bluuebunny/crossref_metadata_2025 huggingface dataset:
A rapid and efficient analytical method for the quantification of a novel anticholinergic compound, R‐phencynonate, by stable isotope‐dilution LC–MS/MS and its application to bioavailability and dose proportionality studies
Authors: Li Jinglai , Liao Sha , Wang Xiaoying , Liu Qian , Meng Fei , Zhang Wenpeng , Zhang Tianhong , Yang Cuiping , Song Xinyi , Luo Huan , Wang Juan , Li Zheng , Zhong Bohua , Zhang Zhenqing
Published: October 2016

A rapid, specific and high‐throughput stable isotope‐dilution LC–MS/MS method was developed and validated with high sensitivity for the quantification of R‐phencynonate (a eutomer of phencynonate racemate) in rat and dog plasma. Plasma samples were deproteinized using acetonitrile and then separated on a C8 column with an isocratic mobile phase containing acetonitrile–water–formic acid mixture (60:40:0.1, v/v/v) at a flow rate of 0.2 mL/min. Each sample had a total run time of 3 min. Quantification was performed using triple quadrupole mass spectrometry in selected reaction monitoring mode with positive electrospray ionization. The method was shown to be highly linear (r2 > 0.99) and to have a wide dynamic range (0.1–100 ng/mL) with favourable accuracy and precision. No matrix effects were observed. The detailed pharmacokinetic profiles of R‐phencynonate at therapeutic doses in rats and dogs were characterized by rapid oral absorption, quick clearance, high volume of distribution and poor absolute bioavailability. R‐Phencynonate lacked dose proportionality over the oral dose range, based on the power model. However, the area under concentration–time curve and the maximum plasma concentration increased linearly in a dose‐dependent manner in both animal models. The absolute bioavailability of R‐phencynonate was 16.6 ± 2.75 and 4.78 ± 1.26% in dogs and rats, respectively.
Meet Your Neighbours. Authoritarians Engage in Intergroup Contact When They have the Opportunity
Authors: Brune Anna , Asbrock Frank , Sibley Chris G.
Published: October 2016

Research indicates that authoritarians tend to avoid intergroup contact. This study tested the hypothesis that living in a neighbourhood with a higher proportion of Asian peoples increases the likelihood of contact with them for the majority (New Zealand Europeans), and that this effect should increase intergroup contact for authoritarians. Multi‐level Random Coefficient Modelling of data from the New Zealand Attitudes and Values Study (N = 3903) indicated that New Zealand Europeans high in authoritarianism in neighbourhoods with a high proportion of Asian peoples have more contact with Asian friends, relative to authoritarians in less ethnically diverse areas. Copyright © 2016 John Wiley & Sons, Ltd.
A case of basal cell carcinoma of the nictitating membrane in a dog
Authors: Rodriguez Galarza Roxanne M. , Shrader Stephanie M. , Koehler Jennifer W. , Abarca Eva
Published: October 2016

Key Clinical Message

A case of a basal cell carcinoma (BCC) of the nictitating membrane (NM) in a 9‐year‐old female spayed dachshund is reported. Computed tomography and resection of theNMfollowed by cryosurgery was performed. Although uncommon,BCCshould be considered as a differential diagnosis for tumors of theNM.
Unusual association of brain hemorrhage and digestive tract occlusion: about two prenatal cases
Authors: Garofalo Giulia , Tecco Laura , Van Rysselberge Michel , Van Bogaert Patrick , Mergan Frederic , Cassart Marie
Published: October 2016

Key Clinical Message

We report two prenatal cases of an exceptional association of digestive tract atresia or perforation with brain hemorrhage. This combination worsens the prognosis leading to termination of pregnancy in one case. We outline the importance of a careful fetal brain examination on imaging in cases of prenatal “acute” abdominal insults.
Micro‐/Mesoporous Zinc–Manganese Oxide/Graphene Hybrids with High Specific Surface Area: A High‐Capacity, Superior‐Rate, and Ultralong‐Life Anode for Lithium Storage
Authors: Yao Wei , Zhao Mengqiang , Dai Yi , Tang Jiali , Xu Jianguang
Published: October 2016

Hierarchical porous mixed metal oxide/graphene two‐dimensional nanostructures, providing an extra active position for lithium storage, represent a hopeful platform for next‐generation anode materials. Herein, we report a facile approach to synthesize micro‐/mesoporous zinc–manganese oxide/graphene (Zn‐Mn‐O/G) hybrids with a specific surface area of 227.6 m2 g−1 in a water/ethanol mixed solvent. Owing to the micro‐/mesoporous structure, large specific area, and strongly coupled effects between Zn‐Mn‐O and the graphene sheets, the hybrids deliver a high capacity of 1216 mAh g−1 at a current density of 500 mA g−1 after 100 cycles, a superior rate performance of 558 mAh g−1 at 8000 mA g−1, as well as ultralong cycle life up to 900 cycles. In addition, if performed in the temperature range of 5 to 45 °C, the Zn‐Mn‐O/G anode demonstrates specific capacities between 748 and 1245 mAh g−1 after 100 cycles.
Adaptive penalties for generalized Tikhonov regularization in statistical regression models with application to spectroscopy data
Authors: Randolph Timothy , Ding Jimin , Kundu Madan G. , Harezlak Jaroslaw
Published: October 2016

