bluuebunny/crossref_metadata_2025 huggingface dataset:
Two‐Dimensional Metal Oxide Nanoflower‐Like Architectures: A General Growth Method and Their Applications in Energy Storage and as Model Materials for Nanofabrication
Authors: Tao Tao , Chen Ying , Chen Yanhui , Fox Daniel S. , Zhang Hongzhou , Zhou Mengqi , Raveggi Massimo , Barlow Anders J. , Glushenkov Alexey M.
Published: November 2016

Nanoflower‐like architectures represent a unique type of nanomaterials in which thin 2D nanosheets are self‐organised into interconnected structures. Lack of restacking between nanosheets and significant internal porosity are the particular advantages of such nanoscale architectures. A general method for the preparation of nanoflowers of a range of oxides (e.g., FeTiO3, TiO2, Mn2O3) through a two‐step procedure of ball milling and subsequent hydrothermal treatment is outlined. Importantly, the synthetic method is valid not only for a single oxide, but is extendable to a family of oxide materials. It is established that the formation of the nanoflowers from ball‐milled powders follows a dissolution–precipitation mechanism; this is confirmed by inductively coupled plasma time of flight mass spectrometry measurements. Additional information on the X‐ray photoelectron spectroscopy characterisation and intermediate stage of growth of the nanostructures is included. Furthermore, two applications of Mn2O3 nanostructures are briefly investigated. Firstly, their properties for energy storage in the electrodes of electrochemical supercapacitors are presented. A capacitive response in the potential window of −0.1–0.9 V versus an Ag/AgCl reference electrode is observed, with an associated increase of the capacitance values over cycling. Secondly, the use of Mn2O3 nanoflowers as model systems for the development of novel nanofabrication techniques (such as nanopatterning with a He+ beam) is investigated.
Sequential N‐Alkylations of Tetrabenzotetraaza[8]circulene as a Tool To Tune Its Optical Properties
Authors: Chen Fengkun , Hong Yong Seok , Kim Dongho , Tanaka Takayuki , Osuka Atsuhiro
Published: November 2016

Sequential N‐alkylations of tetrabenzotetraaza[8]circulene provided mono‐, di‐, tri, and tetra‐N‐alkylated products in a controlled manner. Curiously, only opp isomer was obtained as a di‐N‐alkylated product. Upon increase of the N‐alkyl groups, the absorption and emission spectra exhibit continuous red‐shifts, and the excited‐state lifetimes become shortened, probably because of increased steric congestion at the nitrogen atoms that causes the central core to deviate from planarity. Mixed N‐substituted [8]circulenes have been also prepared.
PEGylated β‐Sheet Breaker Peptides as Inhibitors of β‐Amyloid Fibrillization
Authors: De Santis Serena , Chiaraluce Roberta , Consalvi Valerio , Novelli Federica , Petrosino Maria , Punzi Pasqualina , Sciubba Fabio , Giordano Cesare , Masci Giancarlo , Scipioni Anita
Published: November 2016

Three PEGylated β‐sheet breaker peptides are designed as new inhibitors of β‐amyloid fibrillization. The peptide Ac‐Leu–Pro–Phe–Phe–Asp‐NH2, considered the lead compound, and hexamers in which taurine and β‐alanine substitute the acetyl group, are conjugated to poly(ethylene glycol); this conjugates self‐assemble into nanoparticles. The activity of the PEGylated peptides as inhibitors of amyloid fibrillization are tested in vitro using circular dichroism spectroscopy and scanning electron microscopy. The experimental results indicate that PEGylation does not impair the ability of the β‐sheet breaker peptides to inhibit fibrillogenesis in vitro. Moreover, microscopy images of β‐amyloid incubated for 6 days with the taurine‐containing peptide, suggest that this conjugate has major anti‐fibrillogenesis activity and demonstrate the important role of the sulfonamide function against the amyloid aggregation.
Strong Color Tuning of Self‐Assembled Azo‐Derived Phosphonic Acids upon Hydrogen Bonding
Authors: Girard Pauline , Hémez Julie , Silvestre Virginie , Labrugère Christine , Lartigue Lénaïc , Duvail Jean‐Luc , Ishow Eléna
Published: November 2016

The unexplored combination of a hydroxy‐gem‐bisphosphonic (HBP) unit with strongly absorbing azo dyes leads to the formation of a glassy material with unusual black color. Strong intermolecular hydrogen‐bonding interactions combined with extensive charge transfer are proposed from spectroscopic and mass spectrometry analyses performed in solution and on thin films. Dramatic color switch from blue gray/green to orange is obtained by varying the hydrogen‐bonding acceptor character of the solvent or substrate, thereby paving the way to tunable colored materials using HBP‐functionalized π‐conjugated molecules.
Intestinal helminth infection induces highly functional resident memory CD4+ T cells in mice
Authors: Steinfelder Svenja , Rausch Sebastian , Michael Dörte , Kühl Anja A. , Hartmann Susanne
Published: November 2016

