bluuebunny/crossref_metadata_2025 huggingface dataset:
Thermo‐rheological and interfacial properties of polylactic acid/polyethylene glycol blends toward the melt electrospinning ability
Authors: Nazari Tayebe , Garmabi Hamid
Published: August 2016

The electrospinning ability of PLA/PEG system at the melt state was investigated through the viscoelastic parameters obtained from dynamic shear and extensional rheometers. PLA and PEG were melt‐blended at various composition ratios. Effect of PEG concentration on the PLA thermal behavior was studied by the differential scanning calorimetry (DSC). According to DSC and wide‐angle X‐ray diffraction, the PLA crystallinity increased and the crystalline structure became more completed (α‐crystal form) in the presence of PEG. Viscoelastic parameters such as zero‐shear viscosity and relaxation time as an indication of elasticity were obtained. The results revealed enhanced polymer chain mobility and disentanglement ought to plasticizing effect of PEG. The critical content of PEG about 20–30 wt % at which the solid–liquid phase separation occurred was in good agreement with the viscoelastic properties. Hence, more than 20% PEG the elasticity diminished and the melt strength became zero. The interfacial tension of the PLA and PEG estimated through the rheological and morphological parameters evidenced the good miscibility of PLA/PEG system at the melt electrospinnig temperature. While the high viscose samples (η0 > 1800 Pa/s) PLA and PLA/PEG (95/5) were not spinnable at the spinning temperature of 180 °C, blends containing 10–30% PEG were easily spun. The finest and continuous fiber mats were obtained by electrospinning of PLA/PEG (80/20) blend (df = 4.8 ± 0.8 μm). More than the critical concentration of PEG (Φ > 30%), lacking the elasticity suppressed the melt electro‐spinnability of PLA/PEG. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44120.
Reactive compatibilization of poly(methyl acrylate‐ran‐acrylonitrile)/poly(ethylene) blends through amine–anhydride coupling
Authors: Gill Amardeep , Marić Milan
Published: August 2016

Methyl acrylate/acrylonitrile copolymers (MA/AN) were reactively compatibilized as the dispersed phase into poly(ethylene) (PE) for potential hydrocarbon barrier materials. The MA/AN was made reactive by including p‐aminostyrene (PAS), yielding terpolymers (MA/AN/PAS) with pendant primary amine functionality (number average molecular weight
 = 65–133 kg mol−1, dispersity (Đ)=1.83–2.53, molar composition of PAS in copolymer FPAS = 0.03–0.14, molar composition of AN = FAN = 0.27–0.52). The non‐functional MA/AN and amino functional MA/AN/PAS were each melt blended into PE that was grafted with maleic anhydride (PE‐g‐MAnn) at 200 °C at 70:30 wt % PE‐g‐MAnn:co/terpolymer. After extrusion, the dispersed phase particle size (volume to surface area diameter,
) was coarse (12.6 μm) for the non‐reactive blend whereas it was much lower for the reactive blend (
= 1.2 μm). Coarsening after annealing at 150 °C was slow, but the domain sizes increased only slightly for both cases. The reactive blend was deemed sufficiently stable and thus was suitable as a candidate barrier material for further testing against olefins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44177.
Reactive compatibilization of poly(styrene‐ran‐acrylonitrile)/poly(ethylene) blends through the acid–epoxy reaction
Authors: Gill Amardeep , Hong Celestine , Gromadzki Daniel , Marić Milan
Published: August 2016

Two families of acid functional styrene/acrylonitrile copolymers (SAN) for application as dispersed phase barrier materials in poly(ethylene) (PE) were studied. One type is SAN made by nitroxide mediated polymerization (NMP), which was subsequently chain extended with a styrene/tert‐butyl acrylate (S/tBA) mixture to provide a block copolymer (number average molecular weight Mn = 36.6 kg mol−1 and dispersity Đ = 1.34, after which the tert‐butyl protecting groups were converted to acid groups (SAN‐b‐S/AA). The other acid functional SAN is made by conventional radical terpolymerization (SAN‐AA). SAN‐AA and SAN‐b‐S/AA were each melt blended with PE grafted with epoxy functional glycidyl methacrylate (PE‐GMA) at 160 °C in a twin screw extruder (70:30 wt % PE‐GMA:SAN co/terpolymer). The non‐reactive PE‐g‐GMA/SAN blend had a volume to surface area diameter
 = 3.0 μm while the reactive blends (via epoxy/acid coupling) (PE‐GMA/SAN‐b‐SAA and PE‐GMA/SAN‐AA) had
 = 1.7 μm and 1.1 μm, respectively. After thermal annealing, the non‐reactive blend coarsened dramatically while the reactive blends showed little signs of coarsening, suggesting that the acid/epoxy coupling was effective for morphological stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44178.
Quadratic stabilizability and H∞ control of linear discrete‐time stochastic uncertain systems
Authors: Jiang Xiushan , Tian Xuemin , Zhang Tianliang , Zhang Weihai
Published: August 2016

This paper considers quadratic stabilizability and H∞ feedback control for stochastic discrete‐time uncertain systems with state‐ and control‐dependent noise. Specifically, the uncertain parameters considered are norm‐bounded and external disturbance is an l2‐square summable stochastic process. Firstly, both quadratic stability and quadratic stabilization criteria are presented in the form of linear matrix inequalities (LMIs). Then we design the robust H∞ state and output feedback H∞ controllers such that the system with admissible uncertainties is not only quadratically internally stable but also robust H∞ controllable. Sufficient conditions for the existence of the desired robust H∞ controllers are obtained via LMIs. Finally, some examples are supplied to illustrate the effectiveness of our results.
Finite‐Time Sliding Mode Trajectory Tracking Control of Uncertain Mechanical Systems
Authors: Sun Liang , Zheng Zewei
Published: August 2016

