bluuebunny/crossref_metadata_2025 huggingface dataset:
Dipole–Dipole and H‐Bonding Interactions Significantly Enhance the Multifaceted Mechanical Properties of Thermoresponsive Shape Memory Hydrogels
Authors: Zhang Yinyu , Li Yongmao , Liu Wenguang
Published: November 2014

High strength hydrogels were previously constructed based on dipole–dipole and hydrogen bonding reinforcement. In spite of the high tensile and compressive strengths achieved, the fracture energy of the hydrogels strengthened with sole noncovalent bondings was rather low due to the lack in energy dissipating mechanism. In this study, combined dipole–dipole and hydrogen bonding interactions reinforced (DHIR) hydrogels are synthesized by one‐step copolymerization of three feature monomers, namely acrylonitrile (AN, dipole monomer), acrylamide (AAm, H‐bonding monomer), and 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS, anionic monomer) in the presence of PEGDA575, a hydrophilic crosslinker. The electrostatic repulsion from PAMPS allows the gel network to absorb water readily, and meanwhile the synergistic effect of dipole–dipole and H‐bonding interactions enable the DHIR hydrogel to withstand up to 8.3 MPa tensile stress, 4.8 MPa compressive stress and 140–716% elongation at break with the fracture energy reaching as high as 5500 J/m2. In addition, this DHIR hydrogel exhibits reversible mechanical properties after undergoing cyclic loading and unloading. Interestingly, the DHIR hydrogels with appropriate compositions demonstrate temperature‐tunable mechanical properties as well as accompanied shape memory effect. The dual noncovalent bonding strengthening mechanism reported here offers a universal strategy for significantly enhancing the comprehensive mechanical properties of hydrogels.
Sodium Storage Behavior in Natural Graphite using Ether‐based Electrolyte Systems
Authors: Kim Haegyeom , Hong Jihyun , Park Young‐Uk , Kim Jinsoo , Hwang Insang , Kang Kisuk
Published: November 2014

This work reports that natural graphite is capable of Na insertion and extraction with a remarkable reversibility using ether‐based electrolytes. Natural graphite (the most well‐known anode material for Li–ion batteries) has been barely studied as a suitable anode for Na rechargeable batteries due to the lack of Na intercalation capability. Herein, graphite is not only capable of Na intercalation but also exhibits outstanding performance as an anode for Na ion batteries. The graphite anode delivers a reversible capacity of ≈150 mAh g−1 with a cycle stability for 2500 cycles, and more than 75 mAh g−1 at 10 A g−1 despite its micrometer‐size (≈100 μm). An Na storage mechanism in graphite, where Na+‐solvent co‐intercalation occurs combined with partial pseudocapacitive behaviors, is revealed in detail. It is demonstrated that the electrolyte solvent species significantly affect the electrochemical properties, not only rate capability but also redox potential. The feasibility of graphite in a Na full cell is also confirmed in conjunction with the Na1.5VPO4.8F0.7 cathode, delivering an energy of ≈120 Wh kg−1 while maintaining ≈70% of the initial capacity after 250 cycles. This exceptional behavior of natural graphite promises new avenues for the development of cost‐effective and reliable Na ion batteries.
Enantioselective Synthesis of Chiral Biaryl Chlorides/Iodides by a Chiral Phosphoric Acid Catalyzed Sequential Halogenation Strategy
Authors: Mori Keiji , Kobayashi Manato , Itakura Tsubasa , Akiyama Takahiko
Published: November 2014

We report herein a highly enantioselective synthesis of multisubstituted biaryl chlorides/iodides by sequential halogenation reactions (desymmetrization/kinetic resolution sequence). The selectivity of biaryl chlorides/iodides obtained in the first asymmetric reaction (desymmetrization) could be enhanced by the kinetic resolution‐type asymmetric bromination to afford the corresponding chiral biaryl chlorides/iodides in excellent selectivities (up to 99 % ee).

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Modulating the Binding of Polycyclic Aromatic Hydrocarbons Inside a Hexacationic Cage by Anion–π Interactions
Authors: Hafezi Nema , Holcroft James M. , Hartlieb Karel J. , Dale Edward J. , Vermeulen Nicolaas A. , Stern Charlotte L. , Sarjeant Amy A. , Stoddart J. Fraser
Published: November 2014

We report the template‐directed synthesis of BlueCage6+, a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron‐poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage⋅6 PF6 exhibits a lower association constant Ka than its progenitor ExCage⋅6 PF6. A close inspection reveals that the six PF6− counterions of BlueCage6+ occupy the cavity in a fleeting manner as a consequence of anion–π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the Ka value for pyrene in BlueCage6+ when the PF6− counterions are replaced by much bulkier anions. The presence of anion–π interactions is supported by X‐ray crystallography, and confirms the presence of a PF6− counterion inside its cavity.
Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst
Authors: Neumann Paul , Dib Hanna , Caminade Anne‐Marie , Hey‐Hawkins Evamarie
Published: November 2014

The application of a dendrimer in a redox‐switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well‐defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1‐octen‐3‐ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron‐poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.
Large‐Area Alignment of Tungsten Oxide Nanowires over Flat and Patterned Substrates for Room‐Temperature Gas Sensing
Authors: Cheng Wei , Ju Yanrui , Payamyar Payam , Primc Darinka , Rao Jingyi , Willa Christoph , Koziej Dorota , Niederberger Markus
Published: November 2014

