bluuebunny/crossref_metadata_2025 huggingface dataset:
The origin of widespread species in a poor dispersing lineage (diving beetle genusDeronectes)
Authors: García-Vázquez David , Ribera Ignacio
Published: September 2016

In most lineages, most species have restricted geographic ranges, with only few reaching widespread distributions. How these widespread species reached their current ranges is an intriguing biogeographic and evolutionary question, especially in groups known to be poor dispersers. We reconstructed the biogeographic and temporal origin of the widespread species in a lineage with particularly poor dispersal capabilities, the diving beetle genusDeronectes(Dytiscidae). Most of the ca. 60 described species ofDeronecteshave narrow ranges in the Mediterranean area, with only four species with widespread European distributions. We sequenced four mitochondrial and two nuclear genes of 297 specimens of 109 different populations covering the entire distribution of the four lineages ofDeronectes, including widespread species. Using Bayesian probabilities with an a priori evolutionary rate, we performed (1) a global phylogeny/phylogeography to estimate the relationships of the main lineages within each group and root them, and (2) demographic analyses of the best population coalescent model for each species group, including a reconstruction of the geographical history estimated from the distribution of the sampled localities. We also selected 56 specimens to test for the presence ofWolbachia, a maternally transmitted parasite that can alter the patterns of mtDNA variability. All species of the four studied groups originated in the southern Mediterranean peninsulas and were estimated to be of Pleistocene origin. In three of the four widespread species, the central and northern European populations were nested within those in the northern areas of the Anatolian, Balkan and Iberian peninsulas respectively, suggesting a range expansion at the edge of the southern refugia. In the Mediterranean peninsulas the widespread European species were replaced by vicariant taxa of recent origin. The fourth species (D. moestus) was proven to be a composite of unrecognised lineages with more restricted distributions around the Western and Central Mediterranean. The analysis ofWolbachiashowed a high prevalence of infection amongDeronectes, especially in theD. aubeigroup, where all sequenced populations were infected with the only exception of the Cantabrian Mountains, the westernmost area of distribution of the lineage. In this group there was a phylogenetic incongruence between the mitochondrial and the nuclear sequence, although no clear pattern links this discordance to theWolbachiainfection. Our results suggest that, in different glacial cycles, populations that happened to be at the edge of the newly deglaciated areas took advantage of the optimal ecological conditions to expand their ranges to central and northern Europe. Once this favourable ecological window ended populations become isolated, resulting in the presence of closely related but distinct species in the Mediterranean peninsulas.
The crustal structure of the Arizona Transition Zone and southern Colorado Plateau from multiobservable probabilistic inversion
Authors: Tork Qashqai Mehdi , Carlos Afonso Juan , Yang Yingjie
Published: September 2016

The Arizona Transition Zone is a narrow band that separates two of the main and most contrasting tectonic provinces in western US, namely the southern Colorado Plateau and the southern Basin and Range provinces. As such, the internal crustal structure and physical state of this transitional zone hold clues for understanding (i) the amalgamation of these provinces, (ii) the partitioning of deformation due to both past and present‐day stress fields, and (iii) the role of thermal versus compositional effects in controlling surface observables. Here we employ and expand a novel multiobservable probabilistic inversion method and jointly invert fundamental mode Rayleigh phase velocities, receiver functions, surface heat flow, geoid height, and absolute elevation to obtain an internally consistent 3‐D model of the temperature, density, Vs, and Vp of the Arizona Transition Zone and the southern portions of the Colorado Plateau and Basin and Range. Our results confirm a significant crustal thickening from ∼28 km in the SW of the Arizona Transition Zone and southern Basin and Range to ∼48 km beneath the southern Colorado Plateau. Inverted temperatures agree well with the location of recent volcanism and indicate that the lithosphere‐asthenosphere boundary is not deeper than ∼70 km in most of the region. We find that major pre‐Cambrian surface structures and/or shear zones separate crustal domains with distinct bulk properties, suggesting that the juxtaposed crustal blocks still retain, at least in part, their original characteristics. However, widespread intrusions of significant volumes of mafic magmas have affected these blocks at different depths, locally overprinting their original compositions and creating highly heterogeneous crustal sections. A dominant and large‐scale internal crustal pattern of SW dipping planes/structures is evident in our models, coinciding with the orientation of deep faults previously inferred from earthquake focal mechanisms. While we cannot categorically corroborate the presence of melt or aqueous fluids within the crust, our results are compatible with these scenarios beneath some parts of the Basin and Range, the Mogollon‐Datil, and Springerville volcanic fields.
Characterizing and understanding systematic biases in the vertical structure of clouds in CMIP5/CFMIP2 models
Authors: Cesana G. , Waliser D. E.
Published: September 2016

From a traditional low‐, middle‐, and high‐cloud “layered” perspective as well as a more detailed “level” perspective (40 levels), we compare the vertical distribution of clouds in 12 general circulation models (GCMs) against the GCM‐Oriented Cloud‐Aerosols Lidar and Infrared Pathfinder Satellite Observations Cloud Product (CALIPSO‐GOCCP) using a satellite simulator approach. The layered perspective shows that models exhibit the similar regional biases: an overestimate (underestimate) of high clouds over oceans (continents) in the tropics and a strong underestimate of low clouds over stratocumulus regions. Although high clouds are too infrequent on average, the level perspective reveals that high‐level clouds fill too many upper levels of the column when present (geometrically too thick), suggesting an overestimation of the cloud overlap. Compositing by dynamical regimes and large‐scale relative humidity shows that the models tend to have too many high‐level clouds in moist environments and too few boundary layer clouds in dry environments regardless of dynamical regimes.
Closing the sea level budget on a regional scale: Trends and variability on the Northwestern European continental shelf
Authors: Frederikse Thomas , Riva Riccardo , Kleinherenbrink Marcel , Wada Yoshihide , van den Broeke Michiel , Marzeion Ben
Published: September 2016

