bluuebunny/crossref_metadata_2025 huggingface dataset:
Ecdysone signaling regulates soldier‐specific cuticular pigmentation in the termite Zootermopsis nevadensis
Authors: Masuoka Yudai , Maekawa Kiyoto
Published: May 2016

Termite caste differentiation requires hormonal regulation, but understanding of the role of ecdysone is limited. Here, we investigated the expression and function of ecdysone‐related genes during soldier differentiation in the damp‐wood termite Zootermopsis nevadensis. Ecdysone receptor gene (EcR) was highly expressed in the head just after the presoldier molt. Knockdown of EcR expression in the early presoldier period inhibited the molts into soldiers. However, knockdown in the middle period affected tyrosine metabolic gene expression and inhibited soldier‐specific cuticular tanning. These results suggest that ecdysone activation is involved in soldier‐specific cuticle formation.
Large‐amplitude electric fields in the inner magnetosphere: Van Allen Probes observations of subauroral polarization streams
Authors: Califf S. , Li X. , Wolf R. A. , Zhao H. , Jaynes A. N. , Wilder F. D. , Malaspina D. M. , Redmon R.
Published: May 2016

The subauroral polarization stream (SAPS) is an important magnetosphere‐ionosphere (MI) coupling phenomenon that impacts a range of particle populations in the inner magnetosphere. SAPS studies often emphasize ionospheric signatures of fast westward flows, but the equatorial magnetosphere is also affected through strong radial electric fields in the dusk sector. This study focuses on a period of steady southward interplanetary magnetic field (IMF) during the 29 June 2013 geomagnetic storm where the Van Allen Probes observe a region of intense electric fields near the plasmapause over multiple consecutive outbound duskside passes. We show that the large‐amplitude electric fields near the equatorial plane are consistent with SAPS by investigating the relationship between plasma sheet ion and electron boundaries, associated field‐aligned currents, and the spatial location of the electric fields. By incorporating high‐inclination DMSP data we demonstrate the spatial and temporal variability of the SAPS region, and we suggest that discrete, earthward propagating injections are driving the observed strong electric fields at low L shells in the equatorial magnetosphere. We also show the relationship between SAPS and plasmasphere erosion, as well as a possible correlation with flux enhancements for 100s keV electrons.
Component greenhouse gas fluxes and radiative balance from two deltaic marshes in Louisiana: Pairing chamber techniques and eddy covariance
Authors: Krauss Ken W. , Holm Guerry O. , Perez Brian C. , McWhorter David E. , Cormier Nicole , Moss Rebecca F. , Johnson Darren J. , Neubauer Scott C. , Raynie Richard C.
Published: May 2016

Coastal marshes take up atmospheric CO2 while emitting CO2, CH4, and N2O. This ability to sequester carbon (C) is much greater for wetlands on a per area basis than from most ecosystems, facilitating scientific, political, and economic interest in their value as greenhouse gas sinks. However, the greenhouse gas balance of Gulf of Mexico wetlands is particularly understudied. We describe the net ecosystem exchange (NEEc) of CO2 and CH4 using eddy covariance (EC) in comparison with fluxes of CO2, CH4, and N2O using chambers from brackish and freshwater marshes in Louisiana, USA. From EC, we found that 182 g C m−2 yr−1 was lost through NEEc from the brackish marsh. Of this, 11 g C m−2 yr−1 resulted from net CH4 emissions and the remaining 171 g C m−2 yr−1 resulted from net CO2 emissions. In contrast, −290 g C m2 yr−1 was taken up through NEEc by the freshwater marsh, with 47 g C m−2 yr−1 emitted as CH4 and −337 g C m−2 yr−1 taken up as CO2. From chambers, we discovered that neither site had large fluxes of N2O. Sustained‐flux greenhouse gas accounting metrics indicated that both marshes had a positive (warming) radiative balance, with the brackish marsh having a substantially greater warming effect than the freshwater marsh. That net respiratory emissions of CO2 and CH4 as estimated through chamber techniques were 2–4 times different from emissions estimated through EC requires additional understanding of the artifacts created by different spatial and temporal sampling footprints between techniques.
Editorial: Reviewer selection process and new areas of expertise in GEMS
Authors: Liemohn Michael W. , Balikhin Michael , Kepko Larry , Rodger Alan , Wang Yuming
Published: May 2016

One method of selecting potential reviewers for papers submitted to the Journal of Geophysical Research Space Physics is to filter the user database within the Geophysical Electronic Manuscript System (GEMS) by areas of expertise. The list of these areas in GEMS can be self selected by users in their profile settings. The Editors have added 18 new entries to this list, an increase of 33% more than the previous 55 entries. All space physicists are strongly encouraged to update their profile settings in GEMS, especially their areas of expertise selections, and details of how to do this are provided.
A flexible and robust neural network IASI‐NH3 retrieval algorithm
Authors: Whitburn S. , Van Damme M. , Clarisse L. , Bauduin S. , Heald C. L. , Hadji‐Lazaro J. , Hurtmans D. , Zondlo M. A. , Clerbaux C. , Coheur P.‐F
Published: May 2016