Alignment of nanowires over a large area of flat and patterned substrates is a prerequisite to use their collective properties in devices such as gas sensors. In this work, uniform single‐crystalline ultrathin W18O49 nanowires with diameters less than 2 nm and aspect ratios larger than 100 have been synthesized, and, despite their flexibility, assembled into thin films with high orientational order over a macroscopic area by the Langmuir–Blodgett technique. Alignment of the tungsten oxide nanowires was also possible on top of sensor substrates equipped with electrodes. Such sensor devices were found to exhibit outstanding sensitivity to H2 at room temperature.
Rational Design and Asymmetric Synthesis of Potent and Neurotrophic Ligands for FK506‐Binding Proteins (FKBPs)
Authors: Pomplun Sebastian , Wang Yansong , Kirschner Alexander , Kozany Christian , Bracher Andreas , Hausch Felix
Published: November 2014

To create highly efficient inhibitors for FK506‐binding proteins, a new asymmetric synthesis for pro‐(S)‐C5‐branched [4.3.1] aza‐amide bicycles was developed. The key step of the synthesis is an HF‐driven N‐acyliminium cyclization. Functionalization of the C5 moiety resulted in novel protein contacts with the psychiatric risk factor FKBP51, which led to a more than 280‐fold enhancement in affinity. The most potent ligands facilitated the differentiation of N2a neuroblastoma cells with low nanomolar potency.
Ionic Liquids: Not only Structurally but also Dynamically Heterogeneous
Authors: Zheng Zhuan‐Ping , Fan Wen‐Hui , Roy Soham , Mazur Kamila , Nazet Andreas , Buchner Richard , Bonn Mischa , Hunger Johannes
Published: November 2014

In recent years, the complex and heterogeneous structure of ionic liquids has been demonstrated; however, the consequences on the dynamics have remained elusive. Here, we use femtosecond IR spectroscopy to elucidate the local structural dynamics in protic alkylammonium‐based ionic liquids. The structural relaxation after an ultrafast temperature increase, following vibrational excitation and subsequent relaxation of the N‐D (or N‐H) stretching vibration, is found to vary substantially between the ionic and hydrophobic subdomains. The dynamics in the ionic domains are virtually unaffected by the alkyl chain length and is, therefore, decoupled from viscosity. Equilibration within the hydrophobic subdomains, as evident from the dynamics of the C‐H stretching vibration, is faster than that in the ionic domains and shows a remarkably low thermal activation.
Microwave assisted glycolysis of poly(ethylene terephthalate) catalyzed by 1‐butyl‐3‐methylimidazolium bromide ionic liquid
Authors: Alnaqbi Mohamed A. , Mohsin Mahmoud A. , Busheer Reneesh M. , Haik Yousef
Published: November 2014

The combination of ionic liquid (IL) associated with microwave energy may have some potential application in the chemical recycling of poly (ethylene terephthalate). In this processes, glycolysis of waste poly (ethylene terephthalate) recovered from bottled water containers were thermally depolymerized with solvent ethylene glycol (EG) in the presence of 1‐butyl‐3‐methyl imidazolium bromide ([bmim]Br) as catalyst (IL) under microwave condition. It was found that the glycolysis products consist of bis (2‐hydroxyethyl) terephthalate (BHET) monomer that separated from the catalyst IL in pure crystalline form. The conversion of PET reach up to 100% and the yield of BHET reached 64% (wt %). The optimum performance was achieved by the use of 1‐butyl‐3‐methyl imidazolium bromide as a catalyst, microwave irradiations temperature (170–175°C) and reaction time 1.75–2 h. The main glycolysis products were analyzed by 1H NMR, 13C NMR, LC‐MS, FTIR, DSC, and TGA. When compared to conventional heating methods, microwave irradiation during glycolysis of PET resulted in short reaction time and more control over the temperature. This has allowed substantial saving in energy and processing cost. In addition, a more efficient, environmental‐friendly, and economically feasible chemical recycling of waste PET was achieved in a significantly reduced reaction time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41666.
Mixed directional false discovery rate control in multiple pairwise comparisons using weighted p‐values
Authors: Zhao Haibing , Peddada Shyamal D. , Cui Xinping
Published: November 2014

In many applications, researchers are interested in making q pairwise comparisons among k test groups on the basis of m outcome variables. Often, m is very large. For example, such situations arise in gene expression microarray studies involving several experimental groups. Researchers are often not only interested in identifying differentially expressed genes between a given pair of experimental groups, but are also interested in making directional inferences such as whether a gene is up‐ or downregulated in one treatment group relative to another. In such situations, in addition to the usual errors such as false positive (Type I error) and false negative (Type II error), one may commit directional error (Type III error). For example, in a dose response microarray study, a gene may be declared to be upregulated in the high dose group compared to the low dose group when it is not. In this paper, we introduce a mixed directional false discovery rate (mdFDR) controlling procedure using weighted p‐values to select positives in different directions. The weights are defined as the inverse of two times the proportion of either positive or negative discoveries. The proposed procedure has been proved mathematically to control the mdFDR at level α and to have a larger power (which is defined as the expected proportion of nontrue null hypotheses) than the GSP10 procedure proposed by Guo et al. (2010). Simulation studies and real data analysis are also conducted to show the outperformance of the proposed procedure than the GSP10 procedure.
G‐CSF utilization rate and prescribing patterns in United States: associations between physician and patient factors and GCSF use
Authors: Barnes Gisoo , Pathak Ashutosh , Schwartzberg Lee
Published: November 2014

