bluuebunny/crossref_metadata_2025 huggingface dataset:
A Stably Protonated Adenine Nucleotide with a Highly Shifted pKa Value Stabilizes the Tertiary Structure of a GTP‐Binding RNA Aptamer
Authors: Wolter Antje C. , Weickhmann A. Katharina , Nasiri Amir H. , Hantke Katharina , Ohlenschläger Oliver , Wunderlich Christoph H. , Kreutz Christoph , Duchardt‐Ferner Elke , Wöhnert Jens
Published: November 2016

RNA tertiary structure motifs are stabilized by a wide variety of hydrogen‐bonding interactions. Protonated A and C nucleotides are normally not considered to be suitable building blocks for such motifs since their pKa values are far from physiological pH. Here, we report the NMR solution structure of an in vitro selected GTP‐binding RNA aptamer bound to GTP with an intricate tertiary structure. It contains a novel kind of base quartet stabilized by a protonated A residue. Owing to its unique structural environment in the base quartet, the pKa value for the protonation of this A residue in the complex is shifted by more than 5 pH units compared to the pKa for A nucleotides in single‐stranded RNA. This is the largest pKa shift for an A residue in structured nucleic acids reported so far, and similar in size to the largest pKa shifts observed for amino acid side chains in proteins. Both RNA pre‐folding and ligand binding contribute to the pKa shift.
Synthesis and Investigation of Advanced Energetic Materials Based on Bispyrazolylmethanes
Authors: Fischer Dennis , Gottfried Jennifer L. , Klapötke Thomas M. , Karaghiosoff Konstantin , Stierstorfer Jörg , Witkowski Tomasz G.
Published: November 2016

Herein we present the preparation and characterization of three new bispyrazolyl‐based energetic compounds with great potential as explosive materials. The reaction of sodium 4‐amino‐3,5‐dinitropyrazolate (5) with dimethyl iodide yielded bis(4‐amino‐3,5‐dinitropyrazolyl)methane (6), which is a secondary explosive with high heat resistance (Tdec=310 °C). The oxidation of this compound afforded bis(3,4,5‐trinitropyrazolyl)methane (7), which is a combined nitrogen‐ and oxygen‐rich secondary explosive with very high theoretical and estimated experimental detonation performance (Vdet (theor)=9304 m s−1 versus Vdet(exp)=9910 m s−1) in the range of that of CL‐20. Also, the thermal stability (Tdec=205 °C) and sensitivities of 7 are auspicious. The reaction of 6 with in situ generated nitrous acid yielded the primary explosive bis(4‐diazo‐5‐nitro‐3‐oxopyrazolyl)methane (8), which showed superior properties to those of currently used diazodinitrophenol (DDNP).
Effect of addition of iron on morphology and catalytic activity of PdCu nanoalloy thin film as catalyst in Sonogashira coupling reaction
Authors: Hoseini S. Jafar , Aramesh Nahal , Bahrami Mehrangiz
Published: November 2016

Palladium‐supported catalysts are complex assemblies with a challenging preparation. Minor changes in their preparation conditions can affect the activity, selectivity and lifetime of these catalysts. PdCuFe nanoparticle (NP) thin films were supported on reduced graphene oxide (RGO) by the reduction of the organometallic complex [PdCl2‌(cod)] (cod = cis,cis‐1,5‐cyclooctadiene), and [Cu(acac)2] and [Fe(acac)3] (acac = acetylacetonate) complexes at a toluene–water interface. We have investigated the application of the liquid–liquid interface method for preparing ultrathin films of catalysts and have evaluated the catalytic activity of the prepared NPs for the Sonogashira coupling reaction in micelle media. Also, we have investigated the effect of the addition of iron on the morphology, size and catalytic activity of PdCu/RGO NPs. Our study shows that both of the prepared catalysts (PdCu/RGO and PdCuFe/RGO) are efficient and recoverable catalysts for the Sonogashira carbon–carbon coupling reaction. This method has advantages compared to other routes, such as short reaction times, high to excellent yields, facile and low‐cost method for the preparation of the catalysts, and easy separation and reusability of the catalysts.
Processing and mechanical properties of bio‐derived vinyl ester resin‐based composites
Authors: Shah Priyank N. , Dev Siddharth , Lee Yongwoo , Hansen Christopher J.
Published: November 2016

A “green” vinyl ester resin (GVER) is investigated for use in structural applications. The GVER was formulated using a monodisperse vinyl ester created via a novel synthetic route capable of using bio‐waste material from paper and biodiesel industries. The GVER was used either as a neat resin or as blended with a commercial vinyl ester resin. The processing viscosity and gel times are investigated. The GVER reaches a similar viscosity as the commercial resin with only half the styrene monomer content, thereby reducing the volatile organic compounds associated with manufacturing. Composites of the GVER matrix reinforced by carbon fabric were tested for their tensile and flexural properties. The mechanical performance of the GVER compares favorably with commercial resin and provide a route for composites manufacturing from sustainably sourced vinyl ester matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44642.
Self‐driven graft polymerization of vinyl monomers on poultry chicken feathers in the absence of initiator/catalyst
Authors: Patnam Padma L. , Ray Siddharth S. , Chatterjee Alok K. , Jain Suman L.
Published: November 2016

