bluuebunny/crossref_metadata_2025 huggingface dataset:
Magnetic phase structure of Saturn's 10.7 h oscillations
Authors: Yates J. N. , Southwood D. J. , Dougherty M. K.
Published: March 2015

A source of Saturn's magnetic 10.7 h period oscillations has yet to be identified. The oscillations are known to consist of signals with slightly different periods from separate northern and southern sources. Here we present a novel way of examining observations, focusing on signal phase. We show that although the signals are highly periodic they are usually not sinusoidal and that there are differences in both phase structure and polarization between the outer magnetosphere (on the nightside) and the inner dipolar region. Paying particular attention to the deep midtail passes of 2006, the contrasting behavior between the inner and outer regions is clear with approximate sinusoidal behavior in the dipolar region and a pulse‐like signal once per cycle in the tail. The latter structure seems to indicate that tail magnetic stress is released impulsively once per cycle in the tail. After equinox, in 2010–2011, we find a different picture in the premidnight sector. The predetermined northern and southern frequencies are closer together and apparently show sudden shifts. Our signal reconstruction approach finds instances where it is likely that the narrow band filtering is not able to track completely the basic north and south periods as we find phase jumps indicating unpredicted beats.
BARREL observations of an ICME‐shock impact with the magnetosphere and the resultant radiation belt electron loss
Authors: Halford A. J. , McGregor S. L. , Murphy K. R. , Millan R. M. , Hudson M. K. , Woodger L. A. , Cattel C. A. , Breneman A. W. , Mann I. R. , Kurth W. S. , Hospodarsky G. B. , Gkioulidou M. , Fennell J. F.
Published: March 2015

The Balloon Array for Radiation belt Relativistic Electron Losses (BARREL) mission of opportunity working in tandem with the Van Allen Probes was designed to study the loss of radiation belt electrons to the ionosphere and upper atmosphere. BARREL is also sensitive to X‐rays from other sources. During the second BARREL campaign, the Sun produced an X‐class flare followed by a solar energetic particle event (SEP) associated with the same active region. Two days later on 9 January 2014, the shock generated by the coronal mass ejection (CME) originating from the active region hits the Earth while BARREL was in a close conjunction with the Van Allen Probes. Time History Events and Macroscale Interactions during Substorms (THEMIS) satellite observed the impact of the interplanetary CME (ICME) shock near the magnetopause, and the Geostationary Operational Environmental Satellites (GOES) were on either side of the BARREL/Van Allen Probe array. The solar interplanetary magnetic field was not ideally oriented to cause a significant geomagnetic storm, but compression from the shock impact led to the loss of radiation belt electrons. We propose that an azimuthal electric field impulse generated by magnetopause compression caused inward electron transport and minimal loss. This process also drove chorus waves, which were responsible for most of the precipitation observed outside the plasmapause. Observations of hiss inside the plasmapause explain the absence of loss at this location. ULF waves were found to be correlated with the structure of the precipitation. We demonstrate how BARREL can monitor precipitation following an ICME‐shock impact at Earth in a cradle‐to‐grave view; from flare, to SEP, to electron precipitation.
Strengthening Kuroshio observed at its origin during November 2010 to October 2012
Authors: Chen Zhaohui , Wu Lixin , Qiu Bo , Li Lei , Hu Dunxin , Liu Chengyan , Jia Fan , Liang Xi
Published: March 2015

Direct measurements of Kuroshio at its origin (18°N, east of the Luzon Island) are conducted from November 2010 to October 2012. It is found that the depth‐averaged Kuroshio between 200 and 700 m has increased over 15 cm s−1 during the 2 year observational period and it is accompanied by the pronounced southward shift of the North Equatorial Current (NEC) bifurcation. Further analysis indicates that the Kuroshio's strengthening is confined to the upstream segment east of the Luzon Island while the Kuroshio decreased as it passed the Luzon Strait due to a dipole‐like sea surface height (SSH) trend between 15°N and 23°N. It is demonstrated that the 2 year strengthening of the Kuroshio, as well as the dipole‐like SSH trend can be adequately reproduced by a 1.5 layer nonlinear reduced gravity model, suggesting an important role of upper ocean response to low‐frequency wind forcing in the western Pacific. Salinity at 500 m depth is also found to increase during the concurrent 2 years. This subthermocline salinity increase is a combined outcome of vertical (basin‐scale isopycnal surface movement) and horizontal advections (i.e., strengthened Kuroshio) due to changes in the large‐scale wind‐driven ocean circulation.
Stroke etiology is associated with outcome in posterior circulation stroke
Authors: Chung Chih‐Ping , Yong Chin‐Sern , Chang Feng‐Chi , Sheng Wen‐Yung , Huang Hui‐Chi , Tsai Jui‐Yao , Hsu Hung‐Yi , Hu Han‐Hwa
Published: March 2015

Objective

Stroke research and clinical trials have focused mainly on anterior circulation stroke (ACS). Since clinical characteristics, mechanisms, and outcomes of posterior circulation stroke (PCS) have been reported different from ACS, more PCS studies are required, particularly researching the etiologies, to help establish an optimal management strategy.

Methods

The present study analyzed patients of PCS who were consecutively admitted and registered in Taipei Veterans General Hospital Stroke Registry between 1 January 2012 to 28 February 2014. We demonstrated the distribution of etiologies, compared the clinical characteristics/outcomes among different etiology groups, and used univariate/multivariate analyses to identify the predictors for poor functional outcome (modified Rankin Scale ≥5) at discharge and 3 month.

Results

About 286 patients of PCS were included for analyses. Basilar artery atheromatous branch occlusive disease (BABO, 28.0%) and large artery dissection (25.9%) were the two most common etiologies, followed by large artery atherosclerotic stenosis/occlusion (LAA, 20.6%), cardioembolism (CE, 18.5%) and small vessel disease (7.0%). Age, vascular risk factors, infarct locations and patterns, and outcomes were different among these five etiology groups. Multivariate analyses showed that age >70 y/o (discharge/3 month, OR, 95% CI: 3.05, 1.23–7.56/8.39, 2.32–30.33), admission NIH Stroke Scale >9 (19.50, 8.69–43.75/13.45, 5.59–32.39), and etiology (LAA versus BABO: 5.00, 1.58–15.83/4.00, 1.19–13.4; CE versus BABO: 3.36, 1.02–11.09/4.66, 1.40–15.46) were independently associated with poor functional outcome.