The problem of finite‐time tracking control is studied for uncertain nonlinear mechanical systems. To achieve finite‐time convergence of tracking errors, a simple linear sliding surface based on polynomial reference trajectory is proposed to enable the trajectory tracking errors to converge to zero in a finite time, which is assigned arbitrarily in advance. The sliding mode control technique is employed in the development of the finite‐time controller to guarantee the excellent robustness of the closed‐loop system. The proposed sliding mode scheme eliminates the reaching phase problem, so that the closed‐loop system always holds the invariance property to parametric uncertainties and external disturbances. Lyapunov stability analysis is performed to show the global finite‐time convergence of the tracking errors. A numerical example of a rigid spacecraft attitude tracking problem demonstrates the effectiveness of the proposed controller.
RNA sequencing of transformed lymphoblastoid cells from siblings discordant for autism spectrum disorders reveals transcriptomic and functional alterations: Evidence for sex‐specific effects
Authors: Tylee Daniel S. , Espinoza Alfred J. , Hess Jonathan L. , Tahir Muhammad A. , McCoy Sarah Y. , Rim Joshua K. , Dhimal Totadri , Cohen Ori S. , Glatt Stephen J.
Published: August 2016

Genome‐wide expression studies of samples derived from individuals with autism spectrum disorder (ASD) and their unaffected siblings have been widely used to shed light on transcriptomic differences associated with this condition. Females have historically been under‐represented in ASD genomic studies. Emerging evidence from studies of structural genetic variants and peripheral biomarkers suggest that sex‐differences may exist in the biological correlates of ASD. Relatively few studies have explicitly examined whether sex‐differences exist in the transcriptomic signature of ASD. The present study quantified genome‐wide expression values by performing RNA sequencing on transformed lymphoblastoid cell lines and identified transcripts differentially expressed between same‐sex, proximal‐aged sibling pairs. We found that performing separate analyses for each sex improved our ability to detect ASD‐related transcriptomic differences; we observed a larger number of dysregulated genes within our smaller set of female samples (n = 12 sibling pairs), as compared with the set of male samples (n = 24 sibling pairs), with small, but statistically significant overlap between the sexes. Permutation‐based gene‐set analyses and weighted gene co‐expression network analyses also supported the idea that the transcriptomic signature of ASD may differ between males and females. We discuss our findings in the context of the relevant literature, underscoring the need for future ASD studies to explicitly account for differences between the sexes. Autism Res 2017, 10: 439–455. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Genetic modifications associated with ketogenic diet treatment in the BTBRT+Tf/J mouse model of autism spectrum disorder
Authors: Mychasiuk Richelle , Rho Jong M.
Published: August 2016

Background: Autism spectrum disorder (ASD) is a prevalent and heterogeneous neurodevelopmental disorder characterized by hallmark behavioral features. The spectrum of disorders that fall within the ASD umbrella encompass a distinct but overlapping symptom complex that likely results from an array of molecular and genetic aberrations rather than a single genetic mutation. The ketogenic diet (KD) is a high‐fat low‐carbohydrate anti‐seizure and neuroprotective diet that has demonstrated efficacy in the treatment of ASD‐like behaviors in animal and human studies. Methods: We investigated changes in mRNA and gene expression in the BTBR mouse model of ASD that may contribute to the behavioral phenotype. In addition, we sought to examine changes in gene expression following KD treatment in BTBR mice. Results: Despite significant behavioral abnormalities, expression changes in BTBR mice did not differ substantially from controls; only 33 genes were differentially expressed in the temporal cortex, and 48 in the hippocampus. Examination of these differentially expressed genes suggested deficits in the stress response and in neuronal signaling/communication. After treatment with the KD, both brain regions demonstrated improvements in ASD deficits associated with myelin formation and white matter development. Conclusions: Although our study supports many of the previously known impairments associated with ASD, such as excessive myelin formation and impaired GABAergic transmission, the RNAseq data and pathway analysis utilized here identified new therapeutic targets for analysis, such as Vitamin D pathways and cAMP signaling. Autism Res 2017, 10: 456–471. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Expression of cell cycle proteins in cortical neurons—Correlation with glutamate‐induced neurotoxicity
Authors: Negis Yesim , Karabay Arzu
Published: August 2016

Under physiological conditions, upon differentiation neurons become irreversibly post‐mitotic by down‐regulating cell cycle progression. However, recent studies have provided evidence that aberrant expression of cell cycle related proteins; especially cyclins, cyclin‐dependent kinases, and their inhibitors are accompanied by programmed cell death in neurons. This abnormal phenotype has been postulated to contribute to the pathophysiology of different neurodegenerative diseases. Glutamate is the most abundant and major excitatory neurotransmitter in the central nervous system but high concentrations are reported to be involved in the pathology of many neurodegenerative diseases. The mechanisms of glutamate neurotoxicity have been intensively investigated over the past decades but still remain not fully understood. In this study, we hypothesized that aberrant regulation of cell cycle proteins may be involved in glutamate‐induced neurotoxicity in primary cultures of rat cortical neurons. The results have shown that, glutamate treatment caused apoptosis by inducing active caspase‐3 and p53 expression. Together with this, an increase in cyclin D1 and Cdk4 protein levels, localization of cyclin D1 to nucleus, and a decrease in the cell cycle inhibitor p27 were observed. After glutamate treatment we also detected up‐regulation of protein kinase C‐α (PKC‐α) protein expression. Altogether, the data reported in this study show for the first time that glutamate in cortical neurons changes simultaneously the expression levels of a number of key cell cycle proteins and cell homeostasis regulators. © 2016 BioFactors, 42(4):358–367, 2016
CITA/NLRC5: A critical transcriptional regulator of MHC class I gene expression
Authors: Downs Isaac , Vijayan Saptha , Sidiq Tabasum , Kobayashi Koichi S.
Published: August 2016