An efficient and simple method for graft copolymerization of powdered chicken feather (CF) with vinyl monomers without any free radical initiator is reported. Various vinyl monomers such as glycidyl methacrylate (GMA), styrene (S), and methyl methacrylate (MMA); (20–60 wt % with respect to CF) were successfully grafted to chicken feather (CF) by using sodium dodecyl sulfate (SDS, 0.086–0.5 mmol) in the absence of any catalyst or initiator. Most likely, the hydrophilicity, hydrophobicity, and complex forming properties of chicken feather keratin with surfactant molecules were responsible for efficient grafting of polymers on CF surface. The effect of polymerization conditions, such as monomer concentration, temperature, and time of reaction, on the grafting parameters such as monomer conversion, grafting efficiency, and molar grafting ratio were studied. The described method showed a good potential of using low cost, easily accessible poultry chicken feathers as grafting material and self catalyzing agent for graft copolymerization with vinyl monomers to produce low cost commodity plastic for various end uses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44645.
Superionic Conductivity in Hybrid of 3‐Hydroxypropanesulfonic Acid and Graphene Oxide
Authors: Wakata Kosuke , Karim Mohammad Razaul , Islam Md. Saidul , Ohtani Ryo , Nakamura Masaaki , Koinuma Michio , Hayami Shinya
Published: November 2016

Insertion of 3‐hydroxypropanesulfonicacid (HPS) in the graphene oxide (GO) interlayer results in high proton conductivity (10−2–10−1 S cm−1), owing to an improvement in oxygen content, interlayer distance and water absorbing capacity. This result indicates that hydroxyalkylsulfonicacids can be perfect guest molecules for improving the proton conductivity of carbon materials.
Early Diagnosis of Influenza Virus A Using Surface‐enhanced Raman Scattering‐based Lateral Flow Assay
Authors: Park Hyun Ji , Yang Sung Chul , Choo Jaebum
Published: December 2016

We report a surface‐enhanced Raman scattering (SERS)‐based lateral flow assay (LFA) kit for the rapid diagnosis of influenza virus A. Influenza virus A is highly infectious and causes acute respiratory diseases. Therefore, it is important to diagnose the virus early to prevent a pandemic and to provide appropriate treatment to the patient and vaccination of high‐risk individuals. Conventional diagnostic tests, including virus cell culture and real‐time polymerase chain reaction, take longer than 1 day to confirm the disease. In contrast, a commercially available rapid influenza diagnostic test can detect the infection within 30 min, but it is hard to confirm viral infection using only this test because of its low sensitivity. Therefore, the development of a rapid and simple test for the early diagnosis of influenza infection is urgently needed. To resolve these problems, we developed a SERS‐based LFA kit in which the gold nanoparticles in the commercial rapid kit were replaced with SERS‐active nano tags. It is possible to quantitatively detect the influenza virus A with high sensitivity by measuring the enhanced Raman signal of these SERS nano tags on the LFA strip. The limit of detection (LOD) using our proposed SERS‐based LFA kit was estimated to be 1.9 × 104 PFU/mL, which is approximately one order of magnitude more sensitive than the LOD determined from the colorimetric LFA kit.
Trusting me, trusting you: Evaluating three forms of trust on an information‐rich consumer review website
Authors: Duffy Andrew
Published: November 2016

When faced with a lack of information, consumers turn to trust to make a decision; but what happens to trust when individuals are confronted with the wealth of data on the Internet? This study evaluates three forms of trust in information‐abundant contexts: trust in the site, trust in the reviewers, and a postulated third form, trust‐in‐self. It looks at the roles of these three forms of trust in the information‐rich travel review website TripAdvisor. Two studies of site users, interviews (N = 30) and a survey (N = 237), found trust‐in‐self was highly influential in purchase decision making. Further, even with so much information, consumers sought more; the site is just one source they turn to, and they cross‐check among sources. The study concludes that any trust consumers have in TripAdvisor is not so much in the reviewers or the site, but in their own selves. Copyright © 2016 John Wiley & Sons, Ltd.
Influence of Preparation Method on Size Distribution of the Dispersed Phase of Primary Emulsions
Authors: Kulawik‐Pióro Agnieszka , Tal‐Figiel Barbara
Published: November 2016

The distribution and size of dispersed‐phase droplets impacts the most important parameters of fast disintegrating tablets including their bioavailability. The fact that after reconstruction the most emulsion droplets are bigger than those of primary emulsions led to a study of innovative emulsification techniques, like ultrasonic energy, mechanical mixing, and a combined technique of homogenization and ultrasonic energy. Taking the size of dispersed‐phase droplets as criterion of effectiveness for a procedure to create a primary emulsion, it can be concluded that the proposed emulsification methods of ultrasonic energy and combined technique are not suitable for water phases containing hydrocolloids such as gums.
Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence
Authors: Bosson Johann , Labrador Geraldine M. , Pascal Simon , Miannay François‐Alexandre , Yushchenko Oleksandr , Li Haidong , Bouffier Laurent , Sojic Neso , Tovar Roberto C. , Muller Gilles , Jacquemin Denis , Laurent Adèle D. , Le Guennic Boris , Vauthey Eric , Lacour Jérôme
Published: November 2016

The physicochemical properties of cationic dioxa (1), azaoxa (2), and diaza (3) [6]helicenes demonstrate a much higher chemical stability of the diaza adduct 3 (pKR+=20.4,
=−0.72 V) compared to its azaoxa 2 (pKR+=15.2,
=−0.45 V) and dioxa 1 (pKR+=8.8,
=−0.12 V) analogues. The fluorescence of these cationic chromophores is established, and ranges from the orange to the far‐red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31 % and 9.8 ns, respectively, at 658 nm) are observed. The triplet quantum yields and circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core is achieved through selective and orthogonal post‐functionalization reactions (12 examples, compounds 4–15). The electronic absorption is modulated from the orange to the far‐red spectral range (560–731 nm), and fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70 % (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first‐principles calculations.
Tuning the Energy Transfer Efficiency between Ce3+ and Ln3+ Ions (Ln=Tm, Sm, Tb, Dy) by Controlling the Crystal Phase of NaYF4 Nanocrystals
Authors: Adusumalli Venkata N. K. B. , Koppisetti Heramba V. S. R. M. , Ganguli Sagar , Sarkar Shyam , Mahalingam Venkataramanan
Published: December 2016

