bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rhodium‐Catalyzed Intramolecular C−H Bond Activation with Triazoles: Preparation of Stereodefined Pyrrolidines and Other Related Cyclic Compounds
Authors: Senoo Masato , Furukawa Ayana , Hata Takeshi , Urabe Hirokazu 
Published: November 2015

AbstractOn treatment of triazoles having an N‐sulfonyl‐protected benzylamine moiety with [Rh2(C7H15CO2)4], intramolecular C−H bond insertion takes place at the benzylic position to give cis‐N‐sulfonyl‐2‐aryl‐3‐[(sulfonylimino)methyl]pyrrolidines in good yields and with highly stereoselectivities. Analogously, the similar treatment of triazoles having an ether or even an alkyl moiety affords 2‐alkyl‐ or 2‐aryl‐3‐[(sulfonylimino)methyl]tetrahydrofurans or a 2‐alkyl‐3‐[(sulfonylimino)methyl]cyclopentane in good yields.
Aerobic Dimerization of Enediyne Compounds: Construction of Naphthalene Frameworks
Authors: Wang Dongxu , Ling Fei , Liu Xiang , Li Zexiang , Ma Cheng 
Published: November 2015

AbstractThe first bimolecular oxygenative annulation of enediyne compounds leading to naphthalene frameworks has been developed by using Pd(OAc)2 as the catalyst in the presence of NaI under O2 (1 atm). This reaction provided efficient access to a class of symmetric core‐annulated naphthalenes by the homoannulation of enediyne–imides. Intriguingly, the crossover annulation of enediyne–imides and other functionalized enediynes could also be achieved by the same catalytic system, resulting in the formation of several unsymmetrical naphthalene derivatives. Preliminary mechanistic investigation using 18O isotopic labelling and radical scavengers indicated that radical oxygen incorporation cascades might be involved in this conversion.
The Radical Anion of Cyclopentasilane‐Fused Hexasilabenzvalene
Authors: Tsurusaki Akihiro , Kyushin Soichiro 
Published: November 2015

AbstractThe radical anion of cyclopentasilane‐fused hexasilabenzvalene was synthesized by the reduction of the corresponding neutral compound. X‐ray crystallographic analysis showed a more trans‐bent structure of the disilene moiety than the neutral compound. Theoretical calculations showed that the highly trans‐bent structure is attributed to the hexasilabenzvalene structure. The EPR spectrum showed that an unpaired electron exists mainly at the disilene moiety. In the UV/Vis spectrum, a large bathochromic shift was observed compared with the neutral compound.
Sorption equilibrium and kinetics for cyclohexane, toluene, and water on Athabasca oil sands solids
Authors: Tan Xiaoli , Vagi Lisa , Liu Qi , Choi Phillip , Gray Murray R. 
Published: November 2015

ABSTRACTThe sorption of solvents from the vapour phase to solid substrates is important in producing heavy oil and bitumen, particularly from the oil sands. We investigated the sorption and desorption equilibrium and kinetics of cyclohexane, toluene, and water on kaolinite, fine solids, and organic‐rich fine solids isolated from Athabasca oil sands over a wide range of solvent vapour concentrations using a gravimetric method. The isotherms for both adsorption and desorption of solvent vapour were determined, and the Brunauer‐Emmett‐Teller equation was used to fit the experimental data. The initial kinetic rate constants for the adsorption and desorption of solvent vapour were determined with the linear driving force model. The results were compared and discussed in terms of the type of solvent, the content of organic materials, and the surface area of the solid substrates. The results suggest that, in addition to the adsorption of solvent on mineral surfaces, the contribution from solvent partitioning in the organic materials and the porosity resulting from high amounts of organic materials are significant factors for solvent uptake and kinetic rate constants. In mixed solvent vapours, the competitive sorption of water and cyclohexane was observed in the solid substrates. However, the degree of competitiveness decreased with an increase in the content of organic materials in the substrates.
Structural Determinants of the Selectivity of 3‐Benzyluracil‐1‐acetic Acids toward Human Enzymes Aldose Reductase and AKR1B10
Authors: Ruiz Francesc X. , Cousido‐Siah Alexandra , Porté Sergio , Domínguez Marta , Crespo Isidro , Rechlin Chris , Mitschler André , de Lera Ángel R. , Martín María Jesús , de la Fuente Jesús Ángel , Klebe Gerhard , Parés Xavier , Farrés Jaume , Podjarny Alberto 
Published: November 2015