Immunity to intestinal nematodes requires CD4⁺ Th2‐cell responses, including IL‐4 and IL‐13 production. Chronic infection with intestinal nematodes leads to downregulation of these responses, and few functional T helper (Th) 2 cells are detected in secondary lymphoid organs in the chronic phase or after abrogation of infection. Here, we show with a natural murine infection with Heligmosomoides polygyrus that highly functional memory Th2 cells persist in the lamina propria and in addition in the peritoneal cavity (PC) after abrogation of infection. While both tissue‐resident memory (TRM) populations proliferate in situ and express IL‐4, IL‐5, and IL‐13 upon TCR‐dependent stimulation, only peritoneal memory cells express high levels of the IL‐33 receptor and produce IL‐5 and IL‐13 upon TCR‐independent stimulation with IL‐33 and IL‐7. Most importantly, PC‐derived TRM cells are able to mediate anti‐helminthic effects by decreasing the fecundity of female worms upon transfer into recipient mice. These results show that nonlymphoid compartments can serve as reservoirs for Th2 memory cells, and furthermore that innate effector function of Th2 memory cells is restricted to CD4⁺ memory T cells residing in the PC.
Total Enantioselective Synthesis of the Endophytic Fungal Polyketide Phomolide H and Its Structural Revision
Authors: McNulty James , McLeod David
Published: November 2016

A total synthesis of the proposed structure of the natural polyketide‐macrolactone phomolide H 2 has been achieved following a bidirectional strategy from l‐tartaric acid. The originally assigned structure of phomolide H displayed discordant NMR spectroscopic data in comparison with synthetic 2. The synthetic strategy was extended to prepare diastereomers and epimeric methyl‐ethers of the natural product, structural analysis of which revealed a match of the natural product with diastereomer 27. The structural revision of phomolide H from 2 to the methanol solvate of compound 27 is presented.
Optimising Terpene Synthesis with Flow Biocatalysis
Authors: Tang Xiaoping , Allemann Rudolf K. , Wirth Thomas
Published: November 2016

Sesquiterpenes are an important family of natural products, many of which exhibit important pharmaceutical and agricultural properties. They are biosynthesised from farnesyl diphosphate in sesquiterpene synthase catalysed reactions. Here, we report the development of a highly efficient segmented flow system for the enzyme‐catalysed continuous flow production of sesquiterpenes. Design of experiment (DoE) methods were used to optimise the performance of the flow biocatalysis, and quantitative yields were achieved by using an operationally simple but highly effective segmented flow system.
Mechanism of Chicoric Acid Electrochemical Oxidation and Identification of Oxidation Products by Liquid Chromatography and Mass Spectrometry
Authors: Newair Emad F. , Abdel‐Hamid Refat , Kilmartin Paul A.
Published: November 2016

Electrochemical oxidation of chicoric acid (ChA) was investigated using cyclic voltammetry and chronoamperometry at a glassy carbon electrode. Chicoric acid generates single quasi‐reversible redox wave in cyclic voltammetry over a wide pH range, and an ECEC‐dimerization mechanism is proposed. Effect of glutathione (GSH) on the electrochemical oxidation of chicoric acid (ChA) was investigated in Britton−Robinson buffer solution. Ultra‐high performance liquid chromatography (UPLC) coupled with mass spectrometry (MS) was used to show that the naturally occurring chicoric acid (ChA) underwent an electrochemical oxidation in the presence of glutathione (GSH) to form mono‐, bi‐, tri‐, and four‐glutathione conjugates of chicoric acid and a mono‐glutathione conjugate of a chicoric acid dimer. The obtained results are useful for understanding and predicting the oxidative degradation pathway of chicoric acid.
Fluorescence‐based lateral flow assays for rapid oral fluid roadside detection of cannabis use
Authors: Plouffe Brian D. , Murthy Shashi K.
Published: November 2016

With the recent worldwide changes in the legalization of marijuana, there is a significant need for rapid, roadside screening test for driving under the influence of drugs. A robust, sensitive, lateral flow assay has been developed to detect recent use via oral‐fluid testing for Δ9‐tetrahydrocannabinol (THC). This proof‐of‐concept assay uses a fluorescent‐based immunoassay detection of polymeric beads, conjugated to antibodies against native THC. The fluorescent technique allows for significantly lower limits of detection and higher precision determination of recent marijuana use without the use of urine or blood sampling—thus allowing for roadside identification. Detection levels of 0.01 ng/mL were distinguished from background and the lower limit of quantification was determined to approach 1 ng/mL.
Design, installation, and performance evaluation of a custom dye matrix standard for automated capillary electrophoresis
Authors: Cloete Kevin Wesley , Ristow Peter Gustav , Kasu Mohaimin , D'Amato Maria Eugenia
Published: November 2016

CE equipment detects and deconvolutes mixtures containing up to six fluorescently labeled DNA fragments. This deconvolution is done by the collection software that requires a spectral calibration file. The calibration file is used to adjust for the overlap that occurs between the emission spectra of fluorescence dyes. All commercial genotyping and sequencing kits require the installation of a corresponding matrix standard to generate a calibration file. Due to the differences in emission spectrum overlap between fluorescent dyes, the application of existing commercial matrix standards to the electrophoretic separation of DNA labeled with other fluorescent dyes can yield undesirable results. Currently, the number of fluorescent dyes available for oligonucleotide labeling surpasses the availability of commercial matrix standards. Therefore, in this study we developed and evaluated a customized matrix standard using ATTO 633, ATTO 565, ATTO 550, ATTO Rho6G, and 6‐FAM dyes for which no commercial matrix standard is available. We highlighted the potential genotyping errors of using an incorrect matrix standard by evaluating the relative performance of our custom dye set using six matrix standards. The specific performance of two genotyping kits (UniQTyper™ Y‐10 version 1.0 and PowerPlex® Y23 System) was also evaluated using their specific matrix standards. The procedure we followed for the construction of our custom dye matrix standard can be extended to other fluorescent dyes.
Acupuncture injection for field amplified sample stacking and glass microchip‐based capillary gel electrophoresis
Authors: Ha Ji Won , Hahn Jong Hoon
Published: November 2016