NaYF4 is a superior host matrix to study the luminescence properties of lanthanide (Ln3+) ions. Ln3+ ions in hexagonal‐phase NaYF4 (β‐phase) nanocrystals (NCs) exhibit strong luminescence via an upconversion process compared to cubic NaYF4 (α‐phase) NCs. However, in Ce3+/Ln3+‐doped NaYF4 NCs (Ln=Tm, Tb, Sm, Dy) the α‐phase NaYF4 NCs shows strong luminescence compared to their counterpart β‐phase NCs despite the latter being much larger in size. This is attributed to comparatively large overlap between Ce3+ ions emission band with excited energy levels of those Ln3+ ions in α‐phase compared to β‐phase NCs. This difference is attributed to different crystal‐field splitting of Ce3+ ions 4f–5d band in different crystal environments of the α‐phase (cubic crystal field environment) and β‐phase (trigonal prismatic with equatorials crystal field environment) NaYF4 NCs with respect to their barycenter. The enhanced luminescence from α‐phase NaYF4 NCs is advantageous as they are prepared at a relatively lower temperature and shorter reaction times compared to β‐NaYF4 NCs.
Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence
Authors: Bosson Johann , Labrador Geraldine M. , Pascal Simon , Miannay François‐Alexandre , Yushchenko Oleksandr , Li Haidong , Bouffier Laurent , Sojic Neso , Tovar Roberto C. , Muller Gilles , Jacquemin Denis , Laurent Adèle D. , Le Guennic Boris , Vauthey Eric , Lacour Jérôme
Published: November 2016

Invited for the cover of this issue is the group of Eric Vauthey and Jérôme Lacour. The image depicts a chiral cationic [6]helicene, which is a powerful dye and fluorophore emitting circularly polarized light in the red to far red region. Read the full text of the article at 10.1002/chem.201603591.
From Type I to Type II: Design, Synthesis, and Characterization of Potent Pyrazin‐2‐ones as DFG‐Out Inhibitors of PDGFRβ
Authors: Bethke Eugen , Pinchuk Boris , Renn Christian , Witt Lydia , Schlosser Joachim , Peifer Christian
Published: November 2016

Reversible protein kinase inhibitors that bind in the ATP cleft can be classified as type I or type II binders. Of these, type I inhibitors address the active form, whereas type II inhibitors typically lock the kinase in an inactive form. At the molecular level, the conformation of the flexible activation loop holding the key DFG motif controls access to the ATP site, thereby determining an active or inactive kinase state. Accordingly, type I and type II kinase inhibitors bind to so‐called DFG‐in or DFG‐out conformations, respectively. Based on our former study on highly selective platelet‐derived growth factor receptor β (PDGFRβ) pyrazin‐2‐one type I inhibitors, we expanded this scaffold toward the deep pocket, yielding the highly potent and effective type II inhibitor 5 (4‐[(4‐methylpiperazin‐1‐yl)methyl]‐N‐[3‐[[6‐oxo‐5‐(3,4,5‐trimethoxyphenyl)‐1H‐pyrazin‐3‐yl]methyl]phenyl]benzamide). In vitro characterization, including selectivity panel data from activity‐based assays (300 kinases) and affinity‐based assays (97 kinases) of these PDGFRβ type I (1; 5‐(4‐hydroxy‐3‐methoxy‐phenyl)‐3‐(3,4,5‐trimethoxyphenyl)‐1H‐pyrazin‐2‐one) and II (5) inhibitors showing the same pyrazin‐2‐one chemotype are compared. Implications are discussed regarding the data for selectivity and efficacy of type I and type II ligands.
SnS2 Nanoplates with Specific Facets Exposed for Enhanced Visible‐Light‐Driven Photocatalysis
Authors: Huang Erwei , Yao Xiaolong , Wang Weichao , Wu Guangjun , Guan Naijia , Li Landong
Published: November 2016

A facile hydrothermal strategy is developed for the synthesis of SnS2 nanoplates with specific exposed facets. The crystallographic structure and the specific exposed facets of as‐prepared SnS2 are confirmed by X‐ray diffraction, Raman spectroscopy and TEM analysis, and the surface electronic state and the chemical composition of samples are investigated by X‐ray photoelectron spectroscopy (XPS). The band gaps of SnS2 nanoplates are directly measured from UV/Vis absorption spectra, and their detailed band alignments are determined by Mott–Schottky plots and ultraviolet photoelectron spectroscopy (UPS) analysis, which are well supported by DFT calculations. Significant transient photocurrent responses under visible‐light irradiation from photoelectrochemical analysis reveal that SnS2 samples are active and stable visible‐light‐driven photocatalysts and that SnS2 nanoplates dominated by {101} exposed facets should be better photocatalysts than those dominated by {100} exposed facets. The photocatalytic activities of SnS2 nanoplates are examined in two typical reactions, that is, rhodamine B (RhB) degradation and hydrogen production from water splitting. As expected, SnS2 nanoplates dominated by {101} exposed facets exhibit distinctly higher activity than those dominated by {100} exposed facets in the photocatalytic RhB degradation. For hydrogen production from water splitting, SnS2 nanoplates dominated by {101} exposed facets exhibit significant photocatalytic activity resulting from their suitable band edges to realize the photocatalytic redox reaction, in great contrast to the inactive SnS2 nanoplates dominated by {100} exposed facets.
The neurobiological causes and effects of alloparenting
Authors: Kenkel William M. , Perkeybile Allison M. , Carter C. Sue
Published: November 2016