AbstractThe human enzymes aldose reductase (AR) and AKR1B10 have been thoroughly explored in terms of their roles in diabetes, inflammatory disorders, and cancer. In this study we identified two new lead compounds, 2‐(3‐(4‐chloro‐3‐nitrobenzyl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0048, 3) and 2‐(2,4‐dioxo‐3‐(2,3,4,5‐tetrabromo‐6‐methoxybenzyl)‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0049, 4), which selectively target these enzymes. Although 3 and 4 share the 3‐benzyluracil‐1‐acetic acid scaffold, they have different substituents in their aryl moieties. Inhibition studies along with thermodynamic and structural characterizations of both enzymes revealed that the chloronitrobenzyl moiety of compound 3 can open the AR specificity pocket but not that of the AKR1B10 cognate. In contrast, the larger atoms at the ortho and/or meta positions of compound 4 prevent the AR specificity pocket from opening due to steric hindrance and provide a tighter fit to the AKR1B10 inhibitor binding pocket, probably enhanced by the displacement of a disordered water molecule trapped in a hydrophobic subpocket, creating an enthalpic signature. Furthermore, this selectivity also occurs in the cell, which enables the development of a more efficient drug design strategy: compound 3 prevents sorbitol accumulation in human retinal ARPE‐19 cells, whereas 4 stops proliferation in human lung cancer NCI‐H460 cells.
A Cucurbit[7]uril Based Molecular Shuttle Encoded by Visible Room‐Temperature Phosphorescence
Authors: Gong Yifan , Chen Hui , Ma Xiang , Tian He 
Published: November 2015

AbstractA visible room‐temperature phosphorescence (RTP) signal, generated by complexation of cururbit[7]uril (CB[7]) and bromo‐substituted isoquinoline in aqueous solution, is employed to address the shuttling of a pH‐controlling molecular shuttle fabricated by CB[7] and a phosphor 6‐bromoisoquinoline derivative IQC[5]. The CB[7] host shuttles along the axial guest under acidic conditions, accompanied by a weak RTP emission signal, while deprotonation of the guest IQC[5] makes the CB[7] wheel locate on the phosphor group, leading to intense RTP emission. The switching RTP emission of the molecular shuttle, via pH adjusting, can be visibly identified by the naked eye. This is the first CB‐based molecular shuttle with an RTP signal as the output address of its shuttling and conformation.
Efficient Cp*Ir Catalysts with Imidazoline Ligands for CO2 Hydrogenation
Authors: Xu Shaoan , Onishi Naoya , Tsurusaki Akihiro , Manaka Yuichi , Wang Wan‐Hui , Muckerman James T. , Fujita Etsuko , Himeda Yuichiro 
Published: November 2015

AbstractWe report newly developed iridium catalysts with electron‐donating imidazoline moieties as ligands for the hydrogenation of CO2 to formate in aqueous solution. Interestingly, these new complexes promote CO2 hydrogenation much more effectively than their imidazole analogues and exhibit a turnover frequency (TOF) of 1290 h–1 for the bisimidazoline complex compared to that of 20 h–1 for the bisimidazole complex at 1 MPa and 50 °C. In addition, the hydrogenation proceeds smoothly even under atmospheric pressure at room temperature. The TOF of 43 h–1 for the bisimidazoline complex is comparable to that of a dinuclear complex (70 h–1, highest TOF reported) [Nat. Chem. 2012, 4, 383], which incorporates proton‐responsive ligands with pendent‐OH groups in the second coordination sphere. The catalytic activity of the complex with an N‐methylated imidazoline moiety is much the same as that of the corresponding pyridylimidazoline analogue. This result and the UV/Vis titrations of the imidazoline complexes indicate that the high activity is not attributable to the deprotonation of NH on the imidazoline under the reaction conditions.
Self‐Assembly of Hexameric Macrocycles from PtII/Ferrocene Dimetallic Subunits – Synthesis, Characterization, Chemical Reactivity, and Oxidation Behavior
Authors: Giannetto Antonino , Puntoriero Fausto , Notti Anna , Parisi Melchiorre F. , Ielo Ileana , Nastasi Francesco , Bruno Giuseppe , Campagna Sebastiano , Lanza Santo 
Published: November 2015

