bluuebunny/crossref_metadata_2025 huggingface dataset:
DTBP/TBHP‐Promoted Hydroacylation of Unactivated Alkenes
Authors: Jhuang Huei‐Shu , Reddy Daggula Mallikarjuna , Chen Te‐Hsuan , Lee Chin‐Fa
Published: October 2016

Di‐tert‐butyl peroxide (DTBP)‐promoted intermolecular hydroacylation reaction of alkenes with aromatic aldehydes that provides ketones is described. In this study, 4‐chromanones were formed when 2‐(allyloxy)benzaldehydes were treated with tert‐butyl hydroperoxide (TBHP). The reactions were performed under solvent‐ and metal‐free conditions. Reactions proceeded through the generation of acyl radicals, followed by the reaction with alkenes. Remarkably, not only terminal alkenes but also internal alkenes could serve as the starting materials for intramolecular hydroacylation reaction.
Hip joint mobility in free‐ranging rhesus macaques
Authors: Hammond Ashley S. , Johnson Victoria P. , Higham James P.
Published: October 2016

Objectives

We aimed to test for differences in hip joint range of motion (ROM) between captive and free‐ranging rhesus macaques (Macaca mulatta), particularly for hip joint abduction, which previous studies of captive macaques have found to be lower than predicted.

Materials and methods

Hip ROM was assessed following standard joint measurement methodology in anesthetized adult free‐ranging rhesus macaques (n = 39) from Cayo Santiago, and compared with published ROM data from captive rhesus macaques (n = 16) (Hammond, , American Journal of Physical Anthropology). Significant differences between populations were detected using one‐way analysis of variance (p < .05).

Results

In a sample of pooled sexes and ages, free‐ranging macaques are capable of increased hip abduction, flexion, and internal rotation compared with captive individuals. These differences in joint excursion resulted in free‐ranging individuals having significantly increased ROM for hip adduction–abduction, rotation, flexion–extension, and the distance spanned by the knee during hip abduction. When looking at data for a smaller sample of age‐matched males, fewer ROM differences are significant, but free‐ranging males have significantly increased hip abduction, internal rotation, range of flexion–extension, and distance spanned by the knee during hip abduction compared with captive males of similar age.

Discussion

Our results suggest that a spatially restrictive environment results in decreased hip mobility in cage‐confined animals and ultimately limits the potential limb postures in captive macaques. These results have implications for selection of animal samples in model validation studies, as well as laboratory animal husbandry practices.

KEYWORDS caging, Cayo Santiago, hip abduction, Macaca mulatta, nonhuman primate captive care
Vein of Galen aneurysmal malformation: Pit‐falls in the diagnosis
Authors: Priyadarshi Archana , Luig Melissa
Published: October 2016

Vein of Galen aneurysmal malformation (VGAM) is a rare congenital vascular malformation. We report a case of VGAM being associated with presence of bilateral hydrocephalus, gross cardiomegaly and is unique in two ways. Firstly, clinical presentation was associated with a large discrete cystic swelling along right side of the neck, which has not previously been reported. Secondly, this was a missed diagnosis of VGAM due to omission of colour Doppler study while performing diagnostic fetal cranial ultrasound just prior to delivery, following referral for assessment on a previously identified abnormality.
Process Problems: Intervention Points For Recurring Mediation Logjams
Authors: Jacobs Roger B.
Published: October 2016

Different practice areas reveal different stumbling blocks for neutrals. Patterns emerge, and sticking points surface repeatedly.
Mehrdimensionale Massenspektrometrie von synthetischen Polymeren und modernen Materialien
Authors: Wesdemiotis Chrys
Published: October 2016

Mehrdimensionale Massenspektrometrie koppelt eine geeignete Ionisationsmethode und Massenanalyse (MS) mit der Fragmentierung mittels Tandem‐Massenspektrometrie (MS/MS) und einem Online‐Verfahren der orthogonalen Trennung. Für die Trennung kommen Flüssigkeitschromatographie (LC) und Ionenmobilitätsspektrometrie (IMS) in Frage, wobei die Trennung vor der Ionisation in der Lösung bzw. nach der Ionisation in der Gasphase erfolgt. Die MS liefert Daten zur Elementzusammensetzung, während die MS/MS Unterschiede der Bindungsstabilitäten eines Polymers nutzt, wodurch Daten zur Konnektivität und Sequenz erhalten werden. Die Bedingungen der LC können so gewählt werden, dass eine Trennung nach Polarität, Endgruppenfunktionalität oder hydrodynamischem Volumen möglich wird, während die IMS zusätzliche Selektivität bezüglich der Makromolekülform und ‐architektur liefert. In diesem Kurzaufsatz wird erörtert, wie ausgewählte Kombinationen der MS‐, MS/MS‐, LC‐ und IMS‐Dimensionen in Verbindung mit der entsprechenden Ionisationsmethode eingesetzt werden können, um die Bestandteile, Endgruppen, Sequenzen und Strukturen eines breiten Spektrums an Homopolymer‐ und Copolymermaterialien zu ermitteln, das Mehrkomponentenmischungen, supramolekulare Aggregate, neuartige Hybridmaterialien und große, vernetzte oder nichtionisierbare Polymere umfasst.
Power‐to‐Syngas – eine Schlüsseltechnologie für die Umstellung des Energiesystems?
Authors: Foit Severin R. , Vinke Izaak C. , de Haart Lambertus G. J. , Eichel Rüdiger‐A.
Published: October 2016

