption are varied with decreasing LiBH4/Mg(AlH4)2 molar ratios. Thermodynamic and kinetic investigations reveal that different x values lead to different enthalpy changes for the third and fourth dehydrogenation steps and varied apparent activation energies for the first, second, and third dehydrogenation steps. Thermodynamic and kinetic destabilization caused by the presence of Mg(AlH4)2 is likely to be responsible for the different hydrogen desorption/absorption performances of the LiBH4–x Mg(AlH4)2 composites.
Conjugated Oligomers and Polymers Sheathed with Designer Side Chains
Authors: Pan Chengjun , Zhao Chunhui , Takeuchi Masayuki , Sugiyasu Kazunori 
Published: July 2015

AbstractConjugated polymers (CPs) are often referred to as molecular wires because of their quasi one‐dimensional electronic wavefunctions delocalized along the polymer chains. However, in the solid state, CPs tend to self‐assemble through π‐stacking, which greatly attenuates the one‐dimensional nature. By molecular design, CPs can be molecularly insulated just like electric power cords, resulting in so‐called “insulated” molecular wires (IMWs). In this Focus Review, we will discuss their unique photophysical, electronic, and mechanical properties which originate from the absence of π‐stacking.
RhIII‐Catalyzed C−H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant
Authors: Jiang Quandi , Zhu Changlei , Zhao Huaiqing , Su Weiping 
Published: July 2015

AbstractPhthalide skeletons have been synthesized for the first time through a RhIII‐catalyzed C−H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate‐to‐excellent yields.
Simultaneous Target Flying Mode Identification and Altitude Estimation in Bistatic T/R‐R HFSWR
Authors: Zhao Kongrui , Yu Changjun , Zhou Gongjian , Quan Taifan 
Published: July 2015

AbstractHigh frequency surface wave radar (HFSWR) cannot detect target altitude directly and is unable to identify flight mode. Assuming that the estimation and identification processes are mutually dependent, an integrated method called simultaneous identification and estimation (SIE) is proposed by applying a two‐level multiple model approach to the flight mode probability mass function (pmf) and state probability density function (pdf) simultaneously. The SIE involves two altitude estimation mode‐conditioned model sets, which are established utilizing the variation property of the propagation attenuation at different flight modes. The multiple model approach incorporated in SIE is different from the traditional interacting multiple model (IMM). It is applied at two levels: within each mode‐conditioned estimation model set and across all the mode‐conditioned estimation model sets. Simulations and real trials demonstrate the performance of the proposed SIE method.
GRB‐selected galaxies through cosmic time
Authors: Krühler T. 
Published: July 2015

AbstractTo use the luminous gamma‐ray bursts and their afterglows as messengers from the early Universe has been advocated ever since the discovery of the cosmological nature of the GRB phenomenon in the late nineties. It took, however, until the advent of Swift to detect high‐redshift GRBs in significant numbers, and to provide the localization capabilities to enable statistical samples of GRBs free of selection biases and complete in redshift. I will present and discuss some of the recent progress in the field, with an emphasize on new results derived from sample studies and their implications for the nature of GRBs and their host galaxies. I will particularly focus on observations made with the seven‐channel imager GROND and X‐shooter, an optical/NIR echelle spectrograph mounted at the Very Large Telescope since 2009. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
TANAMI: Multiwavelength and multimessenger observations of active galaxies
Authors: Kadler M. , Ojha R. , TANAMI Collaboration  
Published: July 2015

AbstractExtragalactic jets launched from the immediate vicinity of supermassive black holes in radio‐loud active galactic nuclei (AGN) are key objects in modern astronomy and astroparticle physics. AGN jets carry a fraction of the total gravitational energy released during the accretion of matter onto supermassive black holes and are prime suspects as possible sources of ultrahigh‐energy cosmic rays and the recently detected extraterrestrial neutrinos at PeV energies. TANAMI (Tracking Active galactic Nuclei with Austral Milliarcsecond Interferometry) is a multiwavelength program monitoring AGN jets of the southern sky. It combines high‐resolution imaging and spectral monitoring at radio wavelengths with higher‐frequency observations at IR, optical/UV, X‐ray, and γ‐ray energies. We review recent results of the TANAMI program, highlighting AGN candidate neutrino‐emitters in the error circles of the IceCube PeV neutrino events. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)