AbstractNew compounds Ia–h of the form [(Me2SO)ClPt(HR2DTO κ‐S,S Pt)] (HR2DTO = secondary dithiooxamide, with R = methyl, ethyl, n‐propyl, n‐butyl, n‐decyl, isopropyl, (R)‐1‐phenylethyl, or (S)‐2‐hydroxypropyl; κ‐S,S Pt denotes the coordination of the DTO moiety to the Pt atom) have been prepared and used to synthesize platinum(II)/ferrocene dimetallic species IIa–h of formula [(dppf)Pt(HR2DTO κ‐S,S Pt)]Cl (dppf = 1,1′‐diphosphinoferrocene). Complexes IIa–e, bearing unbranched groups on the dithiooxamide moiety (i.e., R = methyl, ethyl, n‐propyl, n‐butyl, or n‐decyl groups), self‐assemble upon standing to form unprecedented hexameric macrocycles IIIa–e. Compounds IIa–e, IIIa–e, as well as IIf–h, have been characterized by a combination of 1H, 13C, 31P NMR spectroscopy and 2D‐ROESY and diffusion‐ordered NMR spectroscopy (DOSY) experiments; the latter experiments have been used to calculate the hydrodynamic radius of IIa–e and IIIa–e, assisted by the data provided by the X‐ray crystal structure of IIh. Compounds IIIa–e are characterized by the presence of six dppf bridging units occupying the inner rim of the macrocycles and exhibit interesting properties, for example, oxidation of IIIa–e occurs around +0.40 V versus saturated calomel electrode (SCE), whereas oxidation of the type II species occurs at potentials greater than +1.0 V. Oxidation of IIIa–e is explained through a delocalized orbital extending over the six dppf subunits. The reversibility of the self‐assembly process is finally demonstrated by alternate addition of acids and bases to the type III compounds.
Oxidizer Ratio and Oxygen Balance Influence on the Emission Spectra of Green‐Colored Pyrotechnic Flames
Authors: Juknelevicius Dominykas , Kubilius Rytis , Ramanavicius Arunas 
Published: November 2015

AbstractThe pyrotechnic flames of Ba(NO3)2, NH4ClO4, and shellac compositions have been analyzed spectrophotometrically. The oxidizer ratio and oxygen balance were varied in a series of compositions to investigate how this ratio influences the flame emission spectra and burning properties of pyrotechnic compositions. The burning rate, emission spectra, and chromaticity data and their analysis are presented.
Copper‐Catalyzed Double Intramolecular Ullmann Coupling for the Synthesis of Diastereomerically and Enantiomerically Pure 4b,9b‐Dihydrobenzofuro[3,2‐b]benzofurans
Authors: Imrich Hans‐Georg , Conrad Jürgen , Beifuss Uwe 
Published: November 2015

AbstractThe copper‐catalyzed double intramolecular Ullmann coupling of syn‐1,2‐bis(2‐bromoaryl)ethane‐1,2‐diols with catalytic amounts of CuII oxinate as the copper source, K3PO4 as a base, and KI as a reductant in aqueous acetonitrile selectively delivers 4b,9b‐dihydrobenzofuro[3,2‐b]benzofurans in diastereomerically and enantiomerically pure form and yields of up to 90 %. The substrates can be obtained in both diastereomerically and enantiomerically pure form by catalytic dihydroxylation of the corresponding (E)‐stilbenes.
Recent Developments in the Synthesis of 2‐C‐Branched and 1,2‐Annulated Carbohydrates
Authors: Vankar Yashwant D. , Linker Torsten 
Published: November 2015

AbstractThe importance of carbohydrate chemistry in biological and medicinal chemistry has led to enormous developments in the synthesis of carbohydrate mimics. In this context, the synthesis of branched sugars in general and of 2‐C‐branched carbohydrates in particular, as well as the synthesis of 1,2‐annulated sugars, have received immense attention. They serve not only as carbohydrate mimics in the form of stand‐alone molecules, but also as useful intermediates in the synthesis of many natural products, their analogues, and glycosidase inhibitors. This microreview covers the recent synthetic efforts in this area and puts the subject matter into proper perspective for future developments.
Experimental Investigation of Variations in Spark Timing using a Spark‐Ignition Engine with Hydrogen‐Blended Gasoline
Authors: Shivaprasad K. V. , Chitragar P. R. , Kumar G. N. 
Published: November 2015

