bluuebunny/crossref_metadata_2025_split huggingface dataset:
Palladium‐Catalyzed Two‐Component Domino Coupling Reaction of (Z)‐β‐Bromostyrenes with Norbornenes: Synthesis of 1,5‐Enynes
Authors: Mao Jiangang , Li Huifang , Wen Herui , Li Min , Fan Xiaolin , Bao Weiliang 
Published: June 2016

AbstractPolyfunctional molecules, 1,5‐enynes, have been achieved via a palladium(0)‐catalyzed domino coupling reaction of (Z)‐β‐bromostyrenes with norbornenes in the presence of cesium carbonate and N,N‐dimethylformamide. The process involves a double Heck‐type procedure, two‐fold C(sp2)H activation and formation of two carbon‐carbon bonds. There are possibilities of diversified transformation for the domino coupling of (Z)‐β‐bromostyrenes with norbornenes, the procedure is successfully driven to 1,5‐enynes via accurate adjustment of the reaction conditions.magnified image
Transition Metal‐Free Synthesis of 3‐Alkynylpyrrole‐2‐carboxylates via Michael Addition/Intramolecular Cyclodehydration
Authors: Teng Qing‐hu , Xu Yan‐li , Liang Ying , Wang Heng‐shan , Wang Ying‐chun , Pan Ying‐ming 
Published: June 2016

AbstractA transition metal‐free and efficient method for the synthesis of 3‐alkynylpyrrole‐2‐carboxylates from diynones and glycine esters or 2‐aminoacetophenone hydrochloride has been developed. This transformation provides a large range of substituted pyrroles in good to excellent yields with the elimination of water as the only by‐product. The detailed mechanistic studies elucidated that this transformation involves a Michael addition/intramolecular cyclodehydration process.magnified image
Robust and Recyclable Self‐Supported Chiral Nickel Catalyst for the Enantioselective Michael Addition
Authors: Bissessar Damien , Achard Thierry , Bellemin‐Laponnaz Stéphane 
Published: June 2016

AbstractA simple chemical modification of a chiral diamine ligand may produce a robust and recyclable enantioselective catalyst. Metallopolymers based on chiral cyclohexyldiamine‐containing ditopic ligands and nickel(II) complexes have been readily prepared and applied in catalytic enantioselective Michael additions of 1,3‐dicarbonyl compounds to nitroalkenes. High yields and good enantioselectivities have been obtained and the catalytic systems have been recycled up to 11 times without loss of either activity or enantioselectivity at a low catalyst loading of 0.75 mol%. Moreover, the nickel metallopolymers were found to be air‐ and moisture‐stable, which enabled this chemistry to be carried out on the bench without the use of any air‐free techniques and with non‐degassed solvents. Finally, the nature of the catalyst was studied by non‐linear effect experiments, giving a negative non‐linear effect (NLE) as a consequence of an in situ decrease in the ee of the active species consistent with the trapping of homochiral aggregates.magnified image
Iron(III) Chloride‐Catalyzed Tandem Aza‐Prins/Friedel–Crafts Cyclization of 2‐Arylethyl‐2,3‐butadienyl Tosylamides and Aldehydes‐An Efficient Synthesis of Benzo[f]isoquinolines
Authors: Lin Weilong , Cheng Jiajia , Ma Shengming 
Published: June 2016

AbstractAn efficient approach for the synthesis of 1,2,3,4,5,6‐hexahydrobenzo[f]isoquinolines via a tandem aza‐Prins/Friedel–Crafts cyclization from 2‐arylethyl‐2,3‐butadienyl tosylamides and aldehydes has been developed. This iron(III) chloride‐catalyzed cascade cyclization at the room temperature with different types of aldehydes, such as aromatic and heteroaromatic aldehydes, alkyl aldehydes, and α,β‐unsaturated aldehydes, affords the products in moderate to excellent yields (up to 97 %). In this reaction, chlorotrimethylsilane was applied to activate the aldehydes. The cheap catalyst, the mild reaction conditions, and the broad scope of the substrates make this method highly useful.magnified image
Metal‐Free Autoxidative Nitrooxylation of Alkenyl Oximes with Molecular Oxygen
Authors: Zhang Xiao‐Wei , Xiao Zu‐Feng , Zhuang Yan‐Jun , Wang Mei‐Mei , Kang Yan‐Biao 
Published: June 2016