Interpretation

The etiologies of PCS are heterogeneous and shown to be associated with functional outcomes. Our results have shed lights on future pathophysiological research and designs of clinical trials for PCS.
Great Expectations: Perceptual Challenges of Visual Surveillance in Lifeguarding
Authors: Lanagan‐Leitzel Lyndsey K. , Skow Emily , Moore Cathleen M.
Published: March 2015

The presence of lifeguards on beaches and at pools has the potential to prevent many drowning incidents. This article examines the visual components of the lifeguard's job, discussing some of the major challenges they face during surveillance. These include optical challenges (turbidity and turbulence of the water, light refraction, and glare), scene challenges (elevated set size affecting clutter and perceptual ‘blindnesses’), stimulus challenges (searching for multiple targets that are complex, dynamic, ill‐defined, and rare), and attentional challenges, including but not limited to vigilance issues. The differences between basic laboratory research and the lifeguarding task are explored, with recommendations for future study. Copyright © 2015 John Wiley & Sons, Ltd.
Constructing numerically stable Kalman filter‐based algorithms for gradient‐based adaptive filtering
Authors: Kulikova M. V. , Tsyganova J. V.
Published: March 2015

This paper addresses the numerical aspects of adaptive filtering (AF) techniques for simultaneous state and parameters estimation arising in the design of dynamic positioning systems in many areas of research. The AF schemes consist of a recursive optimization procedure to identify the uncertain system parameters by minimizing an appropriate defined performance index and the application of the Kalman filter (KF) for dynamic positioning purpose. The use of gradient‐based optimization methods in the AF computational schemes yields to a set of the filter sensitivity equations and a set of matrix Riccati‐type sensitivity equations. The filter sensitivities evaluation is usually carried out by the conventional KF, which is known to be numerically unstable, and its derivatives with respect to unknown system parameters. Recently, a novel square‐root approach for the gradient‐based AF by the method of the maximum likelihood has been proposed. In this paper, we show that various square‐root AF schemes can be derived from only two main theoretical results. This elegant and simple computational technique replaces the standard methodology based on direct differentiation of the conventional KF equations (with their inherent numerical instability) by advanced square‐root filters (and its derivatives as well). As a result, it improves the robustness of the computations against round off errors and leads to accurate variants of the gradient‐based AFs. Additionally, such methods are ideal for simultaneous state estimation and parameter identification because all values are computed in parallel. The numerical experiments are given. Copyright © 2015 John Wiley & Sons, Ltd.
Flexible Janus Nanoribbons Array: A New Strategy to Achieve Excellent Electrically Conductive Anisotropy, Magnetism, and Photoluminescence
Authors: Ma Qianli , Wang Jinxian , Dong Xiangting , Yu Wensheng , Liu Guixia
Published: March 2015

A new type of flexible Janus nanoribbons array with anisotropic electrical conductivity, magnetism, and photoluminescence has been successfully fabricated by electrospinning technology using a specially designed parallel spinneret. Every single Janus nanoribbon in the array consists of a half side of Fe3O4 nanoparticles/polyaniline/polymethylmethacrylate (PMMA) conductive‐magnetic bifunctionality and the other half side of Tb(BA)3phen/PMMA insulative‐photoluminescent characteristics, and all the Janus nanoribbons are aligned to form array. Owing to the unique nanostructure, the conductance along with the length direction of nanoribbons reaches up to eight orders of magnitude higher than that along with perpendicular direction, which is by far the most excellent conductive anisotropy for anisotropic conductive materials. The Janus nanoribbons array is also simultaneously endowed with magnetic and photoluminescent characteristics. The obtained Janus nanoribbons array will have important applications in the future subminiature electronic equipments owing to its high electrical anisotropy and multifunctionality. Furthermore, the design concept and fabrication technique for the flexible Janus nanoribbons array provide a new and facile approach for the preparation of anisotropic conductive films with multifunctionality.
Chemical Remodeling of Cell‐Surface Sialic Acids through a Palladium‐Triggered Bioorthogonal Elimination Reaction
Authors: Wang Jie , Cheng Bo , Li Jie , Zhang Zhaoyue , Hong Weiyao , Chen Xing , Chen Peng R.
Published: March 2015

We herein report a chemical decaging strategy for the in situ generation of neuramic acid (Neu), a unique type of sialic acid, on live cells by the use of a palladium‐mediated bioorthogonal elimination reaction. Palladium nanoparticles (Pd NPs) were found to be a highly efficient and biocompatible depropargylation catalyst for the direct conversion of metabolically incorporated N‐(propargyloxycarbonyl)neuramic acid (Neu5Proc) into Neu on cell‐surface glycans. This conversion chemically mimics the enzymatic de‐N‐acetylation of N‐acetylneuramic acid (Neu5Ac), a proposed mechanism for the natural occurrence of Neu on cell‐surface glycans. The bioorthogonal elimination was also exploited for the manipulation of cell‐surface charge by unmasking the free amine at C5 to neutralize the negatively charged carboxyl group at C1 of sialic acids.
η3‐Allylkoordination an Zinn(II) – Reaktivität gegenüber Alkinen und Benzonitril
Authors: Krebs Kilian M. , Wiederkehr Jessica , Schneider Julia , Schubert Hartmut , Eichele Klaus , Wesemann Lars
Published: March 2015

Wir berichten über die Synthese und Charakterisierung eines Allyl‐SnII‐Komplexes, der eine η3‐Koordination in Lösung und im Festkörper aufweist. Zwei Beispiele für die Reaktivität des Allylderivates werden vorgestellt: Die Reaktion mit terminalen Alkinen ergibt tricyclische Verbindungen, während die Umsetzung mit Benzonitril über eine C‐H‐Aktivierung zu einem 16 Atome umfassenden Ringsystem führt.
Iron‐catalyzed cross‐coupling of heteroaromatic tosylates with alkyl and aryl Grignard reagents
Authors: Chen Xu , Quan Zheng‐Jun , Wang Xi‐Cun
Published: March 2015

