bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetic Studies on the Palladium(II)‐Catalyzed Oxidative Cross‐Coupling of Thiophenes with Arylboron Compounds and Their Mechanistic Implications
Authors: Schnapperelle Ingo , Breitenlechner Stefan , Bach Thorsten 
Published: October 2015

AbstractReaction orders for the key components in the palladium(II)‐catalyzed oxidative cross‐coupling between phenylboronic acid and ethyl thiophen‐3‐yl acetate were obtained by the method of initial rates. It turned out that the reaction rate not only depended on the concentration of palladium trifluoroacetate (reaction order: 0.97) and phenylboronic acid (reaction order: 1.26), but also on the concentration of the thiophene (reaction order: 0.55) and silver oxide (reaction order: −1.27). NMR spectroscopy titration studies established the existence of 1:1 complexes between the silver salt and both phenylboronic acid and ethyl thiophen‐3‐yl acetate. A low inverse kinetic isotope effect (kH/kD=0.93) was determined upon employing the 4‐deuterated isotopomer of ethyl thiophen‐3‐yl acetate and monitoring its reaction to the 4‐phenyl‐substituted product. A Hammett analysis performed with para‐substituted 2‐phenylthiophenes gave a negative ρ value for oxidative cross‐coupling with phenylboronic acid. Based on the kinetic data and additional evidence, a mechanism is suggested that invokes transfer of the phenyl group from phenylboronic acid to a 1:1 complex of palladium trifluoroacetate and thiophene as the rate‐determining step. Proposals for the structure of relevant intermediates are made and discussed.
Mesoporous Carbon Nanofibers Embedded with MoS2 Nanocrystals for Extraordinary Li‐Ion Storage
Authors: Hu Shan , Chen Wen , Uchaker Evan , Zhou Jing , Cao Guozhong 
Published: October 2015

AbstractMoS2 nanocrystals embedded in mesoporous carbon nanofibers are synthesized through an electrospinning process followed by calcination. The resultant nanofibers are 100–150 nm in diameter and constructed from MoS2 nanocrystals with a lateral diameter of around 7 nm with specific surface areas of 135.9 m2 g−1. The MoS2@C nanofibers are treated at 450 °C in H2 and comparison samples annealed at 800 °C in N2. The heat treatments are designed to achieve good crystallinity and desired mesoporous microstructure, resulting in enhanced electrochemical performance. The small amount of oxygen in the nanofibers annealed in H2 contributes to obtaining a lower internal resistance, and thus, improving the conductivity. The results show that the nanofibers obtained at 450 °C in H2 deliver an extraordinary capacity of 1022 mA h g−1 and improved cyclic stability, with only 2.3 % capacity loss after 165 cycles at a current density of 100 mA g−1, as well as an outstanding rate capability. The greatly improved kinetics and cycling stability of the mesoporous MoS2@C nanofibers can be attributed to the crosslinked conductive carbon nanofibers, the large specific surface area, the good crystallinity of MoS2, and the robust mesoporous microstructure. The resulting nanofiber electrodes, with short mass‐ and charge‐transport pathways, improved electrical conductivity, and large contact area exposed to electrolyte, permitting fast diffusional flux of Li ions, explains the improved kinetics of the interfacial charge‐transfer reaction and the diffusivity of the MoS2@C mesoporous nanofibers. It is believed that the integration of MoS2 nanocrystals and mesoporous carbon nanofibers may have a synergistic effect, giving a promising anode, and widening the applicability range into high performance and mass production in the Li‐ion battery market.
Indium Tribromide Catalyzed Coupling Reaction of Enol Ethers with Silyl Ketene Imines toward the Synthesis of β,γ‐Unsaturated Nitriles
Authors: Nishimoto Yoshihiro , Nishimura Takashi , Yasuda Makoto 
Published: October 2015

AbstractHerein, a coupling reaction of enol ethers with silyl ketene imines in the presence of catalytic amounts of InBr3 and Me3SiBr is described. Kinetic studies have revealed that an indium catalyst and Me3SiBr accelerated the coupling process and the regeneration of the catalyst, respectively. Various types of enol ethers and silyl ketene imines are applicable. In addition, a formal synthesis of verapamil was achieved by using this novel coupling reaction.
Regioselective Synthesis of Polyheterohalogenated Naphthalenes via the Benzannulation of Haloalkynes
Authors: Lehnherr Dan , Alzola Joaquin M. , Lobkovsky Emil B. , Dichtel William R. 
Published: October 2015