AbstractThis study describes an experiment conducted using an electronically controllable single‐cylinder high‐speed gasoline engine to analyze the performance and emissions characteristics of various hydrogen–gasoline blends. The experiments have been conducted for various engine speeds and spark timings at the wide open throttle position. The experimental results revealed that the engine brake thermal efficiency and brake mean effective pressure first increase and then decrease with the increase engine speed at all spark timings. The minimum amount of brake specific energy consumption was observed for 20 % hydrogen addition in the total fuel blend at 3000 rpm engine speed and 14 °crank angle (CA) before top dead center (BTDC) spark timing. Hydrocarbon and carbon monoxide emissions were reduced with the retardation of spark timings. Nitrogen oxide emissions were continuously increased with the addition of hydrogen in the fuel blend as well as spark timing advance.
Why were doctors unable to accomplish their rural‐aid mission in China? A qualitative study
Authors: Yu Hongxing , Luo Jie , Yao Lan , Qian Bo , Shi Tianwei , Feng Youmei 
Published: November 2015

AbstractBackgroundTo alleviate the difficulties of rural residents in receiving timely healthcare, the Chinese government launched a medical rural‐aid program that solicited urban medical professionals to go to rural hospitals for a 1‐year tenure. However, many of urban doctors did not accomplish this task. In this study, we attempted to investigate the reasons behind the failure to fulfill this program and to explore a more feasible solution.MethodsEleven doctors and nurses participated in the focus group discussions. Twenty‐five interviewees, including health administrative officials, doctors and managers from both urban tertiary hospitals and county‐level hospitals, participated in semi‐structured in‐depth telephone interviews. The interview data were summarized and analyzed using the grounded theory.ResultsThe failure of this program was attributed to multiple causes, such as problems with the recipient hospitals, the support hospitals and the participating doctors, and overall defects in the program strategy itself. One major reason is the competition between the recipient hospitals and the support hospitals, which distorted the original purpose of this rural‐aid program.ConclusionThe rural‐aid program strategy should be adjusted. The recipient hospitals should be township‐level health centers rather than county‐level hospitals. In addition, the relevant policies should be amended and improved accordingly. Copyright © 2015 John Wiley & Sons, Ltd.
Group Flow: The Genesis of Innovation
Authors: Buss Laurie 
Published: November 2015

ABSTRACTWith the ever‐increasing complexity of systems, most managers and engineers understand that innovation and solutions require collaboration among multiple contributors. To facilitate harnessing the power of the group, group flow is conducive to efficient and creative work, energizes and engages team members, and supports each of the principles for agile development and design thinking.Group flow occurs when all members of a group are mutually experiencing flow (also called “being in the zone”), with the group's task demanding equal focus and effort from all members. The outcome of engaging group flow is to achieve something greater and more rapidly than each member could do on his or her own: creative solutions, genuine innovation, and decisions with profitable results. with profitable results.Group flow requires autonomy to define the goal and methodology, a protective environment, and tools to direct the focus of group members. By implementing the methodologies in this paper, the transformative systems engineer and leader will begin to see more engagement by employees and a proliferation of profitable new ideas. The author and members of the INCOSE Transformational Systems Engineering Caucus have experienced that a culture conducive to group flow holds immense potential for reward as the genesis of innovation.
Situational Awareness: A Transformational Perspective
Authors: McKinney Dorothy , Iyengar Nirmal , White Dean 
Published: November 2015

ABSTRACTThe Transformation Systems Engineering Caucus, established in the last few years, identifies ways in which systems engineering might become more effective through adaptation of approaches, techniques, and methods from other fields to systems engineering, and the synthesis of new combinations of these approaches. Situational awareness is central in two steps of applying transformational practices and insights to systems engineering efforts: (1) in noticing that there is a need or opportunity to use transformational approaches, and (2) in identifying the specific transformational approaches, methods, techniques, and insights which offer the greatest likelihood of success in completing the systems engineering effort. The purpose of this paper is to describe these uses of situational awareness in support of transformational systems engineering.
Combining Time Variation and Mixed Frequencies: an Analysis of Government Spending Multipliers in Italy
Authors: Cimadomo Jacopo , D'Agostino Antonello 
Published: November 2015