Durch Power‐to‐X‐Konzepte sollte die Emission von Treibhausgasen bei zugleich stabiler Energieversorgung, sogar bei einem hohen Anteil an Stromerzeugung aus erneuerbaren Quellen, signifikant reduziert werden, was sie zu einem Eckpfeiler nachhaltiger Energiesysteme macht. Power‐to‐Syngas, die elektrochemische Konversion von Wasserdampf und Kohlendioxid mithilfe regenerativ erzeugter Elektrizität in Synthesegas für die Produktion synthetischer Treibstoffe und hochwertiger Chemikalien, eignet sich somit hervorragend für die Kupplung energieintensiver Sektoren wie “Verkehr und Transport” und “chemische Industrie”. Durch Co‐Elektrolyse hergestelltes Synthesegas ist daher für die Energiewende essenziell und bietet zudem die Möglichkeit zur CO2‐Valorisierung und zum Schließen von Kohlenstoffkreisläufen. Im Folgenden werden Vorteile und gegenwärtige technische Einschränkungen der Tief‐ und Hochtemperatur‐Co‐Elektrolyse behandelt. Ein besseres Verständnis der Reaktionen und stabile, leistungsstarke Materialien sind für weitere Fortschritte der Co‐Elektrolysetechnologie wesentlich.
Uncovering the Intramolecular Emission and Tuning the Nonlinear Optical Properties of Organic Materials by Cocrystallization
Authors: Zhu Weigang , Zhu Lingyun , Sun Lingjie , Zhen Yonggang , Dong Huanli , Wei Zhixiang , Hu Wenping
Published: October 2016

The spectroscopic and photophysical properties of organic materials in the solid‐state are widely accepted as a result of their molecular packing structure and intermolecular interactions, such as J‐ and H‐aggregation, charge‐transfer (CT), excimer and exciplex. However, in this work, we show that Spe‐F4DIB cocrystals (SFCs) surprisingly retain the energy levels of photoluminescence (PL) states of Spe crystals, despite a significantly altered molecular packing structure after cocrystallization. In comparison, Npe‐F4DIB cocrystals (NFCs) with new spectroscopic states display different spectra and photophysical behaviors as compared with those of individual component crystals. These may be related to the molecular configuration in crystals, and we propose Spe as an “intramolecular emissive” material, thus providing a new viewpoint on light‐emitting species of organic chromophores. Moreover, the nonlinear optical (NLO) properties of Npe and Spe are firstly demonstrated and modulated by cocrystallization. The established “molecule‐packing‐property” relationship helps to rationally control the optical properties of organic materials through cocrystallization.
Thermische Dehydrierung von Methan durch [ReN]+
Authors: Zhou Shaodong , Li Jilai , Schlangen Maria , Schwarz Helmut
Published: October 2016

Die thermische Reaktion des zweiatomigen Rheniumnitridkations [ReN]+ mit Methan wurde mit FT‐ICR‐Massenspektrometrie und quantenchemischen Rechnungen untersucht. Unter besonderer Berücksichtigung mechanistischer Aspekte der Reaktion konnten Szenarien für die kompetitive Erzeugung eines an das Metallzentrum gebundenen Methylen‐ bzw. Cyanwasserstoffliganden entworfen werden. Die Rolle des Stickstoffatoms des reaktiven [ReN]+/CH4‐Paares wurde aufgeklärt und die Ursache der ziemlich unterschiedlichen Reaktivitäten von [ReN]+ und [MnN]+ ermittelt.
Anions Stabilize Each Other inside Macrocyclic Hosts
Authors: Fatila Elisabeth M. , Twum Eric B. , Sengupta Arkajyoti , Pink Maren , Karty Jonathan A. , Raghavachari Krishnan , Flood Amar H.
Published: October 2016

Contrary to the simple expectations from Coulomb's law, Weinhold proposed that anions can stabilize each other as metastable dimers, yet experimental evidence for these species and their mutual stabilization is missing. We show that two bisulfate anions can form such dimers, which stabilize each other with self‐complementary hydrogen bonds, by encapsulation inside a pair of cyanostar macrocycles. The resulting 2:2 complex of the bisulfate homodimer persists across all states of matter, including in solution. The bisulfate dimer's OH⋅⋅⋅O hydrogen bonding is seen in a 1H NMR peak at 13.75 ppm, which is consistent with borderline‐strong hydrogen bonds.
Regiodivergent and Diastereoselective CuH‐Catalyzed Allylation of Imines with Terminal Allenes
Authors: Liu Richard Y. , Yang Yang , Buchwald Stephen L.
Published: October 2016

A copper‐catalyzed, chemoselective hydrometalation process enables the use of simple allenes as allylmetal nucleophile surrogates in imine allylation reactions. By modulating the nitrogen‐protecting group, either highly branched‐ or linear‐selective addition can be achieved from the same allene. Both reactions exhibit excellent diastereoselectivity and broad functional‐group tolerance. Preliminary results indicate that good enantioselectivity can also be achieved in the linear‐selective reaction. Finally, a mechanistic model for the regiodivergence is proposed on the basis of density functional theory calculations.
Iridium‐Catalyzed Carbonylative Synthesis of Chromenones from Simple Phenols and Internal Alkynes at Atmospheric Pressure
Authors: Zhu Fengxiang , Li Yahui , Wang Zechao , Wu Xiao‐Feng
Published: October 2016

A novel procedure on the carbonylative synthesis of chromenones has been developed. With simple phenols and internal alkynes as the substrates, various chromenones were isolated in moderate to good yields with excellent regioselectivity and functional‐group tolerance by using iridium as the catalyst and copper as the promotor at atmospheric pressure. Notably, this is the first example on carbonylative annulation of simple phenols and alkynes.
Length‐Independent Charge Transport in Chimeric Molecular Wires
Authors: Wardrip Austin G. , Mazaheripour Amir , Hüsken Nina , Jocson Jonah‐Micah , Bartlett Andrew , Lopez Robert C. , Frey Nathan , Markegard Cade B. , Kladnik Gregor , Cossaro Albano , Floreano Luca , Verdini Alberto , Burke Anthony M. , Dickson Mary N. , Kymissis Ioannis , Cvetko Dean , Morgante Alberto , Sharifzadeh Sahar , Nguyen Hung D. , Gorodetsky Alon A.
Published: October 2016