AbstractIndependent control of halide substitution at six of the seven naphthalene positions of 2‐arylnaphthalenes is achieved through the regioselective benzannulation of chloro‐, bromo‐, and iodoalkynes. The modularity of this approach is demonstrated through the preparation of 44 polyheterohalogenated naphthalene products, most of which are difficult to access through known naphthalene syntheses. The outstanding regioselectivity of the reaction is both predictable and proven unambiguously by single‐crystal X‐ray diffraction for many examples. This synthetic method enables the rapid preparation of complex aromatic systems poised for further derivatization using established cross‐coupling methods. The power and versatility of this approach makes substituted naphthalenes highly attractive building blocks for new organic materials and diversity‐oriented synthesis.
Collection of NMR Scalar and Residual Dipolar Couplings Using a Single Experiment
Authors: Gil‐Silva Leandro F. , Santamaría‐Fernández Raquel , Navarro‐Vázquez Armando , Gil Roberto R. 
Published: October 2015

AbstractA new DMSO‐compatible aligning gel based on cross‐linked poly(2‐hydroxylethyl methacrylate) (poly‐HEMA) has been developed. Due to a significant difference in bulk magnetic susceptibility between the DMSO inside and outside the gel, it is possible to simultaneously collect isotropic and anisotropic NMR data, such as residual dipolar couplings (RDC), in the same NMR tube. RDC‐assisted structural analysis of menthol and the alkaloid retrorsine is reported as proof of concept.
Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by In situ‐Generated Ni0
Authors: Rebih Fatima , Andreini Manuel , Moncomble Aurélien , Harrison‐Marchand Anne , Maddaluno Jacques , Durandetti Muriel 
Published: October 2015

AbstractA novel Ni0‐catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove‐box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user‐friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents.
Fast Pyrolysis of Fresh Bio Waste and Ensiled Municipal Green Cut
Authors: Weber Christoph , Boscagli Chiara , Raffelt Klaus , Richter Daniel , Zevaco Thomas 
Published: October 2015

AbstractThe aim of the work was to estimate the feasibility of utilizing fresh bio waste and ensiled green cut for the bioliq process, which includes downstream entrained flow gasification in a GSP gasifier. Fast pyrolysis experiments are carried out after leaching and mechanical dewatering. The solid and liquid products of the green cut waste contained up to 94 % of the energy content of the starting material. The pyrolysis products are chemically similar to those of other biomasses, except for a distinct share of fatty acids due to the variability of the feedstock. The results show that the use of these leached and dried waste materials in the bioliq process is possible.
Methodik zur einfachen Standardisierung von Probenahmesystemen auf Basis der beteiligten Fluidphasen
Authors: Trostorf Robin , Kockmann Norbert 
Published: October 2015

AbstractIn chemischen, biotechnologischen und pharmazeutischen Produktionsbetrieben sind viele unterschiedliche Apparateelemente und Anlagenkomponenten im Einsatz, die trotz langjähriger Bemühungen um Standardisierung eine große Vielfalt aufweisen. In diesem Artikel wird eine Vorgehensweise zur Standardisierung von bestehenden Komponenten, die sich häufig wiederholen, hier Probenahmesysteme, vorgestellt. Auf Basis der beteiligten Phasen (Gase, Flüssigkeiten, Suspensionen und Feststoffe) und Prozessbedingungen wird eine Einteilung und Bewertungstabelle erstellt, die einen einfachen Vergleich der bestehenden, aber auch neuen Systeme ermöglicht. Die Auswahl der am besten geeigneten Lösung führt zu einem betriebsinternen Standard, der die Planung, den Betrieb und die Wartung und Ersatzteilhaltung wesentlich vereinfacht.
Einfluss der Plattendicke auf die Kontaktzeit beim elastischen Stoßvorgang
Authors: Müller Peter , Böttcher Ronny , Trüe Michael , Russell Alexander , Aman Sergej , Tomas Jürgen 
Published: October 2015

AbstractMit einer Fallversuchsanlage werden die Stoßzahl und die Kontaktzeit von Stahlkugeln beim Stoßvorgang gegen goldbeschichtete dünne Glasplatten gemessen. Untersucht werden der Einfluss der Aufprallgeschwindigkeit, der Partikelgröße und der Prallplattendicke. Die Ergebnisse lassen sich gut mit dem Modell nach Zener wiedergeben. Die gemessenen Stoßzahlen bleiben allerdings im gesamten Messbereich etwas unterhalb der theoretischen Zenerkurve, da das Modell lediglich die Energiedissipation aufgrund elastischer Wellen (Biegewellen) beinhaltet, weitere Energiedissipationen jedoch nicht beachtet. Bei den Experimenten können zusätzlich Reibung, viskose Einflüsse und plastische Deformation auftreten.
Immunophenotypic and cytogenetic findings of B‐lymphoblastic leukemia/lymphoma associated with combined IGH/BCL2 and MYC rearrangement
Authors: Kelemen Katalin , Holden Jaclyn , Johnson Laura J. , Davion Simone , Robetorye Ryan S. 
Published: October 2015