Alloparenting, defined as care provided by individuals other than parents, is a universal behavior among humans that has shaped our evolutionary history and remains important in contemporary society. Dysfunctions in alloparenting can have serious and sometimes fatal consequences for vulnerable infants and children. In spite of the importance of alloparenting, they still have much to learn regarding the underlying neurobiological systems governing its expression. Here, they review how a lack of alloparental behavior among traditional laboratory species has led to a blind spot in our understanding of this critical facet of human social behavior and the relevant neurobiology. Based on what is known, they draw from model systems ranging from voles to meerkats to primates to describe a conserved set of neuroendocrine mechanisms supporting the expression of alloparental care. In this review we describe the neurobiological and behavioral prerequisites, ontogeny, and consequences of alloparental care. Lastly, they identified several outstanding topics in the area of alloparental care that deserve further research efforts to better advance human health and wellbeing. © 2016 Wiley Periodicals, Inc. Develop Neurobiol 77: 214–232, 2017
Corporate Strategies in Environmental Governance: Marine harvest and regulatory change for sustainable aquaculture
Authors: Vormedal Irja
Published: December 2016

Focusing on Marine Harvest ASA, the world's largest salmon producer, this article examines the role of corporations in promoting sustainable aquaculture and regulation, exploring why a leading multinational may choose to adopt and implement a proactive sustainability strategy. It develops a neo‐pluralist model for conceptualizing drivers behind proactive strategy formation, and finds that a company‐specific combination of simple and mixed motives linking profit‐maximization and risk calculations to a longer‐term normative sustainability agenda can explain why corporations become entrepreneurs for sustainability. It concludes with some reflections on implications of the findings for understanding business in environmental governance more broadly. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Electronic Description of the Photophysics of Homo‐ and Heterodinuclear Cyclometallated Iridium and Rhodium Complexes
Authors: Seth Sourav Kanti , Mandal Soumik , Srikanth K. , Purkayastha Pradipta , Gupta Parna
Published: November 2016

Photophysical properties of homodinuclear complexes 1 (Ir), 2 (Rh) and heterodinuclear complex 3 (Ir–Rh) have been discussed in solution and in the solid state with the help of quantum chemical calculations by combined DFT‐TDDFT methods. Quantum calculations on these three complexes indicate the participation of metal‐to‐ligand and ligand‐to‐ligand charge transfers to the lowest energy absorptions, and electron transitions from the cyclometallating ligand to the ancillary ligand. The emission behaviour in the solution and solid state confirm the participation of the triplet state as obtained from quantum chemical calculations. It is also noted that the emission behaviour in the mixed‐metal complex is controlled by the iridium metal centre. The ground state electronic interactions between the metal centres studied by electrochemistry are weak interactions, however, energy transfer in the excited state is facile across the bridge.
Synthesis and Properties of Large Polycyclic Aromatic Hydrocarbons with Planar and Non‐Planar Structural Motifs
Authors: Rajeshkumar Venkatachalam , Courté Marc , Fichou Denis , Stuparu Mihaiela C.
Published: November 2016

Implementation of non‐planar aromatic motifs in the molecular design of π‐conjugated materials represents a paradigm shift that is interesting from a fundamental research viewpoint but remains largely underdeveloped. To further facilitate this cause, we report on the synthesis and properties of two large polycyclic aromatic compounds (38 carbon atoms). In one compound the planar π‐system pyrene is linked to bowl‐shaped hydrocarbon corannulene through a C=C bond, which is referred to as “corannulene–vinylpyrene”. Photochemical treatment of this compound results in annulation of both aromatic nuclei and formation of the other large fused structure with ten six‐membered aromatic rings, referred to as “corannulene–benzopyrene”. Photophysical and electrochemical studies reveal that the properties of these two structurally related hybrid materials arise from an extended π‐conjugation between the planar and non‐planar motifs and varies depending upon their molecular structure.
An Expedient Synthesis of Carbazoles through Potassium tert‐Butoxide‐Promoted Intramolecular Direct C–H Bond Arylation
Authors: Lin Songbo , He Xingrui , Meng Jinpeng , Gu Haining , Zhang Peizhi , Wu Jun
Published: November 2016

Transition‐metal‐free access to carbazoles was achieved through base‐mediated intramolecular C–C bond formation. Reactions of N‐substituted o‐halodiarylamines with potassium tert‐butoxide in the presence of ethylene glycol or 1,10‐phenanthroline provided carbazoles in moderate to excellent yields. This transformation may proceed through a radical pathway according to a control experiment with a radical scavenger.
An in situ toxicity identification and evaluation water analysis system: Laboratory validation
Authors: Steigmeyer August J. , Zhang Jiamin , Daley Jennifer M. , Zhang Xiaowei , Burton G. Allen
Published: November 2016