In this paper, we describe a new flexible and robust NH3 retrieval algorithm from measurements of the Infrared Atmospheric Sounding Interferometer (IASI). The method is based on the calculation of a spectral hyperspectral range index (HRI) and subsequent conversion to NH3 columns via a neural network. It is an extension of the method presented in Van Damme et al. (2014a) who used lookup tables (LUT) for the radiance‐concentration conversion. The new method inherits the advantages of the LUT‐based method while providing several significant improvements. These include the following: (1) Complete temperature and humidity vertical profiles can be accounted for. (2) Third‐party NH3 vertical profile information can be used. (3) Reported positive biases of LUT retrieval are reduced, and finally (4) a full measurement uncertainty characterization is provided. A running theme in this study, related to item (2), is the importance of the assumed vertical NH3 profile. We demonstrate the advantages of allowing variable profile shapes in the retrieval. As an example, we analyze how the retrievals change when all NH3 is assumed to be confined to the boundary layer. We analyze different averaging procedures in use for NH3 in the literature, introduced to cope with the variable measurement sensitivity and derive global averaged distributions for the year 2013. A comparison with a GEOS‐Chem modeled global distribution is also presented, showing a general good correspondence (within ±3 × 1015 molecules.cm−2) over most of the Northern Hemisphere. However, IASI finds mean columns about 1–1.5 × 1016 molecules.cm−2 (∼50–60%) lower than GEOS‐Chem for India and the North China plain.
miR‐132 mediates a metabolic shift in prostate cancer cells by targeting Glut1
Authors: Qu Wei , Ding Shi‐mei , Cao Gang , Wang She‐jiao , Zheng Xiang‐hong , Li Guo‐hui
Published: May 2016

Prostate cancer is the second leading cause of cancer‐related deaths among men worldwide. Early diagnosis increases survival rates in patients but the survival rate has remained relatively poor over the past years. Increasing evidence shows that altered metabolism is a critical hallmark in prostate cancer. There is a strong need to explore the molecular mechanisms underlying cancer metabolism for prostate cancer therapy. Whether the aberrant expression of microRNA (miRNA) contributes to cancer metabolism is not fully known. In this study, we found that microRNA‐132 (miR‐132) expression is reduced and thus leads to a metabolic switch in prostate cancer cells. miR‐132 performs this role by increasing Glut1 expression, resulting in the enhanced rate of lactate production and glucose uptake. The altered metabolism induced by decreased miR‐132 levels confers the rapid growth of the cancer cells. These data indicate that miR‐132 is involved in regulating the Warburg effect in prostate cancer by inhibiting Glut1 expression.
Aurora A kinase is required for activation of the Fanconi anemia/BRCA pathway upon DNA damage
Authors: Chun Min Jeong , Hwang Soo Kyung , Kim Hyoun Geun , Goh Sung‐Ho , Kim Sunshin , Lee Chang‐Hun
Published: May 2016

Previous studies have linked the DNA damage response to mitotic progression machinery. Mitotic kinases, such as Aurora A kinase and Polo‐like kinase, are involved in the phosphorylation of cell cycle regulators in response to DNA damage. Here, we investigated the potential involvement of Aurora A kinase in the activation of the Fanconi anemia (FA)/BRCA pathway, which participates in cellular response to DNA interstrand cross‐link lesions (ICL). Initially, we detected interactions between Aurora A kinase and FANCA protein, one of the components of the FA nuclear core complex. Silencing of Aurora A kinase led to inhibition of monoubiquitination of FANCD2 and formation of nuclear foci, the final consequences of FA/BRCA pathway activation upon ICL induction. An in vitro kinase assay revealed that Aurora A kinase phosphorylates S165 of FANCA. Moreover, this phosphorylation event was induced by the treatment with mitomycin C (MMC), an ICL‐inducing agent. In cells overexpressing S165A mutant FANCA, monoubiquitination of FANCD2 and nuclear foci formation was impaired and cellular sensitivity to MMC was enhanced. These results suggest that S165 phosphorylation by Aurora A kinase is required for proper activation of the FA/BRCA pathway in response to DNA damage.
Defining Arthritis for Public Health Surveillance: Methods and Estimates in Four US Population Health Surveys
Authors: Murphy Louise B. , Cisternas Miriam G. , Greenlund Kurt J. , Giles Wayne , Hannan Casey , Helmick Charles G.
Published: May 2016

Objective

To determine the variability of arthritis prevalence in 4 US population health surveys.

Methods

We estimated annualized arthritis prevalence in 2011–2012, among adults age ≥20 years, using 2 definition methods, both based on self‐report: 1) doctor‐/health care provider–diagnosed arthritis in the Behavioral Risk Factor Surveillance Survey (BRFSS), National Health and Nutrition Examination Survey (NHANES), National Health Interview Survey (NHIS), and Medical Expenditure Panel Survey (MEPS); and 2) three arthritis definitions based on International Classification of Diseases, Ninth Revision, Clinical Modification (ICD‐9‐CM) criteria in MEPS (National Arthritis Data Workgroup on Arthritis and Other Rheumatic Conditions [NADW‐AORC], Clinical Classifications Software [CCS], and Centers for Disease Control and Prevention [CDC]).

Results

Diagnosed arthritis prevalence percentages using the surveys were within 3 points of one another (BRFSS 26.2% [99% confidence interval (99% CI) 26.0–26.4], MEPS 26.1% [99% CI 25.0–27.2], NHIS 23.5% [99% CI 22.9–24.1], NHANES 23.0% [99% CI 19.2–26.8]), and those using ICD‐9‐CM were within 5 percentage points of one another (CCS 25.8% [99% CI 24.6–27.1]; CDC 28.3% [99% CI 27.0–29.6]; and NADW‐AORC 30.7% [99% CI 29.4–32.1]). The variation in the estimated number (in millions) affected with diagnosed arthritis was 7.8 (BRFSS 58.5 [99% CI 58.1–59.1], MEPS 59.3 [99% CI 55.6–63.1], NHANES 51.5 [99% CI 37.2–65.5], and NHIS 52.6 [99% CI 50.9–54.4]), and using ICD‐9‐CM definitions it was 11.1 (CCS 58.7 [99% CI 54.5–62.9], CDC 64.3 [99% CI 59.9–68.6], and NADW 69.9 [99% CI 65.2–74.5]). Most (57–70%) reporting diagnosed arthritis also reported ICD‐9‐CM arthritis; respondents reporting diagnosed arthritis were older than those meeting ICD‐9‐CM definitions. Proxy response status affected arthritis prevalence differently across surveys.