An Fe(III)‐catalyzed cross‐coupling of N‐heteroaromatic tosylates with aryl and alkyl Grignard reagents is presented. The reaction proceeds at −20°C to room temperature with short reaction time (15–30 min.), and the corresponding products are obtained with moderate to high yields. In particular, low‐cost and abundantly available FeCl3 or Fe(acetylacetonate)3 catalyze the reaction without other special ligands. All tested N‐heteroaromatic tosylates that are available including pyridine and pyrimidine derivatives were subject to the reaction, resulting in the expected products. Copyright © 2015 John Wiley & Sons, Ltd.
Organophosphate‐accelerated copper‐catalyzed C(sp2)–C(sp) Sonogashira‐type cross couplings
Authors: Xu Wei , Yu Bo , Sun Huaming , Zhang Guofang , Zhang Weiqiang , Gao Ziwei
Published: March 2015

A dramatic acceleration in copper‐catalyzed Sonogashira‐type reactions was observed when an organophosphate was used as additive. The catalyst systems featuring low copper loading (0.5 mol% < Cu < 5 mol%) gave Sonogashira‐type products with a broad scope of aromatic and aliphatic terminal alkynes as well as aryl iodides in good to excellent yields. Among the organophosphate/copper catalytic systems, that of 4 mol% Cu(OTf)2/10 mol% (R)‐(−)‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate exhibited the highest catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.
Copper@PMO nanocomposites as a novel reusable heterogeneous catalyst for microwave‐assisted green synthesis of β‐hydroxy‐1,2,3‐triazoles through experimental design protocol
Authors: Naeimi Hossein , Nejadshafiee Vajihe , Masoum Saeed
Published: March 2015

A microwave‐assisted multicomponent reaction was used to prepare a series of β‐hydroxy‐1,2,3‐triazoles in the presence of copper@PMO nanocomposites as a catalyst. Box–Behnken design and response surface methodology were used to optimize the influencing parameters such as catalyst content, reaction time and microwave power, being an economical way of obtaining the optimal reaction conditions based on restricted number of experiments. Aqueous reaction medium, easy recovery of catalyst, efficient recycling and high stability of the catalyst render the protocol sustainable and economic. Copyright © 2015 John Wiley & Sons, Ltd.
SBA‐15‐functionalized melamine–pyridine group‐supported palladium(0) as an efficient heterogeneous and recyclable nanocatalyst for N‐arylation of indoles through Ullmann‐type coupling reactions
Authors: Veisi Hojat , Poor Heravi Mohammad Reza , Hamelian Mona
Published: March 2015

SBA‐15‐functionalized melamine–pyridine group‐supported palladium(0) was found to serve as a heterogeneous and recyclable nanocatalyst for N‐arylation of indoles with aryl iodides under a low catalyst loading (0.3 mol% of Pd) through Ullmann‐type CN coupling reactions. A variety of aryl iodides could be aminated to provide the N‐arylated products in good to excellent yields without the need of an inert atmosphere. Also, this catalyst was found to be an efficient system for the N‐arylation of other nitrogen‐containing heterocycles with aryl iodides. The heterogeneous palladium catalyst could be recovered by simple filtration of the reaction solution and reused for six cycles without significant loss in its activity. Copyright © 2015 John Wiley & Sons, Ltd.
Plasma vs heart tissue concentration in humans – literature data analysis of drugs distribution
Authors: Tylutki Zofia , Polak Sebastian
Published: March 2015

Little is known about the uptake of drugs into the human heart, although it is of great importance nowadays, when science desires to predict tissue level behavior rather than to measure it. Although the drug concentration in cardiac tissue seems a better predictor for physiological and electrophysiological changes than its level in plasma, knowledge of this value is very limited. Tissue to plasma partition coefficients (Kp) come to rescue since they characterize the distribution of a drug among tissues as being one of the input parameters in physiologically based pharmacokinetic (PBPK) models. The article reviews cardiac surgery and forensic medical studies to provide a reference for drug concentrations in human cardiac tissue. Firstly, the focus is on whether a drug penetrates into heart tissue at a therapeutic level; the provided values refer to antibiotics, antifungals and anticancer drugs. Drugs that directly affect cardiomyocyte electrophysiology are another group of interest. Measured levels of amiodarone, digoxin, perhexiline and verapamil in different sites in human cardiac tissue where the compounds might meet ion channels, gives an insight into how these more lipophilic drugs penetrate the heart. Much data are derived from postmortem studies and they provide insight to the cardiac distribution of more than 200 drugs. The analysis depicts potential problems in defining the active concentration location, what may indirectly suggest multiple mechanisms involved in the drug distribution within the heart. Copyright © 2015 John Wiley & Sons, Ltd.
Involvement of microsomal NADPH‐cytochrome P450 reductase in metabolic reduction of drug ketones
Authors: Lehr Matthias , Fabian Jörg , Hanekamp Walburga
Published: March 2015

Recently, it was found that the carbonyl group of 1‐[3‐(4‐phenoxyphenoxy)‐2‐oxopropyl]indole‐5‐carboxylic acid (5), an inhibitor of the pro‐inflammatory enzyme cytosolic phospholipase A2α, is easily reduced by rat liver S9 fractions in vitro. Determination of the inhibitory potency of certain putative inhibitors of carbonyl reducing enzymes on the transformation of the ketone derivative 5 to its alcohol 6 by recombinant microsomal NADPH‐cytochrome P450 reductase and by recombinant cytosolic carbonyl reductase‐1 now reveals that these compounds show a lack of specificity for these two enzymes in part. Thus, an assignment of the roles of different carbonyl reductases in metabolic keto reduction by the use of inhibitors is problematic. In addition, the ability of NADPH‐cytochrome P450 reductase and carbonyl reductase‐1 to reduce the ketone groups of the drugs haloperidol and daunorubicin was examined. Under the conditions applied, a pronounced reductive metabolism was only observed for daunorubicin in the presence of microsomal NADPH‐cytochrome P450 reductase. Similarly, in rat liver S9 fractions a marked reduction of daunorubicin was seen, while haloperidol was only slightly metabolized to its alcohol. After separation of the S9 homogenate into a microsomal and a cytosolic fraction, it became evident that the ketone groups of daunorubicin, haloperidol and compound 5 were mainly reduced by cytosolic enzymes. However, since microsomes also catalysed these carbonyl reductions to some extent, it can be concluded that microsomal NADPH‐cytochrome P450 reductase can contribute to metabolic keto reductions in xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd.
Application of a method used to deconstruct a single dose pharmacokinetic profile from multiple dose data
Authors: Stockmann Chris , Spigarelli Michael G. , Healy Daniel P. , Gottschlich Michele M. , Kagan Richard , Balch Alfred H. , Sherwin Catherine
Published: March 2015