Acupuncture sample injection is a simple method to deliver well‐defined nanoliter‐scale sample plugs in PDMS microfluidic channels. This acupuncture injection method in microchip CE has several advantages, including minimization of sample consumption, the capability of serial injections of different sample solutions into the same microchannel, and the capability of injecting sample plugs into any desired position of a microchannel. Herein, we demonstrate that the simple and cost‐effective acupuncture sample injection method can be used for PDMS microchip‐based field amplified sample stacking in the most simplified straight channel by applying a single potential. We achieved the increase in electropherogram signals for the case of sample stacking. Furthermore, we present that microchip CGE of ΦX174 DNA‐HaeⅢ digest can be performed with the acupuncture injection method on a glass microchip while minimizing sample loss and voltage control hardware.
Supported Cobalt Nanorod Catalysts for Carbon Dioxide Hydrogenation
Authors: Jimenez Juan , Bird Ashley , Santos Santiago Maryorie , Wen Cun , Lauterbach Jochen
Published: November 2016

To create new CO2 hydrogenation catalysts, we developed a methodology in which the selective surface faceting of nanorods is combined with the practicality of a supported catalyst. The basic Co catalyst with preferential {110} surface faceting was supported with either SiO2, Al2O3, or TiO2. We grafted charged ligands onto the Co nanorods to attract the support precursors to the surface of the Co to allow a large contact area between the Co and the support. The large contact area promoted the chemical interaction between the Co and the support, which was verified by using Raman spectroscopy, XRD, and temperature‐programmed reduction. TiO2‐ and Al2O3‐supported Co nanorods showed an increase in activity at low and high reaction temperatures, respectively, whereas the relatively inert SiO2‐supported nanorods possessed the same catalytic performance as unsupported rods.
Exposure to chlorantraniliprole affects the energy metabolism of the caddisfly Sericostoma vittatum
Authors: Rodrigues Andreia C.M. , Gravato Carlos , Quintaneiro Carla , Bordalo Maria D. , Golovko Oksana , Žlábek Vladimír , Barata Carlos , Soares Amadeu M.V.M. , Pestana João L.T.
Published: November 2016

Caddisflies have been included in ecotoxicological studies because of their sensitivity and ecological relevance. The present study aimed to assess the sublethal effects of an anthranilic diamide insecticide, chlorantraniliprole (CAP), to Sericostoma vittatum. Used worldwide, CAP is a persistent compound that has been found in surface waters at concentrations from 0.1 μg/L to 9.7 μg/L. It targets the ryanodine receptors, and the present ecotoxicological assessment focused on biomarkers related to neurotransmission, biotransformation, oxidative stress damage, and endpoints related to energy processing (feeding, energy reserves, and cellular metabolism). Six days of exposure trials revealed that feeding activity was significantly decreased in S. vittatum larvae exposed to 0.9 μg/L CAP. Concomitantly, a reduction in cellular metabolism and a significant decrease in protein content were also observed in caddisfly larvae exposed to CAP, suggesting metabolic depression. The results show that sublethal concentrations of CAP can cause detrimental sublethal effects on S. vittatum total glutathione content at concentrations as low as 0.2 μg/L. Bioenergetics can be used to assess physiological effects of contaminants, and the present results show that exposure to low, environmentally relevant, concentrations of CAP alter energy acquisition and metabolism in nontarget aquatic insects with potential population level effects. Environ Toxicol Chem 2017;36:1584–1591. © 2016 SETAC
Waterproof Breathable Membrane Used as Gas Diffusion Layer in Activated Carbon Air Cathode Microbial Fuel Cells
Authors: Fu Z. , Li K. , Pu L. , Ge B. , Chen Z.
Published: November 2016

One of the main limiting factors for scaling up microbial fuel cells (MFCs) technology is to develop low‐cost and high‐efficiency cathode. A new and simplified approach was developed by using a commercial waterproof breathable membrane (WBM) as gas diffusion layer (GDL) material as substitution for conventional polytetrafluoroethylene (PTFE) GDL. Air‐cathode with the WBM pasted (AC‐P) onto the stainless steel mesh (SSM) achieved a maximum power density of 611 ± 10 mWm−2, which was similar to that using a PTFE GDL by rolling method (645 ± 12 mWm−2, AC‐R). Physical and electrochemical techniques were employed to investigate the morphology and electrochemical characteristics of the cathode. The result demonstrated that AC‐P had a higher current density and internal resistance than AC‐R. Besides, the WBM had a higher porosity and uniform texture. The study showed that the WBM was a kind of good GDL material for easy preparation, low cost and stable performance of cathode construction.
Asymmetry in the Permanent Price Impact of Block Purchases and Sales: Theory and Empirical Evidence
Authors: Frino Alex , Mollica Vito , Romano Maria Grazia , Zhou Zeyang
Published: November 2016

Previous research has identified that the information effects of buyer‐initiated trades are greater than seller‐initiated trades. We develop a theoretical model that predicts block purchases are relatively more informed in bear markets and block sales are relatively more informed in bull markets. Using a sample of large trades executed in the E‐mini S&P 500 index futures and SPDR S&P 500 exchange traded fund, we find evidence consistent with our theoretical model. Our results are robust to volatility and macro‐economic news announcements categorized as bullish or bearish. © 2016 Wiley Periodicals, Inc. Jrl Fut Mark 37:359–373, 2017
Archaeological Landscapes during the 10–8 ka Lake Stanley Lowstand on the Alpena‐Amberley Ridge, Lake Huron
Authors: Sonnenburg Elizabeth , O'Shea John
Published: November 2016