Tikhonov regularization was recently proposed for multivariate calibration. We use this framework for modeling the statistical association between spectroscopy data and a scalar outcome. In both the calibration and regression settings, this regularization process has advantages over methods of spectral preprocessing and dimension‐reduction approaches such as feature extraction or principal component regression. We propose an extension of this penalized regression framework by adaptively refining the penalty term to optimally focus the regularization process. We illustrate the approach using simulated spectra and compare it with other penalized regression models and with a 2‐step method that first preprocesses the spectra then fits a dimension‐reduced model using the processed data. The methods are also applied to magnetic resonance spectroscopy data to identify brain metabolites that are associated with cognitive function.
Chiral N,N′‐Dioxide–Scandium(III) Complex‐Catalyzed Asymmetric Friedel–Crafts Alkylation Reaction of ortho‐Hydroxybenzyl Alcohols with C3‐Substituted N‐Protected Indoles
Authors: Zheng Jianfeng , Lin Lili , Dai Li , Yuan Xiao , Liu Xiaohua , Feng Xiaoming
Published: October 2016

The first Lewis acid catalyzed asymmetric Friedel–Crafts alkylation reaction of ortho‐hydroxybenzyl alcohols with C3‐substituted indoles is described. A chiral N,N′‐dioxide Sc(OTf)3 complex served not only to promote formation of ortho‐quinone methides (o‐QMs) in situ but also induced the asymmetry of the reaction. This methodology enables a novel activation of ortho‐hydroxybenzyl alcohols, thus affording the desired chiral diarylindol‐2‐ylmethanes in up to 99 % yield and 99 % ee. A range of functional groups were also tolerated under the mild reaction conditions. Moreover, this strategy gives concise access to enantioenriched indole‐fused benzoxocines.
Intramolecular Oxidative Arylations in 7‐Azaindoles and Pyrroles: Revamping the Synthesis of Fused N‐Heterocycle Tethered Fluorenes
Authors: Laha Joydev K. , Bhimpuria Rohan A. , Hunjan Mandeep Kaur
Published: October 2016

We revealed intramolecular oxidative arylations in 7‐azaindoles and pyrroles that, for the first time, provided direct access to 7‐azaindole‐ or pyrrole‐fused isoindolines and tetrahydroisoquinolines. In addition, N‐benzylation of 7‐azaindoles or pyrroles with sterically hindered sec‐benzyl alcohols by Mitsunobu reaction followed by intramolecular oxidative arylation allowed access to chiral congeners of fused isoindolines that have little precedence. A new opportunity in the design and synthesis of fluorene‐based organic emitters is demonstrated in the preparation of novel fused N‐heterocycle tethered fluorenes, including a chiral fluorene architecture.
A stereodynamic phosphoramidite ligand derived from 3,3′‐functionalized ortho‐biphenol and its rhodium(I) complex
Authors: Storch Golo , Deberle Luisa , Menke Jan‐Michael , Rominger Frank , Trapp Oliver
Published: October 2016

Stereodynamic ligands and complexes bearing functional groups to attach chiral or achiral binding sites and auxiliaries are highly attractive due to the interesting opportunities for controlling the stereochemical outcome of enantioselective transformations. In this study we report the preparation of a 3,3′‐functionalized biphenol (BIPOL) phosphoramidite ligand (PAm) bearing 3,5‐dichlorobenzoyl (3,5‐DCB) amide binding sites for noncovalent interactions. Upon coordination to [Rh(COD)2]BF4 this substitution pattern directs one of the 3,5‐DCB binding sites in close proximity of the metal center resulting in liberation of both COD ligands and the formation of a [Rh(PAm)2]BF4 complex. Coordination of the amide carbonyl unit was found to be reversible, since the complex acted as an active catalyst in the hydrogenation of dehydroamino acid derivatives. X‐ray crystallographic investigation revealed that the second 3,5‐DCB unit is capable of forming noncovalent π–π interactions connecting both phosphoramidite ligands.
Diastereomeric bactericidal effect of Ru(phenanthroline)2dipyridophenazine
Authors: Mårtensson Anna K. F. , Bergentall Mattias , Tremaroli Valentina , Lincoln Per
Published: October 2016

Metal susceptibility assays and spot plating were used to investigate the antimicrobial activity of enantiopure [Ru(phen)2dppz]2+ (phen =1,10‐phenanthroline and dppz = dipyrido[3,2‐a:2´,3´‐c]phenazine) and [μ‐bidppz(phen)4Ru2]4+ (bidppz =11,11´‐bis(dipyrido[3,2‐a:2´,3´‐c]phenazinyl)), on Gram‐negative Escherichia coli and Gram‐positive Bacillus subtilis as bacterial models. The minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) were determined for both complexes: while [μ‐bidppz(phen)4Ru2]4+ only showed a bactericidal effect at the highest concentrations tested, the antimicrobial activity of [Ru(phen)2dppz]2+ against B. subtilis was comparable to that of tetracyline. In addition, the Δ‐enantiomer of [Ru(phen)2dppz]2+ showed a 2‐fold higher bacteriostatic and bactericidal effect compared to the Λ‐enantiomer. This was in accordance with the enantiomers relative binding affinity for DNA, thus strongly indicating DNA binding as the mode of action.
Technological, management, and persistent innovation in small and medium family firms: The influence of professionalism
Authors: Diéguez‐Soto Julio , Duréndez Antonio , García‐Pérez‐de‐Lema Domingo , Ruiz‐Palomo Daniel
Published: October 2016