It is difficult to assess the toxicity of a single stressor and establish a strong stressor–causality link when multiple stressors coexist. Toxicity identification evaluation (TIE) methodology uses a series of chemical and physical manipulations to fractionate compounds within a matrix and systematically identify potential toxicants. The current US Environmental Protection Agency application of TIE can provide valuable information but often lacks ecological realism and is subject to laboratory-related artifacts. An in situ TIE device (iTIED) was designed to assess the sources of toxicity in aquatic ecosystems. For this laboratory validation, each unit was equipped with a sorbent resin chamber, an organism exposure chamber, a water collection container, and a peristaltic pump. Chemical analyses of water processed by each iTIED unit were compared with both lethal and sublethal molecular responses of the organisms. The compound removal effectiveness of different sorbent resins was also compared. In addition to successfully fractionating diverse chemical mixtures, the iTIED demonstrated a potential for early detection of molecular biomarkers, which could identify chronic toxicity that may go unnoticed in traditional TIE assays. Utilizing this novel in situ system will reduce the uncertainty associated with laboratory-based simulations and aid management efforts in targeting compounds that pose the greatest threat. Environ Toxicol Chem 2017;36:1636–1643. © 2016 SETAC
Multiple linear combination (MLC) regression tests for common variants adapted to linkage disequilibrium structure
Authors: Yoo Yun Joo , Sun Lei , Poirier Julia G. , Paterson Andrew D. , Bull Shelley B.
Published: November 2016

By jointly analyzing multiple variants within a gene, instead of one at a time, gene‐based multiple regression can improve power, robustness, and interpretation in genetic association analysis. We investigate multiple linear combination (MLC) test statistics for analysis of common variants under realistic trait models with linkage disequilibrium (LD) based on HapMap Asian haplotypes. MLC is a directional test that exploits LD structure in a gene to construct clusters of closely correlated variants recoded such that the majority of pairwise correlations are positive. It combines variant effects within the same cluster linearly, and aggregates cluster‐specific effects in a quadratic sum of squares and cross‐products, producing a test statistic with reduced degrees of freedom (df) equal to the number of clusters. By simulation studies of 1000 genes from across the genome, we demonstrate that MLC is a well‐powered and robust choice among existing methods across a broad range of gene structures. Compared to minimum P‐value, variance‐component, and principal‐component methods, the mean power of MLC is never much lower than that of other methods, and can be higher, particularly with multiple causal variants. Moreover, the variation in gene‐specific MLC test size and power across 1000 genes is less than that of other methods, suggesting it is a complementary approach for discovery in genome‐wide analysis. The cluster construction of the MLC test statistics helps reveal within‐gene LD structure, allowing interpretation of clustered variants as haplotypic effects, while multiple regression helps to distinguish direct and indirect associations.
Physiologically based pharmacokinetic model for ethyl tertiary‐butyl ether and tertiary‐butyl alcohol in rats: Contribution of binding to α2u–globulin in male rats and high‐exposure nonlinear kinetics to toxicity and cancer outcomes
Authors: Borghoff Susan J. , Ring Caroline , Banton Marcy I. , Leavens Teresa L.
Published: November 2016

In cancer bioassays, inhalation, but not drinking water exposure to ethyl tertiary‐butyl ether (ETBE), caused liver tumors in male rats, while tertiary‐butyl alcohol (TBA), an ETBE metabolite, caused kidney tumors in male rats following exposure via drinking water. To understand the contribution of ETBE and TBA kinetics under varying exposure scenarios to these tumor responses, a physiologically based pharmacokinetic model was developed based on a previously published model for methyl tertiary‐butyl ether, a structurally similar chemical, and verified against the literature and study report data. The model included ETBE and TBA binding to the male rat‐specific protein α2u–globulin, which plays a role in the ETBE and TBA kidney response observed in male rats. Metabolism of ETBE and TBA was described as a single, saturable pathway in the liver. The model predicted similar kidney AUC0–∞ for TBA for various exposure scenarios from ETBE and TBA cancer bioassays, supporting a male‐rat‐specific mode of action for TBA‐induced kidney tumors. The model also predicted nonlinear kinetics at ETBE inhalation exposure concentrations above ~2000 ppm, based on blood AUC0–∞ for ETBE and TBA. The shift from linear to nonlinear kinetics at exposure concentrations below the concentration associated with liver tumors in rats (5000 ppm) suggests the mode of action for liver tumors operates under nonlinear kinetics following chronic exposure and is not relevant for assessing human risk. Copyright © 2016 The Authors Journal of Applied Toxicology Published by John Wiley & Sons Ltd
Cellular response of osteoblasts to low modulus Ti‐24Nb‐4Zr‐8Sn alloy mesh structure
Authors: Nune K. C. , Misra R. D. K. , Li S. J. , Hao Y. L. , Yang R.
Published: November 2016

Titanium alloys (Ti‐6Al‐4V and Ti‐6Al‐7Nb) are widely used for implants, which are characterized by high elastic modulus (∼110 GPa) with (α + β) structure and that may induce undesirable stress shielding effect and immune responses associated with the presence of toxic elements. In this regard, we have combined the attributes of a new alloy design and the concept of additive manufacturing to fabricate 3D scaffolds with an interconnected porous structure. The new alloy is a β‐type Ti‐24Nb‐4Zr‐8Sn (Ti2448) alloy with significantly reduced modulus. In the present study, we explore the biological response of electron beam melted low modulus Ti2448 alloy porous mesh structure through the elucidation of bioactivity and osteoblast functions. The cellular activity was explored in terms of cell‐to‐cell communication involving proliferation, spreading, synthesis of extracellular and intracellular proteins, differentiation, and mineralization. The formation of fine apatite‐like crystals on the surface during immersion test in simulated body fluid confirmed the bioactivity of the scaffold surface, which provided the favorable osteogenic microenvironment for cell‐material interaction. The combination of unique surface chemistry and interconnected porous architecture provided the desired pathway for supply of nutrients and oxygen to cells and a favorable osteogenic micro‐environment for incorporation (on‐growth and in‐growth) of osteoblasts. The proliferation and differentiation of pre‐osteoblasts and their ability to form a well mineralized bone‐like extracellular matrix (ECM) by secreting bone markers (ALP, calcium, etc.) over the struts of the scaffold point toward the determining role of unique surface chemistry and 3D architecture of the Ti2448 alloy mesh structure in modulating osteoblasts functions. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 859–870, 2017.
Popdc1/Bves Functions in the Preservation of Cardiomyocyte Viability While Affecting Rac1 Activity and Bnip3 Expression
Authors: Kliminski Vitaly , Uziel Orit , Kessler‐Icekson Gania
Published: November 2016