Archaeologists have long been interested in the Lake Stanley lowstand event (∼10–8 ka) in the Lake Huron basin, as archaeological sites from the Late Paleoindian/Early Archaic cultural periods were inundated by subsequent high water levels. Recent archaeological and paleoenvironmental investigations of this submerged landscape have documented stone structures that were likely utilized for caribou
hunting by these cultural groups during the late Lake Stanley lowstand phase of Lake Huron. In 2011 and 2012, a total of 67 core, sediment, and rock samples were collected in a 50 km2 area by divers and a ponar sampler deployed from a survey vessel. These samples were analyzed for sediment size, sorting, morphology and source, organic and carbonate content, testate amoebae, and organic materials. A series of indicators, including distinct microfossil assemblages (such as species only found in sphagnum moss and boggy arctic ponds), rooted trees (tamarack and spruce), and charcoal (ca. 8–9000 yr old) reveal a series of microenvironments that are consistent with a subarctic climate. The analysis of the Alpena‐Amberley Ridge provides a detailed picture of the environment exploited by ancient peoples during the Lake Stanley lowstand period. The methodologies employed in this study can in turn help identify other unique microregions that may yield more archaeological sites with less obvious archaeological footprints.
PreCimp: Pre‐collapsing imputation approach increases imputation accuracy of rare variants in terms of collapsed variables
Authors: Kim Young Jin , Lee Juyoung , Kim Bong‐Jo ,   T2D‐Genes Consortium, Park Taesung
Published: November 2016

Imputation is widely used for obtaining information about rare variants. However, one issue concerning imputation is the low accuracy of imputed rare variants as the inaccurate imputed rare variants may distort the results of region‐based association tests. Therefore, we developed a pre‐collapsing imputation method (PreCimp) to improve the accuracy of imputation by using collapsed variables. Briefly, collapsed variables are generated using rare variants in the reference panel, and a new reference panel is constructed by inserting pre‐collapsed variables into the original reference panel. Following imputation analysis provides the imputed genotypes of the collapsed variables. We demonstrated the performance of PreCimp on 5,349 genotyped samples using a Korean population specific reference panel including 848 samples of exome sequencing, Affymetrix 5.0, and exome chip. PreCimp outperformed a traditional post‐collapsing method that collapses imputed variants after single rare variant imputation analysis. Compared with the results of post‐collapsing method, PreCimp approach was shown to relatively increase imputation accuracy about 3.4–6.3% when dosage r2 is between 0.6 and 0.8, 10.9–16.1% when dosage r2 is between 0.4 and 0.6, and 21.4 ∼ 129.4% when dosage r2 is below 0.4.
Fundamentals of the vibratory driving of piles and sheet piles
Authors: Massarsch K. Rainer , Fellenius Bengt H. , Bodare Anders
Published: November 2016

Vibratory driving is a common method for installing or extracting piles and sheet piles as well as for deep vibratory compaction. The most important parameters are vibration frequency, vibration amplitude and eccentric moment. These parameters govern vibratory driving and, in particular, the soil resistance at the toe and along the shaft of a pile. Pile driving causes oscillating horizontal ground vibrations in coarse‐grained soils. It can be shown that these horizontal vibrations reduce the shaft resistance during driving. The process results in a permanent increase in the horizontal effective stress, which causes arching around the vibrated pile. The increase in horizontal effective stress is also important for deep vibratory compaction. The resonance frequency of the vibrator‐pile‐soil system significantly affects pile penetration and the emission of ground vibrations. At resonance, the vertical vibration velocity in the soil reaches a maximum and pile penetration becomes very slow, whereas beyond resonance, the vibration velocity decreases and the pile penetration speed is high. Field monitoring of the vibratory driving process can be used to optimize vibratory pile driving, as examples have shown. A new concept is proposed in which the driveability can be determined from a correlation between penetration resistance measurements (blows/depth) and penetration speed. The validity of the concept is demonstrated by a case history and project references.
The Effect on Mental Health of Retiring During the Economic Crisis
Authors: Belloni Michele , Meschi Elena , Pasini Giacomo
Published: November 2016

This paper investigates the causal impact of retirement on late‐life mental health, a growing concern for public health, because major depressive disorders are the second leading cause of disability. We shed light on the role of economic conditions in shaping the effect of retirement on mental health by exploiting time and regional variation in the severity of the economic crisis across 10 European countries during 2004–2013. We use data from four waves of the Survey of Health, Ageing and Retirement in Europe and address the potential endogeneity of the retirement decision to mental health by applying a fixed‐effects instrumental variables approach. The results indicate that retirement improves the mental health of men but not that of women. This effect is stronger for blue‐collar men working in regions that have been severely hit by the economic crisis. These findings may be explained by the worsening of working conditions and the rise in job insecurity stemming from the economic downturn: under these circumstances, exit from the labour force is perceived as a relief. Copyright © 2016 John Wiley & Sons, Ltd.
Combinatorial optimization of resilience engineering and organizational factors in a gas refinery by a unique mathematical programming approach
Authors: Azadeh A. , Salehi V. , Mirzayi M. , Roudi E.
Published: November 2016