Long‐term trends and decadal variability of sea level in the North Sea and along the Norwegian coast have been studied over the period 1958–2014. We model the spatially nonuniform sea level and solid earth response to large‐scale ice melt and terrestrial water storage changes. GPS observations, corrected for the solid earth deformation, are used to estimate vertical land motion. We find a clear correlation between sea level in the North Sea and along the Norwegian coast and open ocean steric variability in the Bay of Biscay and west of Portugal, which is consistent with the presence of wind‐driven coastally trapped waves. The observed nodal cycle is consistent with tidal equilibrium. We are able to explain the observed sea level trend over the period 1958–2014 well within the standard error of the sum of all contributing processes, as well as the large majority of the observed decadal sea level variability.
Bimaterial interfaces in the south San Andreas Fault with opposite velocity contrasts NW and SE from San Gorgonio Pass
Authors: Share Pieter‐Ewald , Ben‐Zion Yehuda
Published: September 2016

Analysis of fault zone head waves indicates the existence of two deep large‐scale bimaterial interfaces in the structure of the southern San Andreas Fault (SAF) with opposite sense of velocity contrast. One interface extends from the Cajon Pass area to the San Gorgonio Pass (SGP) region and is associated with a slower seismic velocity on the southwest side of the SAF. The second interface extends from the SGP region to the Coachella Valley and involves a slower seismic velocity on the northeast side. Tomographic imaging of alternating velocity structures supports the velocity contrast reversal across the SAF. The observations and expected properties of bimaterial ruptures suggest that earthquakes nucleating slightly to the NW and SE of SGP tend to propagate along the SAF in the opposite along‐strike directions. This is consistent with geological and seismological evidence in the Mojave and southernmost sections of the SAF.
Far‐field pressurization likely caused one of the largest injection induced earthquakes by reactivating a large preexisting basement fault structure
Authors: Yeck W. L. , Weingarten M. , Benz H. M. , McNamara D. E. , Bergman E. A. , Herrmann R. B. , Rubinstein J. L. , Earle P. S.
Published: September 2016

The Mw 5.1 Fairview, Oklahoma, earthquake on 13 February 2016 and its associated seismicity produced the largest moment release in the central and eastern United States since the 2011 Mw 5.7 Prague, Oklahoma, earthquake sequence and is one of the largest earthquakes potentially linked to wastewater injection. This energetic sequence has produced five earthquakes with Mw 4.4 or larger. Almost all of these earthquakes occur in Precambrian basement on a partially unmapped 14 km long fault. Regional injection into the Arbuckle Group increased approximately sevenfold in the 36 months prior to the start of the sequence (January 2015). We suggest far‐field pressurization from clustered, high‐rate wells greater than 12 km from this sequence induced these earthquakes. As compared to the Fairview sequence, seismicity is diffuse near high‐rate wells, where pressure changes are expected to be largest. This points to the critical role that preexisting faults play in the occurrence of large induced earthquakes.
Incipient sensor fault estimation and accommodation for inverter devices in electric railway traction systems
Authors: Zhang Kangkang , Jiang Bin , Yan Xing‐Gang , Mao Zehui
Published: September 2016

This paper proposes an incipient sensor fault estimation and accommodation method for three‐phase PWM inverter devices in electric railway traction systems. First, the dynamics of inverters and incipient voltage sensor faults are modeled. Then, for the augmented system formed by original inverter system and incipient sensor faults, an optimal adaptive unknown input observer is proposed to estimate the inverter voltages, currents and the incipient sensor faults. The designed observer guarantees that the estimation errors converge to the minimal invariant ellipsoid. Moreover, based on the output regulator via internal model principle, the fault accommodation controller is proposed to ensure that the vod and voq voltages track the desired reference voltages with the tracking error converging to the minimal invariant ellipsoid. Finally, simulations based on the traction system in CRH2 (China Railway High‐speed) are presented to verify the effectiveness of the proposed method. Copyright © 2016 John Wiley & Sons, Ltd.
Anomalous Enhancement of Li‐O2 Battery Performance with Li2O2 Films Assisted by NiFeOx Nanofiber Catalysts: Insights into Morphology Control
Authors: Huang Jiaqiang , Zhang Biao , Bai Zhaowen , Guo Ruiqiang , Xu Zheng‐Long , Sadighi Zoya , Qin Lei , Zhang Tong‐Yi , Chen Guohua , Huang Baoling , Kim Jang‐Kyo
Published: September 2016

It is generally understood that particle‐shaped Li2O2 is preferred in Li‐O2 batteries (LOBs) because the dominance of Li2O2 films may lead to poor electrochemical performance. The influence of Li2O2 morphology and its nucleation mechanism are probed by experiments along with the first‐principle calculations. It is revealed that the LOBs with Li2O2 films deliver unexpectedly improved capacities, longer cycles, and significantly reduced overpotentials assisted by NiFeOx nanofiber catalysts. The energetically favored Li 2a vacancies under LiO2‐rich conditions, small crystallites, and large contact areas with the electrode/electrolyte explain the anomalous performance enhancement. Li2O2 films are formed by a heterogeneous nucleation mechanism and the voltage applied, electrolyte, electrode surface, and use of catalysts are identified as the parameters controlling the mechanisms. The mapped correlations among these parameters shed light on the control of Li2O2 morphology for developing high‐performance LOBs.
Novel Cathode Materials for Na‐Ion Batteries Composed of Spoke‐Like Nanorods of Na[Ni0.61Co0.12Mn0.27]O2 Assembled in Spherical Secondary Particles
Authors: Hwang Jang‐Yeon , Myung Seung‐Taek , Yoon Chong Seung , Kim Sung‐Soo , Aurbach Doron , Sun Yang‐Kook
Published: September 2016