Advanced molecular electronic components remain vital for the next generation of miniaturized integrated circuits. Thus, much research effort has been devoted to the discovery of lossless molecular wires, for which the charge transport rate or conductivity is not attenuated with length in the tunneling regime. Herein, we report the synthesis and electrochemical interrogation of DNA‐like molecular wires. We determine that the rate of electron transfer through these constructs is independent of their length and propose a plausible mechanism to explain our findings. The reported approach holds relevance for the development of high‐performance molecular electronic components and the fundamental study of charge transport phenomena in organic semiconductors.
Conformational Dynamics of apo‐GlnBP Revealed by Experimental and Computational Analysis
Authors: Feng Yitao , Zhang Lu , Wu Shaowen , Liu Zhijun , Gao Xin , Zhang Xu , Liu Maili , Liu Jianwei , Huang Xuhui , Wang Wenning
Published: October 2016

The glutamine binding protein (GlnBP) binds l‐glutamine and cooperates with its cognate transporters during glutamine uptake. Crystal structure analysis has revealed an open and a closed conformation for apo‐ and holo‐GlnBP, respectively. However, the detailed conformational dynamics have remained unclear. Herein, we combined NMR spectroscopy, MD simulations, and single‐molecule FRET techniques to decipher the conformational dynamics of apo‐GlnBP. The NMR residual dipolar couplings of apo‐GlnBP were in good agreement with a MD‐derived structure ensemble consisting of four metastable states. The open and closed conformations are the two major states. This four‐state model was further validated by smFRET experiments and suggests the conformational selection mechanism in ligand recognition of GlnBP.
Power‐to‐Syngas: An Enabling Technology for the Transition of the Energy System?
Authors: Foit Severin R. , Vinke Izaak C. , de Haart Lambertus G. J. , Eichel Rüdiger‐A.
Published: October 2016

Power‐to‐X concepts promise a reduction of greenhouse gas emissions simultaneously guaranteeing a safe energy supply even at high share of renewable power generation, thus becoming a cornerstone of a sustainable energy system. Power‐to‐syngas, that is, the electrochemical conversion of steam and carbon dioxide with the use of renewably generated electricity to syngas for the production of synfuels and high‐value chemicals, offers an efficient technology to couple different energy‐intense sectors, such as “traffic and transportation” and “chemical industry”. Syngas produced by co‐electrolysis can thus be regarded as a key‐enabling step for a transition of the energy system, which offers additionally features of CO2‐valorization and closed carbon cycles. Here, we discuss advantages and current limitations of low‐ and high‐temperature co‐electrolysis. Advances in both fundamental understanding of the basic reaction schemes and stable high‐performance materials are essential to further promote co‐electrolysis.
Vesicles in Nature and the Laboratory: Elucidation of Their Biological Properties and Synthesis of Increasingly Complex Synthetic Vesicles
Authors: Fernandez‐Trillo Francisco , Grover Liam M. , Stephenson‐Brown Alex , Harrison Paul , Mendes Paula M.
Published: October 2016

The important role of vesicles in many aspects of cell function is well‐recognized, but only recently have sophisticated imaging techniques begun to reveal their ubiquity in nature. While we further our understanding of the biological properties of vesicles and their physiological functions, increasingly elegant artificial vesicles are being developed for a wide range of technological applications and basic research. Herein, we examine the state of the art of biological and synthetic vesicles and place their biological features in the context of recent synthetic developments, thus providing a unique overview of these complex and rapidly developing fields. The challenges and opportunities associated with future biological and synthetic studies of vesicles are also presented.
Ligand‐Accelerated Direct C−H Arylation of BINOL: A Rapid One‐Step Synthesis of Racemic 3,3′‐Diaryl BINOLs
Authors: Yang Jin‐Fei , Wang Rong‐Hua , Wang Yin‐Xia , Yao Wei‐Wei , Liu Qi‐Sheng , Ye Mengchun
Published: October 2016

An ortho‐selective rhodium‐catalyzed direct C−H arylation of 1,1′‐bi‐2‐naphthol (BINOL), to deliver the widely used but not easily available 3,3′‐diaryl BINOL, has been developed. This highly efficient one‐step synthetic approach is the shortest route to date and is greatly facilitated by the newly developed ligand system comprising tBu2PCl, Ph2‐cod, and Cy3P⋅HBF4. In addition, the same procedure can facilitate the challenging syntheses of 3‐bulkyaryl BINOLs in good to excellent yields.
Synthesis of Bridged Cyclopentane Derivatives by Catalytic Decarbonylative Cycloaddition of Cyclobutanones and Olefins
Authors: Zhou Xuan , Ko Haye Min , Dong Guangbin
Published: October 2016

Herein, we report an intramolecular rhodium‐catalyzed decarbonylative coupling between cyclobutanones and alkenes that proceeds by C−C activation and provides a distinct approach to a diverse range of saturated bridged cyclopentane derivatives. In this reaction, cyclobutanones serve as cyclopropane surrogates, reacting in a formal (4+2−1) transformation. To demonstrate the efficacy of this method, it was applied in a concise synthesis of the antifungal drug Tolciclate.
Generation of Dicoordinate Boron(I) Units by Fragmentation of a Tetra‐Boron(I) Molecular Square
Authors: Arrowsmith Merle , Auerhammer Dominic , Bertermann Rüdiger , Braunschweig Holger , Bringmann Gerhard , Celik Mehmet Ali , Dewhurst Rian D. , Finze Maik , Grüne Matthias , Hailmann Michael , Hertle Thomas , Krummenacher Ivo
Published: October 2016