With traditional non‐compartmental methods, it is challenging to deconstruct plasma concentration versus time curves to assess the influence of individual doses. This study describes the application of a mathematical approach used to deconstruct a single dose curve using data derived from the second, third, fourth or nth dosing interval. Using data from a prospective clinical trial it is demonstrated that this approach reliably estimates pharmacokinetic parameters measured following two doses of zolpidem tartrate. Additionally, the study demonstrates the application of this approach using previously published data from a single‐ and multiple‐dose pharmacokinetic study of the antibiotic gatifloxacin. Copyright © 2015 John Wiley & Sons, Ltd.
Dynein motors: How AAA+ ring opening and closing coordinates microtubule binding and linker movement
Authors: Schmidt Helgo
Published: March 2015

Dyneins are a family of motor proteins that move along the microtubule. Motility is generated in the motor domain, which consists of a ring of six AAA+ (ATPases associated with diverse cellular activities) domains, the linker and the microtubule‐binding domain (MTBD). The cyclic ATP‐hydrolysis in the AAA+ ring causes the remodelling of the linker, which creates the necessary force for movement. The production of force has to be synchronized with cycles of microtubule detachment and rebinding to efficiently create movement along the microtubule. The analysis of four dynein motor domain crystal structures in the essay presented here provides evidence that this crucial coordination is carried out by open/closed AAA+ ring conformations.
Randomized clinical trial of laparoscopic colectomy with or without natural-orifice specimen extraction
Authors: Wolthuis A M , Fieuws S , Van Den Bosch A , de Buck van Overstraeten A , D'Hoore A
Published: March 2015

Background

Although conventional laparoscopic colectomy is a validated technique, laparoscopic natural-orifice specimen extraction (NOSE) colectomy might improve outcome. This randomized clinical trial compared analgesia requirements, postoperative pain, anorectal function, inflammatory response and cosmesis in laparoscopic NOSE colectomy and conventional laparoscopic colectomy.

Methods

Patients were randomly assigned to undergo laparoscopic NOSE colectomy or conventional laparoscopic colectomy for left-sided colonic disease. The primary endpoint was analgesia requirement. Secondary endpoints were operative outcome, inflammatory response, anorectal function and cosmesis.

Results

Forty patients were enrolled in the study, 20 in each group (15 with diverticulitis and 5 with colorectal cancer in each group). A significant difference was observed in morphine analogue requirements (1 of 20 patients in the NOSE group versus 10 of 20 in the conventional group; P = 0·003). Patient-controlled epidural analgesia was lower in the NOSE group (mean 116 ml versus 221 ml in the conventional group; P < 0·001), as was paracetamol use (mean 11·0 versus 17·0 g respectively; P < 0·001). Postoperative pain scores were lower in the NOSE group: mean maximum visual analogue score of 3·5 versus 2·1 (P < 0·001). One week after hospital discharge, pain scores remained higher in the conventional group: 15 of 20 patients in the conventional group reported pain, compared with one of 20 in the NOSE group (P < 0·001). Inflammatory responses were greater in patients undergoing NOSE colectomy: higher peak C-reactive protein and interleukin 6 levels were observed on postoperative day 2 (P < 0·001) and day 1 (P = 0·002) respectively. Postoperative anorectal function, complications and hospital stay were similar in the two groups.

Conclusion

Laparoscopic NOSE colectomy was associated with less pain and lower analgesia requirements than the conventional laparoscopic extraction. Registration number: NCT01033838 (http://www.clinicaltrials.gov).
Application of a UPLC‐MS/MS method for the analysis of alosetron in human plasma to support a bioequivalence study in healthy males and females
Authors: Chaudhary Darshan V. , Patel Daxesh P. , Shah Jaivik V. , Shah Priyanka A. , Sanyal Mallika , Shrivastav Pranav S.
Published: March 2015

A simple, rapid and sensitive ultra‐performance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) method has been developed and validated for the determination of alosetron (ALO) in human plasma. The assay method involved solid‐phase extraction of ALO and ALO 13C‐d3 as internal standard (IS) on a LichroSep DVB‐HL (30 mg, 1 cm3) cartridge. The chromatography was performed on an Acquity UPLC BEH C18 (50 × 2.1 mm, 1.7 µm) column using acetonitrile and 2.0 mm ammonium formate, pH 3.0 adjusted with 0.1% formic acid (80:20, v/v) as the mobile phase in an isocratic mode. For quantitative analysis, the multiple reaction monitoring transitions studied were m/z 295.1/201.0 for ALO and m/z 299.1/205.1 for IS in the positive ionization mode. The method was validated over a concentration range of 0.01–10.0 ng/mL for ALO. Post‐column infusion experiment showed no positive or negative peaks in the elution range of the analyte and IS after injection of extracted blank plasma. The extent of ion‐suppression/enhancement, expressed as IS‐normalized matrix factor, varied from 0.96 to 1.04. The assay recovery was within 97–103% for ALO and IS. The method was successfully applied to support a bioequivalence study of 1.0 mg alosetron tablets in 28 healthy Indian male and female subjects. Copyright © 2015 John Wiley & Sons, Ltd.
Functional network mediates age‐related differences in reaction time: a replication and extension study
Authors: Gazes Yunglin , Habeck Christian , O'Shea Deirdre , Razlighi Qolamreza R. , Steffener Jason , Stern Yaakov
Published: March 2015

Introduction

A functional activation (i.e., ordinal trend) pattern was previously identified in both young and older adults during task‐switching performance, the expression of which correlated with reaction time. The current study aimed to (1) replicate this functional activation pattern in a new group of fMRI activation data, and (2) extend the previous study by specifically examining whether the effect of aging on reaction time can be explained by differences in the activation of the functional activation pattern.