The Popeye domain containing1, also called Bves (Popdc1/Bves), is a transmembrane protein that functions in muscle regeneration, heart rate regulation, hypoxia tolerance, and ischemia preconditioning. The expression of Popdc1/Bves is elevated in cardiomyocytes maintained in serum free defined medium. We hypothesized that Popdc1/Bves is important for cardiomyocyte survival under the stress of serum deprivation and investigated the mechanisms involved. A deficit in Popdc1/Bves, achieved by siRNA‐mediated gene silencing, results in cardiomyocyte injury and death, upregulation of the pro‐apoptotic protein Bcl‐2/adenovirus E1B 19‐kDa interacting protein3 (Bnip3), as well as reduction in Rac1‐GTPase activity and in Akt phosphorylation. Combined Popdc1/Bves and Bnip3 silencing attenuated cell injury and prevented Bnip3 upregulation induced by the silencing of Popdc1/Bves alone. Chromatin immunoprecipitation indicated an increased binding of the transcription factor FoxO3 to the Bnip3 promoter although augmentation of FoxO3 in the nuclei was not detected. By contrast, the transcription factor NFκB was excluded from the nuclei of Popdc1/Bves deficient cardiomyocytes and exhibited decreased binding to the Bnip3 promoter. The data indicates that Popdc1/Bves plays a role in the preservation of cardiomyocyte viability under serum deficiency through the alteration of Rac1 activity and the regulation of Bnip3 expression by FoxO3 and NFκB transcription factors pointing to Popdc1/Bves as a potential target to enhance heart protection. J. Cell. Biochem. 118: 1505–1517, 2017. © 2016 Wiley Periodicals, Inc.
Supernatants of Adipocytes From Obese Versus Normal Weight Women and Breast Cancer Cells: In Vitro Impact on Angiogenesis
Authors: Bougaret Lauriane , Delort Laetitia , Billard Hermine , Lequeux Charlotte , Goncalves‐Mendes Nicolas , Mojallal Ali , Damour Odile , Vasson Marie‐Paule , Caldefie‐Chezet Florence
Published: November 2016

Breast cancer is correlated with a higher risk of metastasis in obese postmenopausal women. Adipokines, whose plasma concentrations are modulated in obese subjects and adipocytes surround mammary cells, suggesting that adipocyte secretome affect mammary tumorogenesis. We hypothesize that mature adipocyte secretions from obese women conditioned or not by breast neoplasic cells, increase changes on the angiogenesis stages. Supernatants of human mature adipocytes, differentiated from stem cells of either adipose tissue of normal weight (MA20) or obese (MA30) women or obtained from co‐cultures between MA20 and MA30 and breast cancer cell line MCF‐7, were collected. The impact of these supernatants was investigated on proliferation, migration, and tube formation by endothelial cells (HUVEC). MA20 and MA30 showed a preservation of their “metabolic memory” (increase of Leptin, ObR, VEGF, CYP19A1, and a decrease of Adiponectin expression in MA30 compared to MA20). Supernatants from obese‐adipocytes increased HUVEC proliferation, migration, and sprouting like with supernatants obtained from co‐cultures of MA/MCF‐7 regardless the women's BMI. Additional analyses such as the use of neutralizing antibodies, analysis of supernatants (Milliplex®) and variations in gene expression (qRT‐PCR), strongly suggest an implication of IL‐6, or a synergistic action among adipokines, probably associated with that of VEGF or IL‐6. As a conclusion, supernatants from co‐cultures of MA30 and MCF‐7 cells increase proliferation, migration, and sprouting of HUVEC cells. These results provide insights into the interaction between adipocytes and epithelial cancer cells, particularly in case of obesity. The identification of synergistic action of adipokines would therefore be a great interest in developing preventive strategies. J. Cell. Physiol. 232: 1808–1816, 2017. © 2016 Wiley Periodicals, Inc.
Simultaneous determination of thermodynamic and kinetic parameters of aminopolycarbonate complexes of cobalt(II) and nickel(II) based on isothermal titration calorimetry data
Authors: Tesmar Aleksandra , Wyrzykowski Dariusz , Muñoz Eva , Pilarski Bogusław , Pranczk Joanna , Jacewicz Dagmara , Chmurzyński Lech
Published: November 2016

The influence of the different side chain residues on the thermodynamic and kinetic parameters for complexation reactions of the Co2+ and Ni2+ ions has been investigated by using the isothermal titration calorimetry (ITC) technique supported by potentiometric titration data. The study was concerned with the 2 common tripodal aminocarboxylate ligands, namely, nitrilotriacetic acid and N‐(2‐hydroxyethyl) iminodiacetic acid. Calorimetric measurements (ITC) were run in the 2‐(N‐morpholino)ethanesulfonic acid hydrate (2‐(N‐morpholino) ethanesulfonic acid), piperazine‐N,N′‐bis(2‐ethanesulfonic acid), and dimethylarsenic acid buffers (0.1 mol L−1, pH 6) at 298.15 K. The quantification of the metal‐buffer interactions and their incorporation into the ITC data analysis enabled to obtain the pH‐independent and buffer‐independent thermodynamic parameters (K, ΔG, ΔH, and ΔS) for the reactions under study. Furthermore, the kinITC method was applied to obtain kinetic information on complexation reactions from the ITC data. Correlations, based on kinetic and thermodynamic data, between the kinetics of formation of Co2+ and Ni2+ complexes and their thermodynamic stabilities are discussed.
New biosourced chiral molecularly imprinted polymer: Synthesis, characterization, and evaluation of the recognition capacity of methyltestosterone
Authors: Saadaoui Asma , Sanglar Corinne , Medimagh Raouf , Bonhomme Anne , Baudot Robert , Chatti Saber , Marque Sylvain , Prim Damien , Zina Mongia Saïd , Casabianca Herve
Published: November 2016