BackgroundB‐lymphoblastic leukemias (B‐LBL) with combined IGH/BCL2 and MYC rearrangement are rare and their clinical, cytogenetic and immunophenotypic features are not well characterized. Here, we describe a case of a 61‐year‐old woman with B‐LBL associated with these cytogenetic alterations and present a review of the literature of this disease.MethodsFour‐color flow cytometry (FC) was performed on a BD FACSCanto II flow cytometer. Data were analyzed with BD FACSDiva software. Cytogenetic, fluorescence in situ hybridization (FISH), and molecular studies were performed by conventional methods. A review of the literature was performed by a PubMed‐assisted search.ResultsIncluding our case, eight B‐LBLs associated with a documented “double‐hit” karyotype (IGH/BCL2 and 8q24/MYC rearrangement) were identified in the literature (male/female 2/6, age 15‐65). Three occurred de‐novo, and five had a history of a CD10+ B‐cell lymphoma. The typical immunophenotype was CD10, CD19, TdT positive, and negative for CD34 and surface immunoglobulin (Ig), established either by FC or immunohistochemistry. Seven cases were CD20‐, and one case was CD20+. Translocation partners of MYC varied, and included IGH, lambda light chain, and an unknown gene on chromosome 9. Prognosis was poor with median survival of five months.ConclusionsPatients with B‐LBL associated with a combined IGH/BCL2 and MYC rearrangement often have a history of a mature B‐cell lymphoma. The immunophenotype of these cases is different from that of mature “double‐hit” lymphomas; FC is essential to differentiate the B‐LBL cases from the leukemic phase of mature B‐cell lymphomas. © 2015 International Clinical Cytometry Society
A study of cortisol reactivity and recovery among young adolescents: Heterogeneity and longitudinal stability and change
Authors: Ji Juye , Negriff Sonya , Kim Hansung , Susman Elizabeth J. 
Published: October 2015

ABSTRACTThe dominance of reactivity‐based theories of the cortisol response and lack of attention to cortisol recovery makes it difficult to compile an integrated theory of the stress response. This report examined a reactivity and recovery model of the cortisol response using variable‐centered and person‐centered approaches. Age and sex differences and heterogeneity in the pattern of cortisol response were examined. Participants were 135 healthy young adolescents participating in a three‐wave longitudinal study of puberty and psychological development. At each wave, five saliva‐cortisol samples were collected prior to and following a modified Trier Social Stressor Test for Children. Linear, quadratic, and piece‐wise models of latent growth curve analyses and latent class analyses were conducted. Age differences in cortisol reactivity and recovery were found at wave 1 and sex differences in cortisol reactivity emerged at wave 3. Meaningful heterogeneity in the pattern of cortisol response was found cross‐sectionally and longitudinally. The implications of heterogeneity in the cortisol response during early adolescence for developmental science are discussed. © 2015 Wiley Periodicals, Inc. Dev Psychobiol 58: 283–302, 2016.
Temperature rise severely affects pan and soil evaporation in the Negev Desert
Authors: Kidron Giora J. , Kronenfeld Rafael 
Published: October 2015

AbstractGlobal warming may affect the moisture content of soil, subsequently affecting plant productivity. This is all the more so in deserts where water is the major limiting factor. In an attempt to evaluate the possible effect of temperature rise on pan and soil evaporation, the evaporation rates of water from variable‐size pans and of plots of variable degree of shading (all with different water/soil temperatures) were compared. A close link between the water temperature of the pan (resulting from the different diameter‐size pans) and class A pan evaporation was found. The data showed that an increase of 1 °C in the maximum temperatures implied an increase of 0.08 mm/day, i.e. ~8.3% in the evaporation rate of the pan. Similarly, an increase in the subsurface temperatures (at 5 cm depth) substantially decreased the available water content at the 0‐ to 10‐cm soil, with the evaporation rate increasing by 0.07 mm/day (~6.6%) for each 1 °C increase in soil temperature. The findings suggest an increase of ~10% in the evaporation rate of the soil surface for each 1 °C increase in soil temperature. The advantage in estimating the possible effect of temperature rise upon soil evaporation via shaded plots in comparison with the classical approach of soil heating is discussed, as well as the possible effect of temperature rise on biocrusts, seedling germination and plant productivity. Copyright © 2015 John Wiley & Sons, Ltd.
Ecohydrology of groundwater‐dependent grasslands of the semi‐arid Horqin sandy land of inner Mongolia focusing on evapotranspiration partition
Authors: Wu Yao , Liu Tingxi , Paredes Paula , Duan Limin , Wang Haiyan , Wang Tianshuai , Pereira Luis S. 
Published: October 2015