Reduction of carbene‐borane adduct [(cAAC)BBr2(CN)] (cAAC=1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) cleanly yielded the tetra(cyanoborylene) species [(cAAC)B(CN)]4 presenting a 12‐membered (BCN)4 ring. The analysis of the Kohn–Sham molecular orbitals showed significant borylene character of the BI atoms. [(cAAC)B(CN)]4 was found to reduce two equivalents of AgCN per boron center to yield [(cAAC)B(CN)3] and fragmented into two‐coordinate boron(I) units upon reaction with IMeMe (1,3,4,5‐tetramethylimidazol‐2‐ylidene) to yield the corresponding tricoordinate mixed cAAC‐NHC cyanoborylene. The analogous cAAC‐phosphine cyanoborylene was obtained by reduction of [(cAAC)BBr2(CN)] in the presence of excess phosphine.
Synthesis, structure and antiproliferative activity of organometallic iridium(III) complexes containing thiosemicarbazone ligands
Authors: Su Wei , Peng Binghua , Li Peiyuan , Xiao Qi , Huang Shan , Gu Yunqiong , Lai Zefeng
Published: October 2016

A series of half‐sandwich iridium complexes (1–4) with thiosemicarbazone ligands in two types of coordination modes were synthesized and characterized. The molecular structures of compounds 1, 2 and 3 were determined using single‐crystal X‐ray diffraction analysis. The nature of the complexes was studied using density functional theory calculations. The stability of the complexes was investigated using UV–visible absorption spectroscopy. The compounds were further evaluated for their in vitro antiproliferative activities against HeLa, HepG2, CNE‐2, SGC‐7901, KB and HEK‐293 T cell lines. Compound 2 displays the highest antiproliferative activity among the other analogues and cisplatin.
Palladium‐catalyzed highly selective intramolecular bromoamination of alkenes: Efficient synthesis of substituted pyrrolidines
Authors: Zhang Jingfang , Wang Xie , Liu Yulong , Wang Xiaoyun , He Wei
Published: October 2016

A new method has been developed for the preparation of substituted pyrrolidines by the palladium‐catalyzed intramolecular bromoamination of substituted aminoalkenes. The catalytic system and reaction conditions used for this transformation have been fully optimized. Notably, this reaction exhibits excellent selectivity, affording the pyrrolidine products as single 5‐exo‐bromoalkylpyrrolidines in excellent yields. Furthermore, this reaction occurs at room temperature under mild conditions, reaching completion within 1 h.
Process modeling and performance evaluation of commercial‐scale coal‐to‐SNG plant using Indonesia IBC coal with two drying concepts
Authors: Yuan Xiang Zhou , He Chun Yang , Namkung Hueon , Fan Shu Min , Kim Hyung‐Taek
Published: October 2016

The entire process of Coal‐to‐SNG plant had been modeled utilizing Illinois #6 coal as a feedstock. Shell's coal gasification process and Topsøe's recycle energy‐efficient methanation process were utilized in process modeling of gasification and methanation processes. The simulation results of this Coal‐to‐SNG process model using Illinois #6 coal as a feedstock were well‐matched with the experimental data, indicating that this entire model was feasible to do further research using IBC coal as a feedstock. Two drying methods were utilized for drying the IBC coal because of its higher moisture content. When only changing the feedstock from Illinois #6 coal to IBC coal in this Coal‐to‐SNG process model, the CH4 purity and yield were 83.5 mol% and 0.264 kg/kg‐coal (dry basis); however, the CH4 purity and yield reached 94.4 mol% and 0.306 kg/kg‐coal (dry basis) when syngas recycle drying concept was also applied in feedstock process model. The sensitivity and energy analyses were adopted for evaluating performance of this entire process. The total input energy was saved about 30% by utilizing syngas recycle drying concept. When taking coal prices into consideration, the Low Rank Coal‐to‐SNG process using IBC coal as a feedstock with syngas recycle drying concept becomes more feasible and attractive. © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Investigation into the viscoelastic response at various gelation performance, thermal stability and swelling kinetics of fly ash reinforced polymer gels for water control in mature oilfields
Authors: Adewunmi Ahmad A. , Ismail Suzylawati , Sultan Abdullah S.
Published: October 2016

The present crippling crude oil price worldwide demands a new strategy and cost‐effective technology that will promote additional oil recovery in mature oilfields. Herein, crosslinked polyacrylamide (PAM) gels reinforced with coal fly ash (CFA) were investigated for water reduction purpose during enhanced oil recovery. Polyethyleneimine (PEI) is chosen as the crosslinker. Neat PAM/PEI gel and PAM/PEI composite gels filled with various CFA concentrations (0.5 to 2 wt%) were developed and characterized by aging, gravimetric, hybrid rheometer, thermogravimetric analyzer (TGA), scanning electron microscopy (SEM), X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) instruments. Gelation performance of these gels was conducted at 90 °C, and results show that increase in CFA in PAM/PEI gels causes a delay in the gelation time. This indicates that CFA can act as a retarder in polymer gels applied for water control in mature oilfields. Moreover, the PAM/PEI composite gels containing CFA displayed improved viscoelastic properties as compared to the neat PAM/PEI gel at various gelation behaviors that were tested. Additionally, TGA analysis revealed that PAM/PEI gels infused with different CFA amounts possessed high resistance to thermal decomposition. The presence of alumina and silica in high concentrations in CFA induced a strong bond within these polymer gels, which resulted in improved thermal stability. Further, owing to the fact that CFA only absorbed a small amount of water through the hydroxyl and amine groups, its presence decreased the swelling ability of these composite gels. Morphological and structural analysis demonstrated by these gels affirmed the consistency of viscoelastic, thermal and swelling kinetic results. Copyright © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Rheological and crystallization enhancement in polyphenylenesulfide and polyetheretherketone POSS nanocomposites
Authors: Knauer Katrina M. , Brust Gregory , Carr Michael , Cardona Rene J. , Lichtenhan Joseph D. , Morgan Sarah E.
Published: October 2016