New biosourced chiral cross‐linkers were reported for the first time in the synthesis of methyltestosterone (MT) chiral molecularly imprinted polymers (cMIPs). Isosorbide and isomannide, known as 1,4:3,6‐dianhydrohexitols, were selected as starting diols. The cMIPs were synthesized following a noncovalent approach via thermal radical polymerization and monitored by Raman spectroscopy. These cross‐linkers were fully characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and high‐resolution mass spectrometry. The cross‐polarization magic angle spinning 13C NMR, Fourier transform infrared spectroscopy, scanning electron microscopy, and specific surface areas following the Brunauer‐Emmett‐Teller (BET) method were used to characterize the cMIPs. The effect of stereochemistry of cross‐linkers on the reactivity of polymerization, morphology, and adsorption‐recognition properties of the MIP was evaluated. The results showed that the cMIP exhibited an obvious improvement in terms of rebinding capacity for MT as compared with the nonimprinted polymer (NIP).

The highest binding capacity was observed for cMIP‐Is (27.298 mg g−1) for high concentrations (500 mg L−1). However, the isomannide homologue cMIP‐Im showed higher recovery—up to 65% and capacity for low concentrations (15 mg L−1). The experimental data were properly fitted by the Freundlich adsorption isothermal model.
Homogenized monthly upper‐air temperature data set for Australia
Authors: Jovanovic Branislava , Smalley Robert , Timbal Bertrand , Siems Steven
Published: November 2016

We present a homogenized, monthly, upper‐air temperature data set comprising 22 stations across the Australian continent, as well as five Australian remote island sites. The data set is based on 2300 UTC radiosonde soundings, with most records starting in 1958. The data are mostly complete since that time, with missing data more frequent at higher levels. The quality control process involved the examination of station metadata and an objective statistical test to detect discontinuities in the data, for which monthly temperature series were adjusted. Homogenized temperature data were analysed at standard levels. The all‐Australian annual mean temperature shows statistically significant trends over the 1958–2011 period, larger than the trends in surface temperature. Over this period, the annual 850 and 700 hPa mean temperatures show positive trends of 0.21 and 0.16 °C decade−1, respectively, more than the surface temperature which shows positive trend of 0.12 °C decade−1. Mid‐troposphere (the 500, 400 and 300 hPa levels) also shows positive trends of 0.13, 0.15 and 0.20 °C decade−1, respectively. Trends are small and of reverse sign at levels that intercept the tropopause: +0.08 °C decade−1 at 200 hPa and −0.14 °C decade−1 at 150 hPa. In the lower stratosphere (at 100 hPa), temperature trend is strongly negative, −0.39 °C decade−1. A similar vertical structure in the trends was found for the remote islands. The homogenized upper‐air radiosonde records for the Australian region are an independent confirmation of the expected physical response to increased atmospheric greenhouse gas concentrations: (1) a general warming in the troposphere, (2) a cooling in the lower stratosphere and (3) a faster warming of the troposphere than the surface.
Intercomparison of projected changes in climate extremes for South Korea: application of trend preserving statistical downscaling methods to the CMIP5 ensemble
Authors: Eum Hyung‐Il , Cannon Alex J.
Published: November 2016

Global climate models (GCMs) provide the fundamental information used to assess potential impacts of future climate change. However, the mismatch in spatial resolution between GCMs and the requirements of regional applications has impeded the use of GCM projections for impact studies at a regional scale. This study applied statistical post‐processing methods that preserve long‐term temporal trends, bias‐correction/spatial disaggregation with detrended quantile mapping (SDDQM) and BCSD with quantile delta mapping (SDQDM), to downscale 20 CMIP5 GCM climate projections for daily precipitation, minimum temperature, and maximum temperature over South Korea. Using the downscaled CMIP5 climate projections, we investigated absolute changes in extreme indices between the reference and three 30‐year future periods. In addition, the biases in change signals from GCM projections for different statistical downscaling methods were compared to evaluate how well long‐term trends in indices are preserved. The results showed that the statistical downscaling methods significantly improved the skill in reproducing extreme indices. For temperature‐related extreme indices, we found strong significant trends while trends for precipitation‐related indices varied depending on the index and climate projection horizon. Specifically, more frequent, longer duration, and more intense hot extremes may occur under the CMIP5 climate projections, while corresponding decreases may occur for extreme cold indices. Prominent upward trends are found in extreme precipitation events. Regarding analysis of the bias in change signals, SDQDM, which explicitly preserves changes in all quantiles of the underlying variables, better preserved long‐term trends in extreme indices simulated by GCMs.
Applying the National Inpatient Medication Chart audit to electronic medication management systems: what does it tell us?
Authors: McLain Sarah E. , Pogue Tristen L. , Richardson Katrina L. , Westcoast Peter , Gilbert Alice V. , Heywood Maureen J. , Welch Susan A. , Keily Joanna V. , Patel Bhavini K.
Published: November 2016