Major histocompatibility complex (MHC) class I and class II molecules play essential roles in the development and activation of the human adaptive immune system. An NLR protein, CIITA (MHC class II transactivator) has been recognized as a master regulator of MHC class II gene expression, albeit knowledge about the regulatory mechanism of MHC class I gene expression had been limited. Recently identified MHC class I transactivator (CITA), or NLRC5, also belongs to the NLR protein family and constitutes a critical regulator for the transcriptional activation of MHC class I genes. In addition to MHC class I genes, CITA/NLRC5 induces the expression of β2‐microglobulin, TAP1 and LMP2, essential components of the MHC class I antigen presentation pathway. Therefore, CITA/NLRC5 and CIITA are transcriptional regulators that orchestrate the concerted expression of critical components in the MHC class I and class II pathways, respectively. © 2016 BioFactors, 42(4):349–357, 2016
Neferine prevents NF‐κB translocation and protects muscle cells from oxidative stress and apoptosis induced by hypoxia
Authors: Baskaran Rathinasamy , Poornima Paramasivan , Huang Chih Yang , Padma Viswanadha Vijaya
Published: August 2016

Neferine (Nef), a bisbenzylisoquinoline alkaloid from lotus seed embryo has a wide range of pharmacological activities. Possible molecular mechanism for the cytoprotective action of Nef during hypoxic stress has not been explored till now. Hence, this is an attempt to elucidate the molecular mechanism involved in the Nef mediated cytoprotection on hypoxia‐induced cell injury. Cytoprotective dose of Nef in muscle cells (Human rhabdomyosarcoma cells) exposed to hypoxia was determined by MTT assay. Nef at 500 nM offered better cytoprotection and was used for all the experiments. ROS, intracellular calcium accumulation and mitochondrial membrane (ΔψM) potential were measured using fluorescent probes. Further, we evaluated the effect Nef on hypoxia induced inflammatory and apoptotic responses by FACS and analyzing the expression patterns of NF‐κB, COX‐2, HIF‐1α, caspase‐3, caspase‐9, Bcl2, and Bax. The results of this study revealed that pretreatment of the cells with Nef significantly decreased the ΔψM and ROS in the cells subjected to hypoxia. Further, Nef inhibited NF‐κB there by inhibiting the expression of its downstream regulator COX‐2, while it induced the functional HIF‐1α expression. The results also indicate that Nef significantly inhibited the ROS dependent mitochondrial mediated apoptosis induced during hypoxia. The cytoprotection elicited by Nef in a model of hypoxia induced cell death involves both anti‐inflammatory and anti‐apoptotic response. These results suggest that Nef may be used as prophylactic agent against the hypoxic challenge. © 2016 BioFactors, 42(4):407–417, 2016
Quantification of mesembrine and mesembrenone in mouse plasma using UHPLC‐QToF‐MS: Application to a pharmacokinetic study
Authors: Manda Vamshi K. , Avula Bharathi , Ashfaq Mohammad K. , Abe Naohito , Khan Ikhlas A. , Khan Shabana I.
Published: August 2016

Sceletium tortuosum, is an indigenous herb of South Africa which is widely used as an herbal supplement in the treatment of anxiety and stress. Mesembrenone and mesembrine are the two main pharmacologically active alkaloids present in the extract. Despite the wide therapeutic applications of Sceletium extract, there are no reports of in vivo pharmacokinetic properties or analytical methods to quantify these two important alkaloids in plasma. Therefore, the current study aimed to develop and validate a simple and sensitive analytical method for simultaneous quantification of mesembrenone and mesembrine in mouse plasma. Ultra‐high‐performance liquid chromatography–mass spectrometry (UHPLC/QToF‐MS) was employed to achieve our objectives. The compounds were extracted using protein precipitation by methanol (100%) with quinine as an internal standard. The lower limit of quantification for both the compounds was 10 ng/mL. The extraction recovery was between 87 and 93% for both compounds with no matrix effects on the analysis. The accuracy was between 89.5 and 106% and precision was <12.6% for all quality control samples. This validated method was successfully applied to evaluate the i.v. plasma pharmacokinetics of mesembrine and mesembrenone in mouse. However, the oral bioavailability of these alkaloids was poor and the plasma levels were below the detection limits.
Exploitation of multiplayer interaction and development of virtual puppetry storytelling using gesture control and stereoscopic devices
Authors: Liang Hui , Chang Jian , Deng Shujie , Chen Can , Tong Ruofeng , Zhang Jian Jun
Published: August 2016

With the rapid development of human–computer interaction technologies, the new media generation demands novel learning experiences with natural interaction and immersive experience. Considering that digital storytelling is a powerful pedagogical tool for young children, in this paper, we design an immersive storytelling environment that allows multiple players to use naturally interactive hand gestures to manipulate virtual puppetry for assisting narration. A set of multimodal interaction techniques is presented for a hybrid user interface that integrates existing 3D visualization and interaction devices including head‐mounted displays and depth motion sensor. In this system, the young players could intuitively use hand gestures to manipulate virtual puppets to perform a story and interact with props in a virtual stereoscopic environment. We have conducted a user experiment with four young children for pedagogical evaluation, as well as system acceptability and interactivity evaluation by postgraduate students. The results show that our framework has great potential to stimulate learning abilities of young children through collaboration tasks. The stereoscopic head‐mounted display outperformed the traditional monoscopic display in a comparison between the two.
Effect of Hexafluorophosphate and Fluoroethylene Carbonate on Electrochemical Performance and the Surface Layer of Hard Carbon for Sodium‐Ion Batteries
Authors: Dahbi Mouad , Nakano Takeshi , Yabuuchi Naoaki , Fujimura Shun , Chihara Kuniko , Kubota Kei , Son Jin‐Young , Cui Yi‐Tao , Oji Hiroshi , Komaba Shinichi
Published: August 2016