Polyhedral oligomeric silsesquioxane (POSS) additives have been shown to increase melt‐flow and crystallization in thermoplastics. In this study, the effect of incorporation of trisilanolphenyl‐POSS molecules in polyphenylenesulfide (PPS) and polyetheretherketone (PEEK) on rheology, crystallization kinetics, and thermal and mechanical properties was evaluated. Parallel plate rheometry revealed a reduction in the viscosity of PPS and PEEK with the addition of POSS. The magnitude and concentration dependence of rheological modification were shown to depend on the polymer structure and POSS solubility. Isothermal crystallization kinetics were analyzed using the Avrami model and it was found that the addition of POSS accelerated the crystallization rate of PPS blends with no significant effect on PEEK blends. Interestingly, no statistical difference in degradation temperature, tensile modulus, or tensile strength of PPS or PEEK blends was observed. The findings indicate the potential for improvements in melt viscosity and crystallization of high temperature thermoplastics with tailored POSS/polymer interactions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44462.
Hydrophobic cellulose fibers via ATRP and their performance in the removal of pyrene from water
Authors: Arteta Sandra M. , Vera Ricardo , Pérez León D.
Published: October 2016

In the present work, cellulose fibers were modified by grafting with poly(lauryl acrylate) and poly(octadecyl acrylate). The grafted materials were prepared by polymerization of the corresponding monomers via surface initiated atom transfer radical polymerization, starting from cellulose papers previously modified with 2‐bromoisobutyryl groups. The polymerizations were carried out in the presence of ethyl‐2‐bromoisobutyrate, as a sacrificial initiator, added to control the molecular weight of the anchored segments, and polymerization kinetics. The grafting of both polymers was confirmed by infrared spectroscopy and elemental analysis. The effect of grafting these polymers on the thermal stability, morphology, and surface properties of cellulose fibers was studied using thermogravimetric analysis, scanning electron microscopy, and measuring water contact angle, respectively. The results reveal that grafting poly(lauryl acrylate) and poly(octadecyl acrylate) to cellulose confers the filter paper a hydrophobic character, and increases its affinity with pyrene, allowing the removal of this pollutant from water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44482.
Performance evaluation of sodium alginate–Pebax polyion complex membranes for application in direct methanol fuel cells
Authors: Nagar Harsha , Sumana C. , Rao V. V. Basava , Sridhar S.
Published: October 2016

A novel polyion complex membrane was synthesized for direct methanol fuel cell application through the blending of the natural biopolymer sodium alginate (SA) with the synthetic polymer Pebax [poly(ether‐block‐amide)]. The blend was covalently crosslinked with glutaraldehyde (GA) and sulfonated with sulfuric acid (H2SO4), after which characterization by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffractometry, thermogravimetric analysis, and universal testing machine techniques was carried out. The SA–Pebax–GA–H2SO4 membrane exhibited a high ion‐exchange capacity of 2.1 mequiv/g, an optimum water sorption of 17.3%, and a low methanol sorption of 9.5%. A desirably low methanol permeability of 9.25 × 10−8 cm2/s and a high proton conductivity of 0.067 S/cm were obtained as against corresponding values of 1.82 × 10−6 cm2/s and 0.077 S/cm reported for a commercial Nafion 117 membrane. Moreover, a high selectivity of 6.5 × 105 Ss/cm3 with a power density of 0.17 W/cm2 was achieved with the indigenous blend membrane at a potential of 0.34 V. Molecular dynamics simulation was performed along with the estimation of fractional free volume to explain the transport behavior of water and methanol molecules through the membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44485.
Preparation and properties of emulsifier‐/solvent‐free polyurethane‐acrylic hybrid emulsions for binder materials: Effect of the glycidyl methacrylate/acrylonitrile content
Authors: Ryu Young‐Su , Lee Young‐Hee , Kim Jung‐Soo , Park Cha‐Cheol , Kim Han‐Do
Published: October 2016

To obtain binder materials, emulsions of emulsifier‐/solvent‐free waterborne polyurethane‐acrylic hybrids with a fixed acrylic monomer content (30 wt %) were prepared in this study. This study focused on the effect of glycidyl methacrylate (GMA)/acrylonitrile (AN) wt % on the shelf stability, mean particle size and viscosity of hybrid emulsion samples, water swelling %/dynamic mechanical thermal properties/mechanical properties of hybrid film samples, and the failure mode and adhesive strength of binder materials prepared in this study. Characterization of the chemical structures of prepolymers, hybrid materials (binder materials), and atmospheric pressure plasma‐treated polyethylene (PE) has been performed by means of Fourier transformed infrared spectroscopy to determine the presence/disappearance/peak intensity change of functional groups. Various properties such as mean particle size, viscosity, Tg, water swelling %, hardness and mechanical properties, and failure mode and adhesive strength for leather/leather, control PE/leather, and plasma‐treated PE/leather were found to be significantly dependent on the weight ratio of GMA/AN. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44497.
Sustainable biodegradable coffee grounds filler and its effect on the hydrophobicity, mechanical and thermal properties of biodegradable PBAT composites
Authors: Moustafa Hesham , Guizani Chamseddine , Dufresne Alain
Published: October 2016