AbstractA metal‐free aerobic autoxidative nitrooxylation of alkenyl oximes mediated by tert‐butyl nitrite is described. Molecular oxygen is used as the oxidizing reagent, avoiding use of organic trapping reagents such as 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO). The desired products were obtained in generally high yields.magnified image
Organocatalytic Regioselective Chlorosilylation of Oxirane Derivatives: Mild and Effective Insertion of Bulky Silyl Chloride by Using 4‐Methoxypyridine N‐Oxide
Authors: Yoshida Keisuke , Suzuki Hina , Inoue Hiroki , Matsui Kohei , Fujino Yuta , Kanoko Yohei , Itatsu Yukihiro , Takao Ken‐ichi 
Published: June 2016

AbstractThe highly regioselective organocatalytic chlorosilylation of oxirane derivatives using bulky silyl reagents such as (tert‐butyl)diphenylsilyl chloride (TBDPSCl) or triphenylsilyl chloride (Ph3SiCl) was developed. The reaction was effectively catalyzed with 4‐methoxypyridine N‐oxide in the presence of sodium sulfate (Na2SO4). Several silylated halohydrins were obtained with complete regioselectivity and the reaction was applied to the synthesis of carvedilol.magnified image
Genetic modulators of sickle cell disease in French Guiana: Markers of the slave trade
Authors: Simonnet Christine , Elanga Narcisse , Joly Philippe , Vaz Tania , Nacher Mathieu 
Published: June 2016

ObjectivesSickle cell disease (SCD) is the leading genetic disease in French Guiana, reflecting the predominantly African ancestry of the Guianese population. Our purpose was to characterize the genetic modulators of SCD in order to retrace the origin of the population in light of the slave trade.MethodsWe have studied the sickle cell genotype, the βS haplotypes, the alpha and beta thalassemia and the UGT1A1 promoter polymorphisms in 224 Guianese patients with SCD.ResultsThe genotypes of SCD were HbSS 65.6%, HbSC 24.5%, and HbS‐beta thalassemia 9.4%. The most frequent βS haplotypes were the Benin haplotype (65.9% of the chromosomes) and the Bantu (20.5%). Alpha thalassemic deletions were present in 37% of the patients and homozygosity for the (TA)7 allele of the UGT1A1 promoter in 21.4%. When the patients' origins were considered, 3 groups, Noir Marron, Haitians and Creoles, displayed distinctive characteristics. The HbSC genotype, the Benin haplotype, and the homozygous UGT1A1 genotype TA7/TA7 were significantly more frequent in Noir Marron. The Haitian patients were characterized by the occurrence of alpha‐thalassemia and beta‐thalassemia and by a higher prevalence of the Bantu haplotype. In the group of Creole patients, the genotype HbSS was predominant but the other modulators of SCD were associated with intermediate risk.ConclusionsThe results highlight the genetic diversity of the Guianese population and are concordant with historical data on the slave trade showing a West African origin for Noir Marron and a Central African origin for Haitians, while Guianese Creoles are highly admixed. Am. J. Hum. Biol. 28:811–816, 2016. © 2016Wiley Periodicals, Inc.
Catalytic Radical Reduction in Aqueous Solution by a Ruthenium Hydride Intermediate
Authors: Htet Yamin , Tennyson Andrew G. 
Published: June 2016

AbstractSome manganese complexes can catalyze both antioxidant and pro‐oxidant reactions, whereby the disparate reactivity modes are determined by the catalyst environment and afford distinct therapeutic effects. We recently reported the reduction of radicals in buffered aqueous solution catalyzed by a ruthenium complex with biologically relevant non‐tertiary alcohols as terminal reductants. Mechanistic evidence is presented, indicating that this catalytic radical reduction is achieved by a Ru‐hydride intermediate formed by β‐hydride elimination from a Ru‐alkoxide species. A similar mechanism and Ru‐hydride intermediate was previously reported to kill cancer cells with catalytic pro‐oxidant effects. Therefore, our demonstration of catalytic antioxidant effects by the same type of intermediate reveals new potential therapeutic strategies and applications for catalytic systems that form Ru‐hydride intermediates.
14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study
Authors: Robertson Alasdair P. M. , Beattie Nicholas A. , Scott Greig , Man Wing Y. , Jones John J. , Macgregor Stuart A. , Rosair Georgina M. , Welch Alan J. 
Published: June 2016