The development of high‐energy and high‐power density sodium‐ion batteries is a great challenge for modern electrochemistry. The main hurdle to wide acceptance of sodium‐ion batteries lies in identifying and developing suitable new electrode materials. This study presents a composition‐graded cathode with average composition Na[Ni0.61Co0.12Mn0.27]O2, which exhibits excellent performance and stability. In addition to the concentration gradients of the transition metal ions, the cathode is composed of spoke‐like nanorods assembled into a spherical superstructure. Individual nanorod particles also possess strong crystallographic texture with respect to the center of the spherical particle. Such morphology allows the spoke‐like nanorods to assemble into a compact structure that minimizes its porosity and maximizes its mechanical strength while facilitating Na+‐ion transport into the particle interior. Microcompression tests have explicitly verified the mechanical robustness of the composition‐graded cathode and single particle electrochemical measurements have demonstrated the electrochemical stability during Na+‐ion insertion and extraction at high rates. These structural and morphological features contribute to the delivery of high discharge capacities of 160 mAh (g oxide)−1 at 15 mA g−1 (0.1 C rate) and 130 mAh g−1 at 1500 mA g−1 (10 C rate). The work is a pronounced step forward in the development of new Na ion insertion cathodes with a concentration gradient.
Immune Complexes Mimicking Synthetic Vaccine Nanoparticles for Enhanced Migration and Cross‐Presentation of Dendritic Cells
Authors: Kim Sun‐Young , Phuengkham Hathaichanok , Noh Young‐Woock , Lee Hong‐Guen , Um Soong Ho , Lim Yong Taik
Published: September 2016

The well‐designed activation of dendritic cells (DCs) by enhancing the delivery of antigens and immunostimulatory adjuvants into DCs is a key strategy for efficient cancer immunotherapy. Antigen‐antibody immune complexes (ICs) are known to directly bind to and cross‐link Fc‐gamma receptors (FcγRs) on DCs, which induce enhanced migration of DCs to draining lymph nodes through the up‐regulation of the chemokine receptor CCR7 and cross‐presentation inducing cytotoxic T lymphocyte (CTL) response against tumor antigen. In this study, ICs mimicking synthetic vaccine nanoparticles (NPs) are designed and synthesized by the coating of poly (lactic‐co‐glycolic acid) (PLGA) NPs containing adjuvant (CpG oligodeoxynuleotides (ODNs) as toll‐like receptor 9 ligands) with ovalbumin (OVA) proteins (as model antigens) and by the formation of OVA–OVA antibody ICs. Through the combination of FcγRs‐mediated efficient antigen uptake and CpG ODNs‐based immunostimulation, the secretion of TNF‐α (12.3‐fold), IL‐6 (7.29‐fold), and IL‐12 (11‐fold), homing ability to lymph nodes (7.5‐fold), and cross‐presentation (83.8‐fold IL‐2 secretion) are dramatically increased in DCs treated with PLGA(IC/CpG) NPs. Furthermore, mice vaccinated with DCs treated with PLGA(IC/CpG) NPs induced significant tumor (EG7‐OVA) growth inhibition as well as prolonged survival through CTL‐mediated enhanced cytotoxicity, antigen‐specific responses, and IFN‐γ secretion.
Synthesis of Spiro[piperidine‐3,3′‐oxindoles] via Gold(I)‐Catalyzed Dearomatization of N‐Propargyl‐ and N‐Homoallenyl‐2‐bromotryptamines
Authors: Magné Valentin , Blanchard Florent , Marinetti Angela , Voituriez Arnaud , Guinchard Xavier
Published: September 2016

N‐Propargyl‐ and N‐homoallenyl‐2‐bromo‐β‐tryptamines undergo gold(I)‐catalyzed dearomatizing cyclizations to afford 2‐bromospiroindolenines that are in situ hydrolyzed to furnish spirooxindoles in a one‐pot process. Tryptophane derivatives (R2=CO2Et) led upon cyclization to chiral spirooxindoles in excellent diastereoselectivities.

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A novel NDUFS4 frameshift mutation causes Leigh disease in the Hutterite population
Authors: Lamont Ryan E. , Beaulieu Chandree L. , Bernier Francois P. , Sparkes Rebecca , Innes A. Micheil , Jackel‐Cram Candice , Ober Carole , Parboosingh Jillian S. , Lemire Edmond G.
Published: September 2016

Leigh disease is a progressive, infantile‐onset, neurodegenerative disorder characterized by feeding difficulties, failure to thrive, hypotonia, seizures, and central respiratory compromise. Metabolic and neuroimaging investigations typically identify abnormalities consistent with a disorder of mitochondrial energy metabolism. Mutations in more than 35 genes affecting the mitochondrial respiratory chain encoded from both the nuclear and mitochondrial genomes have been associated with Leigh disease. The clinical presentations of five individuals of Hutterite descent with Leigh disease are described herein. An identity‐by‐descent mapping and candidate gene approach was used to identify a novel homozygous c.393dupA frameshift mutation in the NADH dehydrogenase (ubiquinone) Fe‐S protein 4 (NDUFS4) gene. The carrier frequency of this mutation was estimated in >1,300 Hutterite individuals to be 1 in 27. © 2017 Wiley Periodicals, Inc.
A Stable Crystalline Triarylphosphine Oxide Radical Anion
Authors: Schaub Tobias A. , Zolnhofer Eva M. , Halter Dominik P. , Shubina Tatyana E. , Hampel Frank , Meyer Karsten , Kivala Milan
Published: September 2016