Electrochemical sodium insertion for hard carbon is examined in a cyclic alkylene carbonate based solution containing a NaClO4 or NaPF6 salt with a fluoroethylene carbonate (FEC) additive to study electrolyte dependency for sodium‐ion batteries. NaPF6‐based electrolytes provide superior reversibility and cyclability of sodium insertion into hard carbon compared with NaClO4‐based ones. The FEC‐derived passivation film improves capacity retention because of better passivation with a thinner surface layer, as revealed by hard and soft X‐ray photoelectron spectroscopy (PES). The use of both the NaPF6 salt and FEC additive results in a synergetic effect on passivation for the hard‐carbon electrode, leading to enhanced cycle performance. Hard‐carbon electrodes with polyvinylidene difluoride binder in propylene carbonate based electrolytes containing NaPF6 and FEC demonstrate excellent capacity retention with a reversible capacity of about 250 mAh g−1. The difference in capacity retention for the electrolytes is expected to originate as a consequence of the difference in the surface interphase layer formed on the hard‐carbon electrodes. Surface analyses with PES and time‐of‐flight secondary ion mass spectrometry reveal differences in surface and passivation chemistry which depend on the salts, solvents, and FEC additives used for the hard‐carbon negative electrodes.
Electrocontrolled Swelling and Water Uptake of a Three‐Dimensional Conducting Polypyrrole Hydrogel
Authors: Antonio Jadielson L. , Höfler Lajos , Lindfors Tom , Córdoba de Torresi Susana I.
Published: August 2016

Polypyrrole 3D hydrosponges of tubular structure were synthesized and electrochemically characterized. The Fourier transform infrared attenuated total reflection (FTIR‐ATR) spectroscopy technique was employed to study the water uptake of the hydrosponges under different conditions. This technique presents several advantages over conventional swelling measurements due to its specificity that allows analyzing the kinetics of water uptake at the molecular level. In combination with mathematical modeling, FTIR‐ATR spectroscopy also enables the calculation of the water diffusion coefficients in the hydrogels. The experimental setup also allows electroswelling of the hydrosponges to be studied. The results presented herein are complementary to those obtained with the electrochemical quartz crystal microbalance with dissipation (EQCM‐D) technique and make it possible to determine the actual role played by water in the ionic exchange occurring in conducting polymers during their redox processes. Whereas EQCM‐D shows the whole mass change in the film provoked by injection/ejection of ions and solvent molecules, FTIR‐ATR spectroscopy follows water flux only, which thus allows separation of the solvent contribution.
Colloidal Surface Active Maghemite Nanoparticles for Biologically Safe CrVI Remediation: from Core‐Shell Nanostructures to Pilot Plant Development
Authors: Magro Massimiliano , Domeneghetti Stefania , Baratella Davide , Jakubec Petr , Salviulo Gabriella , Bonaiuto Emanuela , Venier Paola , Malina Ondřej , Tuček Jiří , Ranc Václav , Zoppellaro Giorgio , Zbořil Radek , Vianello Fabio
Published: August 2016

The present study is aimed at the exploration of achievable improvements for CrVI ex situ and in situ water remediation by using novel naked colloidal maghemite (γ‐Fe2O3) nanoparticles (surface active maghemite nanoparticles, SAMNs). The reliability of SAMNs for CrVI binding and removal was demonstrated, and SAMN@CrVI complex was characterized, as well as the covalent nature of the absorption was unequivocally proved. SAMNs were structurally and magnetically well conserved after CrVI binding. Thus, in consideration of their affinity for CrVI, SAMNs were exploited in a biological model system, mimicking a real in situ application. The assay evidenced a progressive reduction of revertant colonies of Salmonella typhimurium TA100 strain, as maghemite nanoparticles concentration increased, till the complete suppression of CrVI mutagen effect. Finally, an automatic modular pilot system for continuous magnetic removal and recovery of CrVI from water is proposed. SAMNs, thanks to their colloidal, binding, and catalytic properties, represent a promising tool as a reliable nanomaterial for water remediation by CrVI.
Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands
Authors: Hui Joseph K.‐H. , Kishida Hiroyuki , Ishiba Keita , Takemasu Kenta , Morikawa Masa‐aki , Kimizuka Nobuo
Published: August 2016

A new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.
Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS3O10]− in A[HS3O10] (A=Na, K, Rb)
Authors: Schindler Lisa Verena , Klüner Thorsten , Wickleder Mathias S.
Published: August 2016

The reaction of Na2SO4 and K2SO4 with fuming sulfuric acid (65 % SO3) yielded colorless extremely sensitive crystals of Na[HS3O10] (monoclinic; P21/n (No. 14); Z=4; a=707.36(2), b=1378.56(4), c=848.10(3) pm; β=94.817(1)°; V=824.09(4)⋅106 pm3) and K[HS3O10] (orthorhombic; Pccn (No. 56); Z=4; a=1057.16(3), b=807.81(2), c=897.57(2) pm; V=766.51(3)⋅106 pm3). The analogous rubidium compound Rb[HS3O10] (orthorhombic; Pnma (No. 62); Z=4; a=891.43(3), b=1095.34(4), c=839.37(3) pm; V=819.58(5)⋅106 pm3) originates from the reaction of Rb2CO3 and SO3. All of the different structures contain the hitherto unknown anion [HS3O10]− and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS3O10]−. The preparation of the [HS3O10]− anion can be seen as an important milestone on our way to the still elusive polysulfuric acids.
Characterization of Tetracyanopyridine (TCNPy)‐Based Magnets: V[TCNPy]2⋅z (CH2Cl2) (Tc=111 K) and V[TCNPy]3⋅z (CH2Cl2) (Tc=90 K)
Authors: Hao Jingjun , Davidson Royce A. , Kareis Christopher M. , Kavand Marzieh , van Schooten Kipp J. , Boehme Christoph , Wöß Eva , Knör Günther , Miller Joel S.
Published: August 2016