Febrile neutropenia (FN) is a common complication among patients with chemotherapy‐induced myelotoxicity and is associated with a number of negative outcomes including prolonged hospitalization, increased medical costs, increased risk of mortality, dose reductions, and delays. Granulocyte‐colony‐stimulating factor (G‐CSF), granulocyte–macrophage‐colony stimulating factor (GM‐CSF), and pegylated G‐CSF are effective at reducing risk and duration of neutropenia‐related events. However, despite guidelines, the use of G‐CSF and pegylated G‐CSF in the United States has not been consistent and pattern of care studies have focused primarily on G‐CSF. A number of studies found that G‐CSF is underutilized in patients undergoing chemotherapy treatments associated with a high risk of FN, while being over utilized in patients with a low‐risk FN. Wide variations in overuse, underuse, and misuse of G‐CSF are associated with a number of physician and patient factors. Improved awareness of the guidelines, feedback to providers regarding proper usage, and understanding of chemotherapy regimens associated with very low risks as well as high risks (>20%) of FN is some of the approaches that could lead to improving care.
Evaluate educational aspects of student conduct processes
Authors: Bennett Laura
Published: November 2014

Campus officials throughout the country are revising policies, procedures and training for those who handle reports of sexual misconduct, including sexual violence. It all comes in response to efforts to comply with the Violence Against Women Act, the April 2011 “Dear Colleague Letter,” and Office for Civil Rights Investigations.
Balloon dilation atrial septostomy for advanced pulmonary hypertension in patients on prostanoid therapy
Authors: Kuhn Brooks T. , Javed Usman , Armstrong Ehrin J. , Singh Gagan D. , Smith Thomas W. , Whitcomb Charles J. , Allen Roblee P. , Rogers Jason H.
Published: November 2014

Background: Prostanoid therapy improves quality of life and may increase survival in patients with advanced pulmonary hypertension (PH). Balloon dilated atrial septostomy (BDAS) can palliate or bridge to transplantation for patients resistant to medical therapy. The safety and efficacy of BDAS in the prostanoid era has not previously been reported. Methods: All patients had progressive symptoms despite prostanoid therapy at the time of their first BDAS. Sixteen patients who underwent a total of 23 septostomies between 2004 and 2014 were included in this retrospective case series. Results: Patients were aged 47.6 years ± 11.3 with 12/16 women. Etiologies included idiopathic (7), methamphetamine (6), scleroderma (1), and anorexigen (2). One patient died within 24 hr post‐procedure. Thirty‐day and 1‐year survival were 75% and 64%, respectively. Six of the septostomies were revisions, including two which were ultimately stented. Three subjects were successfully bridged to transplant. Pulmonary capillary wedge pressure (PCWP) increased from a mean of 13 to 17 mm Hg, cardiac index increased from 2.1 to 2.4 L/min/m2, and arterial saturation decreased from 90.7 ± 4.3 to 82.5 ± 5.6%. All non‐survivors at 30 days were male and had higher baseline serum creatinine, mean RAP, right ventricular end diastolic pressure (RVEDP), and left ventricle (LV) filling pressures, and lower right ventricle (RV) ejection fraction. Mortality was associated with unchanged post‐septostomy cardiac output despite an increase in left ventricular end diastolic pressure (LVEDP). Conclusions: BDAS may be an alternate therapy for select PH patients who have symptomatic progression despite prostanoid therapy. Survival is comparable to prior reports of BDAS in the pre‐prostanoid era. © 2014 Wiley Periodicals, Inc.
Recycling Powered by Release of Carbon Dioxide
Authors: Laurell Nash Anna , Widyan Khalid , Moberg Christina
Published: November 2014

In a cyclic process, fed with external chemical energy generated by the transformation of a compound with high chemical potential to carbon dioxide, the undesired enantiomer from a catalytic asymmetric reaction is continuously recycled to starting reagent. This minor enantiomer recycling is characterized by gradually increasing yields and product enantiomeric ratios. The requirements for maintaining a cyclic procedure are discussed; the necessity of a coupled exergonic process is demonstrated experimentally.
Freestanding Sulfur/3D Carbon Fiber Membrane Cathodes for Advanced Lithium–Sulfur Batteries
Authors: Chen Wei , Zhang Zhian , Li Qiang , Lai Yanqing , Li Jie
Published: November 2014

A freestanding membrane of a 3D network of carbon fibers coated with nitrogen‐doped carbon spheres (NC@FCF) was designed through the carbonization of modified filter paper, on the surface of which polydopamine spheres were deposited. It is found that the NC@FCF membrane is composed of interlaced and circuitous carbon fibers, and the carbon spheres are distributed in the interspaces among carbon fibers. After infiltration with sulfur, the S‐NC@FCF membrane was directly used as a cathode for Li–S batteries. The freestanding cathode exhibits an excellent rate capability, large charge–discharge capacity, and outstanding cycle performance, exhibiting an initial discharge capacity of 1143.7 mAh g−1 and maintaining 778.2 mAh g−1 after 200 cycles at 0.5 C. The excellent electrochemical performance results from the synergistic effect of the 3D carbon‐fiber network, which provides electronic conduction pathways, and the porous structure formed through the accumulation of carbon spheres, which can encapsulate S, absorb polysulfides, and facilitate Li+ transfer.
Sulfur Encapsulated in a TiO2‐Anchored Hollow Carbon Nanofiber Hybrid Nanostructure for Lithium–Sulfur Batteries
Authors: Zhang Zhian , Li Qiang , Jiang Shaofeng , Zhang Kai , Lai Yanqing , Li Jie
Published: November 2014