AbstractThree isomers of [(Cp*Ru)2C2B10H12], the first examples of 14‐vertex heteroboranes containing 14‐skeletal electron pairs, have been synthesized by the direct electrophilic insertion of a {Cp*Ru+} fragment into the anion [4‐Cp*‐4,1,6‐RuC2B10H12]−. All three compounds have the same unique polyhedral structure having an approximate Cs symmetry and featuring a four‐atom trapezoidal face. X‐ray diffraction studies could confidently identify only one of the two cage C atoms in each structure. The other C atom position has been established by a combination of i) best fitting of computed and experimental 11B and 1H NMR chemical shifts, and ii) consideration of the lowest computed energy for series of isomers studied by DFT calculations. In all three isomers, one cage C atom occupies a degree‐4 vertex on the short parallel edge of the trapezium.
Quantification of Stereochemical Communication in Metal–Organic Assemblies
Authors: Castilla Ana M. , Miller Mark A. , Nitschke Jonathan R. , Smulders Maarten M. J. 
Published: June 2016

AbstractThe derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per “incorrect” amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra‐ and inter‐vertex coupling constants are used to track the degree of stereochemical communication across a range of metal–organic assemblies (employing different ligands, peripheral amines, and metals); temperature‐dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal–organic container molecules.
Ordered PdCu‐Based Nanoparticles as Bifunctional Oxygen‐Reduction and Ethanol‐Oxidation Electrocatalysts
Authors: Jiang Kezhu , Wang Pengtang , Guo Shaojun , Zhang Xu , Shen Xuan , Lu Gang , Su Dong , Huang Xiaoqing 
Published: June 2016

AbstractThe development of superior non‐platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen‐reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells, but still a great challenge. Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu‐based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo. Under the dual tuning on the composition and intermetallic phase, the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol‐oxidation reaction (EOR) than those of disordered PdCuM NPs, the commercial Pt/C and Pd/C catalysts. The density functional theory (DFT) calculations reveal that the improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on the Pd surface owing to the smaller atomic size of Cu, Co, and Ni.
Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source
Authors: Kawamura Shintaro , Sodeoka Mikiko 
Published: June 2016

AbstractAn efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal‐free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp3 carbon to construct synthetically useful skeletons.
Influence of magnesium sulfate whiskers on the structure and properties of melt‐stretching polypropylene microporous membranes
Authors: Lei Caihong , Cai Qi , Xu Ruijie , Chen Xiande , Xie Jiayi 
Published: June 2016

ABSTRACTThe influence of magnesium sulfate (MgSO4) whiskers on the structure and properties of polypropylene cast films and stretched microporous membranes was investigated. We found that for the cast films, MgSO4 showed some nucleation effects, and the introduction of MgSO4 led to the decrease of the orientation degree along the machine direction (MD), whereas that along the transverse direction (TD) was improved; this indicated that MgSO4 whiskers were mainly arranged along the TD. The introduction of MgSO4 up to 10 wt % did not induce apparent changes in the pore structure and air permeability properties of the stretched microporous membranes but improved the electrolyte absorption ability. The most pronounced change for the stretched microporous membranes was the strength along the TD. It was increased by 110% when the MgSO4 content was 2 wt %. During the fabrication of microporous membranes, only stretching along the MD was carried out to initiate pore formation; this resulted in a lower strength along the TD. This study gave us a method for improving the mechanical properties of stretched microporous membranes along the TD. The obtained microporous membranes with better electrolyte absorption and higher mechanical strength along the TD could be used in lithium‐ion batteries as separators. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43884.
Modification of liquid silicone rubber by octavinyl‐polyhedral oligosilsesquioxanes
Authors: Bai Hongqiang , Huang Chi , Jun Liao , Li Houbin 
Published: June 2016