The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) with V(CO)6 in CH2Cl2 forms new organic‐based magnets of V[TCNPy]x⋅z (CH2Cl2) (x=2, 3) composition. Analysis of the IR spectra suggests that the TCNPy is reduced and coordinated to VII sites through the nitriles. V[TCNPy]x order as ferrimagnets with 111 and 90 K Tc values for V[TCNPy]2 and V[TCNPy]3, respectively. Their respective remanent magnetizations and coercive fields are 1260 and 250 emuOe mol−1 and 9 and 6 Oe at 5 K, and they exhibit some spin‐glass behavior.
Asymmetric Total Synthesis of (−)‐Erogorgiaene and Its C‐11 Epimer and Investigation of Their Antimycobacterial Activity
Authors: Incerti‐Pradillos Celia A. , Kabeshov Mikhail A. , O'Hora Paul S. , Shipilovskikh Sergei A. , Rubtsov Aleksandr E. , Drobkova Vera A. , Balandina Svetlana Yu. , Malkov Andrei V.
Published: August 2016

A short, nine‐step, highly enantioselective synthesis of (−)‐erogorgiaene and its C‐11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy‐Cope rearrangement and cationic cyclisation. (−)‐Erogorgiaene exhibited promising antitubercular activity against multidrug‐resistant strains of Mycobacterium tuberculosis.
Electrochemical Oxidative C−H/N−H Coupling between γ‐Lactams and Anilines
Authors: Gong Ming , Huang Jing‐Mei
Published: August 2016

A mild method for the direct C−H/N−H coupling between γ‐lactams and anilines through electrochemical oxidation has been developed. The protocol proceeded smoothly without metal catalysts at room temperature to afford γ‐substituted γ‐lactams in good yields. It has been revealed that the quasi‐divided cell which provided high current density on the anode was crucial for this reaction.
Mild Amide‐Cleavage Reaction Mediated by Electrophilic Benzylation
Authors: Yamada Kohei , Karuo Yukiko , Tsukada Yuichi , Kunishima Munetaka
Published: August 2016

An extremely mild method for amide‐cleavage by using the triazine‐based benzylating reagent 4‐(4,6‐diphenoxy‐1,3,5‐triazin‐2‐yl)‐4‐benzylmorpholinium trifluoromethanesulfonate (DPT‐BM), which spontaneously releases benzyl cation species when being dissolved at room temperature, has been developed. O‐Benzylation of the amide with DPT‐BM and the subsequent hydrolysis of the resulting intermediate benzyl imidate salt afford the corresponding amine and benzyl ester, which can be converted by hydrogenolysis into a carboxylic acid under neutral conditions. O‐Benzylation proceeds depending on both steric and electronic factors around the amide group. Thus, some amides have been selectively cleaved over other amides. Furthermore, intramolecular chemoselective cleavage of an amide group in the presence of an ester group was achieved. Such selective hydrolytic reactions cannot be performed with Meerwein reagents as well as under acidic or basic hydrolytic conditions.
Trace Determination and Pressure Estimation of Fluorine F2 Caused by Irradiation Damage in Minerals and Synthetic Fluorides
Authors: Celinski Vinicius R. , Ditter Michael , Kraus Florian , Fujara Franz , Schmedt auf der Günne Jörn
Published: August 2016

Irradiated alkali and earth alkali halides can form metal colloids and halogen molecules, which stay trapped inside the crystal. In this paper we provide 19F NMR spectroscopic evidence of trapped F2 fluids in heavy ion‐bombarded synthesized LiF crystals as well as in a variety of the mineral Villiaumite (NaF). This is the 2nd mineral in which F2 is unambiguously detected in nature. The trace quantification of the latter is in the order of magnitude of 10−6 mol g−1. Pressures and densities of the F2 fluids are estimated based on the theory of nuclear spin relaxation in dilute gases.
Changes in cytogenetics and molecular genetics in acute myeloid leukemia from childhood to adult age groups
Authors: Creutzig Ursula , Zimmermann Martin , Reinhardt Dirk , Rasche Mareike , von Neuhoff Christine , Alpermann Tamara , Dworzak Michael , Perglerová Karolína , Zemanova Zuzana , Tchinda Joelle , Bradtke Jutta , Thiede Christian , Haferlach Claudia
Published: August 2016

BACKGROUND

To obtain better insight into the biology of acute myeloid leukemia (AML) in various age groups, this study focused on the genetic changes occurring during a lifetime.

METHODS

This study analyzed the relation between age and genetics from birth to 100 years in 5564 patients with de novo AML diagnosed from 1998 to 2012 (1192 patients from nationwide pediatric studies [AML Berlin‐Frankfurt‐Münster studies 98 and 2004] and 4372 adults registered with the Munich Leukemia Laboratory).