We examine the effect of professional management on innovation in family‐owned firms. Since professionalism is a critical but controversial issue that can influence the innovative capacity of family businesses, we aim to determine if professional management improves innovation outcomes from a comprehensive perspective. Using a sample of 583 Spanish family firms, we demonstrate that professionalism in management exerts a positive influence on innovation from both technological (product and process innovation) and management perspectives. We also find that firms managed by external professionals are willing to develop higher innovative activity and that professionalism contributes positively to persistent innovation. Copyright © 2016 ASAC. Published by John Wiley & Sons, Ltd.
Adiabatic Electron‐Transfer Reactions on Semiconducting Electrodes
Authors: Schmickler Wolfgang , Santos Elizabeth , Bronshtein Michael , Nazmutdinov Renat
Published: October 2016

Theoretical treatments of electrochemical reactions at semiconductors are usually based on theories that presume a weak interaction between the reactant and the electrode. Herein a theory is developed that is valid for arbitrary interaction strengths, and its consequences are explored within a simple coupling scheme. This model can be used as a framework for the investigation of specific catalytic reactions including photoelectrocatalysis.
Tungsten Carbide: A Remarkably Efficient Catalyst for the Selective Cleavage of Lignin C−O Bonds
Authors: Guo Haiwei , Zhang Bo , Li Changzhi , Peng Chang , Dai Tao , Xie Haibo , Wang Aiqin , Zhang Tao
Published: October 2016

A remarkably effective method for the chemoselective cleavage of the C−O bonds of typical β‐O‐4 model compounds and the deconstruction of lignin feedstock was developed by using tungsten carbide as the catalyst. High yields of C−O cleavage products (up to 96.8 %) from model compounds and liquid oils (up to 70.7 %) from lignin feedstock were obtained under low hydrogen pressure (0.69 MPa) in methanol. The conversion efficiency was determined to a large extent by solvent effects and was also affected by both the electronic and steric effects of the lignin model compounds. In situ W2C/activated carbon (AC)‐catalyzed hydrogen transfer from methanol to the substrate was proposed to be responsible for the high performance in methanol solvent. The conversion of 2‐(2‐methoxyphenoxy)‐1‐phenylethanol showed that the catalyst could be reused five times without a significant loss in activity for C−O bond cleavage, whereas the selectivity to value‐added styrene increased markedly owing to partial oxidation of the W2C phase according to X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy characterization. 2 D‐HSQC‐NMR spectroscopy analysis showed that W2C/AC exhibited high activity not only for β‐O‐4 cleavage but also for the deconstruction of more resistant α‐O‐4 and β‐β linkages, so that a high yield of liquid oil was obtained from lignin. Corn stalk lignin was more liable to be depolymerized than birch lignin owing to its loosened structure (scanning electron microscopy results), larger surface area (BET results), and lower molecular weight (gel‐permeation chromatography results), whereas its liquid oil composition was more complicated than that of birch wood lignin in that the former lignin contained more p‐hydroxyphenyl units and the former contained noncanonical units.
Bio‐Electrocatalytic Application of Microorganisms for Carbon Dioxide Reduction to Methane
Authors: Schlager Stefanie , Haberbauer Marianne , Fuchsbauer Anita , Hemmelmair Christine , Dumitru Liviu Mihai , Hinterberger Gabriele , Neugebauer Helmut , Sariciftci Niyazi Serdar
Published: October 2016

We present a study on a microbial electrolysis cell with methanogenic microorganisms adapted to reduce CO2 to CH4 with the direct injection of electrons and without the artificial addition of H2 or an additional carbon source except gaseous CO2. This is a new approach in comparison to previous work in which both bicarbonate and gaseous CO2 served as the carbon source. The methanogens used are known to perform well in anaerobic reactors and metabolize H2 and CO2 to CH4 and water. This study shows the biofilm formation of those microorganisms on a carbon felt electrode and the long‐term performance for CO2 reduction to CH4 using direct electrochemical reduction. CO2 reduction is performed simply by electron uptake with gaseous CO2 as the sole carbon source in a defined medium. This “electrometabolism” in such microbial electrolysis cells depends strongly on the potential applied as well as on the environmental conditions. We investigated the performance using different adaption mechanisms and a constant potential of −700 mV vs. Ag/AgCl for CH4 generation at 30–35 °C. The experiments were performed by using two‐compartment electrochemical cells. Production rates with Faradaic efficiencies of around 22 % were observed.
Selective Oxidative Esterification from Two Different Alcohols via Photoredox Catalysis
Authors: Yi Hong , Hu Xia , Bian Changliang , Lei Aiwen
Published: October 2016

Esters functionalities are important building blocks that are extensively used in the chemical industry and academic laboratories. Direct oxidative esterification from easy‐available alcohols to esters would be a much more appealing approach, especially using O2 as terminal oxidant. Inputting external energy by photocatalysis for dioxygen activation, a mild and simple method for ester synthesis from two different alcohols has been achieved in this work. This reaction is performed under neutral conditions using O2 as the terminal oxidant. A variety of primary alcohols, especially long chain alcohols and secondary alcohols are tolerated in this system.
Educational Darwinism: How can we use planning to adapt and thrive?
Authors: Murray Jill , Pricci Erica Barone
Published: October 2016