ABSTRACTTo develop an efficient, simple, and biocompatible method for improving the thermal and mechanical properties of an addition‐type liquid silicone rubber (LSR), octavinyl‐polyhedral oligosilsesquioxane (OPOSS) modified LSR samples were prepared through the addition of 0.5–4.0 wt % OPOSS as a modifier to a platinum‐based silicone curing system before vulcanization. The characterization and measurement of the OPOSS and LSR samples were carried out by Fourier transform infrared spectroscopy, X‐ray diffraction, NMR, gas chromatography/mass spectrometry (electron impact ionization), scanning electron microscopy, thermogravimetric analysis/differential scanning calorimetry, and universal testing. The experimental results show that the crosslinking of the OPOSS and LSR polymer had a significantly positive effect on the thermal and mechanical properties. Compared with the unmodified sample, its tensile strength was enhanced by 423–508%, its tear resistance was increased from 22 to 44%, the residue at 600 °C was increased by 36–75% in an N2 atmosphere and 8–65% in an air atmosphere, respectively. These results were obviously superior to those from other similar reported methods that used larger molecular or nonreactive polyhedral oligosilsesquioxane (POSS) derivatives as modifiers at similar POSS loadings. Furthermore, a significant correlation was found between the loading rate of OPOSS and the thermal properties. However, the mechanical properties seemed negatively correlated with the OPOSS content within the experimental range; this may have been due to a material defect caused by the uneven distribution and agglomeration. The results of this study proved that the incorporation of OPOSS into an LSR polymer matrix by a hydrosilylation reaction could be an efficient way to improve the mechanical properties, thermal stability, and biocompatibility of LSR in the future. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43906.
Organic thermoelectric modules produced by electrochemical polymerization
Authors: Culebras Mario , de Lima Mauricio M. , Gómez Clara , Cantarero Andrés 
Published: June 2016

ABSTRACTIn this work, we present a method to develop organic thermoelectric modules by means of electrochemical polymerization using exclusively a p‐type material. The polymer device is built in a planar geometry, with the advantage that it is not necessary to incorporate a heat sink. The method is scalable to an industrial process and it can be the key for the fabrication of large scale thermoelectric modules. A prototype of the thermoelectric device was fabricated in the form of 16 large aspect ratio (2 mm wide times 80 mm long) parallel stripes deposited on flexible substrates. In our prototype, a Seebeck coefficient of 413 μV/K has been achieved. The power generation has been increased up to 25 nW by connecting several devices in parallel. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 43927.
For the Win: Risk‐Sensitive Decision‐Making in Teams
Authors: Gonzales Josh , Mishra Sandeep , Camp Ronald D. 
Published: June 2016

AbstractRisk‐sensitivity theory predicts that decision‐makers should prefer high‐risk options in high need situations when low‐risk options will not meet these needs. Recent attempts to adopt risk‐sensitivity as a framework for understanding human decision‐making have been promising. However, this research has focused on individual‐level decision‐making, has not examined behavior in naturalistic settings, and has not examined the influence of multiple levels of need on decision‐making under risk. We examined group‐level risk‐sensitive decision‐making in two American football leagues: the National Football League (NFL) and the National College Athletic Association (NCAA) Division I. Play decisions from the 2012 NFL (Study 1; N = 33 944), 2013 NFL (Study 2; N = 34 087), and 2012 NCAA (Study 3; N = 15 250) regular seasons were analyzed. Results demonstrate that teams made risk‐sensitive decisions based on two distinct needs: attaining first downs (a key proximate goal in football) and acquiring points above parity. Evidence for risk‐sensitive decisions was particularly strong when motivational needs were most salient. These findings are the first empirical demonstration of team risk‐sensitivity in a naturalistic organizational setting. Copyright © 2016 John Wiley & Sons, Ltd.
„[A]n der Front des Kampfes um den Menschen selbst“. Anthropogenetik und Anthropotechnik im sowjetischen Diskurs der 1920er Jahre
Authors: Liggieri Kevin 
Published: June 2016