A hollow carbon nanofiber hybrid nanostructure anchored with titanium dioxide (HCNF@TiO2) was prepared as a matrix for effective trapping of sulfur and polysulfides as a cathode material for Li–S batteries. The synthesized composites were characterized and examined by X‐ray diffraction, nitrogen adsorption–desorption measurements, field‐emission scanning electron microscopy, scanning transmission electron microscopy, and electrochemical methods such as galvanostatic charge/discharge, rate performance, and electrochemical impedance spectroscopy tests. The obtained HCNF@TiO2–S composite showed a clear core–shell structure with TiO2 nanoparticles coating the surface of the HCNF and sulfur homogeneously distributed in the coating layer. The HCNF@TiO2–S composite exhibited much better electrochemical performance than the HCNF–S composite, which delivered an initial discharge capacity of 1040 mA h g−1 and maintained 650 mAh g−1 after 200 cycles at a 0.5 C rate. The improvements of electrochemical performances might be attributed to the unique hybrid nanostructure of HCNF@TiO2 and good dispersion of sulfur in the HCNF@TiO2–S composite.
Robust Ethylenedioxythiophene–Vinylene Oligomers from Fragile Thiophene–Vinylene Cores: Synthesis and Optical, Chemical and Electrochemical Properties of Multicharged Shapes
Authors: Mayorga Burrezo Paula , Pelado Beatriz , Ponce Ortiz Rocío , De la Cruz Pilar , López Navarrete Juan T. , Langa Fernando , Casado Juan
Published: November 2014

Oligomers of ethylendioxythiophene–vinylene have been prepared. Their optical, electrochemical and chemical properties have been studied in detail by absorption and emission spectroscopy as well as cyclic voltammetry, Raman techniques and spectroelectrochemistry complemented with quantum chemical calculations. A comparison with their non‐ethylendioxy and non‐vinylene parents has been done. The inclusion of the EDO plus the vinylene function generates more robust electronic ground states regarding the largely flexible thiophene–vinylene (n TV) oligomeric homologues. The redox features of the new compounds are also rich of oxidative processes arising as an interesting stabilising balance effect between the oxygen fragment in the EDO groups (mesomeric effect) and the linear π‐conjugated structure. The oxidised species have been characterised, which show the ability for the formation of mixed valence charge‐transfer complexes and π dimers of different oxidation states, in particular, in the electrochemical medium, resulting that the electrochemical response is accounted for a succession of aggregation and electron‐transfer steps. With this work, a full understanding of the optical and electronic properties of these new oligomers in the context of the oligomer approach has been proposed.
Ionic‐Radius‐Driven Selection of the Main‐Group‐Metal Cage for Intermetalloid Clusters [Ln@PbxBi14−x]q− and [Ln@PbyBi13−y]q− (x/q=7/4, 6/3; y/q=4/4, 3/3)
Authors: Ababei Rodica , Massa Werner , Weinert Bastian , Pollak Patrik , Xie Xiulan , Clérac Rodolphe , Weigend Florian , Dehnen Stefanie
Published: November 2014

Reactions of the binary, pseudo‐homoatomic Zintl anion (Pb2Bi2)2− with Ln(C5Me4H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane‐1,2‐diamine/toluene yielded ten [K([2.2.2]crypt)]+ salts of lanthanide‐doped semimetal clusters with 13 or 14 surface atoms. Single‐crystal X‐ray diffraction and energy‐dispersive X‐ray spectroscopy indicated the presence of the anions [Ln@Pb6Bi8]3−, [Ln@Pb3Bi10]3−, [Ln@Pb7Bi7]4−, or [Ln@Pb4Bi9]4− in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and 139La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14‐atom cages with the ionic radius of the embedded Ln3+ ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln3+ ions keep their expected paramagnetic or diamagnetic nature.
Stepwise Strategy to Cyclometallated PtII Complexes with N‐Heterocyclic Carbene Ligands: A Luminescence Study on New β‐Diketonate Complexes
Authors: Fuertes Sara , García Hector , Perálvarez Mariano , Hertog Wim , Carreras Josep , Sicilia Violeta
Published: November 2014

The imidazolium salt 3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazolium iodide (2) has been treated with silver(I) oxide and [{Pt(μ‐Cl)(η3‐2‐Me‐C3H4)}2] (η3‐2‐Me‐C3H4=η3‐2‐methylallyl) to give the intermediate N‐heterocyclic carbene complex [PtCl(η3‐2‐Me‐C3H4)(H$\widehat{CC}$*‐κC*)] (3) (H$\widehat{CC}$*‐κC*=3‐methyl‐1‐(naphthalen‐2‐yl)‐1H‐imidazol‐2‐ylidene). Compound 3 undergoes regiospecific cyclometallation at the naphthyl ring of the NHC ligand to give the five‐membered platinacycle compound [{Pt(μ‐Cl)($\widehat{CC}$*)}2] (4). Chlorine abstraction from 4 with β‐diketonate Tl derivatives rendered the corresponding neutral compounds [Pt($\widehat{CC}$*)(L‐O,O′)] {L=acac (HL=acetylacetone) 5, phacac (HL=1,3‐diphenyl‐1,3‐propanedione) 6, hfacac (HL=hexafluoroacetylacetone) 7}. All of the compounds (3–7) were fully characterized by standard spectroscopic and analytical methods. X‐ray diffraction studies were performed on 5–7, revealing short PtPt and π–π interactions in the solid‐state structure. The influence of the R‐substituents of the β‐diketonate ligand on the photophysical properties and the use of the most efficient emitter, 5, as phosphor converter has also been studied.
Multicomponent Self‐Assembly with a Shape‐Persistent N‐Heterotriangulene Macrocycle on Au(111)
Authors: Cui Kang , Schlütter Florian , Ivasenko Oleksandr , Kivala Milan , Schwab Matthias G. , Lee Shern‐Long , Mertens Stijn F. L. , Tahara Kazukuni , Tobe Yoshito , Müllen Klaus , Mali Kunal S. , De Feyter Steven
Published: November 2014