Conclusion

Public health practitioners and decision makers are frequently charged with choosing a single number to represent arthritis prevalence in the US population. We encourage them to consider the surveys’ purpose, design, measurement methods, and statistical precision when choosing an estimate.
Charge Transfer to LaAlO3/SrTiO3 Interfaces Controlled by Surface Water Adsorption and Proton Hopping
Authors: Adhikari Sanjay , Garcia‐Castro Andrés C. , Romero Aldo H. , Lee Hyungwoo , Lee Jung‐Woo , Ryu Sangwoo , Eom Chang‐Beom , Cen Cheng
Published: May 2016

Electronic properties of low dimensional systems are particularly sensitive to surface adsorbates. Clear understanding of such phenomena can lead to highly effective and nondestructive material engineering techniques. In this work, water adsorption at the surface of LaAlO3/SrTiO3 heterostructures is systematically studied. The saturation of surface dangling bonds by spontaneous water chemisorptions is found to be a main enabler of the formation of the interface 2D electron gas. In particular, when imbalanced distributions of water based ions, namely protons and hydroxyls, are generated, interface electron doping or depletion becomes surface adsorbates dominant and independent of the LaAlO3 layer thickness. The investigations also reveal the importance of hydrogen bonding through molecular water layers, which provides an energetically feasible pathway for manipulating the surface‐bond protons and thus the interface electrical characteristics.
MoS2 Nanosheets with Widened Interlayer Spacing for High‐Efficiency Removal of Mercury in Aquatic Systems
Authors: Ai Kelong , Ruan Changping , Shen Mengxia , Lu Lehui
Published: May 2016

Molybdenum disulphide (MoS2) has been an attractive target for investigations in the fields of catalysis, sensing, energy storage, electronics, and optoelectronics. However, its potential application in the important area of environmental cleanup has not yet been effectively explored. With an intrinsically sulfur‐rich characteristic and unique 2D structure, MoS2 should be capable of mercury capture and removal. However, successful attempts to apply MoS2 to mercury removal are quite rare, presumably because the vast majority of sulfur atoms are located inside the bulk of MoS2 and are therefore inaccessible for mercury ions. Here, the first experimental evidence that MoS2 nanosheets with widened interlayer spacing are capable of mercury capture, with an extremely high mercury uptake capacity closely matching the theoretically predicted value (2506 mg g−1) and the largest distribution coefficient value (3.53 × 108 mL g−1) is provided. Remarkably, a single treatment of industrial wastewater (polyvinyl chloride industry) with this modified MoS2 could efficiently reduce the mercury concentration (126 p.p.b.) below U.S. Environmental Protection Agency limits for drinking water standards. The findings open up the possibility of expanding the applications of transition metal dichalcogenides in environmental remediation.
Perovskite Materials for Light‐Emitting Diodes and Lasers
Authors: Veldhuis Sjoerd A. , Boix Pablo P. , Yantara Natalia , Li Mingjie , Sum Tze Chien , Mathews Nripan , Mhaisalkar Subodh G.
Published: May 2016

Organic–inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light‐emitting diodes, lasers, and light‐emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light‐emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A−1 have been achieved. Although perovskite light‐emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light‐emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower‐dimensionality layered and three‐dimensional perovskites, nanostructures, charge‐transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light‐emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light‐emitting devices.
Development of soft‐sphere contact models for thermal heat conduction in granular flows
Authors: Morris A. B. , Pannala S. , Ma Z. , Hrenya C. M.
Published: May 2016

Conductive heat transfer to flowing particles occurs when two particles (or a particle and wall) come into contact. The direct conduction between the two bodies depends on the collision dynamics, namely the size of the contact area and the duration of contact. For soft‐sphere discrete‐particle simulations, it is computationally expensive to resolve the true collision time because doing so would require a restrictively small numerical time step. To improve the computational speed, it is common to increase the “softness” of the material to artificially increase the collision time, but doing so affects the heat transfer. In this work, two physically‐based correction terms are derived to compensate for the increased contact area and time stemming from artificial particle softening. By including both correction terms, the impact that artificial softening has on the conductive heat transfer is removed, thus enabling simulations at greatly reduced computational times without sacrificing physical accuracy. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4526–4535, 2016
Higher plasma orexin A levels in children with Prader–Willi syndrome compared with healthy unrelated sibling controls
Authors: Manzardo Ann M. , Johnson Lisa , Miller Jennifer L. , Driscoll Daniel J. , Butler Merlin G.
Published: May 2016

Prader–Willi syndrome (PWS) is a rare genetic neurodevelopmental disorder associated with maladaptive social behavior, hyperphagia, and morbid obesity. Orexin A is a hypothalamic neuropeptide important as a homeostatic regulator of feeding behavior and in energy metabolism through actions in the lateral hypothalamus. Dysregulation of orexin signaling may contribute to behavioral problems and hyperphagia seen in PWS and we sought to assess orexin A levels in PWS relative to controls children. Morning fasting plasma orexin A levels were analyzed in 23 children (aged 5–11 years) with genetically confirmed PWS and 18 age and gender matched healthy unrelated siblings without PWS. Multiplex immune assays utilized the Milliplex Human Neuropeptide Magnetic panel and the Luminex platform. Natural log‐transformed orexin A data were analyzed using general linear model adjusting for diagnosis, gender, age, total body fat and body mass index (BMI). Plasma orexin A levels were significantly higher (P < 0.006) in children with PWS (average ±SD = 1028 pg/ml ± 358) compared with unrelated siblings (average ±SD = 609 pg/ml ± 351; P < 0.001). Orexin A levels correlated with age in females and were significantly elevated in PWS even after these effects were controlled. These findings support the hypothesis that dysregulation of orexin signaling may contribute to behavioral problems and hyperphagia in PWS. Further studies are warranted to better understand the complex relationship between orexin A levels and the problematic behaviors consistently found in individuals with PWS. © 2016 Wiley Periodicals, Inc.
[FeFe]‐Hydrogenase with Chalcogenide Substitutions at the H‐Cluster Maintains Full H2 Evolution Activity
Authors: Noth Jens , Esselborn Julian , Güldenhaupt Jörn , Brünje Annika , Sawyer Anne , Apfel Ulf‐Peter , Gerwert Klaus , Hofmann Eckhard , Winkler Martin , Happe Thomas
Published: May 2016