AbstractThe Horqin sandy steppe is an ecosystem where groundwater‐dependent grasslands are main components. To study the dynamics of soil water and evapotranspiration, and its partition into transpiration and soil evaporation, the SIMDualKc model was applied to two sites in the Agula eco‐hydrological study area, Inner Mongolia, China. This model adopts the dual crop coefficient approach to compute daily crop evapotranspiration (ETc) and uses a parametric function to compute capillary rise from a shallow watertable. The application refers to three years of field observations, 2008 with high rainfall and higher watertable, 2009 with low rainfall and lower watertable, and 2011 with average rainfall and watertable conditions. Model calibration and validation were performed comparing simulated against observed soil water content throughout the vegetation seasons, with regression coefficients close to 1.0 and small root mean square errors (RMSE < 0.013 cm3 cm−3). The groundwater contribution represented 41–47% of the actual ETc in the higher rainfall year and 56–59% in the dry year, which clearly shows the role of groundwater in sustaining grasslands in the Horqin steppe. The ratio between transpiration and actual ETc ranged 88 to 94%, which is much higher than observations in other grasslands because capillary rise contributes to extraction by crop roots, not to soil evaporation. Simulations relative to lowering the watertable show that groundwater contribution decreases up to 25% for a dry year with a consequent decrease of transpiration of 24%. Hence, there is the need for developing appropriate groundwater protection measures to preserve the Horqin landscape. Copyright © 2015 John Wiley & Sons, Ltd.
Initial 3‐year outcomes with left ventricular assist devices in a country with a nascent heart transplantation program
Authors: Pya Yuriy , Bekbossynova Makhabbat , Jetybayeva Saltanat , Bekbossynov Serik , Andossova Saltanat , Salov Roman , Medressova Assel , Novikova Svetlana , Murzagaliyev Muradym 
Published: October 2015

AbstractAimsThe need for the left ventricular assist devices (LVAD) in patients with end‐stage heart failure is well established, but prior to 2011, this was not available to patients in Kazakhstan. We describe the development of the sole LVAD programme in the context of a nascent heart transplantation programme and clinical outcomes for the first three years.Methods and resultsFrom November 2011 to November 2014, 146 patients underwent implantation of 152 VADs (approximately 50 devices implanted per year). We retrospectively analyzed data from 135 LVAD patients who received HeartMate II (n = 95) or HeartWare (n = 40) devices. In 75 patients LVAD was used as a bridge‐to‐transplantation and in 60 patients as destination therapy, but only 3 of 135 LVAD patients received heart transplant. Forty‐three patients of the LVAD cohort had died by the end of the follow‐up period. The mean time on LVAD was 466 ± 330 days (range 5–1200 days). Kaplan–Meier survival estimates for patients who continued on LVAD support were 93% after 1 month, 86% after 6 months and 77% after 12 months. The most common complications within the first 30 days after implant included right ventricular failure (n = 20, 1.85 events/patient‐year), renal failure (n = 19, 1.76 events/patient‐year) and bleeding (n = 33, 3.0 events/patient‐year). Beyond 30 days adverse events included driveline infections (n = 46, 0.56 events/patient‐year) and stroke (n = 33, 0.21 events/patient‐year).ConclusionsLVADs are an important therapeutic alternative to heart transplantation in the context of a developing heart transplant programme with outcomes that are comparable to those reported by other centres.
Ventricular conduction abnormalities as predictors of long‐term survival in acute de novo and decompensated chronic heart failure
Authors: Tolppanen Heli , Siirila‐Waris Krista , Harjola Veli‐Pekka , Marono David , Parenica Jiri , Kreutzinger Philipp , Nieminen Tuomo , Pavlusova Marie , Tarvasmaki Tuukka , Twerenbold Raphael , Tolonen Jukka , Miklik Roman , Nieminen Markku S. , Spinar Jindrich , Mueller Christian , Lassus Johan 
Published: October 2015