Method

A total of 47 young and 50 older participants were included in the extension analysis. Participants performed task‐switching as the activation task and were cued by the color of the stimulus for the task to be performed in each block. To test for replication, two approaches were implemented. The first approach tested the replicability of the predictive power of the previously identified functional activation pattern by forward applying the pattern to the Study II data and the second approach was rederivation of the activation pattern in the Study II data.

Results

Both approaches showed successful replication in the new data set. Using mediation analysis, expression of the pattern from the first approach was found to partially mediate age‐related effects on reaction time such that older age was associated with greater activation of the brain pattern and longer reaction time, suggesting that brain activation efficiency (defined as “the rate of activation increase with increasing task difficulty” in Neuropsychologia 47, 2009, 2015) of the regions in the Ordinal trend pattern directly accounts for age‐related differences in task performance.

Discussion

The successful replication of the functional activation pattern demonstrates the versatility of the Ordinal Trend Canonical Variates Analysis, and the ability to summarize each participant's brain activation map into one number provides a useful metric in multimodal analysis as well as cross‐study comparisons.
Terpenoids from Rhizomes of Alpinia japonica Inhibiting Nitric Oxide Production
Authors: Li Qiang‐Ming , Luo Jian‐Guang , Yang Ming‐Hua , Kong Ling‐Yi
Published: March 2015

A new sesquiterpenoid, 1, and three new diterpenoids, 3–5, along with five known compounds, 2 and 6–9, were isolated from rhizomes of Alpinia japonica. The structures of the new compounds were determined as (1R,4R,6S,7S,9S)‐4α‐hydroxy‐1,9‐peroxybisabola‐2,10‐diene (1), methyl (12E)‐16‐oxolabda‐8(17),12‐dien‐15‐oate (3), (12R)‐15‐ethoxy‐12‐hydroxylabda‐8(17),13(14)‐dien‐16,15‐olide (4), and methyl (11E)‐14,15,16‐trinorlabda‐8(17),11‐dien‐13‐oate (5) by means of spectroscopic data. The absolute configurations at C(4) in 1 and C(12) in 4 were deduced from the circular dichroism (CD) data of the in situ‐formed [Rh2(CF3COO)4] complexes. Inhibitory effects of the isolates on NO production in lipopolysaccharide‐induced RAW264.7 macrophages were evaluated, and 2–4, 6, and 7 were found to exhibit inhibitory activities with IC50 values between 14.6 and 34.3 μM.
Bioactive Diphenyl Ether Derivatives from a Gorgonian‐Derived Fungus Talaromyces sp.
Authors: Chen Min , Han Lei , Shao Chang‐Lun , She Zhi‐Gang , Wang Chang‐Yun
Published: March 2015

Three new diphenyl ether derivatives, talaromycins A–C (1–3, resp.), together with six known analogs, 4–9, were isolated from a gorgonian‐derived fungus, Talaromyces sp. The structures of the new compounds were determined by analysis of extensive NMR spectroscopic data. All of the isolated metabolites, 1–9, were evaluated for their cytotoxic and antifouling activities. Compound 4 exhibited pronounced cytotoxicity against the tested human cell lines with the IC50 values ranging from 4.3 to 9.8 μM. Compounds 3, 5, 8, and 9 showed potent antifouling activities against the larval settlement of the barnacle Balanus amphitrite with the EC50 values ranging from 2.2 to 4.8 μg/ml.
Surface Modification of Carbon Nitride Polymers by Core–Shell Nickel/Nickel Oxide Cocatalysts for Hydrogen Evolution Photocatalysis
Authors: Zhang Guigang , Li Guosheng , Wang Xinchen
Published: March 2015

Ni/NiO core–shell cocatalysts have been prepared on the surface of graphitic carbon nitride by a facile in situ immersion strategy to promote photocatalytic H2 evolution activity under the light irradiation of the conjugated polymer. The physicochemical properties of the as‐prepared hybridized materials were characterized by several techniques, which include XRD, UV‐Raman spectroscopy, diffuse reflectance spectroscopy, photoluminescence spectroscopy, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy, to investigate the composition, texture, surface properties, and optical properties of the samples. In comparison with an unmodified carbon nitride polymer, the Ni/NiO‐decorated sample shows an increased photocatalytic H2 evolution rate and good durability because of the promoted surface kinetics that increase the charge‐transfer rate and reduce the overpotential for H2 evolution dramatically.
Evaluation of smoothing techniques in the run to run optimization of fed‐batch processes with u‐PLS
Authors: Camacho José , Lauri David , Lennox Barry , Escabias Manolo , Valderrama Mariano
Published: March 2015

Run to run (R2R) optimization based on unfolded Partial Least Squares (u‐PLS) is a promising approach for improving the performance of batch and fed‐batch processes as it is able to continuously adapt to changing processing conditions. Using this technique, the regression coefficients of PLS are used to modify the input profile of the process in order to optimize the yield. When this approach was initially proposed, it was observed that the optimization performed better when PLS was combined with a smoothing technique, in particular a sliding window filtering, which constrained the regression coefficients to be smooth. In the present paper, this result is further investigated and some modifications to the original approach are proposed. Also, the suitability of different smoothing techniques in combination with PLS is studied for both end‐of‐batch quality prediction and R2R optimization. The smoothing techniques considered in this paper include the original filtering approach, the introduction of smoothing constraints in the PLS calibration (Penalized PLS), and the use of functional analysis (Functional PLS). Two fed‐batch process simulators are used to illustrate the results. Copyright © 2015 John Wiley & Sons, Ltd.
Photoinduced Formation of an Azobenzene‐Based CD‐Active Supramolecular Cyclic Dimer
Authors: Sogawa Hiromitsu , Terada Kayo , Miyagi Yu , Shiotsuki Masashi , Inai Yoshihito , Masuda Toshio , Sanda Fumio
Published: March 2015