Triarylphosphine oxides (Ar3P=O) are being intensely studied as electron‐accepting (n‐type) materials. Despite the widespread application of these compounds as electron conductors, experimental data regarding the structural and electronic properties of their negatively charged states remain scarce owing to their propensity for follow‐up chemistry. Herein, a carefully designed triarylphosphine oxide scaffold is disclosed that comprises sterically demanding spirofluorenyl moieties to shield the central phosphoryl (P=O) moiety. This compound undergoes chemical one‐electron reduction to afford an exceptionally stable radical anion, which was isolated and characterized by X‐ray crystallography for the very first time. The experimental data, corroborated by computational studies, shall allow for the construction of phosphine oxide materials with enhanced stability.
Copper‐Catalyzed Vicinal Diphosphination of Styrenes: Access to 1,2‐Bis(diphenylphosphino)ethane‐Type Bidentate Ligands from Olefins
Authors: Okugawa Yuto , Hirano Koji , Miura Masahiro
Published: September 2016

A copper/N‐heterocyclic carbene (NHC) catalyzed oxidative vicinal diphosphination of styrenes with diphenyl(trimethylsilyl)phosphine proceeds in the presence of LiOtBu and a pyridine N‐oxide/MnO2 combined oxidant to deliver the corresponding 1,2‐bis(diphenylphosphino)ethanes (DPPEs) in good yields. The present copper catalysis can provide access to the DPPE‐type ligands directly from the relatively simple alkenes.
Water‐in‐Supercritical CO2 Microemulsion Stabilized by a Metal Complex
Authors: Luo Tian , Zhang Jianling , Tan Xiuniang , Liu Chengcheng , Wu Tianbin , Li Wei , Sang Xinxin , Han Buxing , Li Zhihong , Mo Guang , Xing Xueqing , Wu Zhonghua
Published: September 2016

Herein we propose for the first time the utilization of a metal complex for forming water‐in‐supercritical CO2 (scCO2) microemulsions. The water solubility in the metal‐complex‐stabilized microemulsion is significantly improved compared with the conventional water‐in‐scCO2 microemulsions stabilized by hydrocarbons. Such a microemulsion provides a promising route for the in situ CO2 reduction catalyzed by a metal complex at the water/scCO2 interface.
New application of henna extract as an asphaltene inhibitor: an experimental study
Authors: Monjezi Eiman , Rostami Alireza , Joonaki Edris , Shadizadeh Seyyed Reza
Published: September 2016

Taking preventive measures of asphaltene precipitation is of great significance in petroleum production and development. Therefore, a new chemical remediation was developed in the current study. The major objective of this experimental study is investigation of the effects of chemically extracted henna on the behaviour of asphaltene in the Bangestan crude oil during pressure decline due to asphaltene precipitation in the coreflood experiments. The application of henna leaf‐derived inhibitor and their influences on the asphaltene precipitation in the oil wells have not yet been addressed in the literature. Coreflood test results illustrate that subjection of the crude oil to chemically extracted henna decreases the asphaltene precipitation which was obtained by IP143 method. Also, it was concluded that permeability reduction with Bangestan crude oil during coreflooding with henna extract in n‐hexane is less than when it was flooded with pure n‐hexane. The consequence of this investigation is the first break‐in application of chemically extracted henna in oil industry. To this end, the results of the present work can assist us in the subsequent researches about the usage of chemically derived natural compounds for the aims of asphaltene precipitation prevention in underground hydrocarbon reservoirs. © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Blebbishields and mitotic cells exhibit robust macropinocytosis
Authors: Jinesh Goodwin G. , Kamat Ashish M.
Published: September 2016

Cancer stem cells can survive and undergo transformation after apoptosis by initiating robust endocytosis. Endocytosis in‐turn drives formation of serpentine filopodia, which promote construction of blebbishields from apoptotic bodies. However, the status and role of macropinocytosis in blebbishields is not known. Here, we show by scanning electron microscopy and by macropinocytosis assays that blebbishields exhibit robust macropinocytosis. Inhibiting dynamin‐mediated endocytosis does not affect macropinocytosis in blebbishields or in mitotic cells. In addition, inhibiting macropinocytosis did not inhibit construction of blebbishields from apoptotic bodies. Thus, although apoptotic cancer stem cells exhibit robust macropinocytosis, macropinocytosis is not essential to generate blebbishields, although it may play other roles in blebbishield biology. © 2016 BioFactors, 43(2):181–186, 2017
NMR‐based Fragment Screening of Inhibitors Against p300 CH1 and HIF‐1α CTAD Interaction
Authors: Eo Yumi , Shim Myungbo , Phuong Thuy Nguyen Thi , Hoa Phuong Pham , Ahn Dae‐Ro , Ahn Hee‐Chul
Published: September 2016