The [FeFe]‐hydrogenase HYDA1 from Chlamydomonas reinhardtii is particularly amenable to biochemical and biophysical characterization because the H‐cluster in the active site is the only inorganic cofactor present. Herein, we present the complete chemical incorporation of the H‐cluster into the HYDA1‐apoprotein scaffold and, furthermore, the successful replacement of sulfur in the native [4FeH] cluster with selenium. The crystal structure of the reconstituted pre‐mature HYDA1[4Fe4Se]H protein was determined, and a catalytically intact artificial H‐cluster variant was generated upon in vitro maturation. Full hydrogen evolution activity as well as native‐like composition and behavior of the redesigned enzyme were verified through kinetic assays, FTIR spectroscopy, and X‐ray structure analysis. These findings reveal that even a bioinorganic active site with exceptional complexity can exhibit a surprising level of compositional plasticity.
Eintopf‐N2C/C2C/N2N‐Proteinligationsstrategien zur Analyse schwacher Protein‐Protein‐Wechselwirkungen
Authors: Zhao Lei , Ehrt Christiane , Koch Oliver , Wu Yao‐Wen
Published: May 2016

Schwache Protein‐Protein‐Wechselwirkungen sind von zentraler Bedeutung für die Dynamik der Zelle. Leider verhindern geringe Halbwertszeiten eine zufriedenstellende Charakterisierung dieser Komplexe. Die von uns etablierte, leicht umsetzbare und hochspezifische Methode ermöglicht die Erzeugung stabiler Komplexe durch kovalente Verknüpfung räumlich benachbarter Proteintermini. Um das Spektrum möglicher Ligationsreaktionen zu erweitern, wurden drei Strategien angewendet: die bereits etablierte native chemische Ligation (N‐zu‐C‐Terminus, N2C), sowie die Ligation der C‐Termini (C‐zu‐C‐Terminus, C2C) oder N‐Termini (N‐zu‐N‐Terminus, N2N) der wechselwirkenden Proteine in einem Reaktionsansatz. Für die schwache Wechselwirkung zwischen Ypt1 und GDI konnte dabei eine Präferenz für die C2C‐Ligation beobachtet werden (t1/2=4.8 min, annähernd quantitative Umsetzung). Analysen des Ypt1‐GDI‐Addukts ergeben, dass die Wechselwirkung mit der Ypt1‐G‐Domäne das Öffnen der Lipidbindetasche von GDI induziert und die Bindung einer Prenyleinheit ermöglicht. Diese Untersuchungen liefern somit Einblicke in das Rab‐vermittelte Membranrecycling. Der Einsatz der Ligationsstrategie für das transiente KRas‐Homodimer unterstreicht ihre allgemeine Anwendbarkeit.
Differentially Isotope‐Labeled Nucleosomes To Study Asymmetric Histone Modification Crosstalk by Time‐Resolved NMR Spectroscopy
Authors: Liokatis Stamatios , Klingberg Rebecca , Tan Song , Schwarzer Dirk
Published: May 2016

Post‐translational modifications (PTMs) of histones regulate chromatin structure and function. Because nucleosomes contain two copies each of the four core histones, the establishment of different PTMs on individual “sister” histones in the same nucleosomal context, that is, asymmetric histone PTMs, are difficult to analyze. Here, we generated differentially isotope‐labeled nucleosomes to study asymmetric histone modification crosstalk by time‐resolved NMR spectroscopy. Specifically, we present mechanistic insights into nucleosomal histone H3 modification reactions in cis and in trans, that is, within individual H3 copies or between them. We validated our approach by using the H3S10phK14ac crosstalk mechanism, which is mediated by the Gcn5 acetyltransferase. Moreover, phosphorylation assays on methylated substrates showed that, under certain conditions, Haspin kinase is able to produce nucleosomes decorated asymmetrically with two distinct types of PTMs.
Synthesis and structure of a new ternary monocopper(II) complex containing mixed ligands of 2,2′‐diamino‐4,4′‐bithiazole and picrate:in vitroanticancer activity, molecular docking and reactivity towards DNA
Authors: Wang Xi‐Ling , Zheng Kang , Wang Ling‐Yang , Li Yan‐Tuan , Wu Zhi‐Yong , Yan Cui‐Wei
Published: May 2016

A new ternary monocopper(II) complex with co‐ligands of 2,2′‐diamino‐4,4′‐bithiazole (dabt) and picrate (pic), namely [Cu(dabt)(pic)2], has been synthesized and characterized using elemental analyses, molar conductance measurements, infrared and electronic spectral studies and single‐crystal X‐ray diffraction. The crystal structure analyses revealed that the copper(II) ion has a {CuN2O4} distorted octahedral coordination environment. The hydrogen bonding interactions contribute to a three‐dimensional supramolecular structure in the crystal. The reactivity towards herring sperm DNA showed that the copper(II) complex can interact with DNA in the mode of intercalation. The molecular docking of the complex with DNA sequence d(ACCGACGTCGGT)2demonstrated that the copper(II) complex is stabilized by hydrogen bonding interaction. Thein vitroanticancer activities suggested that the copper(II) complex is active against selected tumor cell lines. The effects of the two co‐ligands in the copper(II) complex on DNA‐binding events andin vitroanticancer activity are preliminarily discussed. Copyright © 2016 John Wiley & Sons, Ltd.
Role of epoxidation on segmental motion of polyisoprene as studied by broadband dielectric spectroscopy
Authors: Luo Ming‐Chao , An Ran , Gao Xiao‐Xiao , Zeng Jian , Huang Guang‐Su
Published: May 2016