A series of new photo‐responsive amino acid‐derived azobenzenedicarboxylic acid derivatives (S)‐1 a–e were synthesized. Compound (S)‐1 a in the trans form exhibited no circular dichroism (CD) signal in DMF under ambient conditions, whereas intense Cotton effects were observed upon UV irradiation, indicating the formation of a chiral supramolecular structure in the cis form. The CD signals disappeared when trifluoroacetic acid (TFA) was added to the solution. The ester counterpart [(S)‐1 a′] showed no CD signal. Hydrogen bonding between the carboxy groups seemed necessary for constructing the supramolecular structure. The kinetic studies of cis to trans isomerization of (S)‐1 a demonstrated that the formation of a chiral supramolecule enhances the stability of the cis‐azobenzene structure. The ESI mass spectrum of stilbenedicarboxylic acid (S)‐4, an analogue of (S)‐1 b, confirmed the formation of a dimer. A theoretical CD study revealed that (S)‐1 a in the cis form should be present as a cyclic chiral dimer.
Luminescent Nitridophosphates CaP2N4:Eu2+, SrP2N4:Eu2+, BaP2N4:Eu2+, and BaSr2P6N12:Eu2+
Authors: Pucher Florian J. , Marchuk Alexey , Schmidt Peter J. , Wiechert Detlef , Schnick Wolfgang
Published: March 2015

Nitridophosphates MP2N4:Eu2+ (M=Ca, Sr, Ba) and BaSr2P6N12:Eu2+ have been synthesized at elevated pressures and 1100–1300 °C starting from the corresponding azides and P3N5 with EuCl2 as dopant. Addition of NH4Cl as mineralizer allowed for the growth of single crystals. This led to the successful structure elucidation of a highly condensed nitridophosphate from single‐crystal X‐ray diffraction data (CaP2N4:Eu2+ (P63, no. 173), a=16.847(2), c=7.8592(16) Å, V=1931.7(6) Å3, Z=24, 2033 observed reflections, 176 refined parameters, wR2=0.096). Upon excitation by UV light, luminescence due to parity‐allowed 4f6(7F)5d1→4f7(8S7/2) transition was observed in the orange (CaP2N4:Eu2+, λmax=575 nm), green (SrP2N4:Eu2+, λmax=529 nm), and blue regions of the visible spectrum (BaSr2P6N12:Eu2+ and BaP2N4:Eu2+, λmax=450 and 460 nm, respectively). Thus, the emission wavelength decreases with increasing ionic radius of the alkaline‐earth ions. The corresponding full width at half maximum values (2240–2460 cm−1) are comparable to those of other known Eu2+‐doped (oxo)nitrides emitting in the same region of the visible spectrum. Following recently described quaternary Ba3P5N10Br:Eu2+, this investigation represents the first report on the luminescence of Eu2+‐doped ternary nitridophosphates. Similarly to nitridosilicates and related oxonitrides, Eu2+‐doped nitridophosphates may have the potential to be further developed into efficient light‐emitting diode phosphors.
Formation of an Imino‐Stabilized Cyclic Tin(II) Cation from an Amino(imino)stannylene
Authors: Ochiai Tatsumi , Franz Daniel , Irran Elisabeth , Inoue Shigeyoshi
Published: March 2015

The novel amino(imino)stannylene 1 was prepared by conversion of HNIPr (NIPr=bis(2,6‐diisopropylphenyl)imidazolin‐2‐imino) with one equivalent of Lappert’s tin reagent (Sn[N(SiMe3)2]2). Treatment of 1 with DMAP (4‐dimethylaminopyridine) yields its Lewis acid–base adduct 2. The reaction of 1 with one equivalent of trimethylsilyl azide results in replacement of the amino group at the tin center by an N3 substituent with concomitant elimination of N(SiMe3)3 to afford dimeric [N3SnNIPr]2 (3). Remarkably, the reaction of 1 with B(C6F5)3 produces the novel tin(II) monocation 4+[MeB(C6F5)3]− comprising a four‐membered stannacycle through methyl‐abstraction from the trimethylsilyl group.
Trifluoromethylation‐Initiated Remote Cross‐Coupling of Carbonyl Compounds to Form Carbon–Heteroatom/Carbon Bonds
Authors: Huang Lin , Zheng Sheng‐Cai , Tan Bin , Liu Xin‐Yuan
Published: March 2015

By involving the reversal of conventional reactivity expectations without external oxidants, we describe a novel and convenient protocol of remote cross‐coupling of carbonyl compounds with a series of common and simple nucleophiles. This cross‐coupling is triggered by radical trifluoromethylation of alkenes, thereby achieving highly selective remote difunctionalization of alkenes and α‐position of the carbonyl group for facile access to trifluoromethyl α‐halo‐ and α‐cyanocarbonyl compounds. The reaction exhibits a broad substrate scope with excellent functionality tolerance and many different types of nucleophiles; further synthetic applicability of the obtained compounds proved to be suitable, thus showing great potential for synthetic utility.
Catalytic Asymmetric Addition of Meldrum’s Acid, Malononitrile, and 1,3‐Dicarbonyls to ortho‐Quinone Methides Generated In Situ Under Basic Conditions
Authors: Caruana Lorenzo , Mondatori Martina , Corti Vasco , Morales Sara , Mazzanti Andrea , Fochi Mariafrancesca , Bernardi Luca
Published: March 2015

A new approach to the utilization of highly reactive and unstable ortho‐quinone methides (o‐QMs) in catalytic asymmetric settings is presented. The enantioselective reactions are catalysed by bifunctional organocatalysts, and the o‐QM intermediates are formed in situ from 2‐sulfonylalkyl phenols through base‐promoted elimination of sulfinic acid. The use of mild Brønsted basic conditions for transiently generating o‐QMs in catalytic asymmetric processes is unprecedented, and allows engaging productively in the reactions nucleophiles such as Meldrum’s acid, malononitrile and 1,3‐dicarbonyls. The catalytic transformations give new and general entries to 3,4‐dihydrocoumarins, 4H‐chromenes and xanthenones. These frameworks are recurring structures in natural product and medicinal chemistry, as testified by the formal syntheses of (R)‐tolterodine and (S)‐4‐methoxydalbergione from the catalytic adducts.
ChemInform Abstract: Pentacoordinate Phosphorus in a High‐Pressure Polymorph of Phosphorus Nitride Imide P4N6(NH).
Authors: Baumann Dominik , Schnick Wolfgang
Published: March 2015