NMR spectroscopy of p300 CH1 and HIF‐1α CTAD complex was conducted to investigate the conformational status of the complex and to screen the protein–protein interaction inhibitors. The individual p300 CH1 and HIF‐1α CTAD were unstructured or partially structured; however, the complex had well‐defined folded structure. Since the 1H‐15N HSQC spectrum of p300 CH1 or HIF‐1α CTAD in the free state was completely different from that in the bound state, it was possible to discriminate whether the protein was in the complex state or not. Fragment compounds were titrated to p300 CH1 and HIF‐1α CTAD complex and some showed inhibition of protein–protein interaction based on the analyses of NMR spectra. The result shows that NMR‐based screening is possible to discover the fragment chemicals which inhibit the formation of p300 CH1 and HIF‐1α CTAD complex.
Parallel Detection of Anti‐Tuberculosis Antibodies upon a Liquid Crystal‐based Optical Sensor
Authors: Rim Jinseob , Kim Hyeong Jin , Jang Chang‐Hyun
Published: September 2016

In the present study, we developed a label‐free liquid crystal (LC)‐based system to simultaneously detect anti‐tuberculosis (TB) antibodies against multiple antigens. Multiple TB antigens were discretely immobilized on a substrate with nano‐patterns replicated from a buckled poly(dimethylsiloxane) to orient LCs uniformly. After the antibody solution was introduced to surface‐immobilized antigens, non‐specific antibodies did not have any effect on the orientation of LCs; however, the antigen–antibody complexes formed by specific interactions disturbed the orientation of LCs by masking the anisotropic surface topography. The orientational behavior of LCs was visualized with a polarizing optical microscope. The limit of detection was from 0.15 to 1.5 µg/mL. With this method, antibodies in the solution of interest can be identified, which will facilitate the development of a new diagnostic approach for TB.
Fluorescent and Colorimetric Chemosensors for Anions, Metal Ions, Reactive Oxygen Species, Biothiols, and Gases
Authors: Liu Yifan , Hu Ying , Lee Songyi , Lee Dayoung , Yoon Juyoung
Published: September 2016

Colorimetric and fluorescent chemosensors have been actively studied in recent years, and this article covers our contributions to colorimetric and fluorescent chemosensors in detecting anions, metal ions, reactive oxygen species (ROS), reactive nitrogen species (RNS), biothiols, and gases. The chemosensors discussed in this article are categorized according to their corresponding analytes, and the final part is devoted to polydiacetylene‐based chemosensors. We hope that this article will be beneficial in the design of chemosensors for various important analytes.
Prediction of Crystal Density and Explosive Performance of High‐Energy‐Density Molecules Using the Modified MSEP Scheme
Authors: Kim Chan Kyung , Cho Soo Gyeong , Li Jun , Park Byung‐Ho , Kim Chang Kon
Published: September 2016

Fast screening to identify a promising high‐energy‐density molecule (HEDM) is of significant importance in developing high‐performance explosives and propellants. Our molecular surface electrostatic potential (MSEP) method applies well to various physicochemical properties of organic and energetic molecules. In order to apply our method in an efficient way, we utilize molecular structures optimized by semiempirical methods to develop a fast screening approach that is applicable to a large number of HEDM candidates. As a benchmarking test, solid densities, heats of formation, and explosive performances of HEDMs are calculated using the “modified MSEP scheme.” In validating this new scheme, the absolute average errors in crystal densities based on our new scheme are in a range 0.064–0.078 g/cc, which serves as input data in estimating the explosive performance using Cheetah or EXPLO5 package. The fast screening procedure based on our mMSEP (AM1) scheme provides somewhat worse results than the original MSEP scheme in various aspects of the explosive's performance.
Effect of electrostatic interactions on the ultrafiltration behavior of charged bacterial capsular polysaccharides
Authors: Hadidi Mahsa , Buckley John J. , Zydney Andrew L.
Published: September 2016

Charged polysaccharides are used in the food industry, as cosmetics, and as vaccines. The viscosity, thermodynamics, and hydrodynamic properties of these charged polysaccharides are known to be strongly dependent on the solution ionic strength because of both inter‐ and intramolecular electrostatic interactions. The goal of this work was to quantitatively describe the effect of these electrostatic interactions on the ultrafiltration behavior of several charged capsular polysaccharides obtained from Streptococcus pneumoniae and used in the production of Pneumococcus vaccines. Ultrafiltration data were obtained using various Biomax™ polyethersulfone membranes with different nominal molecular weight cutoffs. Polysaccharide transmission decreased with decreasing ionic strength primarily because of the expansion of the charged polysaccharide associated with intramolecular electrostatic repulsion. Data were in good agreement with a simple theoretical model based on solute partitioning in porous membranes, with the effective size of the different polysaccharide serotypes evaluated using size exclusion chromatography at the same ionic conditions. These results provide fundamental insights and practical guidelines for exploiting the effects of electrostatic interactions during the ultrafiltration of charged polysaccharides. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1531–1538, 2016
The use of adjuvant chemotherapy for pancreatic cancer varies widely between hospitals: a nationwide population‐based analysis
Authors: Bakens Maikel J. , van der Geest Lydia G. , van Putten Magreet , van Laarhoven Hanneke W. , Creemers Geert‐Jan , Besselink Marc G. , Lemmens Valery E. , de Hingh Ignace H. ,   the Dutch Pancreatic Cancer Group
Published: September 2016