Poly(butylene adipate‐co‐terephthalate) (PBAT) and coffee grounds (CG) wastes are biodegradable materials. The high cost of PBAT restricts its marketability; the lignocellulosic CG were used as a reinforcing agent for PBAT. Thus, the present work focuses mainly on the preparation and characterization of bio‐based PBAT composites filled with CG bio‐additives with affordable cost, and with potential use in a variety of eco‐friendly fields such as packaging, biomedical devices, and composting. The PBAT polymer was melt blended with various contents of CG powder using twin screw extrusion. The compatibility and dispersion state of investigated biocomposites in presence or absence of PEG as plasticizer were investigated by using scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The effect of the addition of PEG on PBAT/CG was characterized by differential scanning calorimetry (DSC), tensile properties, contact angle measurements, and thermogravimetric analysis. The chemical interaction between hydroxyl groups of CG particles and PEG plasticizer was achieved by these techniques. A pyrolysis kinetic model was proposed to identify the kinetic parameters of the thermal degradation of PBAT and CG powder. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44498.
Sulfonated polyphenylsulfone asymmetric membranes: Effect of coagulation bath (acetic acid‐NaHCO3/isopropanol) on morphology and antifouling properties
Authors: Yam‐Cervantes M. A. , Santiago‐García J. L. , Loría‐Bastarrachea M. I. , Duarte‐Aranda S. , Alberto Ruiz‐Treviño F. , Aguilar‐Vega M.
Published: October 2016

Sulfonated polyphenylsulfone porous asymmetric membranes, S‐PPSU with different sulfonation degrees, 21, 33, 50 wt %, were prepared by phase inversion. Two different coagulation baths were explored for asymmetric membrane preparation: acetone/isopropanol and acetic acid (AA)‐NaHCO3/isopropanol. The latter bath allows better morphology control for the nucleation and pore formation of the membrane. Scanning electron microscopy of membranes shows that pore interconnectivity is improved, when the mixture of AA‐NaHCO3/isopropanol was used for asymmetric S‐PPSU ultrafiltration membranes preparation. S‐PPSU asymmetric membranes show an increasing hydrophilicity with increasing sulfonation degree. Asymmetric membrane antifouling properties improve as the concentration of sulfonic groups increases in the membrane showing twice the flux recovery ratio and lower BSA protein absorption in static and dynamic flux tests. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44502.
Structure characterization and adsorption properties of tetraethylenepentamine ion exchange fiber
Authors: Li Mingyu , Ding Kefu , Zeng Qingxuan , Li Zhihao
Published: October 2016

A novel tetraethylenepentamine ion exchange fiber (TAIEF) was prepared using polypropylene grafted styrene (PP‐g‐ST) fiber as raw material. The chemical structure of TAIEF was characterized using infrared spectrum (IR) method. TAIEF had good appearance and shape after reaction in SEM images, the TGA curves revealed that both PP‐g‐ST fiber and acetyl PP‐g‐ST fiber had good thermal stability below 250 °C, and the weight loss rate of TAIEF is 9% from 50 °C to 200 °C obtained by TGA. TAIEF adsorption capacity to Fe(III) is larger than that of In(III) in the pH value 1.00 to 3.00, while the pH value is at 2.50 to 3.00, TAIEF adsorption capacity to Fe(II) and Zn(II) are smaller than that of In(III). The selective adsorption ability to Fe(III) is higher than In(III), and the selective absorptivity to In(III) is better than Fe(II) and Zn(II). The mechanism was explained of TAIEF favorable selective adsorption to In(III) and Fe(III) ions in mixed solutions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44513.
Structural characterization and electrical properties of carbon nanotubes/epoxy polymer composites
Authors: Boukheir Sofia , Len Adél , Füzi János , Kenderesi Viktor , Achour Mohammed Essaid , Éber Nándor , Costa Luis Cadillon , Oueriagli Amane , Outzourhit Abdelkader
Published: October 2016

The purpose of this study is to identify the relationship between the electrical and structural characteristics of multiwalled carbon nanotubes dispersed into the polymer matrix of a resin. In a first step, the composites were characterized by small‐angle neutron scattering, which provide information about the bulk dispersion of nanotubes in the matrix and form three‐dimensional networks with a surface fractal behavior. In the second step, a dielectric and electrical study was carried out in the frequency range between 1 Hz and 10 MHz at room temperature. We have found that the electric and dielectric behavior of these composites can be described by Jonscher's universal dielectric response. We show that the critical exponents describing the concentration dependence of the conductivity and the dielectric constant, obtained in the vicinity of the percolation threshold, are in good agreement with the theoretical values. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44514.
Radiographic and Magnetic Resonance Imaging Identification of Thoracolumbar Spine Variants with Implications for the Positioning of the Conus Medullaris in Rhesus Macaques
Authors: Ohlsson Marcus , Nieto Jaime H. , Christe Kari L. , Villablanca J. Pablo , Havton Leif A.
Published: October 2016

The anatomy of the vertebral column in mammals may differ between species and between subjects of the same species, especially with regards to the composition of the thoracolumbar spine. We investigated, using several noninvasive imaging techniques, the thoracolumbar spine of a total of 44 adult rhesus macaques of both genders. Radiographic examination of the vertebral column showed a predominant spine phenotype with 12 rib‐bearing thoracic vertebrae and 7 lumbar vertebrae without ribs in 82% of subjects, whereas a subset of subjects demonstrated 13 rib‐bearing thoracic vertebrae and 6 lumbar vertebrae without ribs. Computer tomography studies of the thoraco‐lumbar spine in two cases with a pair of supernumerary ribs showed facet joints between the most caudal pair of ribs and the associated vertebra, supporting a thoracic phenotype. Magnetic resonance imaging (MRI) studies were used to determine the relationship between the lumbosacral spinal cord and the vertebral column. The length of the conus medullaris portion of the spinal cord was 1.5 ± 0.3 vertebral units, and its rostral and caudal positions in the spinal canal were at 2.0 ± 0.3 and 3.6 ± 0.4 vertebral units below the thoracolumbar junction, respectively (n = 44). The presence of a set of supernumerary ribs did not affect the length or craniocaudal position of the conus medullaris, and subjects with13 rib‐bearing vertebrae may from a functional or spine surgical perspective be considered as exhibiting12 thoracic vertebrae and an L1 vertebra with ribs. Anat Rec, 300:300–308, 2017. © 2016 Wiley Periodicals, Inc.
Design and Synthesis of 4‐Anilinothieno[2,3‐d]pyrimidine‐Based Compounds as Dual EGFR/HER‐2 Inhibitors
Authors: Abd El Hadi Soha R. , Lasheen Deena S. , Hassan Mahmoud A. , Abouzid Khaled A. M.
Published: October 2016