The title γ‐P4N6(NH) polymorph is obtained by high‐temperature high‐pressure synthesis using P3N5 and NH4Cl in the molar ratio of 4:1 (multianvil cell, 14 GPa, 1200 °C, 3 h).
ChemInform Abstract: Three Structure Types and Intermediate Cerium Valence in the Solid Solution CeRu1—xNixSn.
Authors: Niehaus Oliver , Abdala Paula M. , Touzani Rachid St. , Fokwa Boniface P. T. , Poettgen Rainer
Published: March 2015

Single crystals of the solid solutions CeRu1‐xNixSn (x = 0.12—1) are obtained by melting stoichiometric mixtures of the elements (arc welded Nb ampoules, 1670 K, 5 min; controlled cooling).
ChemInform Abstract: Stacking Faults in a Layered Cobalt Tellurium Phosphate Oxochloride.
Authors: Zimmermann Iwan , Johnsson Mats
Published: March 2015

Purple single crystalline plates of Co2Te3(PO4)O6Cl are obtained from the solid state reaction of an equimolar mixture of CoCl2, CoO, TeO2, and (NH4)H2PO4 (evacuated silica tube, 550 °C, 70 h).
ChemInform Abstract: On the Ternary RExMg1‐xAl2 (RE: Gd—Tm), RE3Ag5.+‐.xMg11 .+‐.x, REAg4+xMg2‐x, RE4Ag10.3Mg12 and RE4Ag10+xMg3‐x (RE: Ce—Nd, Sm) Phases.
Authors: Verbovytskyy Yuriy , Goncalves Antonio Pereira
Published: March 2015

Twenty ternary Mg based alloys (14 of them for the first time) are prepared by melting and annealing the elements (Al2O3 or graphite container, 1.
ChemInform Abstract: Mixed Pentele‐Chalcogen Cationic Chains from Aluminum and Gallium Halide Melts.
Authors: Eich Andreas , Bredow Thomas , Beck Johannes
Published: March 2015

Reactions of Te or Se with Bi or Sb in GaCl3 and AlI3 melts in the presence of SbCl3, BiCl3, or SbCl3 as weak oxidants yield the compounds (Sb2Te2)[GaCl4] (I), (Sb2Te2)I[AlI4] (II), (Bi2Te2)Cl[GaCl4] (III), (Bi2Se2)Cl[GaCl4] (IV), (Sb3Te4)[GaCl4] (V), and (SbTe4)[Ga2Cl7] (VI) with the one‐dimensional polymeric cations (Sb2Te2+)n, (Sb2Te22+)n, (Bi2Te22+)n, (Bi2Se22+)n, (Sb3Te4+)n, and (SbTe4+)n (evacuated glass ampoules, 50‐190 °C, 12‐21 d).
ChemInform Abstract: Solid‐State Crystal‐to‐Crystal Phase Transitions and Reversible Structure—Temperature Behavior of Phosphovanadomolybdic Acid, H5PV2Mo10O40.
Authors: Barats‐Damatov Delina , Shimon Linda J. W. , Feldman Yishay , Bendikov Tatyana , Neumann Ronny
Published: March 2015

The crystal packing and secondary structure of H5PV2Mo12O40 (prepared according to the literature) is analyzed by powder XRD and reveals 4 unique structures (36, 14, 8 units of crystal H2O, the latter in two modifications) and 3 reversible solid phase transitions between 25 and 55 °C depending on the loss of solvated H2O and concomitant contraction of the cell volume and increase of packing density.
ChemInform Abstract: Coexistence of 3d‐Ferromagnetism and Superconductivity in [(Li1‐xFex)OH](Fe1‐yLiy)Se.
Authors: Pachmayr Ursula , Nitsche Fabian , Luetkens Hubertus , Kamusella Sirko , Brueckner Felix , Sarkar Rajib , Klauss Hans‐Henning , Johrendt Dirk
Published: March 2015

(Li0.795Fe0.205)OH (Fe0.915Li0.085)Se is hydrothermally prepared from a mixture of iron metal, selenourea, and LiOH in H2O (autoclave, 150 °C, 8 d) and characterized by powder and single crystal XRD, SEM, 57Fe‐Moessbauer spectroscopy, and DFT electronic structure calculations.
ChemInform Abstract: An Enhancement ZT and Spin State Transition of Ca3Co4O9 with Pb Doping.
Authors: Demirel S. , Altin E. , Oz E. , Altin S. , Bayri A.
Published: March 2015

Ca3‐xPbxCo4O9 (x = 0‐0.75) are prepared by solid state reaction of stoichiometric amounts of CaCO3, Co2O3, and PbO (Al2O3 crucible, 900 °C, 1 d) followed by calcination and sintering in O2 (900 °C, 72 h).
ChemInform Abstract: Structure and Magnetism in Hexagonal Tungsten Bronze Metal Oxides AM1/3W8/3O9 (A—K, Rb, Cs; M—Cr, Fe).
Authors: Ivanov S. A , Sahu J. R. , Voronkova V. I. , Mathieu R. , Nordblad P.
Published: March 2015

Phase‐pure AM1/3W8/3O9 (A: K, Rb, Cs; M: CrIII, FeIII) are prepared by calcination and sintering of stoichiometric mixtures of Cr2O3, Fe2O3, alkali carbonates, and WO3 (800 °C, 12 h).
ChemInform Abstract: Coupling of Crystal Structure and Magnetism in the Layered, Ferromagnetic Insulator CrI3.
Authors: McGuire Michael A. , Dixit Hemant , Cooper Valentino R. , Sales Brian C.
Published: March 2015

Single crystals of CrI3 are grown by chemical vapor transport reaction of stoichiometric amounts of Cr and I2 in a temperature gradient (evacuated quartz tubes, 650 °C→500‐550 °C, several days).
ChemInform Abstract: A New Thermodynamic Parameter GCE for Identification of Glass Forming Compositions.
Authors: Ghazi Sarwat Syed , Ramya M. , Sabahut Ali Prince , Raj Baldev , Ravi K. R.
Published: March 2015