Multicomponent network formation by using a shape‐persistent macrocycle (MC6) at the interface between an organic liquid and Au(111) surface is demonstrated. MC6 serves as a versatile building block that can be coadsorbed with a variety of organic molecules based on different types of noncovalent interactions at the liquid–solid interface. Scanning tunneling microscopy (STM) reveals the formation of crystalline bicomponent networks upon codeposition of MC6 with aromatic molecules, such as fullerene (C60) and coronene. Tetracyanoquinodimethane, on the other hand, was found to induce disorder into the MC6 networks by adsorbing on the rim of the macrocycle. Immobilization of MC6 itself was studied in two different noncovalently assembled host networks. MC6 assumed a rather passive role as a guest and simply occupied the host cavities in one network, whereas it induced a structural transition in the other. Finally, the central cavity of MC6 was used to capture C60 in a complex three‐component system. Precise immobilization of organic molecules at discrete locations within multicomponent networks, as demonstrated here, constitutes an important step towards bottom‐up fabrication of functional surface‐based nanostructures.
Iridium Catalyzed Carbocyclizations: Efficient (5+2) Cycloadditions of Vinylcyclopropanes and Alkynes
Authors: Melcher Michaela‐Christina , von Wachenfeldt Henrik , Sundin Anders , Strand Daniel
Published: November 2014

Third‐row transition metal catalysts remain a largely untapped resource in cycloaddition reactions for the formation of medium‐sized rings. Herein, we report the first examples of iridium‐catalyzed inter‐ and intramolecular vinylcyclopropane (VCP)–alkyne (5+2) cycloadditions. DFT modeling suggests that catalysis by iridium(I) proceeds through a mechanism similar to that previously reported for rhodium(I)‐catalyzed VCP–alkyne cycloadditions, but a smaller free energy span for iridium enables substantially faster catalysis under favorable conditions. The system is characterized by up to quantitative yields and is amenable to an array of disubstituted alkynes and vinylcyclopropanes.
Oxidative Addition at a Carbene Center: Synthesis of an Iminoboryl–CAAC Adduct
Authors: Dahcheh Fatme , Stephan Douglas W. , Bertrand Guy
Published: November 2014

The reaction of a cyclic (alkyl)(amino)carbene (CAAC) with dichloro‐ and dibromobis(trimethylsilyl)aminoborane results in the formation of haloiminoborane–CAAC adducts. When the iodo analogue is used, an oxidative addition at the carbene center affords a cationic iminoboryl–CAAC adduct, featuring a boron–nitrogen triple bond. Similar salts are also obtained by halide abstraction from the chloro‐ and bromoiminoborane–CAAC adducts. The reactivity of all of these compounds towards CO2 is discussed.
ChemInform Abstract: Solvent‐Free Synthesis of a Secondary N‐Benzhydrylamine as a Chiral Reagent for Asymmetric Deprotonation of Bicyclic N‐Benzylamino Ketones.
Authors: Nodzewska Aneta , Sidorowicz Katarzyna , Sienkiewicz Michal
Published: November 2014

(R)‐N‐benzhydryl‐1‐phenylethylamine is utilized as chiral auxiliary in asymmetric deprotonations of N‐benzyl analogues of tropinone and granatanone.
ChemInform Abstract: Palladium‐Catalyzed Carbonylation of Aryl Bromides with N‐Substituted Cyanamides
Authors: Lian Zhong , Friis Stig D. , Lindhardt Anders T. , Skrydstrup Troels
Published: November 2014

The carbonylation is performed using a slight excess of CO‐gas which is produced ex situ from (II) in a two‐chamber reaction system.
ChemInform Abstract: Highly Efficient Deoxygenation of Sulfoxides Using Hydroxyapatite‐Supported Ruthenium Nanoparticles.
Authors: Takahashi Yusuke , Mitsudome Takato , Mizugaki Tomoo , Jitsukawa Koichiro , Kaneda Kiyotomi
Published: November 2014

The catalyst can be recycled and is reused without loss of activity.
ChemInform Abstract: One‐Pot Synthesis of Novel Heterocyclic Compounds via Tandem Reactions.
Authors: Huq C. A. M. A. , Sivakumar S.
Published: November 2014

The title compounds (III), (V), (VII) are obtained by a tandem oxy‐Cope rearrangement/SN displacement reaction, a tandem dianionic oxy‐Cope rearrangement/nucleophilic substitution at carbonyl carbon, and a tandem anionic oxy‐Cope rearrangement/transannular reaction, respectively.
ChemInform Abstract: Covalently Anchored Carboxylic Acid on Uniform Spherical Silica Nanoparticles with Narrow Slit Like Mesopores for the Synthesis of Pyrroloacridinones: CuI‐Catalyzed Further C(sp3)—H Oxyfunctionalization for C=O Formation.
Authors: Ray Suman , Bhaumik Asim , Pramanik Malay , Mukhopadhyay Chhanda
Published: November 2014

The catalyst can be reused at least six times with only slight decreases in yield.
ChemInform Abstract: Zeolite‐Catalyzed Method for the Preparation of 2,3‐Dihydroquinazolin‐4(1H)‐ones.
Authors: Takacs Anna , Fodor Anna , Nemeth Janos , Hell Zoltan
Published: November 2014

Title compounds are prepared by the reaction of isatoic anhydride, amines and aromatic aldehydes.
ChemInform Abstract: Access to Novel Imidazo[1,5‐a]pyrazine Scaffolds by the Combined Use of a Three‐Component Reaction and a Base‐Assisted Intramolecular Cyclization.
Authors: Attanasi Orazio A. , Favi Gianfranco , Giorgi Gianluca , Majer Roberta , Perrulli Francesca Romana , Santeusanio Stefania
Published: November 2014