Adjuvant chemotherapy after pancreatoduodenectomy for pancreatic cancer is currently considered standard of care. In this nationwide study, we investigated which characteristics determine the likelihood of receiving adjuvant chemotherapy and its effect on overall survival. The data were obtained from the Netherlands Cancer Registry. All patients alive 90 days after pancreatoduodenectomy for M0‐pancreatic cancer between 2008 and 2013 in the Netherlands were included in this study. The likelihood to receive adjuvant chemotherapy was analyzed by multilevel logistic regression analysis and differences in time‐to‐first‐chemotherapy were tested for significance by Mann–Whitney U test. Overall survival was assessed by Kaplan–Meier method and Cox regression analysis. Of the 1195 patients undergoing a pancreatoduodenectomy for pancreatic cancer, 642 (54%) patients received adjuvant chemotherapy. Proportions differed significantly between the 19 pancreatic centers, ranging from 26% to 74% (P < 0.001). Median time‐to‐first‐chemotherapy was 6.7 weeks and did not differ between centers. Patients with a higher tumor stage, younger age, and diagnosed more recently were more likely to receive adjuvant treatment. The 5‐year overall survival was significantly prolonged in patients treated with adjuvant chemotherapy—23% versus 17%, log‐rank = 0.01. In Cox regression analysis, treatment with adjuvant chemotherapy significantly prolonged survival compared with treatment without adjuvant chemotherapy. The finding that elderly patients and patients with a low tumor stage are less likely to undergo treatment needs further attention, especially since adjuvant treatment is known to prolong survival in most of these patients.
Adrenaline inhibits osteogenesis via repressing miR‐21 expression
Authors: Chen Danying , Wang Zuolin
Published: September 2016

Sympathetic signaling is involved in bone homeostasis; however, the cellular and molecular mechanisms remain unknown. In this study, we found that the psychological stress mediator adrenaline inhibited osteogenic differentiation of human bone marrow‐derived stem cells (hMSC) by reducing microRNA‐21 (miR‐21) expression. Briefly, adrenaline significantly inhibited the osteogenic differentiation of hMSCs, as observed with both Alizarin red staining and maker gene expression (RUNX2, OSX, OCN, and OPN). During this process, miR‐21 was suppressed by adrenaline via inhibition of histone acetylation, as verified by H3K9Ac chromatin immunoprecipitation (ChIP) assay. MiR‐21 was confirmed to promote hMSC osteogenic differentiation, and overexpression of miR‐21 reversed the impeditive effect of adrenaline on hMSC osteogenic differentiation. Our results demonstrate that down‐regulation of miR‐21 is responsible for the adrenaline‐mediated inhibition of hMSC osteogenic differentiation. These findings indicate a regulation of bone metabolism by psychological stress and also provide a molecular basis for psychological stress‐associated bone diseases.
An Efficient Rhodium‐Catalyzed Carbonylative Annulation of Internal Alkynes and Anilines To Produce Maleimides
Authors: Zhu Fengxiang , Li Yahui , Wang Zechao , Wu Xiao‐Feng
Published: September 2016

A selective and efficient procedure for the carbonylative synthesis of polysubstituted maleimides was developed. With rhodium as the catalyst and acetylacetone (acac) as the ligand, various desired maleimide derivatives were isolated in moderate to excellent yields with good functional group tolerance from the corresponding internal alkynes and anilines.
Multivariate resolution of flattened absorption spectra with weighted least squares; weight selection and rotational ambiguity
Authors: Skvortsov Alexey N.
Published: September 2016

Multivariate curve resolution (MCR) of absorption spectra is now a ubiquitously used tool. However, MCR methods, which use ordinary least squares (OLS) approach, assume that the measurement uncertainties are unbiased and homoscedastic. This is not true for absorption measurements, in which uncertainty variance and bias both increase as the true absorbance increases. The bias produces a well‐known flattening/saturation of the peaks at high optical densities, which makes the data nonlinear and unsuitable for OLS‐based MCR analysis. This problem can be reduced by using weighted least squares (WLS).

In the present paper, the ability of WLS‐based MCR to handle simulated and real datasets with realistic optical noise and flattening was assessed. Three weighting schemes were tested: OLS (unity weights), weights based on the maximum likelihood principle (MLP) and the physics of absorption measurement, and weights based on empirical cutoff (zero weights for saturated data points). The abilities of MCR to recover the true profiles and to evaluate rotational ambiguity of the solutions were compared for the 3 weighting schemes. MLP‐ and cutoff‐based WLS‐MCR produced better resolution of flattened data than OLS, but the success of the extension to strongly flattened spectra depended on data structure. MLP‐based MCR was general and stable, while cutoff‐based MCR was more sensitive to the data but could recover unbiased profiles. Generally, the use of WLS can expand MCR functionality to the analysis of flattened spectra.

The specifics of finding WLS bilinear solutions and approaches to migrate factor‐based MCR methods from OLS to WLS are also discussed.
Circularly Polarized Luminescence: A Review of Experimental and Theoretical Aspects
Authors: Longhi Giovanna , Castiglioni Ettore , Koshoubu Jun , Mazzeo Giuseppe , Abbate Sergio
Published: September 2016

We review the present status of experiments and calculations for circularly polarized luminescence (CPL) of simple organic molecules and of stimuli‐responsive organic molecules. Together with the historical report of the main instrumental approaches, a few crucial points about experiments are tackled, with the aim of defining measurement protocols, in view of the wide availability of commercial apparatuses in the near future. The calculations aimed at interpreting the CPL spectra, mostly based on time‐dependent Density Functional Theory (TD‐DFT) calculations, which started around 2010, are reviewed, limiting the discussion to small to mid‐sized molecules. Some applications of CPL spectra of organic molecules‐based systems are presented, with a focus especially on two fields: material science and biology. Chirality 28:696–707, 2016. © 2016 Wiley Periodicals, Inc.
Detection of the designer benzodiazepine metizolam in urine and preliminary data on its metabolism
Authors: Kintz Pascal , Richeval Camille , Jamey Carole , Ameline Alice , Allorge Delphine , Gaulier Jean‐Michel , Raul Jean‐Sébastien
Published: September 2016