RESULTS

The frequencies of cytogenetic subgroups were age‐dependent. Favorable subtypes (t(8;21), inv(16)/t(16;16), and t(15;17)) decreased in general from the pediatric age group (2 to < 18 years; 33%) to the oldest groups (<5% for > 70 years; P < .0001). Unfavorable cytogenetics (–7/del(7), –5/del(5q) or 5p, inv(3)/t(3;3), t(6;9), complex karyotype, 12p, 17p, and 11q23/mixed‐lineage leukemia aberrations, excluding t(9;11)) were frequent (42%) in infants (<2 years), had a low frequency in children and young adults (<22%), and increased in frequency up to 36% in patients older than 85 years (P = .01). This was even more significant for complex karyotypes (P ≤ .0001), which also showed a strong increase in the absolute age‐specific incidence with age. Interestingly, the frequency of 11q23 abnormalities decreased from infants to older patients. The proportion of clinically relevant molecular aberrations of CCAAT/enhancer binding protein α, nucleophosmin (NPM1), and NPM1/fms‐related tyrosine kinase 3–internal tandem duplication increased with age.

CONCLUSIONS

Altogether, with the exclusion of infants, a significant decrease in the proportion of favorable cytogenetic subtypes and an increase in unfavorable cytogenetics were observed with increasing age. These findings indicate different mechanisms for the pathogenesis of AML; these different mechanisms also suggest directions for etiological research and contribute to the more unfavorable prognosis with increasing age. Cancer 2016;122:3821–3830. © 2016 American Cancer Society.
Family‐based exome‐wide assessment of maternal genetic effects on susceptibility to childhood B‐cell acute lymphoblastic leukemia in hispanics
Authors: Archer Natalie P. , Perez‐Andreu Virginia , Scheurer Michael E. , Rabin Karen R. , Peckham‐Gregory Erin C. , Plon Sharon E. , Zabriskie Ryan C. , De Alarcon Pedro A. , Fernandez Karen S. , Najera Cesar R. , Yang Jun J. , Antillon‐Klussmann Federico , Lupo Philip J.
Published: August 2016

BACKGROUND

Children of Hispanic ancestry have a higher incidence of acute lymphoblastic leukemia (ALL) compared with other ethnic groups, but to the authors' knowledge, the genetic basis for these racial disparities remain incompletely understood. Genome‐wide association studies of childhood ALL to date have focused on inherited genetic effects; however, maternal genetic effects (the role of the maternal genotype on phenotype development in the offspring) also may play a role in ALL susceptibility.

METHODS

The authors conducted a family‐based exome‐wide association study of maternal genetic effects among Hispanics with childhood B‐cell ALL using the Illumina Infinium HumanExome BeadChip. A discovery cohort of 312 Guatemalan and Hispanic American families and an independent replication cohort of 152 Hispanic American families were used.

RESULTS

Three maternal single‐nucleotide polymorphisms (SNPs) approached the study threshold for significance after correction for multiple testing (P<1.0 × 10−6): MTL5 rs12365708 (testis expressed metallothionein‐like protein [tesmin]) (relative risk [RR], 2.62; 95% confidence interval [95% CI], 1.61‐4.27 [P = 1.8 × 10−5]); ALKBH1 rs6494 (AlkB homolog 1, histone H2A dioxygenase) (RR, 3.77; 95% CI, 1.84‐7.74 [P = 3.7 × 10−5]); and NEUROG3 rs4536103 (neurogenin 3) (RR, 1.75; 95% CI, 1.30‐2.37 [P = 1.2 × 10−4]). Although effect sizes were similar, these SNPs were not nominally significant in the replication cohort in the current study. In a meta‐analysis comprised of the discovery cohort and the replication cohort, these SNPs were still not found to be statistically significant after correction for multiple comparisons (rs12365708: pooled RR, 2.27 [95% CI, 1.48‐3.50], P = 1.99 × 10−4; rs6494: pooled RR, 2.31 [95% CI, 1.38‐3.85], P = .001; and rs4536103: pooled RR, 1.67 [95% CI, 1.29‐2.16] P = 9.23 × 10−5).

CONCLUSIONS

In what to the authors' knowledge is the first family‐based based exome‐wide association study to investigate maternal genotype effects associated with childhood ALL, the results did not implicate a strong role of maternal genotype on disease risk among Hispanics; however, 3 maternal SNPs were identified that may play a modest role in susceptibility. Cancer 2016;122:3697‐704. © 2016 American Cancer Society.
A novel prognostic model for osteosarcoma using circulating CXCL10 and FLT3LG
Authors: Flores Ricardo J. , Kelly Aaron J. , Li Yiting , Nakka Manjula , Barkauskas Donald A. , Krailo Mark , Wang Lisa L. , Perlaky Laszlo , Lau Ching C. , Hicks M. John , Man Tsz‐Kwong
Published: August 2016

BACKGROUND

Osteosarcoma (OS) is the most common malignant pediatric bone tumor. The identification of novel biomarkers for early prognostication will facilitate risk‐based stratification and therapy. This study investigated the significance of circulating cytokines/chemokines for predicting the prognosis at the initial diagnosis.

METHODS

Luminex assays were used to measure cytokine/chemokine concentrations in blood samples from a discovery cohort of OS patients from Texas Children's Hospital (n = 37) and an independent validation cohort obtained from the Children's Oncology Group (n = 233). After the validation of the biomarkers, a multivariate model was constructed to stratify the patients into risk groups.