In this article, the broadband dielectric spectroscopy (BDS) is used to investigate the relaxation behavior of polyisoprene (PI) epoxidized to various levels and the special consideration is devoted to the effect of epoxidation degree on segmental relaxation. To associate segmental relaxation with molecular structure, several empirical equations are used to fit experimental data. Furthermore, we want to discuss the origin of the change of segmental relaxation. Thermal measurement reveals that glass transition temperature of epoxidized PI (EPI) increase with the increase of epoxidation degrees. The epoxidation modification increases the breadth of the dielectric dispersion. Oxirane groups as steric interference enhance the cooperativity of segmental relaxation process and retard the relaxation process, which results in the increase of coupling parameter. Specifically, Vogel–Fulcher–Tammann equation shows the relationship between correlation length and temperature. These results further illustrate the effect of epoxidation group on segmental motion of PI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43879.
Functionalized Benzimidazole Scaffolds: Privileged Heterocycle for Drug Design in Therapeutic Medicine
Authors: Ajani Olayinka O. , Aderohunmu Damilola V. , Ikpo Chinwe O. , Adedapo Adebusayo E. , Olanrewaju Ifedolapo O.
Published: May 2016

Benzimidazole derivatives are crucial structural scaffolds found in diverse libraries of biologically active compounds which are therapeutically useful agents in drug discovery and medicinal research. They are structural isosteres of naturally occurring nucleotides, which allows them to interact with the biopolymers of living systems. Hence, there is a need to couple the latest information with the earlier documentations to understand the current status of the benzimidazole nucleus in medicinal chemistry research. This present work unveils the benzimidazole core as a multifunctional nucleus that serves as a resourceful tool of information for synthetic modifications of old existing candidates in order to tackle drug resistance bottlenecks in therapeutic medicine. This manuscript deals with the recent advances in the synthesis of benzimidazole derivatives, the widespread biological activities as well as pharmacokinetic reports. These present them as a toolbox for fighting infectious diseases and also make them excellent candidates for future drug design.
How Hand Osteoarthritis, Comorbidity, and Pain Interact to Determine Functional Limitation in Older People: Observations From the European Project on OSteoArthritis Study
Authors: Siviero Paola , Zambon Sabina , Limongi Federica , Castell Maria Victoria , Cooper Cyrus , Deeg Dorly J. H. , Denkinger Michael D. , Dennison Elaine M. , Edwards Mark H. , Gesmundo Antonella , Otero Ángel , Pedersen Nancy L. , Peter Richard , Queipo Rocio , Timmermans Erik J. , van Schoor Natasja M. , Maggi Stefania ,   for the EPOSA Research Group
Published: May 2016

Objective

To examine the role of comorbidity and pain in the associations of hand osteoarthritis (OA) with self‐reported and performance‐based physical function in a general population of elderly persons.

Methods

We studied data from 2,942 participants ages 65–85 years in the European Project on OSteoArthritis, a collaborative observational study of 6 European cohorts (from Germany, Italy, The Netherlands, Spain, Sweden, and the UK). Outcome measures included self‐reported physical function of the hands measured by the AUStralian/CANadian Osteoarthritis Hand Index (AUSCAN) for hand OA physical function subscale and performance‐based grip strength measured using a strain gauge dynamometer.

Results

Comorbidity was not a confounder in the association of hand OA with self‐reported and performance‐based functional limitations, while the role of pain as a mediator was confirmed. Anxiety, depression, stroke, and osteoporosis were associated with AUSCAN scores reflecting more impairment. Depression and osteoporosis were associated with less grip strength.

Conclusion

Although comorbidity was decidedly and independently associated with hand functional limitation, it had no effect on the relationship of hand OA with physical function. Hand OA was found to be associated with both self‐reported and performance‐based physical function impairment; the association was found to be partially mediated by pain, which reduced its impact.
Coating Strategies Using Layer‐by‐layer Deposition for Cell Encapsulation
Authors: Oliveira Mariana B. , Hatami Javad , Mano João F.
Published: May 2016

The layer‐by‐layer (LbL) deposition technique is widely used to develop multilayered films based on the directed assembly of complementary materials. In the last decade, thin multilayers prepared by LbL deposition have been applied in biological fields, namely, for cellular encapsulation, due to their versatile processing and tunable properties. Their use was suggested as an alternative approach to overcome the drawbacks of bulk hydrogels, for endocrine cells transplantation or tissue engineering approaches, as effective cytoprotective agents, or as a way to control cell division. Nanostructured multilayered materials are currently used in the nanomodification of the surfaces of single cells and cell aggregates, and are also suitable as coatings for cell‐laden hydrogels or other biomaterials, which may later be transformed to highly permeable hollow capsules. In this Focus Review, we discuss the applications of LbL cell encapsulation in distinct fields, including cell therapy, regenerative medicine, and biotechnological applications. Insights regarding practical aspects required to employ LbL for cell encapsulation are also provided.
Azole‐Anion‐Based Aprotic Ionic Liquids: Functional Solvents for Atmospheric CO2 Transformation into Various Heterocyclic Compounds
Authors: Zhao Yanfei , Wu Yunyan , Yuan Guangfeng , Hao Leiduan , Gao Xiang , Yang Zhenzhen , Yu Bo , Zhang Hongye , Liu Zhimin
Published: May 2016

The chemical transformation of atmospheric CO2 is of great significance yet still poses a great challenge. Herein, azole‐anion‐based aprotic ionic liquids (ILs) were synthesized by the deprotonation of weak proton donors (e.g., 2‐methylimidazole, 4‐methylimidazole, and 2,4‐dimethylimidazole) with tetrabutylphosphonium hydroxide, [Bu4P][OH]. We found that these ILs, such as [Bu4P][2‐MIm], could activate atmospheric CO2 through the formation of carbamates. The resultant carbamate intermediates could further react with various types of substrate, including propargylic alcohols, 2‐aminobenzonitriles, ortho‐phenylenediamines, and 2‐aminothiophenol, thereby producing α‐alkylidene cyclic carbonates, quinazoline‐2,4(1 H,3 H)‐diones, benzimidazolones, and benzothiazoline, respectively, in moderate‐to‐good yields. Thus, we have achieved the transformation of CO2 at atmospheric pressure, and we expect this method to open up new routes for the synthesis of various oxygen‐containing heterocyclic compounds under metal‐free conditions.
Streamlined mean field variational Bayes for longitudinal and multilevel data analysis
Authors: Lee Cathy Yuen Yi , Wand Matt P.
Published: May 2016