A thermodynamic model (GCE) based on the chemical mixing enthalpy ΔHchem and the elastic enthalpy ΔHelastic is proposed for numerical identification of metallic glass forming compositions.
ChemInform Abstract: Molybdenum Phosphosulfide: An Active, Acid‐Stable, Earth‐Abundant Catalyst for the Hydrogen Evolution Reaction.
Authors: Kibsgaard Jakob , Jaramillo Thomas F.
Published: March 2015

Surface‐sulfur modified MoP catalyst is prepared by drop casting aliquots of 0.25 M (NH4)6Mo7O24 and (NH4)2HPO4 solutions on a Ti foil support followed by drying, thermal reduction (5% H2/N2, 650 °C, 2 h), and thermal sulfidation (10% H2S/H2, 400 °C, 15 min).
ChemInform Abstract: Photocatalytic Water Oxidation by a Pyrochlore Oxide upon Irradiation with Visible Light: Rhodium Substitution into Yttrium Titanate.
Authors: Kiss Borbala , Didier Christophe , Johnson Timothy , Manning Troy D. , Dyer Matthew S. , Cowan Alexander J. , Claridge John B. , Darwent James R. , Rosseinsky Matthew J.
Published: March 2015

A stable visible‐light driven photocatalyst (λ ≥ 450 nm) for H2O oxidation is prepared by Rh substitution into the pyrochlore Y2Ti2O7 to a maximum level of 2% by stoichiometric solid state reactions of Y2O3, TiO2, and Rh2O3 under air (Pt foil lined alumina boat, 1300 °C, 2 d).
ChemInform Abstract: Synthesis and Characterization of the Phosphates Na1+xMg1+xCr2‐x(PO4)3 (x = 0; 0.2) and NaZnCr2(PO4)3 with the α‐CrPO4 Structure.
Authors: Souiwa Khalifa , Hidouri Mourad , Toulemonde Olivier , Duttine Mathieu , Amara Mongi B.
Published: March 2015

Single crystals of Na1.2Mg1.2Cr1.8(PO4)3 are prepared by drying (353 K, 24 h) a 6N HNO3 solution of Na2CO3, Mg(NO3)2, Cr(NO3)3, (NH4)H2PO4, and MoO3 followed by a complex heating schedule (the formed Na2Mo2O7 is used as a flux in 3‐fold molar excess; Pt crucible, 473‐873 K, 24 h/stage; 1523 K, 1 h).
ChemInform Abstract: A New Decaoxidooctaborate(2‐) Anion, [B8O10(OH)6]2‐: Synthesis and Characterization of [Co(en)3][B5O6(OH)4] [B8O10(OH)6)]·5H2O (en = 1,2‐Diaminoethane).
Authors: Altahan Mohammed A. , Beckett Michael A. , Coles Simon J. , Horton Peter N.
Published: March 2015

Single crystals of [Co(en)3][B5O6(OH)4] [B8O10(OH)6]·5H2O are prepared by addition of B(OH)3 to a H2O/MeOH solution of [Co(en)3][OH]3 (gentle warming, 3 h; 41% yield).
ChemInform Abstract: Crystal Structures of New R3CoAl3Ge2 (R: Gd—Er) Quaternary Compounds and Magnetic Properties and Lattice Thermal Expansion of Gd3CoAl3Ge2.
Authors: He Wei , Zeng Weijing , Lin Guoqiang
Published: March 2015

Ln3CoAl3Ge2 (Ln: Gd—Er) quaternary compounds are prepared by arc melting of the elements followed by annealing (evacuated quartz tubes, 1023 K, 720 h).
ChemInform Abstract: Enantioselective Mannich Reaction of β‐Keto Esters with Aromatic and Aliphatic Imines Using a Cooperatively Assisted Bifunctional Catalyst.
Authors: Neuvonen Antti J. , Pihko Petri M.
Published: March 2015

The title reaction tolerates aliphatic and aromatic substituents on both reaction partners, affording products (III) as a mixture of inseparable diastereomers with low or without any diastereoselectivity.
ChemInform Abstract: Palladium‐Catalyzed Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Michael Acceptors: Construction of Vicinal Quaternary Stereocenters.
Authors: Khan Ajmal , Yang Lei , Xu Jing , Jin Long Yi , Zhang Yong Jian
Published: March 2015

The title reaction provides multifunctionalized tetrahydrofurans such as (III) and (V) bearing all‐carbon quaternary stereocenters in high yields with high relative and absolute stereocontrol.
ChemInform Abstract: Asymmetric [3 + 2]‐Cycloaddition of Morita—Baylis—Hillman Carbonates with Maleimides Catalyzed by Chiral Ferrocenylphosphines.
Authors: Tu Aiping , Hu Haiwen , Du Tieqi , Zhong Weihui
Published: March 2015

New, air‐stable chiral ferrocenylphosphines are designed, synthesized, and applied to promote the title cycloaddition reaction.
ChemInform Abstract: Asymmetric Reductive Aldol‐Type Reaction with Carbonyl Compounds Using Dialkyl Tartrate as a Chiral Ligand.
Authors: Isoda Motoyuki , Sato Kazuyuki , Tokura Yoriko , Tarui Atsushi , Omote Masaaki , Ando Akira
Published: March 2015

(R,R)‐Diisopropyl tartrate is used as a source of chirality in the inter‐ or intramolecular reductive aldol‐type synthesis of β‐hydroxy esters, however, the chiral induction is rather poor.
ChemInform Abstract: Highly Enantioselective Phosphination and Hydrophosphonylation of Azomethine Imines: Using Chiral Squaramide as a Hydrogen Bonding Organocatalyst
Authors: Kong Ling‐Pei , Li Nai‐Kai , Zhang Shao‐Yun , Chen Xiang , Zhao Min , Zhang Ya‐Fei , Wang Xing‐Wang
Published: March 2015

29 examples for phosphination and 12 examples for hydrophosphonylation
ChemInform Abstract: An in situ Directing Group Strategy for Chiral Anion Phase‐Transfer Fluorination of Allylic Alcohols.
Authors: Zi Weiwei , Wang Yi‐Ming , Toste F. Dean
Published: March 2015

The enantioselective fluorination of allylic alcohols relies on an in situ generated directing group which is crucial for achieving effective enantiocontrol.