This study is an attempt to evaluate the mutual impacts of resilience engineering (RE) and managerial and organizational factors in a large gas refinery. RE is a paradigm for safety management that focuses on how to help people cope with complexity under pressure to achieve success. The data obtained from questionnaire are analyzed by statistical methods and data envelopment analysis (DEA) approach. The results of Cronbach's alpha test show that the data are reliable. The results of DEA demonstrate that learning and flexibility among all RE factors have the greatest impact on managerial and organizational factors. In addition, the organizational factors have a greater influence on RE in comparison with managerial factors. Spearman's test was used to verify the results of this study. This is the first study that identifies the most important factors of integrated managerial and organizational factors and RE through a unique mathematical programming approach in a gas refinery.
Membrane Binding of Parkinson's Protein α‐Synuclein: Effect of Phosphorylation at Positions 87 and 129 by the S to D Mutation Approach
Authors: Kumar Pravin , Schilderink Nathalie , Subramaniam Vinod , Huber Martina
Published: November 2016

Human α‐synuclein, a protein relevant in the brain with so‐far unknown function, plays an important role in Parkinson's disease. The phosphorylation state of αS was related to the disease, prompting interest in this process. The presumed physiological function and the disease action of αS involves membrane interaction. Here, we study the effect of phosphorylation at positions 87 and 129, mimicked by the mutations S87A, S129A (nonphosphorylated) and S87D, S129D (phosphorylated) on membrane binding. Local binding is detected by spin‐label continuous‐wave electron paramagnetic resonance. For S87A/D, six positions (27, 56, 63, 69, 76, and 90) are probed; and for S129A/D, three (27, 56, and 69). Binding to large unilamellar vesicles of 100 nm diameter of 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phospho‐(1′‐rac‐glycerol) and 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine in a 1 : 1 composition is not affected by the phosphorylation state of S129. For phosphorylation at S87, local unbinding of αS from the membrane is observed. We speculate that modulating the local membrane affinity by phosphorylation could tune the way αS interacts with different membranes; for example, tuning its membrane fusion activity.
An Appreciation of Organic Solid‐State Chemistry and Challenges in the Field of “Molecules, Materials, Medicines”
Authors: Jones William
Published: November 2016

Over many years, much of what has motivated a considerable amount of research in the general area of organic solid‐state chemistry concerns an understanding of how molecular packing within an organic solid affects its physical and chemical properties. Whilst the motivation for this understanding may have changed over time, the fundamental issues remain the same. An understanding of the effect of crystal attributes (e.g., polymorph, habit and particle size) on chemical, physical, photophysical and electronic properties is still vital to the development of organic solids with optimised properties. While progress has been made in analytical skills (including sophisticated developments in instrumentation), along with major developments in computational techniques, there are still many challenges. This paper, with a primary focus on pharmaceuticals, provides a brief, and not comprehensive, personal overview of the progress that has been made and has yet to be made. Amongst the chemists and crystallographers who have contributed significantly to the subject is Jack Dunitz and some of his seminal papers appear in several of the issues discussed.
The Development of Alkoxide‐Directed Metallacycle‐Mediated Annulative Cross‐Coupling Chemistry
Authors: Micalizio Glenn C. , Mizoguchi Haruki
Published: November 2016

Alkoxide‐directed metallacycle‐mediated cross‐coupling is a rapidly growing area of reaction methodology in organic chemistry. Over the last decade, developments have resulted in more than thirty new and highly selective intermolecular (or “convergent”) C−C bond‐forming reactions that have established powerful retrosynthetic relationships in stereoselective synthesis. While early studies were focused on developing transformations that forge a single C−C bond by way of a functionalized and unsaturated metallacyclopentane intermediate, recent advances mark the ability to employ this organometallic intermediate in additional stereoselective transformations. Among these more advanced coupling processes, those that embrace the metallacycle in subsequent [4+2] chemistry have resulted in the realization of a number of highly selective annulative cross‐coupling reactions that deliver densely functionalized and angularly substituted carbocycles. This review discusses the early development of this chemistry, recent advances in reaction methodology, and shares a glimpse of the power of these processes in natural product synthesis.
Synthesis of the Right‐Side Structure of Type B Physalins
Authors: Morita Masaki , Kojima Shuntaro , Ohkubo Megumi , Koshino Hiroyuki , Hashizume Daisuke , Hirai Go , Maruoka Keiji , Sodeoka Mikiko
Published: November 2016

We present a full account of our synthetic studies on the racemic DEFGH‐ring moiety of physalins, featuring domino ring transformation of a tricyclic key intermediate. We also report the results of a detailed mechanistic examination of the domino ring transformation, as well as a reoptimization of the 2,3‐Wittig rearrangement and methylation steps. Furthermore, we have newly established a method for the preparation of an optically active synthetic intermediate by enzymatic kinetic resolution. Our work provides access to both natural and nonnatural right‐side physalin structures.
Nrf2 Activation as a Protective Feedback to Limit Cell Death in High Glucose‐Exposed Cardiomyocytes
Authors: Tsai Cheng‐Yen , Wen Su‐Ying , Cheng Shi‐Yann , Wang Chung‐Hsing , Yang Yao‐Chih , Viswanadha Vijaya Padma , Huang Chih‐Yang , Kuo Wei‐Wen
Published: November 2016