Dual inhibition of the epidermal growth factor receptor (EGFR) and the human epidermal growth factor receptor 2 (HER‐2) is an attractive cancer therapeutic approach. In this study, new series of 4‐anilinothieno[2,3‐d]pyrimidines were designed, synthesized, and tested as dual EGFR/HER‐2 kinase inhibitors. Five compounds (8a, 8b, 8e–g) demonstrated low to submicromolar inhibition of both kinases with IC50 values of 1.2, 0.6, 0.3, 0.2, 0.4 μM and 8.2, 3.4, 1.3, 0.5, 2.7 μM for the EGFR and HER‐2, respectively. Introduction of a 5,6‐tetramethylene moiety into the thienopyrimidine core bearing a 4‐(3‐fluorobenzyloxy)‐3‐chloroaniline tail resulted in a favorable increase in both the EGFR and HER‐2 inhibitory activities. Compound 8f (IC50 EGFR/HER‐2: 0.2/0.5 μM) also exhibited significant cell growth inhibition on some specific NCI cell lines, especially ovarian, breast, non‐small‐cell lung cancer, and renal cancer cell lines.
Gene Expression and Pharmacodynamic Changes in 1,760 Systemic Lupus Erythematosus Patients From Two Phase III Trials of BAFF Blockade With Tabalumab
Authors: Hoffman Robert W. , Merrill Joan T. , Alarcón‐Riquelme Marta M. E. , Petri Michelle , Dow Ernst R. , Nantz Eric , Nisenbaum Laura K. , Schroeder Krista M. , Komocsar Wendy J. , Perumal Narayanan B. , Linnik Matthew D. , Airey David C. , Liu Yushi , Rocha Guilherme V. , Higgs Richard E.
Published: October 2016

Objective

To characterize baseline gene expression and pharmacodynamically induced changes in whole blood gene expression in 1,760 systemic lupus erythematosus (SLE) patients from 2 phase III, 52‐week, randomized, placebo‐controlled, double‐blind studies in which patients were treated with the BAFF‐blocking IgG4 monoclonal antibody tabalumab.

Methods

Patient samples were obtained from SLE patients from the ILLUMINATE‐1 and ILLUMINATE‐2 studies, and control samples were obtained from healthy donors. Blood was collected in Tempus tubes at baseline, week 16, and week 52. RNA was analyzed using Affymetrix Human Transcriptome Array 2.0 and NanoString.

Results

At baseline, expression of the interferon (IFN) response gene was elevated in patients compared with controls, with 75% of patients being positive for this IFN response gene signature. There was, however, substantial heterogeneity of IFN response gene expression and complex relationships among gene networks. The IFN response gene signature was a predictor of time to disease flare, independent of anti–double‐stranded DNA (anti‐dsDNA) antibody and C3 and C4 levels, and overall disease activity. Pharmacodynamically induced changes in gene expression following tabalumab treatment were extensive, occurring predominantly in B cell–related and immunoglobulin genes, and were consistent with other pharmacodynamic changes including anti‐dsDNA antibody, C3, and immunoglobulin levels.

Conclusion

SLE patients demonstrated increased expression of an IFN response gene signature (75% of patients had an elevated IFN response gene signature) at baseline in ILLUMINATE‐1 and ILLUMINATE‐2. Substantial heterogeneity of gene expression was detected among individual patients and in gene networks. The IFN response gene signature was an independent risk factor for future disease flares. Pharmacodynamic changes in gene expression were consistent with the mechanism of BAFF blockade by tabalumab.
Rheumatoid Arthritis Naive T Cells Share Hypermethylation Sites With Synoviocytes
Authors: Rhead Brooke , Holingue Calliope , Cole Michael , Shao Xiaorong , Quach Hong L. , Quach Diana , Shah Khooshbu , Sinclair Elizabeth , Graf John , Link Thomas , Harrison Ruby , Rahmani Elior , Halperin Eran , Wang Wei , Firestein Gary S. , Barcellos Lisa F. , Criswell Lindsey A.
Published: October 2016

Objective

To determine whether differentially methylated CpGs in synovium‐derived fibroblast‐like synoviocytes (FLS) of patients with rheumatoid arthritis (RA) were also differentially methylated in RA peripheral blood (PB) samples.

Methods

For this study, 371 genome‐wide DNA methylation profiles were measured using Illumina HumanMethylation450 BeadChips in PB samples from 63 patients with RA and 31 unaffected control subjects, specifically in the cell subsets of CD14+ monocytes, CD19+ B cells, CD4+ memory T cells, and CD4+ naive T cells.

Results

Of 5,532 hypermethylated FLS candidate CpGs, 1,056 were hypermethylated in CD4+ naive T cells from RA PB compared to control PB. In analyses of a second set of CpG candidates based on single‐nucleotide polymorphisms from a genome‐wide association study of RA, 1 significantly hypermethylated CpG in CD4+ memory T cells and 18 significant CpGs (6 hypomethylated, 12 hypermethylated) in CD4+ naive T cells were found. A prediction score based on the hypermethylated FLS candidates had an area under the curve of 0.73 for association with RA case status, which compared favorably to the association of RA with the HLA–DRB1 shared epitope risk allele and with a validated RA genetic risk score.