Designer benzodiazepines provide an attractive alternative to prescribed benzodiazepines for abuse purposes as they are readily available via the Internet without control. Metizolam was ordered via the Internet and a 2 mg blue tablet was orally administered to a 54‐year‐old man. Urine samples were collected over 6 days in polypropylene tubes. After liquid/liquid extraction at pH 9.5, metizolam was analyzed by ultra‐performance liquid chromatography‐electrospray ionization‐tandem mass spectrometry (UPLC‐ESI‐MS/MS) using a standard method devoted to benzodiazepines, and ions transitions, at m/z 328.9 > 275.0 and 328.9 > 300.0. Metizolam was detectable in hydrolyzed urine during the 46‐h period, with concentrations always lower than 11 ng/mL. About 0.3% of the initial dose was excreted in urines as total unchanged metizolam during the first 24 h. The most relevant potential CYP‐ and UGT‐dependent metabolites of metizolam were investigated in vitro using human liver microsome incubation and, subsequently, liquid chromatography coupled with quadrupole‐time of flight mass spectrometry (UHPLC‐Q‐TOF‐MS) analysis. Three mono‐hydroxylated metabolites were produced including a hydroxylation compound at the 2‐ethyl moiety of metizolam (M1) as quantitatively main metabolite, and a N‐hydroxymetiazolam (M2). The structure of the third metabolite (M3) could not be elucidated because of a too low experimental production rate. Two authentic urine samples were analyzed using the same analytical method to search for metabolites of metizolam. M1, together with its glucuronide (M1‐Glu), and M2 were observed in urine at the 8 h mark, whereas only M1 and M1‐Glu were still detected in urine at 30 h post administration. Copyright © 2016 John Wiley & Sons, Ltd.
Generation of Janus kinase 1 (JAK1) conditional knockout mice
Authors: Sakamoto Kazuhito , Wehde Barbara L. , Rädler Patrick D. , Triplett Aleata A. , Wagner Kay‐Uwe
Published: September 2016

The biological functions of the Janus kinase 1 (JAK1) are suggested to be pleiotropic since this signal transducer is ubiquitously expressed and coupled to a variety of cytokine receptors. Consequently, mice that are deficient in this tyrosine kinase were reported to die shortly after birth. To facilitate studies that address the biological and molecular functions of JAK1 during postnatal development, we performed gene targeting in embryonic stem cells and generated a Cre/lox‐based conditional knockout mouse model. Expression of Cre recombinase in the germline converted the Jak1 conditional knockout allele (Jak1fl) into a null allele (Jak1‐) that when subsequently crossed into homozygosity led to a complete absence of the JAK1 protein in developing embryos. JAK1 deficient embryos were visibly smaller starting at E15.5. Newborn pups exhibited signs of apnea and died within hours after birth. The examination of fibroblasts from conditional knockout embryos and their littermate wildtype controls expressing JAK1 showed that lack of this Janus kinase resulted in an impaired tyrosine phosphorylation and activation of the downstream Signal Transducers and Activators of Transcription (STATs) 1, 3, and 6. JAK1 conditional knockout mice will be an invaluable tool to study cytokine signaling during normal development and disease progression in adult animals.
Development of methane conversion factor models for Zebu beef cattle fed low‐quality crop residues and by‐products in tropical regions
Authors: Kaewpila Chatchai , Sommart Kritapon
Published: September 2016

The enteric methane conversion factor (Ym) is an important country‐specific value for the provision of precise enteric methane emissions inventory reports. The objectives of this meta‐analysis were to develop and evaluate the empirical Ym models for the national level and the farm level for tropical developing countries according to the IPCC's categorization. We used datasets derived from 18 in vivo feeding experiments from 1999 to 2015 of Zebu beef cattle breeds fed low‐quality crop residues and by‐products. We found that the observed Ym value was 8.2% gross energy (GE) intake (~120 g methane emission head−1 day−1) and ranged from 4.8% to 13.7% GE intake. The IPCC default model (tier 2, Ym = 6.5% ± 1.0% GE intake) underestimated the Ym values by up to 26.1% compared with its refinement of 8.4% ± 0.4% GE intake for the national‐level estimate. Both the IPCC default model and the refined model performed worse in predicting Ym trends at the farm level (root mean square prediction error [MSPE] = 15.1%–23.1%, concordance correlation coefficient [CCC] = 0.16–0.18, R2 = .32). Seven of the extant Ym models based on a linear regression approach also showed inaccurately estimated Ym values (root MSPE = 16.2%–36.0%, CCC = 0.02–0.27, R2 < .37). However, one of the developed models, which related to the complexity of the energy use efficiencies of the diet consumed to Ym, showed adequate accuracy at the farm level (root MSPE = 9.1%, CCC = 0.75, R2 = .67). Our results thus suggest a new Ym model and future challenges for estimating Zebu beef cattle production in tropical developing countries.
Tropical forest loss and its multitrophic effects on insect herbivory
Authors: Morante‐Filho José Carlos , Arroyo‐Rodríguez Víctor , Lohbeck Madelon , Tscharntke Teja , Faria Deborah
Published: September 2016