RESULTS

The circulating concentrations of C‐X‐C motif chemokine ligand 10 (CXCL10), Fms‐related tyrosine kinase 3 ligand (FLT3LG), interferon γ (IFNG), and C‐C motif chemokine ligand 4 (CCL4) were significantly associated with overall survival in both cohorts. Among these candidates, CXCL10 and FLT3LG were independent of the existing prognostic factor, metastasis at diagnosis, and CCL4 further discriminated cancer cases from controls. CXCL10, FLT3LG, and the metastatic status at diagnosis were combined to develop a multivariate model that significantly stratified the patients into 4 distinct risk groups (P = 1.6 × 10−8). The survival analysis showed that the 5‐year overall survival rates for the low‐, intermediate‐, high‐, and very high–risk groups were 77%, 54%, 47%, and 10%, respectively, whereas the 5‐year event‐free survival rates were 64%, 47%, 27%, and 0%, respectively. Neither CXCL10 nor FLT3LG tumor expression was significantly associated with survival.

CONCLUSIONS

High circulating levels of CXCL10 and FLT3LG predicted worse survival for patients with OS. Because both CXCL10 and FL3LG axes are potentially targetable, further study may lead to novel risk‐based stratification and therapy for OS. Cancer 2017;144–154. © 2016 American Cancer Society.
Inclusion of Ethyl Acetoacetate Bearing 7‐Hydroxycoumarin Dye by β‐Cyclodextrin and its Cooperative Assembly with Mercury(II) Ions: Spectroscopic and Molecular Modeling Studies
Authors: Aliaga Margarita E. , Fierro Angélica , Uribe Iván , García‐Río Luis , Cañete Álvaro
Published: August 2016

The inclusion of the fluorescent organic dye, ethyl 3‐(7‐hydroxy‐2‐oxo‐2H‐chromen‐3‐yl)‐3‐oxopropanoate (1) by the host β‐cyclodextrin (β‐CD), and its response toward mercuric ions (Hg2+), was studied by UV/Vis, fluorescence, and 1H NMR spectroscopic analyses, mass spectrometry and molecular modeling studies. 1H NMR measurements together with molecular modeling studies for dye 1 demonstrate that it exhibits two tautomeric forms (keto and enol); however, when the dye is included into the β‐CD cavity, the enol form predominates. Moreover, by using spectroscopic and spectrometry techniques, a 1:1 stoichiometry was determined for the complexes formed between dye 1 (enol form) and β‐CD, with a binding constant (Kb1=1.8×104 m−1) and for the dye 1 (keto form)‐Hg2+ (Kb2=2.3×103 m−1). Interestingly, in the presence of 1–β‐CD complex and mercuric ions, a ternary supramolecular system (Hg–1–β‐CD complex) was established, with a 1:1:1 stoichiometry and a Kb3 value of 4.3×103 m−1, with the keto form of the dye being the only one present in this assembly. The three‐component system provides a starting point for the development of novel and directed supramolecular assemblies.
Spatially Heterogeneous Nature of Self‐Catalytic Reaction in Hetero‐Double Helix Formation of Helicene Oligomers
Authors: Kushida Yo , Sawato Tsukasa , Saito Nozomi , Shigeno Masanori , Satozono Hiroshi , Yamaguchi Masahiko
Published: August 2016

A 1:1 mixture of pseudoenantiomeric aminomethylenehelicene oligomers, (P)‐tetramer and (M)‐pentamer, in fluorobenzene show a self‐catalytic phenomenon in the formation of hetero‐double helices from random coils. This study visualizes the spatially heterogeneous nature of the self‐catalytic reaction in dilute solution. UV/Vis imaging analysis of the mixture at 70 °C, containing random coils, exhibits a homogeneous bright area. When the solution is cooled from 70 to 30 °C and held at that temperature, dark domains of approximately 1 mm in size appear, which move approximately at a rate of 1 mm min−1. The dark domains indicate that weaker UV/Vis absorption results from the formation of hetero‐double helices, which is supported by circular dichroism (CD) imaging experiments. Then a homogeneous mixture is regenerated upon heating to 55 °C, as shown by CD imaging. Under self‐catalytic conditions, a homogeneous solution spontaneously changed to a heterogeneous solution in the process of hetero‐double‐helix formation.
Masked N‐Heterocyclic Carbene‐Catalyzed Alkylation of Phenols with Organic Carbonates
Authors: Lui Matthew Y. , Yuen Alexander K. L. , Masters Anthony F. , Maschmeyer Thomas
Published: August 2016

An easily prepared masked N‐heterocyclic carbene, 1,3‐dimethylimidazolium‐2‐carboxylate (DMI‐CO2), was investigated as a “green” and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low‐toxicity and renewable alkylating agents, such as dimethyl‐ and diethyl carbonate, in a focused microwave reactor. DMI‐CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8‐diazabicycloundec‐7‐ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N‐heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo‐soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs.
Shear tests on external clay unit masonry walls / Monolithische Ziegelaußenwände unter Schubbeanspruchung
Authors: Kranzler Thomas
Published: August 2016

Monolithic external walls are commonly made of thermally insulated clay blocks that do not require any additional external thermal insulation such as an external thermally insulated composite system (ETICS). To reduce thermal bridge losses, the support length (a) of the slab on the wall is shorter than the wall thickness (t): a < t. The influence on the shear capacity of the respective masonry walls has not yet been tested and analysed. The paper presents the results of shear tests on monolithic external walls with a reduced support length under static‐cyclic and pseudo‐dynamic loading. The test results will be compared with the shear resistance calculated according to DIN EN 1996 with consideration of the German National Annex and the results according to the relevant Technical Approval.
Reliability of masonry walls subjected to in‐plane loading: A slip failure along head joints / Zuverlässigkeit von Mauerwerkswänden bei Belastung in der Ebene: Versagen entlang der Stoßfugenflucht
Authors: Asenov Miloš , Mojsilović Nebojša , Mićić Tatjana
Published: August 2016