Darwin's theory of evolution claimed that only the strongest, most adaptable species survive. Until recent years, the business models in higher education never really came into question. Now the merging of affordability, access, and outcomes is forcing colleges and universities to face the reality that consumers are shopping for the value of a college degree. The current structure of a tuition‐driven model where tuition outpaces inflation is one that cannot be sustained by many institutions across the country. These factors, along with others, are forcing higher education to adapt and change in ways that are at the very least uncomfortable and, at worst, unachievable.
Work against common myths to promote access, equity
Authors: Hope Joan
Published: October 2016

COLUMBUS, Ohio — When Patricia McGuire became president of Trinity Washington University in 1989, the institution faced significant enrollment and economic challenges. Following a transformation that led to a diverse student body, Trinity thrives.
The effects of demographic stochasticity and parameter uncertainty on predicting the establishment of introduced species
Authors: Palamara Gian Marco , Carrara Francesco , Smith Matthew J. , Petchey Owen L.
Published: October 2016

Invasive species are a serious threat to biodiversity worldwide and predicting whether an introduced species will first establish and then become invasive can be useful to preserve ecosystem services. Establishment is influenced by multiple factors, such as the interactions between the introduced individuals and the resident community, and demographic and environmental stochasticity. Field observations are often incomplete or biased. This, together with an imperfect knowledge of the ecological traits of the introduced species, makes the prediction of establishment challenging. Methods that consider the combined effects of these factors on our ability to predict the establishment of an introduced species are currently lacking. We develop an inference framework to assess the combined effects of demographic stochasticity and parameter uncertainty on our ability to predict the probability of establishment following the introduction of a small number of individuals. We find that even moderate levels of demographic stochasticity influence both the probability of establishment, and, crucially, our ability to correctly predict that probability. We also find that estimation of the demographic parameters of an introduced species is fundamental to obtain precise estimates of the interaction parameters. For typical values of demographic stochasticity, the drop in our ability to predict an establishment can be 30% when having priors on the demographic parameters compared to having their accurate values. The results from our study illustrate how demographic stochasticity may bias the prediction of the probability of establishment. Our method can be applied to estimate probability of establishment of introduced species in field scenarios, where time series data and prior information on the demographic traits of the introduced species are available.
Assessing polar bear (Ursus maritimus) population structure in the Hudson Bay region using SNPs
Authors: Viengkone Michelle , Derocher Andrew Edward , Richardson Evan Shaun , Malenfant René Michael , Miller Joshua Moses , Obbard Martyn E. , Dyck Markus G. , Lunn Nick J. , Sahanatien Vicki , Davis Corey S.
Published: October 2016

Defining subpopulations using genetics has traditionally used data from microsatellite markers to investigate population structure; however, single‐nucleotide polymorphisms (SNPs) have emerged as a tool for detection of fine‐scale structure. In Hudson Bay, Canada, three polar bear (Ursus maritimus) subpopulations (Foxe Basin (FB), Southern Hudson Bay (SH), and Western Hudson Bay (WH)) have been delineated based on mark–recapture studies, radiotelemetry and satellite telemetry, return of marked animals in the subsistence harvest, and population genetics using microsatellites. We used SNPs to detect fine‐scale population structure in polar bears from the Hudson Bay region and compared our results to the current designations using 414 individuals genotyped at 2,603 SNPs. Analyses based on discriminant analysis of principal components (DAPC) and STRUCTURE support the presence of four genetic clusters: (i) Western—including individuals sampled in WH, SH (excluding Akimiski Island in James Bay), and southern FB (south of Southampton Island); (ii) Northern—individuals sampled in northern FB (Baffin Island) and Davis Strait (DS) (Labrador coast); (iii) Southeast—individuals from SH (Akimiski Island in James Bay); and (iv) Northeast—individuals from DS (Baffin Island). Population structure differed from microsatellite studies and current management designations demonstrating the value of using SNPs for fine‐scale population delineation in polar bears.
Comparing estimates of population change from occupancy and mark–recapture models for a territorial species
Authors: Conner Mary M. , Keane John J. , Gallagher Claire V. , Munton Thomas E. , Shaklee Paula A.
Published: October 2016