Hyperglycemia leads to excess reactive oxygen species (ROS) generation, which causes many diabetic complications, such as cardiomyopathy. Nuclear factor erythroid 2‐related factor 2 (Nrf2), a redox‐sensing transcription factor, can up‐regulate its downstream antioxidant gene expressions in response to oxidative stress. However, the regulatory signal pathway in which high glucose (HG) induces Nrf2 activation is still unclear. Our results demonstrated that HG (33 mM) can indeed stimulate Nrf2 protein expression and translocation into the nucleus in cardiomyocytes, enhancing the downstream antioxidant protein levels. Using siRNAs, p38, JNK, PKCα, and PKCδ, as well as ROS scavengers, it was observed that the dependence of PKCα/PKCδ on ROS production to enhance JNK and p38 phosphorylation mediated HG‐induced cardiac Nrf2 expression and activation. Knockdown of Nrf2 by siRNA transfection increased cleaved‐caspase3, reduced Bcl2 in the cellular protein level and further exacerbated HG‐induced apoptosis. In addition, all of these proteins induced by HG in vitro were also increased in STZ‐induced diabetic rat ventricles in vivo. Our study demonstrated that HG‐induced cardiac Nrf2 activation occurs through PKCα/PKCδ—ROS—JNK/p38 signaling. These findings may provide a therapeutic target to counteract the oxidative stress associated with diabetic cardiomyopathy. J. Cell. Biochem. 118: 1659–1669, 2017. © 2016 Wiley Periodicals, Inc.
Placental‐Specific Overexpression of sFlt‐1 Alters Trophoblast Differentiation and Nutrient Transporter Expression in an IUGR Mouse Model
Authors: Kühnel Elisabeth , Kleff Veronika , Stojanovska Violeta , Kaiser Stephanie , Waldschütz Ralph , Herse Florian , Plösch Torsten , Winterhager Elke , Gellhaus Alexandra
Published: November 2016

Since it is known that placental overexpression of the human anti‐angiogenic molecule sFlt‐1, the main candidate in the progression of preeclampsia, lead to intrauterine growth restriction (IUGR) in mice by lentiviral transduction of mouse blastocysts, we hypothesize that sFlt‐1 influence placental morphology and physiology resulting in fetal IUGR. We therefore examined the effect of sFlt‐1 on placental morphology and physiology at embryonic day 18.5 with histologic and morphometric analyses, transcript analyses, immunoblotting, and methylation studies. Interestingly, placental overexpression of sFlt‐1 leads to IUGR in the fetus and results in lower placental weights. Moreover, we observed altered trophoblast differentiation with reduced expression of IGF2, resulting in a smaller placenta, a smaller labyrinth, and the loss of glycogen cells in the junctional zone. Changes in IGF2 are accompanied by small changes in its DNA methylation, whereas overall DNA methylation is unaffected. In addition, the expression of placental nutrient transporters, such as the glucose diffusion channel Cx26, is decreased. In contrast, the expression of the fatty acid transporter CD36 and the cholesterol transporter ABCA1 is significantly increased. In conclusion, placental sFlt‐1 overexpression resulted in a reduction in the differentiation of the spongiotrophoblast into glycogen cells. These findings of a reduced exchange area of the labyrinth and glycogen stores, as well as decreased expression of glucose transporter, could contribute to the intrauterine growth restriction phenotype. All of these factors change the intrauterine availability of nutrients. Thus, we speculate that the alterations triggered by increased anti‐angiogenesis strongly affect fetal outcome and programming. J. Cell. Biochem. 118: 1316–1329, 2017. © 2016 Wiley Periodicals, Inc.
Sensitivity of TP53‐Mutated Cancer Cells to the Phytoestrogen Genistein Is Associated With Direct Inhibition of Plk1 Activity
Authors: Shin Sol‐Bi , Woo Sang‐Uk , Chin Young‐Won , Jang Young‐Joo , Yim Hyungshin
Published: November 2016

Polo‐like kinase 1 (Plk1), a conserved Ser/Thr mitotic kinase, has been identified as a promising target for anticancer drug development because its overexpression is correlated with malignancy. Here, we found that genistein, an isoflavone, inhibits Plk1 kinase activity directly. Previously the mitotic disturbance phenomenon induced by treatment with genistein was not fully explained by its inhibitory effect on EGFR. In kinase profiling assays, it showed selectivity relative to a panel of kinases, including EGFR. Treatment with genistein induced cell death in a concentration‐dependent manner in cancer cells from diverse tissue origins, but not in non‐transformed cells such as hTERT‐RPE or MCF10A cells. We also observed that genistein tended to be more selective against cancer cells with mutations in the TP53 gene. TP53‐depeleted LNCaP and NCI‐H460 cells using shRNA targeting human TP53 were more sensitive to cell death by treatment of genistein. Furthermore, genistein induced mitotic arrest by inhibiting Plk1 activity and, consequently, led to mitotic catastrophe and apoptosis. These data suggest that genistein may be a promising anticancer drug candidate due to its inhibitory activity against Plk1 as well as EGFR and effectiveness toward cancer cells, especially those with p53‐mutation. J. Cell. Physiol. 232: 2818–2828, 2017. © 2016 Wiley Periodicals, Inc.
Amino acid profile and sensory characteristics of dry fermented pork loins produced with a mixture of probiotic starter cultures
Authors: Neffe‐Skocińska Katarzyna , Okoń Anna , Kołożyn‐Krajewska Danuta , Dolatowski Zbigniew
Published: November 2016

BACKGROUND

Proteolysis is a biochemical process in dry‐aged meat products where proteins are metabolized and broken down to polypeptides, peptides, and free amino acids. In the literature it is reported that an appropriate choice of probiotic starter culture limits proteolytic changes in dry‐fermented meat products. In this study the combined effect of a mixture of probiotic starter cultures on the free amino acid profile, total count of lactic acid bacteria, and the sensory quality of dry‐aged pork loins after fermentation and after storing the vacuum‐packed samples was evaluated.