Forest loss threatens biodiversity, but its potential effects on multitrophic ecological interactions are poorly understood. Insect herbivory depends on complex bottom‐up (e.g., resource availability and plant antiherbivore defenses) and top‐down forces (e.g., abundance of predators and herbivorous), but its determinants in human‐altered tropical landscapes are largely unknown. Using structural equation models, we assessed the direct and indirect effects of forest loss on insect herbivory in 40 landscapes (115 ha each) from two regions with contrasting land‐use change trajectories in the Brazilian Atlantic rainforest. We considered landscape forest cover as an exogenous predictor and (1) forest structure, (2) abundance of predators (birds and arthropods), and (3) abundance of herbivorous arthropods as endogenous predictors of insect leaf damage. From 12 predicted pathways, 11 were significant and showed that (1) leaf damage increases with forest loss (direct effect); (2) leaf damage increases with forest loss through the simplification of vegetation structure and its associated dominance of herbivorous insects (indirect effect); and further demonstrate (3) a lack of top‐down control of herbivores by predators (birds and arthropods). We conclude that forest loss favors insect herbivory by undermining the bottom‐up control (presumably reduced plant antiherbivore defense mechanisms) in forests dominated by fast‐growing pioneer plant species, and by improving the conditions required for herbivores proliferation.
Copyrolysed C3N4‐Ag/ZnO Ternary Heterostructure Systems for Enhanced Adsorption and Photocatalytic Degradation of Tetracycline
Authors: Panneri Suyana , Ganguly Priyanka , Nair Balagopal N. , Mohamed Abdul Azeez Peer , Warrier Krishna Gopakumar , Hareesh Unnikrishnan Nair. S.
Published: September 2016

The graphitic carbon nitride (g‐C3N4) Ag/ZnO (CAZ) nanocomposite heterostructure was prepared by the copyrolysis of a precursor mixture containing melamine and nitrates of zinc and silver. This one‐pot synthetic approach facilitated the incorporation of fine dispersions of Ag and ZnO on C3N4 sheets. The CAZ sample thus prepared exhibited higher adsorption capacity and enhanced sunlight‐induced photocatalytic activity towards tetracycline degradation when compared with compositions of g‐C3N4‐Ag, g‐C3N4‐ZnO, ZnO‐Ag, and g‐C3N4. Incorporation of ZnO helped to utilize the UV component of sunlight, whereas ultrafine dispersions of Ag on the surface of the composite created intimate interfaces, facilitating the direct migration of photoinduced electrons to the Ag surface for an efficient separation of photogenerated electron‐hole pairs. The present work exemplifies a simple and convenient synthetic protocol for processing the tricomponent heterostructured system of g‐C3N4‐Ag/ZnO for the effective degradation of pollutants such as tetracycline.
Oxidative Cleavage of Styrenes Catalyzed by a PdII Complex of an 8‐Hydroxyquinolinonate Ligand
Authors: Jhong Hong‐Ming , Liu Yi‐Hung , Peng Shie‐Ming , Liu Shiuh‐Tzung
Published: September 2016

Synthesis and catalytic activity of palladium complexes of 8‐(pyridin‐2‐ylmethoxy)quinolinone (3) were investigated. Complexation of 3 with [Pd(CH3CN)2Cl2] gave the dimeric palladium complex [{N,N‐(3)PdCl}2] (4). The structure of 4 was characterized by 1H/13C NMR spectroscopy and mass spectrometry, and further confirmed by X‐ray crystallography. Complex 4 acts as a catalyst for oxidative cleavage of C=C bonds, and it catalyzes the hydration of styrenes in an anti‐Markovnikov Wacker manner to give terminal aldehydes as the initial product, which then undergo C–C cleavage to yield the corresponding benzaldehydes. Systematic studies of this catalysis were performed.
Propargyl‐Substituted Thiocarbamoylbenzamidines of Technetium and Rhenium: Steps towards Bioconjugation with Use of Click Chemistry
Authors: Castillo Gomez Juan Daniel , Hagenbach Adelheid , Abram Ulrich
Published: September 2016

A new propargyl‐substituted thiocarbamoylbenzamidine has been synthesized. The compound acts as a tetradentate ligand and forms stable complexes with {ReVO}3+ and {TcVO}3+ cores. Click couplings of the resulting complexes with benzylazide lead to prototype triazole derivatives, which were analyzed by NMR and IR spectroscopy and mass spectrometry, as well as by X‐ray diffraction. A similar coupling procedure has been applied to an azido‐modified angiotensin‐II peptide, which gives the desired rhenium(V) bioconjugate in good yield. The ease of this coupling and the stability of the conjugate recommend such tetradentate thiocarbamoylbenzamidines also for clinically relevant bioconjugates with 99mTc.
Enantioselective Synthesis of Spiro[indoline‐3,2′‐pyrroles] through N‐Heterocyclic‐Carbene‐Catalyzed Formal [3+2] Annulation
Authors: Wang Chengyuan , Zhu Shiya , Wang Guanjun , Li Zhuopeng , Hui Xin‐Ping
Published: September 2016

An N‐heterocyclic‐carbene‐catalyzed asymmetric formal [3+2] annulation reaction of isatin N‐Boc ketimines (Boc = tert‐butyloxycarbonyl) and 3‐bromoenals was developed for the construction of spiro[indoline‐3,2′‐pyrrole] derivatives with one quaternary chiral center in good yields (up to 81 % yield) with excellent enantioselectivity (up to 99 % ee).
Covalent Organic Helical Cages as Sandwich Compound Containers
Authors: Míguez‐Lago Sandra , Cid M. Magdalena , Alonso‐Gómez J. Lorenzo
Published: September 2016

A covalent organic helical cage (COHC) with D3 symmetry bearing two 1,3,5‐trimethylphenyl cores and six di‐tert‐butyldiethynylallene moieties was synthesized and fully characterized. This molecular structure cage, unlike a previously reported one, favors inclusion‐complex formation with organometallic sandwich compounds due to the presence of methyl groups on the aryl rings. The strong chiroptical responses of these COHCs, along with their ability to entrap guest molecules, enabled the detection of a ruthenium sandwich compound by means of electronic circular dichroism (ECD) spectroscopy.