Application of aliphatic isothiocyanates other than (XX) fails.
ChemInform Abstract: Palladium‐Catalyzed Cross‐Coupling of 5‐Acyl and 5‐Formyl‐1,2,4‐triazines and Their Derivatives with Heteroaromatic Tin Compounds.
Authors: Branowska Danuta , Olender Ewa , Rykowski Andrzej
Published: November 2014

The title process is investigated in detail under conditions A) and B).
ChemInform Abstract: Intermolecular and Regioselective Access to Polysubstituted Benzo‐ and Dihydrobenzo[c]azepine Derivatives: Modulating the Reactivity of Group 6 Non‐Heteroatom‐Stabilized Alkynyl Carbene Complexes.
Authors: Gonzalez Jairo , Gomez Aranzazu , Funes‐Ardoiz Ignacio , Santamaria Javier , Sampedro Diego
Published: November 2014

A three‐component reaction of Fischer carbene complexes (I), lithium acetylides and benzaldehyde imines offers an efficient approach to stable tungsten containing benzazepinium zwitterions.
ChemInform Abstract: Total Synthesis of Biselyngbyolide A.
Authors: Tanabe Yurika , Sato Eisuke , Nakajima Naoya , Ohkubo Akifumi , Ohno Osamu , Suenaga Kiyotake
Published: November 2014

Starting from a known chiral aldehyde, the first total synthesis of biselyngbyolide A (I) succeeds in 16 steps with an overall yield of 2.1%.
ChemInform Abstract: Magnetic Properties of Ceramic Nanocomposites
Authors: Majumder D. D. , Majumder D. D. , Karan S.
Published: November 2014

Review: 158 refs.
ChemInform Abstract: Magnetism of Keplerates
Authors: Koegerler Paul
Published: November 2014

Review: 57 refs.
ChemInform Abstract: 1,3‐Halogen Migration as an Entry to Aryl Coppers from an Unintuitive Starting Material
Authors: Van Hoveln R. J. , Schmid S. C. , Schomaker J. M.
Published: November 2014

Review: 18 refs.
ChemInform Abstract: Asymmetric Synthesis of Chiral Amines from Ketones: How to Apply Biocatalysis and Find a Suitable Enzyme
Authors: Wardenga Rainer , Bednarczyk Agata , Hoehne Matthias
Published: November 2014

Review: 13 refs.
ChemInform Abstract: Recent Advances in the Design Strategies for Porphyrin‐based Coordination Polymers
Authors: Zha Quanzheng , Rui Xing , Wei Tiantian , Xie Yongshu
Published: November 2014

Review: 89 refs.
ChemInform Abstract: Neutron Scattering Studies on URu2Si2
Authors: Bourdarot Frederic , Raymond Stephane , Regnault Louis‐Pierre
Published: November 2014

Review: 60 refs.
ChemInform Abstract: Photomobile Polymer Materials with Crosslinked Liquid‐Crystalline Structures: Molecular Design, Fabrication, and Functions
Authors: Ube Toru , Ikeda Tomiki
Published: November 2014

Review: 101 refs.
ChemInform Abstract: Perspectives and Advances of Microalgal Biodiesel Production with Supercritical Fluid Technology
Authors: Zeng Dan , Li Ruosong , Yan Ting , Fang Tao
Published: November 2014

Review: 110 refs.
Modélisation par homogénéisation d'une colonne d'absorption réactive
Authors: Girard Coralie , Couture Frédéric , Reneaume Jean‐Michel , Cezac Pierre
Published: November 2014

RESUME

Le garnissage d'une colonne d'absorption réactive est assimilé à un milieu poreux. Ainsi la modélisation des phénomènes de transports réactifs est basée sur une méthode d'homogénéisation par prise de moyenne volumique, technique originale pour le domaine. Le modèle est appliqué à l'absorption du dioxyde de carbone (CO2) dans une solution aqueuse d'hydroxyde de sodium (NaOH). Dans ce cas, les réactions sont supposées instantanément équilibrées. Les simulations instationnaires fournissent des informations locales sur le procédé tel que les champs de vitesse, de pression, de concentration et de température au sein du milieu.
Bladder cancer collaborative stage variables and their data quality, usage, and clinical implications: A review of SEER data, 2004‐2010
Authors: Charlton Mary E. , Adamo Margaret (Peggy) , Sun Leon , Deorah Sundeep
Published: November 2014

BACKGROUND

Several changes were made to bladder cancer staging guidelines between the 6th and 7th editions of the American Joint Committee on Cancer (AJCC) Staging Manual. Also, Collaborative Stage (CS) Data Collection System version 2 (CSv2) implemented for 2010 Surveillance, Epidemiology, and End Results (SEER) cases involved collection of 3 new site‐specific factors (SSFs): World Health Organization/International Society of Urological pathology grade (SSF1), size of metastasis in regional lymph nodes (SSF2), and extranodal extension (SSF3). Our objective was to evaluate these new SSFs to assist researchers in their use/interpretation and to describe data quality issues to be addressed moving forward.

METHODS

Staging trends were assessed for invasive and noninvasive bladder cancer cases from 2004 to 2010. Among 2010 cases, staging was compared using the AJCC 6th and 7th edition guidelines, and evaluation of completeness/quality of the SSFs was performed in relevant subgroups.