SummaryIn this paper, we propose a time‐varying parameter vector autoregression (VAR) model with stochastic volatility which allows for estimation on data sampled at different frequencies. Our contribution is twofold. First, we extend the methodology developed by Cogley and Sargent (Drifts and volatilities: monetary policies and outcomes in the post WWII U.S.Review of Economic Studies2005;8: 262–302) and Primiceri (Time varying structural vector autoregressions and monetary policy.Review of Economic Studies2005;72: 821–852) to a mixed‐frequency setting. In particular, our approach allows for the inclusion of two different categories of variables (high‐frequency and low‐frequency) into the same time‐varying model. Second, we use this model to study the macroeconomic effects of government spending shocks in Italy over the 1988:Q4–2013:Q3 period. Italy—as well as most other euro area economies—is characterized by short quarterly time series for fiscal variables, whereas annual data are generally available for a longer sample before 1999. Our results show that the proposed time‐varying mixed‐frequency model improves on the performance of a simple linear interpolation model in generating the true path of the missing observations. Second, our empirical analysis suggests that government spending shocks tend to have positive effects on output in Italy. The fiscal multiplier, which is maximized at the 1‐year horizon, follows a U‐shape over the sample considered: it peaks at around 1.5 at the beginning of the sample; it then stabilizes between 0.8 and 0.9 from the mid 1990s to the late 2000s, before rising again to above unity during the recent crisis. Copyright © 2015 John Wiley & Sons, Ltd.
Identification and Estimation of Online Price Competition With an Unknown Number of Firms
Authors: An Yonghong , Baye Michael R. , Hu Yingyao , Morgan John , Shum Matt 
Published: November 2015

SummaryThis paper considers identification and estimation of a general model for online price competition. We show that when the number of competing firms is unknown the underlying parameters of the model can still be identified and estimated employing recently developed results on measurement errors. We illustrate our methodology using UK data for personal digital assistants and employ the estimates to simulate competitive effects. Our results reveal that heightened competition has differential effects on the prices paid by different consumer segments. Copyright © 2015 John Wiley & Sons, Ltd.
The Proteasome Inhibitor Bortezomib Maintains Osteocyte Viability in Multiple Myeloma Patients by Reducing Both Apoptosis and Autophagy: A New Function for Proteasome Inhibitors
Authors: Toscani Denise , Palumbo Carla , Dalla Palma Benedetta , Ferretti Marzia , Bolzoni Marina , Marchica Valentina , Sena Paola , Martella Eugenia , Mancini Cristina , Ferri Valentina , Costa Federica , Accardi Fabrizio , Craviotto Luisa , Aversa Franco , Giuliani Nicola 
Published: November 2015

ABSTRACT

Multiple myeloma (MM) is characterized by severely imbalanced bone remodeling. In this study, we investigated the potential effect of proteasome inhibitors (PIs), a class of drugs known to stimulate bone formation, on the mechanisms involved in osteocyte death induced by MM cells. First, we performed a histological analysis of osteocyte viability on bone biopsies on a cohort of 37 MM patients with symptomatic disease. A significantly higher number of viable osteocytes was detected in patients treated with a bortezomib (BOR)-based regimen compared with those treated without BOR. Interestingly, both osteocyte autophagy and apoptosis were affected in vivo by BOR treatment. Thereafter, we checked the in vitro effect of BOR to understand the mechanisms whereby BOR maintains osteocyte viability in bone from MM patients. We found that osteocyte and preosteocyte autophagic death was triggered during coculturing with MM cells. Our evaluation was conducted by analyzing either autophagy markers microtubule-associated protein light chain 3 beta (LC3B) and SQSTM1/sequestome 1 (p62) levels, or the cell ultrastructure by transmission electron microscopy. PIs were found to increase the basal levels of LC3 expression in the osteocytes while blunting the myeloma-induced osteocyte death. PIs also reduced the autophagic death of osteocytes induced by high-dose dexamethasone (DEX) and potentiated the anabolic effect of PTH(1-34). Our data identify osteocyte autophagy as a new potential target in MM bone disease and support the use of PIs to maintain osteocyte viability and improve bone integrity in MM patients. © 2015 American Society for Bone and Mineral Research.