Monitoring studies often use marked animals to estimate population abundance at small spatial scales. However, at smaller scales, occupancy sampling, which uses detection/nondetection data, may be useful where sites are approximately territories, and occupancy dynamics should be strongly correlated with population dynamics. Occupancy monitoring has advantages in that it is less expensive and invasive, and marked animals are not needed. Here, we used empirical data to determine whether and when change in occupancy is a good proxy for population change for a territorial species. As part of this overall goal, we also compared maximum‐likelihood estimates using a model‐averaging approach with a Bayesian MCMC approach. We used field data collected from 1993 to 2013 on three study areas for California spotted owls (Strix occidentalis occidentalis), a territorial species. Although correlations for trajectories of realized population change (Δt) between territory occupancy and Pradel models were moderate to high for Bayesian MCMC‐based estimates and high for model‐averaged estimates, magnitudes of the trajectories were different with the Pradel model reporting greater magnitudes of change. For the two areas showing a decline, Δt for the Pradel model was approximately 20–30% lower than for the occupancy model, and 25% higher in the area showing an increase. These differences can arise because the occupancy model is less sensitive, in that if two owls share a territory, the loss of one may be reflected in survival and, consequently in Δt by the Pradel model, but because the territory remains occupied it is not reflected by the occupancy model. Bayesian MCMC‐based and model‐averaged estimates of Δt were in close agreement in pattern (correlation ≥0.74) and magnitude (relative differences of last Δt were ≤5%) for both occupancy and mark–resight models. Results from the Pradel model may lead to conservation actions necessary to avoid high extinction or extirpation risk for small populations, while results from the territory occupancy model may result in status quo management. We found both Bayesian MCMC‐based and model‐averaged estimates of Δt robust approaches to evaluate population trends. However, we recommend the Bayesian MCMC approach for estimating risk (e.g., probability of declines) for retrospective analyses.
Precipitating factors and 90‐day outcome of acute heart failure: a report from the intercontinental GREAT registry
Authors: Arrigo Mattia , Gayat Etienne , Parenica Jiri , Ishihara Shiro , Zhang Jian , Choi Dong‐Ju , Park Jin Joo , Alhabib Khalid F. , Sato Naoki , Miro Oscar , Maggioni Aldo P. , Zhang Yuhui , Spinar Jindrich , Cohen‐Solal Alain , Iwashyna Theodore J. , Mebazaa Alexandre ,   on behalf of the GREAT Network
Published: October 2016

Aims

Several clinical conditions may precipitate acute heart failure (AHF) and influence clinical outcome. In this study we hypothesized that precipitating factors are independently associated with 90‐day risk of death in AHF.

Methods and results

The study population consisted of 15 828 AHF patients from Europe and Asia. The primary outcome was 90‐day all‐cause mortality according to identified precipitating factors of AHF [acute coronary syndrome (ACS), infection, atrial fibrillation (AF), hypertension, and non‐compliance]. Mortality at 90 days was 15.8%. AHF precipitated by ACS or by infection showed increased 90‐day risk of death compared with AHF without identified precipitants [hazard ratio (HR) 1.69, 95% confidence interval (CI) 1.44–1.97, P < 0.001; and HR 1.51, 95% CI 1.18–1.92, P = 0.001), while AHF precipitated by AF showed lower 90‐day risk of death (HR 0.56, 95% CI 0.42–0.75, P < 0.001), after multivariable adjustment. The risk of death in AHF precipitated by ACS was the highest during the first week after admission, while in AHF precipitated by infection the risk of death had a delayed peak at week 3. In AHF precipitated by AF, a trend toward reduced risk of death during the first weeks was shown. At weeks 5–6, AHF precipitated by ACS, infection, or AF showed similar risk of death to that of AHF without identified precipitants.

Conclusions

Precipitating factors are independently associated with 90‐day mortality in AHF. AHF precipitated by ACS or infection is independently associated with higher, while AHF precipitated by AF is associated with lower 90‐day risk of death.
Survival of mature T cells in the periphery is intrinsically dependent on GIMAP1 in mice
Authors: Datta Preeta , Webb Louise M.C. , Avdo Inxhina , Pascall John , Butcher Geoffrey W.
Published: October 2016

An effective immune system depends upon the survival of mature T cells in the periphery. Members of the GIMAP family of GTPases have been proposed to regulate this homeostasis, supported by the paucity of peripheral T cells in rodents deficient for either GIMAP1 or GIMAP5. It is unclear whether this lack of T cells is a consequence of an ontological defect, causing the thymus to generate and export T cells incapable of surviving in the periphery, or whether (alternatively or additionally) mature T cells intrinsically require GIMAP1 for survival. Using the ERT2Cre+ transgene, we conditionally deleted Gimap1 in C57BL/6 mice and demonstrate that GIMAP1 is intrinsically required for the survival of mature T cells in the periphery. We show that, in contrast to GIMAP5, this requirement is independent of the T‐cells' activation status. We investigated the nature of the survival defect in GIMAP1‐deficient CD4+ T cells and show that the death occurring after GIMAP1 ablation is accompanied by mitochondrial depolarization and activation of the extrinsic apoptotic pathway. This study shows that GIMAP1 is critical for maintaining the peripheral T‐cell pool in mice and offers a potent target for the treatment of T‐cell‐mediated diseases.
Catalytic Asymmetric Synthesis of Chiral Dihydrobenzofurans through a Formal [4+1] Annulation Reaction of Sulfur Ylides and In Situ Generated ortho‐Quinone Methides
Authors: Yang Qing‐Qing , Xiao Wen‐Jing
Published: October 2016

The first example of a catalytic asymmetric formal [4+1] annulation reaction between sulfur ylides and in situ generated ortho‐quinone methides (o‐QMs) is reported in this work. A C2‐symmetric chiral urea was identified to be the best H‐bonding catalyst, affording a wide range of chiral 2,3‐dihydrobenzofurans in high yields and moderate enantioselectivities [70–98 % yields, up to 89:11 e.r. (enantiomeric ratio)].
Transition‐Metal‐Free Synthesis of a Known Intermediate in the Formal Synthesis of (–)‐Steganacin
Authors: Augros David , Yalcouye Boubacar , Choppin Sabine , Chessé Matthieu , Panossian Armen , Leroux Frédéric R.
Published: October 2016