Abstract“[A]n der Front des Kampfes um den Menschen selbst”. Anthropogenetics and Anthropotechnics in Soviet Thought. The period between 1920 and 1930 reveals in Russia a practical manifestation of the technologies of the self, which see the body not only in a poetic‐symbolical way, but practically as a material of shaping and rebuilding. In this bio‐social discourse of a genetically perfected ‘new man’, Russian theorists of eugenics are looking back on traditional parallels of animal and plant breeding. The most influential group of eugenics were the Russian biologists, especially the key players and the founders of the Russian genetics research Nikolai Kol′tsov (1872–1940) and Aleksandr Serebrovskii (1892–1948). It will be demonstrated that ‘human breeding’ (Russ. ‘Antropotekhnika’) is based both on the semantics and on the methodology of traditional animal and plant breeding.
Twenty years trends in mortality rates from stroke in Klaipeda
Authors: Kazlauskas Henrikas A. , Raskauskiene Nijole , Radziuviene Rima , Janusonis Vinsas 
Published: June 2016

AbstractBackgroundDuring the past decades, mortality from stroke decreased in many western European countries; however, changes concerning long‐term stroke mortality in eastern European countries are less evident.ObjectiveTo assess age‐ and gender‐specific trends in stroke mortality in Klaipeda (Lithuania) from 1994 to 2013.DesignDescriptive epidemiological study.Setting/subjectsPermanent population of Klaipeda.MethodsData on 2509 permanent residents of Klaipeda aged 35–79 years who died from stroke between 1994 and 2013 were gathered. Directly, age‐standardized (European population) stroke mortality rates were analyzed using joinpoint regression separately for specific age groups (35–64, 65–79, and 35–79 years) and by gender. Annual percentage change (APC) and 95% CIs were presented.ResultsStroke mortality in the 35‐ to 79‐year‐old age group peaked in 1994–1997, it then decreased by −9.9% (95% CI: −18.7, −0.2) yearly up until 2001 and leveled off by −0.2% (−5.1, 4.9) between 2001 and 2013. Among men aged 35–64 years, mortality decreased substantially by 12.8% (−21.5, −3.3) per year from 1994 to 2001 and turned positive by 6.3% (0.8, 12.1) between 2000 and 2013. Among women aged 35–64 years, mortality decreased significantly by 15.5% (−28.1, −0.7) from 1994 to 2000. There was evidence of recent plateauing of trends for 35‐ to 64‐year‐old women between 2000 and 2013. In the 65‐ to 79‐year‐old age group, mortality decreased from 1994 onward yearly by −5.5% (−7.9, −3.0) in women and by −3.3% (−5.6, −0.9) in men.ConclusionsJoinpoint regression revealed steadily decreasing trend in stroke mortality between 1994 and 2001. The decline in death rates flattened out in the recent decade. Mortality rates varied among age groups and were more pronounced in adults aged 35–64 years. It is essential to monitor and manage stroke risk factors, especially among middle‐aged population.
Essential techniques for laparoscopic surgery simulation
Authors: Qian Kun , Bai Junxuan , Yang Xiaosong , Pan Junjun , Zhang Jianjun 
Published: June 2016

AbstractLaparoscopic surgery is a complex minimum invasive operation that requires long learning curve for the new trainees to have adequate experience to become a qualified surgeon. With the development of virtual reality technology, virtual reality‐based surgery simulation is playing an increasingly important role in the surgery training. The simulation of laparoscopic surgery is challenging because it involves large non‐linear soft tissue deformation, frequent surgical tool interaction and complex anatomical environment. Current researches mostly focus on very specific topics (such as deformation and collision detection) rather than a consistent and efficient framework. The direct use of the existing methods cannot achieve high visual/haptic quality and a satisfactory refreshing rate at the same time, especially for complex surgery simulation. In this paper, we proposed a set of tailored key technologies for laparoscopic surgery simulation, ranging from the simulation of soft tissues with different properties, to the interactions between surgical tools and soft tissues to the rendering of complex anatomical environment. Compared with the current methods, our tailored algorithms aimed at improving the performance from accuracy, stability and efficiency perspectives. We also abstract and design a set of intuitive parameters that can provide developers with high flexibility to develop their own simulators. Copyright © 2016 John Wiley & Sons, Ltd.