AbstractAimsData on the prognostic role of left and right bundle branch blocks (LBBB and RBBB), and nonspecific intraventricular conduction delay (IVCD; QRS ≥ 110 ms, no BBB) in acute heart failure (AHF) are controversial. Our aim was to investigate electrocardiographic predictors of long‐term survival in patients with de novo AHF and acutely decompensated chronic heart failure (ADCHF).Methods and ResultsWe analysed the admission electrocardiogram of 982 patients from a multicenter European cohort of AHF with 3.9 years' mean follow‐up. Half (51.5%, n = 506) of the patients had de novo AHF. LBBB, and IVCD were more common in ADCHF than in de novo AHF: 17.2% vs. 8.7% (P < 0.001) and 20.6% vs. 13.2% (P = 0.001), respectively, and RBBB was almost equally common (6.9% and 8.1%; P = 0.5), respectively. Mortality during the follow‐up was higher in patients with RBBB (85.4%) and IVCD (73.7%) compared with patients with normal ventricular conduction (57.0%); P < 0.001 for both. The impact of RBBB on prognosis was prominent in de novo AHF (adjusted HR 1.93, 1.03–3.60; P = 0.04), and IVCD independently predicted death in ADCHF (adjusted HR 1.79, 1.28–2.52; P = 0.001). Both findings were pronounced in patients with reduced ejection fraction. LBBB showed no association with increased mortality in either of the subgroups. The main results were confirmed in a validation cohort of 1511 AHF patients with 5.9 years' mean follow‐up.ConclusionsConduction abnormalities predict long‐term survival differently in de novo AHF and ADCHF. RBBB predicts mortality in de novo AHF, and IVCD in ADCHF. LBBB has no additive predictive value in AHF requiring hospitalization.
What does the lay public know about heart failure? Findings from the Heart Failure Awareness Day Initiative
Authors: Störk Stefan , Kavoliuniene Ausra , Vinereanu Dragos , Ludwig Rafael , Seferovic Petar , Dickstein Kenneth , Anker Stefan D. , Filippatos Gerasimos , Ponikowski Pjotr , Lainscak Mitja 
Published: October 2015

ABSTRACTAim & MethodsOne critical factor enhancing the implementation of successful diagnostic and therapeutic strategies into clinical practice is awareness among the lay public. We describe awareness in a contemporary, multinational convenience sample of subjects attending the Heart Failure Awareness (HFA) Day Initiatives in 2013.ResultsWe analysed 2,438 subjects (Germany 33%, Lithuania 42%, Romania 8%, Slovenia 17%) : 53% were female, 58% were aged >60 years, 11% (had) worked in the medical sector, 82% heard about HF before. Shortness of breath and tiredness were correctly identified as symptoms of heart failure in 71% and 61%, but only 52% recognized swelling of feet and legs as a clinical sign; 31% considered heart failure a normal symptom of old age, and only 38% realized the particularly poor prognosis after a heart failure related hospitalization. Subjects who had heard about heart failure before had a lower prevalence of common misbeliefs about HF.ConclusionIn subjects participating in the HFA Day initiative 2013, the level of awareness was unsatisfactory, and important misconceptions remain. The educational and awareness activities for both the population at large and also for decision makers should be broadened and intensified.
Synthesis and Luminescence Properties of Cycloplatinated Complexes with a Chelating N∧C Pyridine‐Derived N‐Heterocyclic Carbene – Influence of 2,4,6‐Triphenyl­phosphinine versus Triphenylphosphine
Authors: Moussa Jamal , Freeman Gemma R. , Williams J. A. Gareth , Chamoreau Lise‐Marie , Herson Patrick , Amouri Hani 
Published: October 2015

AbstractTwo cycloplatinated complexes of the form [Pt(NC)CH3(P)]+ incorporating a rare, bidentate NC‐chelating pyridylpyridylidene ligand are reported. The phosphorus‐based ligand P is either 2,4,6‐triphenylphosphinine or triphenylphosphine. These mononuclear complexes have been fully characterised in solution and by single‐crystal X‐ray diffraction analysis. UV/Vis absorption and photoluminescence spectroscopy studies reveal strong phosphorescence from the phosphinine compound at 77 K but no emission from its triphenylphosphine analogue. This contrasting behaviour can be traced to the π‐acceptor ability of the phosphabenzene ring, as corroborated by electrochemical and time‐dependent DFT (TD‐DFT) calculations.