RESULTS

Age‐adjusted incidence rates and proportions of cases by stage remained steady from 2004 to 2010. Changes from the AJCC 6th to 7th editions caused no substantial movement between stages. SSF1 had a known value in 82% of cases, which was higher than the traditional SEER grade/differentiation variable. SSF2 and SSF3 were less complete, with 41% and 37% having known values, respectively, among cases with lymph node involvement (according to CS lymph node variable).

CONCLUSIONS

SSF1 was more complete and straightforward to interpret than the traditional grade/differentiation variable. SSF2 and SSF3 were less complete, may be associated with data quality issues, and should only be used among cases with known lymph node involvement Cancer 2014;120(23 suppl):3815‐25. © 2014 American Cancer Society.
Site‐specific factors for cancer of the corpus uteri from SEER registries: Collaborative stage data collection system, version 1 and version 2
Authors: Jamison Patricia M. , Altekruse Sean F. , Chang Joanne T. , Zahn Jennifer , Lee Richard , Noone Anne‐Michelle , Barroilhet Lisa
Published: November 2014

BACKGROUND

Uterine cancer is the fourth leading cancer among US women. Changes in uterine cancer staging were made from the American Joint Committee on Cancer (AJCC) 6th to 7th edition staging manuals, and 8 site‐specific factors (SSFs) and 3 histologic schemas were introduced. Carcinomas account for 95% of cases and are the focus of this report.

METHODS

Distributions of SSF values were examined for 11,601 cases of malignant cancer of the corpus uteri and uterus, NOS (not otherwise specified) diagnosed in Surveillance, Epidemiology, and End Results (SEER) Program registries during 2010. AJCC 6th and 7th edition staging distributions were compared for 11,176 cases using data in both staging systems. AJCC 6th edition staging distributions during 2004‐2010 were examined. AJCC 7th edition SSFs required by SEER were International Federation of Gynecology and Obstetrics stage (SSF1), peritoneal cytology (SSF2), number of positive pelvic lymph nodes (SSF3), number of pelvic lymph nodes examined (SSF4), number of positive para‐aortic lymph nodes (SSF5), and number of para‐aortic lymph nodes examined (SSF6).

RESULTS

For SSFs related to lymph nodes, a third of cases were classified as “not applicable,” reflecting that lymph node dissection is not indicated for cases with stage1A and stage 4 diagnoses. AJCC 7th edition criteria assigned more cases to stage I (72.9%) than AJCC 6th edition criteria (68.7%). Annual counts significantly increased during 2004‐2010, as did counts for AJCC 6th edition stages INOS, IA, IB, IC, IIIA, IIIB, IIIC, and IVB. The proportion of cases diagnosed with stage I cancer was stable, whereas stages II and IV decreased and stage III increased.

CONCLUSIONS

Five SSFs were suitable for analysis: peritoneal cytology results (SSF2), numbers of positive pelvic lymph nodes (SSF3), pelvic lymph nodes examined (SSF4), positive para‐aortic lymph nodes (SSF5), and para‐aortic lymph nodes examined (SSF6). Cancer 2014;120(23 suppl):3836‐45. © 2014 American Cancer Society.
Struggles in exporting complex surgical advances
Authors: Weight Christopher
Published: November 2014

The diffusion of complex surgical innovations is challenging and slow and, in some cases, may not be in the patient's best interest. Perhaps better patient education and empowerment will allow the best care at lower cost.
Impact of biochemical failure classification on clinical outcome: A secondary analysis ofRadiationTherapyOncologyGroup 9202 and 9413
Authors: Hamstra Daniel A. , Bae Kyounghwa , Hanks Gerald , Hu Chen , Shipley William U. , Pan Charlie C. , Roach Mack , Lawton Colleen A. , Sandler Howard M.
Published: November 2014

BACKGROUND

Biochemical failure (BF) after radiation therapy is defined on the basis of a rising prostate‐specific antigen (PSA) level (A1 failure) or any event that prompts the initiation of salvage androgen‐deprivation therapy without PSA failure (A2). It was hypothesized that A2 failure may have a different prognosis.

METHODS

Data for 2799 eligible patients from Radiation Therapy Oncology Group (RTOG) 9202 and RTOG 9413 were analyzed. BF was defined according to the 1997 American Society for Therapeutic Radiology and Oncology consensus definition as A1 for PSA failure or as A2 for the start of salvage hormone therapy before 3 consecutive PSA rises.

RESULTS

Rates of all‐cause mortality (hazard ratio [HR], 1.7; 95% confidence interval [CI], 1.5‐2.0;P < .0001) and distant metastasis (DM; HR, 1.6; 95% CI, 1.3‐2.0;P < .0001) were greater with A2 failure. The 5‐year overall survival (OS) rates were 88.2% and 74.6% for A1 and A2, respectively (P < .0001), and the DM rates were 15.7% and 29.0%, respectively (P < .0001). The DM rate was greater at 5 years for A2 patients with DM as the first sign of failure versus patients with other A2 failures (87.3% vs 11.7%,P < .001), and this also correlated with worse OS at 5 years: 81.1% for A2 failure without DM and 52.8% with DM (P < .001). After the removal of patients with DM, the difference between A1 and A2 BF persisted for OS (P = .002) but not for DM (P = .16)

CONCLUSIONS

These results suggest that patients with rising PSA levels alone have less risk than those with A2 failures; although DM was the largest contributor of adverse risk to A2 failure, it did not account for all excess risk in A2 failure.Cancer2015;121:844–852.©2014 American Cancer Society.
A comprehensive DCF performance analysis in noisy industrial wireless networks
Authors: Maadani Mohsen , Motamedi Seyed Ahmad
Published: November 2014