Conclusion

FLS‐representative DNA methylation signatures derived from the PB may prove to be valuable biomarkers for the risk of RA or for disease status.
Baricitinib, Methotrexate, or Combination in Patients With Rheumatoid Arthritis and No or Limited Prior Disease‐Modifying Antirheumatic Drug Treatment
Authors: Fleischmann Roy , Schiff Michael , van der Heijde Désirée , Ramos‐Remus Cesar , Spindler Alberto , Stanislav Marina , Zerbini Cristiano A. F. , Gurbuz Sirel , Dickson Christina , de Bono Stephanie , Schlichting Douglas , Beattie Scott , Kuo Wen‐Ling , Rooney Terence , Macias William , Takeuchi Tsutomu
Published: October 2016

Objective

We undertook this phase III study to evaluate baricitinib, an orally administered JAK‐1/JAK‐2 inhibitor, as monotherapy or combined with methotrexate (MTX) compared to MTX monotherapy in patients with active rheumatoid arthritis (RA) who had received no or minimal conventional synthetic disease‐modifying antirheumatic drugs (DMARDs) and who were naive to biologic DMARDs.

Methods

A total of 588 patients were randomized 4:3:4 to receive MTX monotherapy (once weekly), baricitinib monotherapy (4 mg once daily), or the combination of baricitinib and MTX for 52 weeks. The primary end point assessment was a noninferiority comparison of baricitinib monotherapy to MTX monotherapy based on the proportion of patients meeting the American College of Rheumatology 20% improvement criteria (achieving an ACR20 response) at week 24.

Results

The study met its primary objective. Moreover, baricitinib monotherapy was found to be superior to MTX monotherapy at week 24, with a higher ACR20 response rate (77% versus 62%; P ≤ 0.01). Similar results were observed for combination therapy. Compared to MTX monotherapy, significant improvements in disease activity and physical function were observed for both baricitinib groups as early as week 1. Radiographic progression was reduced in both baricitinib groups compared to MTX monotherapy; the difference was statistically significant for baricitinib plus MTX. The rates of serious adverse events (AEs) were similar across treatment groups, while rates of some treatment‐emergent AEs, including infections, were increased with baricitinib plus MTX. Three deaths were reported, all occurring in the MTX monotherapy group. Malignancies, including nonmelanoma skin cancer, were reported in 1 patient receiving MTX monotherapy, 1 receiving baricitinib monotherapy, and 4 receiving baricitinib plus MTX.

Conclusion

Baricitinib alone or in combination with MTX demonstrated superior efficacy with acceptable safety compared to MTX monotherapy as initial therapy for patients with active RA.
Selective Modification of Chitin and Chitosan: En Route to Tailored Oligosaccharides
Authors: Carvalho Luísa C. R. , Queda Fausto , Santos Cátia V. Almeida , Marques M. Manuel B.
Published: October 2016

Chitin and chitosan are attractive biopolymers with enormous structural possibilities for chemical modification, creating platforms for new chemical entities with a broad scope of applications, ranging from material science to medicine. During the last few years, incredible efforts have been dedicated to the regioselective modification of these biopolymers paving the way for improved properties and tailored activities. Herein, the most recent advances in chitin/chitosan regioselective modification, reaction conditions, selectivity, and the impact on its applications are highlighted. Moreover, the recent focus on chitooligosaccharides, their regioselective and chemoselective functionalization, as well as their role in biological studies, including molecular recognition with several biological targets are also covered.
Deep learning for finance: deep portfolios
Authors: Heaton J. B. , Polson N. G. , Witte J. H.
Published: October 2016

We explore the use of deep learning hierarchical models for problems in financial prediction and classification. Financial prediction problems – such as those presented in designing and pricing securities, constructing portfolios, and risk management – often involve large data sets with complex data interactions that currently are difficult or impossible to specify in a full economic model. Applying deep learning methods to these problems can produce more useful results than standard methods in finance. In particular, deep learning can detect and exploit interactions in the data that are, at least currently, invisible to any existing financial economic theory. Copyright © 2016 John Wiley & Sons, Ltd.
Bemessung von Gebäuden in Brettsperrholzbauweise unter Erdbebenbeanspruchung
Authors: Andreolli Mauro , Tomasi Roberto
Published: October 2016

Bei Brettsperrholz (BSP) handelt es sich um ein Massivholzprodukt, welches in Europa seit mehr als zehn Jahren erfolgreich hergestellt und verwendet wird. Die Vorteile in Bezug auf das Tragverhalten, einen konstruktionsbedingt schnelleren Bauablauf und zunehmende qualitative Anforderungen haben zu einer breiten Anwendung dieses Massivholzprodukts im Wohnungsbau geführt. In diesen Gebäuden erfolgt die Aussteifung gegenüber horizontal einwirkenden Kräften wie Wind und Erdbeben über die Wandscheiben der einzelnen Geschosse, wobei die auftretenden Kräfte (Schubfluss und abhebende Kräfte) mittels metallischen Verbindungsmitteln (Schubwinkel und Zuganker) in die Unterkonstruktion eingeleitet werden.

Der Einsatz von mechanischen Verbindungsmitteln wie Nägel und Schrauben in den Fugen (Wand–Wand und Wand–Decke) verleiht dem Gebäude ein in sich steifes Tragverhalten. In den folgenden Abschnitten wird das Grundkonzept für die Bemessung von BSP‐Gebäuden gegenüber Horizontallasten veranschaulicht. Insbesondere wird auf das Tragverhalten der Anschlusssysteme und dabei auf die jüngsten Forschungsprojekte, die im Bereich der theoretischen und experimentellen Untersuchungen an der Universität Trient durchgeführt wurden, eingegangen. Die praktische Anwendung der durchgeführten Forschungsarbeiten wurde durch die Entwicklung eines Software‐Tools für die Bemessung von mehrgeschossigen BSP‐Gebäuden ermöglicht.