RESULTS

LOCK900 and BB12 probiotic strains were the technologically best two‐species mixture of starter cultures for the production of probiotic dry‐aged pork loins. They allowed us to obtain products with high and stable bacterial count and acceptable sensory quality, both after 21 days of fermentation and after 2 months of cold storage. Changes in the free amino acid profile and increased intensity of the selected sensory attributes result from a significant share of probiotics in meat proteolysis occurring during fermentation and storage.

CONCLUSION

The results suggest the relevance of using probiotic bacteria as a two‐species starter culture for the production of dry‐aged products. © 2016 Society of Chemical Industry
Kinetics of the Anaerobic Reaction of para‐Substituted Phenols with Nitrogen Dioxide
Authors: Reyes Jael , Lissi Eduardo , López‐Alarcón Camilo , Rubio María A.
Published: November 2016

para‐Substituted phenols in aqueous solution under anaerobic conditions readily react with nitrogen dioxide (NO2●) over a wide range of experimental conditions. The rate and rate law of the process were dependent on phenol concentration and solution pH. The kinetic order in phenol changed from one (low concentration) to zero (high concentration), a result attributable to total NO2● capture. Initial consumption rate (r0) of phenols versus pH plots showed parabolic behavior with a minimum rate at pH ca. 5. On the other hand, the maximum rate took place at high pH (pH>10) and involved the protonated phenols. The reaction rate of para‐substituted phenols with NO2● correlated with the bond dissociation energy and with Hammett's parameter. Based on such results and also supported by analysis of products carried out by HPLC‐MS/MS, our data conclusively show that, in spite of the fast acid–base interchanges of phenols and the interconversion of the different nitrogen oxides, the mechanisms of phenols nitration mediated by NO2● or HONO are clearly different.
Investigation of corrosion behavior of 3003 aluminum alloy in flue gas condensate
Authors: Yang H. J. , Gao Y. M. , Qin W. C. , Ma S. Q. , Wei Y. K.
Published: November 2016

The corrosion behavior of 3003 aluminum alloy in different media was investigated by electrochemical approaches and immersion tests. It was shown that the corrosion of aluminum alloy was influenced by the composition of the solution. The results indicated that the nitrite ion (NO2−) acted as a corrosion inhibitor. The addition of sulfate ion (SO42−) or nitrate ion (NO3−) can weaken this inhibiting effect. Chloride ion (Cl−) and SO42− can accelerate the corrosion of 3003 aluminum alloy greatly.
Photopolymerization Behavior of Coordinated Ionic Liquids Formed from Organic Monomers with Alkali and Alkaline Earth Metal Bistriflimide Salts
Authors: Whitley John W. , Benefield Shellby C. , Liu Haining , Burnette Michael T. , Turner C. Heath , Bara Jason E.
Published: November 2016

Coordinated ionic liquid (IL) monomers provide many of the benefits of conventional ILs in radical polymerization with the advantage of relatively simple synthesis and recovery of the polymer product. Previous studies have reported high solubilities of lithium bistriflimide in polar organic monomers such as methyl methacrylate (MMA), 1‐vinylimidazole (VIm) and others. Here, coordinated IL monomers are formed comprising a variety of alkali and alkaline earth Mn+(Tf2N−)n salts with MMA and VIm, and polymerization behavior is investigated using real‐time attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT‐IR). The size and valency of the coordinated Mn+ cations are observed to strongly influence monomer reactivity, as evidenced by significant changes in FT‐IR spectra. This work further demonstrates that the bulky, delocalized [Tf2N]− anion allows for facile introduction of a wide range of Mn+ cations into organic polymers without phase separation, which may open opportunities for new composite materials.

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Anhidrosis in multiple system atrophy involves pre‐ and postganglionic sudomotor dysfunction
Authors: Coon Elizabeth A. , Fealey Robert D. , Sletten David M. , Mandrekar Jay N. , Benarroch Eduardo E. , Sandroni Paola , Low Phillip A. , Singer Wolfgang
Published: November 2016

Background

The objective of this study was to characterize the degree, pattern, lesion site, and temporal evolution of sudomotor dysfunction in multiple system atrophy (MSA) and to evaluate differences by parkinsonian (MSA‐parkinsonism) and cerebellar (MSA‐cerebellar) subtypes.

Methods

All cases of MSA evaluated at Mayo Clinic Rochester between 2005 and 2010 with postganglionic sudomotor testing and thermoregulatory sweat test were reviewed. Pattern and lesion site (preganglionic, postganglionic, or mixed) were determined based on thermoregulatory sweat test and postganglionic sudomotor testing.

Results

The majority of the 232 patients were MSA‐parkinsonism (145, 63%). Initial postganglionic sudomotor testing was abnormal in 59%, whereas thermoregulatory sweat test was abnormal in 95% of all patients. MSA‐parkinsonism patients were more likely to have an abnormal thermoregulatory sweat test compared with MSA‐cerebellar (98% versus 90%, P = 0.006) and had a higher mean percentage of anhidrosis (57%) compared with MSA‐cerebellar (48%; P = 0.033). Common anhidrosis patterns were regional (38%) and global (35%). The site of the lesion was preganglionic in 47% and mixed (preganglionic and postganglionic) in 41%. The increase in anhidrosis per year was 6.2% based on 70 repeat thermoregulatory sweat tests performed on 29 patients. The frequency of postganglionic sudomotor abnormalities increased over time.