The Australian Commission on Safety and Quality in Health Care (ACSQHC) coordinates nation‐wide audits of the National Inpatient Medication Chart (NIMC). Electronic Medication Management Systems (eMMS) are beginning to replace NIMCs in Australian hospitals. This article describes the NIMC audit experience in two Australian tertiary hospitals that have established eMMS. Medication charts at both hospitals were audited using the ACSQHC‐provided audit tools (2012 Version). At both hospitals, eMMS charts exhibited higher levels of compliance with audit criteria than NIMCs, except for documentation of indication for medication. With eMMS, both hospitals exceeded national averages on many audited parameters, with the exceptions of documentation of weight and indication for medication. eMMS produces clearer, more complete medication orders and patient information, which may improve quality and safety of prescribing and reduce medication errors. Feedback was provided to the ACSQHC regarding aspects of the NIMC audit that did not align with eMMS for consideration in future audits.
Isotope ratio mass spectrometry in combination with chemometrics for characterization of geographical origin and agronomic practices of table grape
Authors: Longobardi Francesco , Casiello Grazia , Centonze Valentina , Catucci Lucia , Agostiano Angela
Published: November 2016

BACKGROUND

Although table grape is one of the most cultivated and consumed fruits worldwide, no study has been reported on its geographical origin or agronomic practice based on stable isotope ratios. This study aimed to evaluate the usefulness of isotopic ratios (i.e. 2H/1H, 13C/12C, 15N/14N and 18O/16O) as possible markers to discriminate the agronomic practice (conventional versus organic farming) and provenance of table grape.

RESULTS

In order to quantitatively evaluate which of the isotopic variables were more discriminating, a t test was carried out, in light of which only δ13C and δ18O provided statistically significant differences (P ≤ 0.05) for the discrimination of geographical origin and farming method. Principal component analysis (PCA) showed no good separation of samples differing in geographical area and agronomic practice; thus, for classification purposes, supervised approaches were carried out. In particular, general discriminant analysis (GDA) was used, resulting in prediction abilities of 75.0 and 92.2% for the discrimination of farming method and origin respectively.

CONCLUSION

The present findings suggest that stable isotopes (i.e. δ18O, δ2H and δ13C) combined with chemometrics can be successfully applied to discriminate the provenance of table grape. However, the use of bulk nitrogen isotopes was not effective for farming method discrimination. © 2016 Society of Chemical Industry
Effect of deamidation‐induced modification on umami and bitter taste of wheat gluten hydrolysates
Authors: Liu Bo‐Ye , Zhu Ke‐Xue , Guo Xiao‐Na , Peng Wei , Zhou Hui‐Ming
Published: November 2016

BACKGROUND

Bitter taste is the main limiting factor for various applications of protein hydrolysates. Frequently used physicochemical methods for debittering protein hydrolysates come with some undesired side effects. Deamidation‐induced modification would be a very promising technique to improve the flavor of wheat gluten hydrolysates (WGHs). This study was designed to determine the effect of deamidation with certain enzymes or acid treatment on the chemical composition, bitterness and umami properties of WGHs. The difference between umami peptide and free glutamic acid on the suppression of bitterness is emphatically discussed. The optimal scheme is proposed based on the flavor of WGHs and the yield of peptides.

RESULTS

The generation of umami substances suppressed bitter signal transduction. When the content of umami substances was relatively high, the umami‐enhancing properties of umami peptides were obviously effective. The intensity of umami taste was high enough to further suppress bitter taste in the course of neurocognitive functioning.

CONCLUSION

When WGHs were treated with Glutaminase for 180 min, the umami taste score increased from 1.62 to 4.27 and the bitter taste score decreased from 1.33 to 0.65. © 2016 Society of Chemical Industry
Clinical auditing as an instrument for quality improvement in breast cancer care in the Netherlands: The national NABON Breast Cancer Audit
Authors: van Bommel Annelotte C.M. , Spronk Pauline E.R. , Vrancken Peeters Marie‐Jeanne T.F.D. , Jager Agnes , Lobbes Marc , Maduro John H. , Mureau Marc A.M. , Schreuder Kay , Smorenburg Carolien H. , Verloop Janneke , Westenend Pieter J. , Wouters Michel W.J.M. , Siesling Sabine , Tjan ‐ Heijnen Vivianne C.G. , van Dalen Thijs ,   On behalf of the NABON Breast Cancer Audit
Published: November 2016

Background

In 2011, the NABON Breast Cancer Audit (NBCA) was instituted as a nation‐wide audit to address quality of breast cancer care and guideline adherence in the Netherlands. The development of the NBCA and the results of 4 years of auditing are described.

Methods

Clinical and pathological characteristics of patients diagnosed with invasive breast cancer or in situ carcinoma (DCIS) and information regarding diagnosis and treatment are collected in all hospitals (n = 92) in the Netherlands. Thirty‐two quality indicators measuring care structure, processes and outcomes were evaluated over time and compared between hospitals.

Results

The NBCA contains data of 56,927 patients (7,649 DCIS and 49,073 invasive cancers). Patients being discussed in pre‐ and post‐operative multidisciplinary team meetings improved (2011: 83% and 91%; 2014: 98% and 99%, respectively) over the years. Tumour margin positivity rates after breast‐conserving surgery for invasive cancer requiring re‐operation were consistently low (∼5%). Other indicators, for example, the use of an MRI‐scan prior to surgery or immediate breast reconstruction following mastectomy showed considerable hospital variation.

Conclusions

Results shown an overall high quality of breast cancer care in all hospitals in the Netherlands. For most quality indicators improvement was seen over time, while some indicators showed yet unexplained variation. J. Surg. Oncol. 2017;115:243–249. © 2016 Wiley Periodicals, Inc.