Streamlined mean field variational Bayes algorithms for efficient fitting and inference in large models for longitudinal and multilevel data analysis are obtained. The number of operations is linear in the number of groups at each level, which represents a two orders of magnitude improvement over the naïve approach. Storage requirements are also lessened considerably. We treat models for the Gaussian and binary response situations. Our algorithms allow the fastest ever approximate Bayesian analyses of arbitrarily large longitudinal and multilevel datasets, with little degradation in accuracy compared with Markov chain Monte Carlo. The modularity of mean field variational Bayes allows relatively simple extension to more complicated scenarios.
Design of new patient-reported outcome measures to assess quality of life, symptoms and treatment satisfaction in patients with abdominal aortic aneurysm
Authors: Peach G , Romaine J , Wilson A , Holt P J E , Thompson M M , Hinchliffe R J , Bradley C
Published: May 2016

Background

No condition-specific patient-reported outcome measures exist for patients with abdominal aortic aneurysm (AAA). The aim of this work was to develop three questionnaires to assess quality of life (QoL), symptoms and treatment satisfaction in patients with AAA.

Methods

Semistructured interview techniques were used to explore patients' experiences of having an AAA in a series of focus groups and in-depth interviews. The information gathered was used to inform design and selection of items for the new tools; the overall structure of the new questionnaires was based on tools developed previously for patients with diabetes and other conditions.

Results

Fifty-four patients (51 men, 3 women; mean age 71·9 years) were recruited from four NHS Trusts to participate in focus groups or interviews, either while under surveillance, or following AAA repair (using open or endovascular techniques). The Aneurysm-Dependent Quality of Life Questionnaire (AneurysmDQoL) is an individualized measure of the impact of AAA on patients' QoL. Twenty-three domains were chosen specifically for their relevance to patients with AAA, with a further two overview items to assess overall QoL and the impact of AAA on QoL. The Aneurysm Symptom Rating Questionnaire (AneurysmSRQ) is a 44-item measure assessing physical and psychological symptoms reported by patients with AAA. The Aneurysm Treatment Satisfaction Questionnaire (AneurysmTSQ) contains 11 items, suitable for patients before and after surgical intervention.

Conclusion

The iterative development process reported here has confirmed that these three new tools have good face and content validity for patients with AAA.
The descending branch of the lateral circumflex femoral artery as an alternative conduit for coronary artery bypass grafting: Experience from an anatomical, radiological and histological study
Authors: Loskot Petr , Tonar Zbynek , Baxa Jan , Valenta Jiri
Published: May 2016

The descending branch of the lateral circumflex femoral artery (DBLCFA) has been suggested as an option for use in coronary artery bypass grafting (CABG). Our aim was to combine radiological examination, surgical and anatomical preparation, and histological assessment of the DBLCFA to map its variability and to assess the benefits of this conduit in cardiac surgery. The pelvic and femoral arteries were examined by CT angiography (CTA) in 100 patients (aged 68.3 ± 9.3 years) to assess the variability of the DBLCFA. Anatomical dissections were performed on 20 cadavers. In 15 patients, an autologous DBLCFA was implanted during CABG. In 35 samples, possible atherosclerotic lesions were examined histologically. The length of the potential DBLCFA conduits measured by CTA was 9.3 ± 2.9 cm, without correlating with the length of the thigh. Anatomical variations that would prevent the DBLCFA from being used in CABG were found in 27 out of 100 patients. Except for focal thickening of the intima, eccentric hypertrophy of the intima was found in three out of 35 samples. No inflammatory infiltration, foam cells, atheroma, or calcifications were found histologically. The DBLCFA is not to be used routinely or in preference to other grafts of choice. However, owing to its moderate variability, sufficient length, caliber, and rare atherosclerosis, it can be used in the absence of other suitable grafts as an alternative conduit implanted as a composite Y‐graft end‐to‐side to the internal thoracic artery in patients without diabetic angiopathy, neuropathy or peripheral artery disease who are undergoing extensive or repeat coronary revascularization. Clin. Anat. 29:779–788, 2016. © 2016 Wiley Periodicals, Inc.
Bleeding complications of triple antithrombotic therapy after percutaneous coronary interventions
Authors: Faza Nadeen N. , Mentias Amgad , Parashar Akhil , Chaudhury Pulkit , Barakat Amr F. , Agarwal Shikhar , Wayangankar Siddharth , Ellis Stephen G. , Murat Tuzcu E. , Kapadia Samir R.
Published: May 2016

Background

5% of patients undergoing coronary stenting have an indication for anticoagulation. The aim of our study was to determine the bleeding rates and complications in patients on triple oral antithrombotic therapy (TOAT) after coronary stenting.

Methods

We studied patients who underwent coronary stenting in our institution between 2003‐2013 and were started on TOAT. Bleeding was the primary outcome.

Results

Totally, 999 patients were treated with TOAT with a median follow up of 127 days. All patients were treated with warfarin as an anticoagulant. 267 patients (26.7%) developed a total of 331 bleeding events. 100 patients had bleeding during the first 30 days of therapy. Major bleeding, minor bleeding, bleeding requiring medical attention, and minimal bleeding developed in 2.9%, 3.3%, 17.2%, and 3.3% of the patients respectively as their most significant bleeding event. Patients with anticoagulation initiated at time of stenting had a significantly higher bleeding rate compared to those already on chronic anticoagulation [adjusted HR (95% CI): 1.37 (1.03–1.79), P = 0.03]. The bleeding likelihood was significantly higher for patients with drug‐eluted stents (DES) compared to bare‐metal stents (BMS) [adjusted OR (95% CI): 1.52 (1.14 − 2.04), P < 0.05]. Patients with atrial fibrillation had an increased rate of bleeding after 6 month of initiation of TOAT with significantly worse outcomes.