The formal synthesis of the two enantiomers of a natural, axially chiral biaryl, steganacin, is reported. The previously developed atropo‐diastereoselective coupling of an aryne and an aryllithium (“aryne coupling”) allows for this synthesis. In each step, the axial configuration of the biaryl could be maintained. The key intermediate, identified previously, was accessed without using transition metals, which demonstrates the potential of the aryne coupling reaction as a complementary or alternative to transition‐metal‐catalyzed coupling reactions.
A Genosensor for Sickle Cell Anemia Trait Determination
Authors: Brazaca Laís C. , Bramorski Camila B. , Cancino‐Bernardi Juliana , Janegitz Bruno C. , Zucolotto Valtencir
Published: October 2016

Sickle cell anemia (SCA) is a common recessive genetic condition in which patients produce an abnormal form of hemoglobin. The disease is common mainly among African individuals and in parts of the continent up to 40 % of the population presents its genetic trait. Currently, disease diagnosis and trait determination are performed using polymerase chain reaction, liquid chromatography and electrophoresis. Although these methods present high sensitivity and are well established, they are costly and require specialized equipment to be performed. We developed an electrochemical genosensor for simple and low cost SCA trait determination. The device was based on the immobilization of single DNA strands containing the disease related mutation on gold platforms using the self‐assembled monolayers technique. The determination of SCA trait was then performed using electrochemical impedance spectroscopy. The genosensor displayed a wide linear range (0.01 to 7.5 μmol L−1, R2=0.979), with a detection limit of 7.0 nmol L−1. Furthermore, the device was able to distinguish between DNA sequences containing or not the mutation (target and non‐target sequences) with precision and great reproducibility (10.4 %, n=3). It is expected that such sensor increases the number of SCA trait determination, promoting early diagnosis and genetically counseling.
Iron–Air Battery Operating at High Temperature
Authors: Trocino Stefano , Zignani Sabrina C. , Lo Faro Massimiliano , Antonucci Vincenzo , Aricò Antonino S.
Published: October 2016

A simple configuration for an Fe–air rechargeable battery operating at high temperature was investigated. Two different ceramic electrolytes, that is, gadolinia‐doped ceria (CGO) and strontium/magnesium‐doped lanthanum gallate (LSGM), were studied. Strontium‐doped lanthanum ferrite‐cobaltite (LSFCO) perovskite was used as the air electrode, whereas an Fe0/Fe2O3–CGO composite was used as the Fe electrode. The synthesized CGO and LSGM supporting electrolytes were characterized by proper ionic conductivity for this application (7.4×10−2 S cm−1 at 800 °C). The LSFCO perovskite electrode showed excellent reversibility in symmetrical cells. Low overpotentials were recorded for the evolution of oxygen (0.1 V at 1.7 A cm−2) and the oxygen reduction process (0.1 V at 2.4 A cm−2) at 800 °C. The high‐temperature battery based on the CGO electrolyte showed a pronounced propensity to spontaneously discharge. This was caused by redox behavior involving the interconversion between the Ce4+ and Ce3+ ions in the crystallographic structure, which caused a parasitic electron drag through the electrolyte. On the other hand, the LSGM‐based battery showed promising cyclability characteristics at 800 °C with an open‐circuit voltage higher than 1 V, an electric capacity of 0.3 Ah g−1, and an energy density of 0.22 Wh g−1. However, significant improvements in the coulombic efficiency (≈42 %) for this battery system are necessary for practical applications.
Development of a fermented quinoa‐based beverage
Authors: Ludena Urquizo Fanny Emma , García Torres Silvia Melissa , Tolonen Tiina , Jaakkola Mari , Pena‐Niebuhr Maria Grazzia , von Wright Atte , Repo‐Carrasco‐Valencia Ritva , Korhonen Hannu , Plumed‐Ferrer Carme
Published: October 2016

Quinoa is a crop that originated from the Andes. It has high nutritional value, outstanding agro‐ecological adaptability, and low water requirements. Quinoa is an excellent crop alternative to help overcome food shortages, and it can also have a role in the prevention of developed world lifestyle diseases, such as type‐2 diabetes, cardiovascular diseases, osteoporosis, inflammatory and autoimmune diseases, etc. In order to expand the traditional uses of quinoa and to provide new, healthier and more nutritious food products, a fermented quinoa‐based beverage was developed. Two quinoa varieties (Rosada de Huancayo and Pasankalla) were studied. The fermentation process, viscosity, acidity, and metabolic activity during the preparation and storage of the drink were monitored, as well as the preliminary organoleptic acceptability of the product. The drink had viable and stable microbiota during the storage time and the fermentation proved to be mostly homolactic. Both quinoa varieties were suitable as base for fermented products; Pasankalla, however, has the advantage due to higher protein content, lower saponin concentration, and lower loss of viscosity during the fermentation process. These results suggest that the differences between quinoa varieties may have substantial effects on food processes and on the properties of final products. This is a factor that should be taken into account when planning novel products based on this grain.
A methodology for designing maximum allowable wellhead pressure for CO2 injection: application to the Shenhua CCS demonstration project, China
Authors: Bai Bing , Li Xiaochun , Wu Haiqing , Wang Yongsheng , Liu Mingze
Published: October 2016