Conclusions

Our findings suggest: (1) sudomotor dysfunction is almost invariably present in MSA and even more common and severe in MSA‐parkinsonism than MSA‐cerebellar; (2) a preganglionic pattern of sweat loss is common in MSA; however, pre‐ and postganglionic abnormalities may coexist; and (3) the increasing frequency of postganglionic sudomotor dysfunction over time suggests involvement of postganglionic fibers or sweat glands later in the disease course. © 2016 International Parkinson and Movement Disorder Society
The pathobiology of vascular malformations: insights from human and model organism genetics
Authors: Wetzel‐Strong Sarah E , Detter Matthew R , Marchuk Douglas A
Published: November 2016

Vascular malformations may arise in any of the vascular beds present in the human body. These lesions vary in location, type, and clinical severity of the phenotype. In recent years, the genetic basis of several vascular malformations has been elucidated. This review will consider how the identification of the genetic factors contributing to different vascular malformations, with subsequent functional studies in animal models, has provided a better understanding of these factors that maintain vascular integrity in vascular beds, as well as their role in the pathogenesis of vascular malformations. Copyright © 2016 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.
Favorable outcomes after in utero transfusion in fetuses with alpha thalassemia major: a case series and review of the literature
Authors: Kreger Emily M. , Singer Sylvia T. , Witt Russell G. , Sweeters Nancy , Lianoglou Billie , Lal Ashutosh , Mackenzie Tippi C. , Vichinsky Elliott
Published: November 2016

Objective

Alpha thalassemia major (ATM) is often fatal in utero due to severe hydrops fetalis. Although in utero transfusions (IUTs) are increasingly used to allow fetal survival in ATM, prenatal and postnatal outcomes are not well described.

Methods

We retrospectively reviewed cases of ATM at our institution treated with consecutive IUT. Clinical records were reviewed for transfusion history, neurodevelopmental outcomes, anatomic abnormalities, survival to hematopoietic cell transplantation, and transfusion independence. A systematic review was performed, and additional reported cases are discussed.

Results

Three patients who underwent IUT for ATM were identified, and review of the literature revealed 17 reported cases. Of patients who received IUT, reported neurodevelopmental deficits occurred in 29% (4/14) and anatomic abnormalities in 55% (11/20). Four patients eventually underwent successful hematopoietic cell transplantation. Transfusion volumes were less than suggested guidelines for other causes of fetal anemia in 91.7% of the transfusions.

Conclusion

This series demonstrates the potential for achieving full fetal development with normal neurologic outcomes in those affected by ATM. It provides support for continued patient and provider education about current benefits and risks of active prenatal therapy for fetuses with ATM, as well as continued research to optimize therapeutic strategies such as in utero transplantation. © 2016 John Wiley & Sons, Ltd.
Enhancement of electrical conductivity and other related properties of epoxidized natural rubber/carbon nanotube composites by optimizing concentration of 3‐aminopropyltriethoxy silane
Authors: Nakaramontri Yeampon , Nakason Charoen , Kummerlöwe Claudia , Vennemann Norbert
Published: November 2016

Carbon nanotube (CNT)‐filled epoxidized natural rubber (ENR) composites were prepared by mixing in an internal mixer and thereafter on a two‐roll mill. Silane coupling agent, namely 3‐aminopropyltriethoxy silane (APTES), was directly incorporated in the ENR‐CNT composites during mixing of rubber and CNTs in the mixer, to perform in situ functionalization. It was found that pre‐crosslinking of ENR and APTES occurred especially at high APTES concentrations, such as 0.06 mL/(g of CNTs) and caused strong CNT agglomeration in the ENR matrix. However, the pre‐crosslinking could be reduced or avoided by decreasing the APTES concentration. In the concentration range 0.01–0.015 mL/(g of CNTs) of APTES, the APTES molecules were grafted on the CNT surfaces and generated new chemical linkages with the ENR. This improved the CNT dispersion in the ENR matrix and enhanced the composite properties. A very low approximately 0.5 phr of CNT threshold concentration for electric percolation was achieved in this type of composites. Also, three‐dimensional connected CNT networks were found to form in the ENR matrix at very low APTES levels. Thus, the electrical conductivity achieved in these composites reached the level required of conductive materials. POLYM. ENG. SCI., 57:381–391, 2017. © 2016 Society of Plastics Engineers
Automation of PRM‐dependent D3‐Leu tracer enrichment in HDL to study the metabolism of apoA‐I, LCAT and other apolipoproteins
Authors: Lee Lang Ho , Andraski Allison B. , Pieper Brett , Higashi Hideyuki , Sacks Frank M. , Aikawa Masanori , Singh Sasha A.
Published: November 2016

We developed an automated quantification workflow for PRM‐enabled detection of D3‐Leu labeled apoA‐I in high‐density lipoprotein (HDL) isolated from humans. Subjects received a bolus injection of D3‐Leu and blood was drawn at eight time points over three days. HDL was isolated and separated into six size fractions for subsequent proteolysis and PRM analysis for the detection of D3‐Leu signal from ∼0.03 to 0.6% enrichment. We implemented an intensity‐based quantification approach that takes advantage of high‐resolution/accurate mass PRM scans to identify the D3‐Leu 2HM3 ion from non‐specific peaks. Our workflow includes five modules for extracting the targeted PRM peak intensities (XPIs): Peak centroiding, noise removal, fragment ion matching using Δm/z windows, nine intensity quantification options, and validation and visualization outputs. We optimized the XPI workflow using in vitro synthesized and clinical samples of D0/D3‐Leu labeled apoA‐I. Three subjects’ apoA‐I enrichment curves in six HDL size fractions, and LCAT, apoA‐II and apoE from two size fractions were generated within a few hours. Our PRM strategy and automated quantification workflow will expedite the turnaround of HDL apoA‐I metabolism data in clinical studies that aim to understand and treat the mechanisms behind dyslipidemia.