Conclusions

TOAT after coronary stenting is associated with high bleeding rates. Patients with AF had worse outcomes. Patients with newly initiated anticoagulation at time of stenting bleed significantly more than people already on chronic anticoagulation prior to stenting. © 2016 Wiley Periodicals, Inc.
Inert Can Be Advantageous: Advisable Reconstruction and Application of Palladium Chloride for the Preferential Oxidation of the Hydrogen Impurity in Carbon Monoxide Streams
Authors: Qiao Luyang , Li Qiaohong , Zhou Zhangfeng , Si Rui , Yao Yuangen
Published: May 2016

Preferential oxidation of the H2 impurity in CO streams is crucial for the catalytic conversion of CO into ethylene glycol. It is uncertain as to whether H2 can overthrow the dominance of CO and finally lead the reaction. Not only is this a typical research issue, but it is also extremely critical for practical applications. So far, no catalyst has shown selectivity higher than 50 % owing to competitive adsorption of CO. In this work, we report a PdClx‐based catalyst that can readily overcome the challenge mentioned above. Over this catalyst, the selectivity of H2 oxidation is promoted by more than 40 % relative to that over the conventional Pd/Al2O3 catalyst and reaches a value of 87 %. The turnover frequency of undesired CO oxidation is inhibited by at least one order of magnitude. We found that the reconstructed palladium chloride was highly selective to this reaction by facile inhibition of the adsorption and oxidation of CO.
Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2‐Phenylethylamine
Authors: Schütz Markus , Bouchet Aude , Chiavarino Barbara , Crestoni Maria Elisa , Fornarini Simonetta , Dopfer Otto
Published: May 2016

Fluorination of pharmaceutical compounds is a common tool to modulate their physiochemical properties. We determine the effects of site‐specific aromatic fluorine substitution on the geometric, energetic, vibrational, and electronic properties of the protonated neurotransmitter 2‐phenylethylamine (xF‐H+PEA, x=ortho, meta, para) by infrared multiphoton photodissociation (IRMPD) in the fingerprint range (600–1750 cm−1) and quantum chemical calculations at the B3LYP‐D3/aug‐cc‐pVTZ level. The IRMPD spectra of all ions are assigned to their folded gauche conformers stabilized by intramolecular NH+⋅⋅⋅π hydrogen bonds (H‐bonds) between the protonated amino group and the aromatic ring. H→F substitution reduces the symmetry and allows for additional NH+⋅⋅⋅F interactions in oF‐H+PEA, leading to three distinct gauche conformers. In comparison to oF‐H+PEA, the fluorination effects on the energy landscape (energy ordering and isomerization barriers) in pF‐H+PEA and mF‐H+PEA with one and two gauche conformers are less pronounced. The strengths of the intramolecular NH+⋅⋅⋅F and NH+⋅⋅⋅π bonds are analyzed by the noncovalent interaction (NCI) method.
A One‐Pot Synthesis of N‐Aryl‐2‐Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes
Authors: Niemi Teemu , Perea‐Buceta Jesus E. , Fernández Israel , Hiltunen Otto‐Matti , Salo Vili , Rautiainen Sari , Räisänen Minna T. , Repo Timo
Published: May 2016

The multicomponent assembly of pharmaceutically relevant N‐aryl‐oxazolidinones through the direct insertion of carbon dioxide into readily available anilines and dibromoalkanes is described. The addition of catalytic amounts of an organosuperbase such as Barton's base enables this transformation to proceed with high yields and exquisite substrate functional‐group tolerance under ambient CO2 pressure and mild temperature. This report also provides the first proof‐of‐principle for the single‐operation synthesis of elusive seven‐membered ring cyclic urethanes.
Thieno[3,4‐c]phosphole‐4,6‐dione: A Versatile Building Block for Phosphorus‐Containing Functional π‐Conjugated Systems
Authors: Takeda Youhei , Hatanaka Kota , Nishida Takuya , Minakata Satoshi
Published: May 2016

A versatile phosphorus‐containing π‐conjugated building block, thieno[3,4‐c]phosphole‐4,6‐dione (TPHODO), has been developed. The utility of this simple but hitherto unknown building block has been demonstrated by preparing novel functional organophosphorus compounds and bandgap‐tunable conjugated polymers.
ChemInform Abstract: Reactions of 2‐Cyclohexen‐1‐ones and Cyclohexane‐1,3‐diones with Chloromethylene Iminium Salts.
Authors: KATRITZKY A. R. , MARSON C. M.
Published: May 2016

Reaction of the cyclohexane‐1,3‐diones (I) and (IV), the 2‐cyclohexen1‐‐ones (VII), cyclohexane‐1,4‐dione (XI) and the dihydronaphthalene (XIII) with Vilsmeier complexes, generated from POCl3 and the formamides (II), (V), or (IX), yields the products shown in the reaction scheme.
ChemInform Abstract: Synthesis via Vinyl Sulfones. Part 23. Addition of Organometallic Reagents to Cyclooctenyl Phenyl Sulfones.
Authors: HARDINGER S. A. , FUCHS P. L.
Published: May 2016

A series of cyclooctenyl and cyclooctadienyl phenyl sulfones, e.g. (IV), (X), (XIV), and (XVII), are synthesized as outlined in the reaction scheme.
ChemInform Abstract: Structural Assignment to (E)‐ and (Z)‐2‐Methyl‐1,3,5‐triphenyl‐2‐pentene‐1,5‐diones and Configurational Studies on Some 1,5‐Enedione Enolates.
Authors: BECHER J. , JACOBSEN J. P. , STIDSEN C. E. , ZIMMERMANN T. , FISCHER G. W.
Published: May 2016