Maximum allowable wellhead pressure is an effective indicator for both site safety control and government regulation of CO2 geological storage projects. In many carbon capture and storage (CCS) projects, the injection rate may also be set as an obligatory objective. For such a problem of multi‐objective design, no systematic design methodology has been opened in the publicly available literature. Although a numerical simulator can be employed to obtain the wellhead pressure through a series of trial processes of calculations, this will usually need more model parameters and a large number of computations, especially when there are more reservoirs. In this study, an extensible methodological framework for designing a maximum allowable wellhead pressure for CO2 injection was developed. The methodology is based on a thermal‐hydraulic coupling model of wellbore and reservoir flows suitable for arbitrary number of reservoirs. The new methodology can automatically accommodate multiple design objectives, such as site stability and total injection rate. As a result of explicit solutions employed, the methodology has the advantage of less computation and high speed. Using this method, we recommended a maximum allowable wellhead pressure of 13.0 MPa for the Shenhua CCS demonstration project in China, which has been accepted by the expert committee of the project. The large amount of verification data and four‐year successful injections in the project have proved the effectiveness of the new method. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd.
Are Health State Valuations from the General Public Biased? A Test of Health State Reference Dependency Using Self‐assessed Health and an Efficient Discrete Choice Experiment
Authors: Jonker Marcel F. , Attema Arthur E. , Donkers Bas , Stolk Elly A. , Versteegh Matthijs M.
Published: October 2016

Health state valuations of patients and non‐patients are not the same, whereas health state values obtained from general population samples are a weighted average of both. The latter constitutes an often‐overlooked source of bias. This study investigates the resulting bias and tests for the impact of reference dependency on health state valuations using an efficient discrete choice experiment administered to a Dutch nationally representative sample of 788 respondents. A Bayesian discrete choice experiment design consisting of eight sets of 24 (matched pairwise) choice tasks was developed, with each set providing full identification of the included parameters. Mixed logit models were used to estimate health state preferences with respondents' own health included as an additional predictor. Our results indicate that respondents with impaired health worse than or equal to the health state levels under evaluation have approximately 30% smaller health state decrements. This confirms that reference dependency can be observed in general population samples and affirms the relevance of prospect theory in health state valuations. At the same time, the limited number of respondents with severe health impairments does not appear to bias social tariffs as obtained from general population samples. Copyright © 2016 John Wiley & Sons, Ltd.
Neutrophil‐lymphocyte ratio at diagnosis is an independent prognostic factor in patients with nodular sclerosis Hodgkin lymphoma: results of a large multicenter study involving 990 patients
Authors: Marcheselli Raffaella , Bari Alessia , Tadmor Tamar , Marcheselli Luigi , Cox Maria Christina , Pozzi Samantha , Ferrari Angela , Baldini Luca , Gobbi Paolo , Aviv Ariel , Pugliese Giuseppe , Federico Massimo , Polliack Aaron , Sacchi Stefano
Published: October 2016

Several studies have demonstrated the prognostic value of neutrophil‐lymphocyte ratio (NLR) in patients with solid tumors and non–Hodgkin lymphoma. In contrast, there is only sparse data on its prognostic role in patients with classical Hodgkin lymphoma (cHL). The aim of our study was to establish whether NLR could serve as an independent prognostic factor in a cohort of 990 patients with nodular sclerosis (NS)‐cHL. After analysis of the log hazard ratio (HR) as a function of NLR, we chose the value 6 as cutoff. Patients with NLR >6 had a worse progression‐free survival and overall survival compared to those with NLR ≤6; 84% vs 75% and 92% vs 88%, at 5 years, with an HR of 1.65 and 1.82, respectively. Multivariate analysis showed that the risk remained high with HR 1.44 and HR 1.54 in progression‐free survival and overall survival, respectively. In summary, our study shows that NLR is a robust and independent prognostic parameter in NS‐cHL, both in early and advanced disease. It is inexpensive and simple to apply. Thus, we conclude that NLR, possibly in combination with the international prognostic score and absolute monocyte count, is a useful guide for physicians treating NS‐cHL patients.
Developing adaptive QM/MM computer simulations for electrochemistry
Authors: Dohm Sebastian , Spohr Eckhard , Korth Martin
Published: October 2016

We report the development of adaptive QM/MM computer simulations for electrochemistry, providing public access to all sources via the free and open source software development model. We present a modular workflow‐based MD simulation code as a platform for algorithms for partitioning space into different regions, which can be treated at different levels of theory on a per‐timestep basis. Currently implemented algorithms focus on targeting molecules and their solvation layers relevant to electrochemistry. Instead of using built‐in forcefields and quantum mechanical methods, the code features a universal interface, which allows for extension to a range of external forcefield programs and programs for quantum mechanical calculations, thus enabling the user to readily implement interfaces to those programs. The purpose of this article is to describe our codes and illustrate its usage. © 2016 Wiley Periodicals, Inc.
Poly(ethylene glycol acrylate)‐functionalized hydrogels for heparan sulfate oligosaccharide recognition
Authors: Mothéré Mouna , Singabraya Dominique , Driguez Pierre‐Alexandre , Siñeriz Fernando , Papy‐Garcia Dulce
Published: October 2016