The use of wireless technology in industrial networks is becoming more popular because of its flexibility, reduction of cable cost, and deployment time. Providing an accurate model to study the most important parameters of these networks, the timeliness and reliability, is essential in assessing the network metrics and choosing proper protocol settings. The Institute of Electrical and Electronics Engineers (IEEE) 802.11 is a common and established wireless technology, and several analytical models have been proposed to assess its performance; however, most of them are accurate only for a limited network situation, especially data networks that have large packet payloads and are used at high signal to noise ratios, and cannot be applied to study the performance of industrial networks that have short packet lengths and are used in harsh and noisy environments. In this paper, a novel three‐dimensional discrete‐time Markov chain model has been proposed for the IEEE 802.11‐based industrial wireless networks using the distributed coordination function as the medium access control mechanism in the worst‐case saturated traffic. It considers both causes of the backoff freezing: busy channel and the successive interframe space waiting time. In this way, it provides a much more accurate estimation of the channel access and error probabilities, resulting in a more accurate network parameter calculation. Also, based on the proposed model, a comprehensive packet delay analysis, including average, jitter, and cumulative distribution function, has been provided for the near 100% reliable industrial scenario and error‐prone channel condition, which in comparison with similar pieces of work provides much more accurate results. Copyright © 2014 John Wiley & Sons, Ltd.
Work proactively to eliminate accessibility barriers in active‐learning campus spaces
Authors: Gomez Cynthia
Published: November 2014

A roundup of news of interest to disability services providers. To contribute an item to ETC., email Editor Cynthia Gomez at cgomez@wiley.com.
Vertebrate nervous system posteriorization: Grading the function of Wnt signaling
Authors: Green David , Whitener Amy E. , Mohanty Saurav , Lekven Arne C.
Published: November 2014

The establishment of anteroposterior identity in the vertebrate neural plate has been a subject of investigation for decades, but molecular explanations of posteriorization were only revealed beginning in the late 1980s. A model has emerged from several key studies that identifies Wnt signaling as a key posteriorizing agent, which evidence suggests specifies anteroposterior fates in a concentration‐dependent manner. In this review, we consider the historical context of posteriorization studies and evaluate models for Wnt‐dependent posteriorization. With new information about the mode of delivery of many signaling ligands, we propose alternative scenarios to reconcile the Wnt gradient model with the complex process of gastrulation and potential non‐secretory mechanisms of Wnt delivery. Developmental Dynamics 244:507–512, 2015. © 2014 Wiley Periodicals, Inc.
Direct and indirect selection on flowering time, water‐use efficiency (WUE, δ13C), and WUE plasticity to drought in Arabidopsis thaliana
Authors: Kenney Amanda M. , McKay John K. , Richards James H. , Juenger Thomas E.
Published: November 2014

Flowering time and water‐use efficiency (WUE) are two ecological traits that are important for plant drought response. To understand the evolutionary significance of natural genetic variation in flowering time, WUE, and WUE plasticity to drought in Arabidopsis thaliana, we addressed the following questions: (1) How are ecophysiological traits genetically correlated within and between different soil moisture environments? (2) Does terminal drought select for early flowering and drought escape? (3) Is WUE plasticity to drought adaptive and/or costly? We measured a suite of ecophysiological and reproductive traits on 234 spring flowering accessions of A. thaliana grown in well‐watered and season‐ending soil drying treatments, and quantified patterns of genetic variation, correlation, and selection within each treatment. WUE and flowering time were consistently positively genetically correlated. WUE was correlated with WUE plasticity, but the direction changed between treatments. Selection generally favored early flowering and low WUE, with drought favoring earlier flowering significantly more than well‐watered conditions. Selection for lower WUE was marginally stronger under drought. There were no net fitness costs of WUE plasticity. WUE plasticity (per se) was globally neutral, but locally favored under drought. Strong genetic correlation between WUE and flowering time may facilitate the evolution of drought escape, or constrain independent evolution of these traits. Terminal drought favored drought escape in these spring flowering accessions of A. thaliana. WUE plasticity may be favored over completely fixed development in environments with periodic drought.
Under what conditions do climate‐driven sex ratios enhance versus diminish population persistence?
Authors: Boyle Maria , Hone Jim , Schwanz Lisa E. , Georges Arthur
Published: November 2014

For many species of reptile, crucial demographic parameters such as embryonic survival and individual sex (male or female) depend on ambient temperature during incubation. While much has been made of the role of climate on offspring sex ratios in species with temperature‐dependent sex determination (TSD), the impact of variable sex ratio on populations is likely to depend on how limiting male numbers are to female fecundity in female‐biased populations, and whether a climatic effect on embryonic survival overwhelms or interacts with sex ratio. To examine the sensitivity of populations to these interacting factors, we developed a generalized model to explore the effects of embryonic survival, hatchling sex ratio, and the interaction between these, on population size and persistence while varying the levels of male limitation. Populations with TSD reached a greater maximum number of females compared to populations with GSD, although this was often associated with a narrower range of persistence. When survival depended on temperature, TSD populations persisted over a greater range of temperatures than GSD populations. This benefit of TSD was greatly reduced by even modest male limitation, indicating very strong importance of this largely unmeasured biologic factor. Finally, when males were not limiting, a steep relationship between sex ratio and temperature favoured population persistence across a wider range of climates compared to the shallower relationships. The opposite was true when males were limiting – shallow relationships between sex ratio and temperature allowed greater persistence. The results highlight that, if we are to predict the response of populations with TSD to climate change, it is imperative to 1) accurately quantify the extent to which male abundance limits female fecundity, and 2) measure how sex ratios and peak survival coincide over climate.