The (E)‐ and (Z)‐configuration of the dione (II) and its higher melting isomer (IV) are confirmed by 1H and 13C NMR.
ChemInform Abstract: New (2.2)Paracyclophane‐1,9‐dienes from 1,9(10)‐Dibromo(2.2)paracyclophane‐1,9‐diene.
Authors: STOEBBE M. + , REISER O. , NAEDER R. + , DE MEIJERE A.
Published: May 2016

Photobromination of (I) and following HBr elimination gives a mixture of the 1,9‐ and 1,10‐dibromoparacyclophanes (IIa) and (IIIb), both of which can be isolated.
ChemInform Abstract: Synthesis of Oxygenated 3‐p‐Benzoquinonyl‐ and 3‐Aryl‐4‐hydroxycoumarins.
Authors: RANI B. S. U. , DARBARWAR M.
Published: May 2016

The coumarins (I) are coupled with p‐benzoquinone (II) to yield the benzoquinolylcoumarins (III).
ChemInform Abstract: Reactions on Heterocycles Containing the 2‐Acyl‐2‐propenone Structure. Part 6. A Novel Preparation of 6‐Oxo‐6H‐(1)benzopyrano(4,3‐b)quinoline Derivatives.
Authors: HEBER D.
Published: May 2016

The chlorocoumarin‐3‐carbaldehydes (I) are coupled with the para‐substituted anilines (II) in the presence of aluminum trichloride, yielding the quinolinobenzopyranones (III) or (IV).
ChemInform Abstract: Synthesis and Properties of a Series of Ruthenium Dihydrogen Complexes.
Authors: CHINN M. S. , HEINEKEY D. M.
Published: May 2016

Protonation of the Ru complex (I) affords the cationic dihydrogen complexes (II).
ChemInform Abstract: DT Diaphorase: A Quinone Reductase with Special Functions in Cell Metabolism and Detoxication
Authors: ‐ ‐
Published: May 2016

Review: (international conference at the Arrhenius Laboratory, University of Stockholm, June 1986; containing a historical review with 183 refs.
ChemInform Abstract: Moessbauer Study of Iron Oxide Surface Layers Formed on Fine Iron Particles
Authors: MAEDA Y. , ARAMAKI M. , TAKASHIMA Y. , OOGAI M. , GOTO T.
Published: May 2016

(15 nm diameter, 100 nm long).
ChemInform Abstract: Lithium Insertion into V4O9.
Authors: HAMMOUCHE A. , HAMMOU A.
Published: May 2016

Coulometric titration and galvanostatic cycling results obtained for Li/V4O9 cells with solid polymeric electrolyte operating at 80 °C indicate that four Li per formula can be inserted at low current.
ChemInform Abstract: Novel Phosphides of Rare Earth Metals and Nickel.
Authors: CHIKHRII S. I. , ORISHCHIN S. V. , KUZ'MA YU. B.
Published: May 2016

The novel compound Tb1‐xNiP (x = 0.05) is synthesized from the elements at 1070 K within 350 h. The X‐ray analysis of a single crystal reveals that this compound has the space group P63/mmc with Z=4.
ChemInform Abstract: Triple Oxides La(M2/3Mo1/3)O3 (M: Mn, Mg) with Perovskite Structure.
Authors: BAZUEV G. V. , MAKAROVA O. V. , SHVEIKIP G. P.
Published: May 2016

A 9:5:12:1 molar mixture of La2O3, MoO3, MO and elemental Mo in a vacuum of 1.33·10‐3 Pa is heated first to 873 K for 6 h and to 1423 K (M: Mn) or 1623 K (M: Mg) for 36 h to afford the title compounds.
ChemInform Abstract: Electronic Ground States, Chemical Reactivity, and Related Properties of Square‐Planar Platinum(II) Dithio Complexes.
Authors: BAKALBASSIS E. G. , KATSOULOS G. A. , TSIPIS C. A.
Published: May 2016

EHMO‐SCCC calculations are carried out on four model Pt(II) complexes of the type (I)‐(IV).
ChemInform Abstract: Flash Photolysis and Quenching Studies of Copper(I) Systems in the Presence of Lewis Bases: Inorganic Exciplexes?
Authors: PALMER C. E. A. , MCMILLIN D. R. , KIRMAIER C. , HOLTEN D.
Published: May 2016

Picosecond flash photolysis studies of the complexes (I) are carried out.
ChemInform Abstract: Asymmetric Reduction of Aromatic Ketones and Asymmetric Hydroboration of 2‐Phenyl‐1‐alkenes with the Reagent Prepared from Borane ‐ Methyl Sulfide and (1S,2S)‐(+)‐2‐Amino‐3‐methoxy‐1‐phenyl‐1‐propanol.
Authors: MANDAL A. K. , KASAR T. G. , MAHAJAN S. W. , JAWALKAR D. G.
Published: May 2016

The chiral amino alcohol (I) is treated with the borane ‐ dimethyl sulfide complex to form a reagent which is used for the asymmetric reduction of the aryl alkyl ketones (IIa) ‐ (IIc) and tert‐butyl methyl ketone (IId), yielding the optically active secondary alcohols (III).
ChemInform Abstract: Chemoselective Reduction of Nitrobenzylidenemalonic Diester by an NADH Model.
Authors: XU H.‐J. , DENG G. , YU Q.
Published: May 2016

Reduction of the p‐nitrobenzylidenemalonic ester (I) is performed under two different conditions using the dihydropyridine (II) as a model compound for NADH.
ChemInform Abstract: Reactivity of Hypervalent Species of Silicon: Cleavage of the Allyl‐ Silicon Bond.
Authors: CERVEAU G. , CHUIT C. , CORRIU R. J. P. , REYE C.
Published: May 2016

The reactivities of the silicon‐allyl bonds in the penta‐coordinated silicon compounds (I) and (II) are compared.