Masonry structures are a sustainable, economical and traditionally widely used type of construction. However, current masonry design codes are rather conservative, so there is a growing need for revision i.e. calibration of safety factors to improve the allocation of material resources. In this paper, we investigate the probability of occurrence of slip failure along head joints (perpends) in masonry subjected to in‐plane loading. An appropriate limit state function is established and the masonry material properties and loads are defined as random variables in order to simulate likelihood of occurrence of a slip failure regime along the head joints. Furthermore, an example of masonry wall with probabilistic analysis outcomes using Monte Carlo simulation is presented and recommendations for further work are provided.
Rapid response to eating disorder treatment: A systematic review and meta‐analysis
Authors: Linardon Jake , Brennan Leah , de la Piedad Garcia Xochitl
Published: August 2016

Objective

This review aimed to (a) examine the effects of rapid response on behavioral, cognitive, and weight‐gain outcomes across the eating disorders, (b) determine whether diagnosis, treatment modality, the type of rapid response (changes in disordered eating cognitions or behaviors), or the type of behavioral outcome moderated this effect, and (c) identify factors that predict a rapid response.

Method

Thirty‐four articles met inclusion criteria from six databases. End of treatment and follow‐up outcomes were divided into three categories: Behavioral (binge eating/purging), cognitive (EDE global scores), and weight gain. Average weighted effect sizes(r) were calculated.

Results

Rapid response strongly predicted better end of treatment and follow‐up cognitive and behavioral outcomes. Moderator analyses showed that the effect size for rapid response on behavioral outcomes was larger when studies included both binge eating and purging (as opposed to just binge eating) as a behavioral outcome. Diagnosis, treatment modality, and the type of rapid response experienced did not moderate the relationship between early response and outcome. The evidence for weight gain was mixed. None of the baseline variables analyzed (eating disorder psychopathology, demographics, BMI, and depression scores) predicted a rapid response.

Discussion

As there is a solid evidence base supporting the prognostic importance of rapid response, the focus should shift toward identifying the within‐treatment mechanisms that predict a rapid response so that the effectiveness of eating disorder treatment can be improved. There is a need for future research to use theories of eating disorders as a guide to assess within‐treatment predictors of rapid response. © 2016 Wiley Periodicals, Inc. Int J Eat Disord 2016; 49:905–919
Exploring the Nature of the Nanocavity and Channels in Apoferritin and Apoferritin–Sodium Dodecyl Sulfate Complex Using an Enhanced Antenna Effect through the Encapsulation of EuIII–Tetracycline
Authors: Sanyal Sagarika , Sardar Pinki Saha , Roy Maitrayee Basu , Pratihar Swatilekha , Samanta Sugata , Mukherjee Moumita , Roy Pritam , Dasgupta Swagata , Ghosh Sanjib
Published: August 2016

The drug tetracycline hydrochloride (TC), which has cytotoxic and cytostatic effects on tumor cells, has been encapsulated within the nanocavity of apoferritin in the form of its EuIII complex (Eu3TC). The Eu3TC complex was encapsulated within apoferritin through disassembly followed by reassembly of the protein and exhibited significantly enhanced EuIII emission in comparison with that of free Eu3TC in aqueous buffer at pH 8. The steady‐state and transient measurement of the emission of each species in the ternary system suggest that the effective sensitization of EuIII emission may be ascribed to a comparatively rigid environment for the bound TC after encapsulation that promotes efficient energy transfer to the EuIII ions. Emission studies in D2O revealed that the microenvironment of the EuIII ion is shielded from O–H oscillators in the ternary system, and the extent of shielding is greater after the encapsulation of the complex within the apoferritin cavity. The rotational correlation time (θc) of bound TC and docking studies also support the contention that the TC is in a more buried environment after encapsulation within the apoferritin cavity. A competition study with sodium dodecyl sulfate (SDS) revealed that SDS does not interfere with the binding of TC to apoferritin. The biocompatible system consisting of Eu3TC encapsulated within the cavity of apoferritin may be used as an efficient targeted drug transporter, and the sensitization of the EuIII emission may also enable its use as a biosensor.
A Mixed Porphyrin–Schiff Base Dysprosium(III) Single‐Molecule Magnet
Authors: Ma Qi , Zeng Suyuan , Feng Xuenan , Cao Wei , Wang Hailong , Dou Jianmin , Jiang Jianzhuang
Published: August 2016

The mixed porphyrin–Schiff base potassium dysprosium(III) complex [K(TBPP)Dy(L)(CH3CN)2] [H2TBPP = 5,10,15,20‐tetrakis(4‐tert‐butylphenyl)porphyrin; H2L = N,N′‐bis(3‐methoxysalicylidene)benzene‐1,2‐diamine; 1] was isolated from the reaction between the metal‐free Schiff base ligand H2L and the half‐sandwich porphyrinato dysprosium compound [Dy(TBPP)(acac)] (Hacac = acetylacetone) in the presence of KOH. A sandwich‐type double‐decker structure has been unambiguously revealed by single‐crystal X‐ray diffraction analysis. Static and dynamic magnetic measurements disclosed the slow relaxation behavior of this new double‐decker compound and indicated its single‐molecule magnet (SMM) nature. Comparative studies on the magnetic properties of 1, the homoleptic bis[5,10,15,20‐tetrakis(4‐tert‐butylphenyl)porphyrinato]dysprosium double‐decker [DyH(TBPP)2] (2), and the bis(Schiff base)dysprosium double‐decker {[Dy[Zn(L)Cl]2(DMF)2]·Cl} (3, DMF = N,N‐dimethylformamide) indicate the effect of the ligand field (LF), through the deviation of the dysprosium coordination geometry from the ideal D4d form, on the SMM properties of 1–3 in addition to the effect of the charge distribution over the DyIII ion.