Heparan sulfates are complex polysaccharides belonging to the family of glycosaminoglycans that participate to the regulation of cell behavior and tissue homeostasis. The biological activities conferred to heparan sulfates are largely dependent on the content and positioning of the sulfate groups along their saccharidic units. At present, identification of particular sulfation patterns in biologically relevant heparan sulfate sequences remains challenging. Although several approaches for structure analysis exist, the complexity of heparan sulfates makes new and original approaches still required. Here, we used molecular imprinting technologies to prepare a library of polyethylene glycol acrylate functionalized hydrogels with the aim to investigate their applicability as specific recognizing systems for fondaparinux, a synthetic pentasaccharide analog to the antithrombin binding site of heparin. Adequate choice of the hydrogel composition and controlling rebinding conditions were important determinants for improving the sulfated oligosaccharide recognition specificity and selectivity. Our results suggest that molecular imprinting approaches could be a possibility for the specific recognition of biologically active sequences in heparan sulfates.
Validation of clinical risk scores for laparoscopic liver resections of colorectal liver metastases: A 10‐year observed follow‐up study
Authors: Barkhatov Leonid , Fretland Åsmund A. , Kazaryan Airazat M. , Røsok Bård I. , Brudvik Kristoffer W. , Waage Anne , Bjørnbeth Bjørn A. , Sahakyan Mushegh A. , Edwin Bjørn
Published: October 2016

Objective

The aim of this study was to validate clinical risk scores in patients underwent laparoscopic resection of colorectal liver metastases (CLM) with 5 years follow‐up or more, and assess 5‐ and 10‐year actual survival in this group.

Methods

A total of 516 laparoscopic liver resections were performed in 406 patients with CLM between February 1998 and September 2015. A follow‐up of 5 and 10 years could be assessed in 144 and 29 patients, respectively. The Fong score, pre‐ and postoperative Basingstoke Predictive Index (BPI), Nordlinger score, and Iwatsuki score were validated.

Results

Five‐ and ten‐year cancer‐related actual survival was 54% and 32%, respectively. The Fong score, pre‐ and postoperative BPI and the Nordlinger score divided patients into risk groups with significant difference in survival between the groups. However, predicted 5‐year survival rates were lower than the actual 5‐year survival (mean difference in 17%,13%, 20%, and 30%, respectively).

Conclusion

The Fong score, pre‐ and postoperative BPI and the Nordlinger score systems can be used to predict survival for laparoscopically operated patients in the era of multimodal‐treatment after adjusting of survival rates. The actual five‐ and 10‐year survival after laparoscopic resection of CLM is similar to results previously published for open liver resection. J. Surg. Oncol. 2016;114:757–763. © 2016 Wiley Periodicals, Inc.
Clinical outcomes for patients after surgery and radiation therapy for mesenchymal chondrosarcomas
Authors: De Amorim Bernstein Karen , Liebsch Norbert , Chen Yen‐Lin , Niemierko Andrzej , Schwab Joseph H. , Raskin Kevin , Lozano‐Calderon Santiago A. , Cote Gregory , Harmon David C. , Choy Edwin , Haynes Alex , Mullen John , Hornicek Francis J. , DeLaney Thomas F.
Published: October 2016

Introduction

We report the outcome of 23 patients with mesenchymal chondrosarcomas treated with surgery and radiation therapy +/− chemotherapy. The intent of the project was to review the impact of patient and treatment variables on treatment outcome, in particular with regard to extent of surgery and radiation dose.

Patients and Methods

Twenty‐three patients with mesenchymal chondrosarcomas were treated with surgery and radiation therapy (min. dose 44 Gy; max. dose 78 Gy; median dose 60 Gy; mean dose 61 Gy).

Results

The median survival for the entire cohort of patients was 21.65 years (95% confidence interval ± 4.25). The 5‐ and 10‐year OS was 78.6%. Median disease‐free survival for the 23 patients was 7.2 years. Disease‐free survival (DFS) at 3 and 5 years was 70.7% and 57.8%, respectively. The local control rate at 5 and 10 years was 89.5% (95%CI 64.1–97.3%). Only three patients experienced local failure, three patients had regional failure, and eight developed distant metastases.

Conclusions

In this cohort of patients local tumor control was high when using a combination of surgery and radiation. There was not a clear relationship between radiation dose and local tumor control. J. Surg. Oncol. 2016;114:982–986. © 2016 Wiley Periodicals, Inc.
The impact of resection method and patient factors on quality of life among stage IA non‐small cell lung cancer surgical patients
Authors: Schwartz Rebecca M. , Yip Rowena , Flores Raja M. , Olkin Ingram , Taioli Emanuela , Henschke Claudia ,   For the I‐ELCAP Investigators
Published: October 2016

Background and Objectives

Given the increased number of treatment options for stage IA lung cancer patients, there is a growing body of literature that focuses on comparing each option's relative impact on quality of life (QoL). The current study seeks to further understand the differences in these patients’ QoL according to surgical approach.

Methods

Screening‐diagnosed first primary pathologic stage IA non‐small‐cell lung cancer surgical patients from the I‐ELCAP cohort who answered a baseline and 1‐year follow‐up QoL questionnaire (SF‐12) were included in the analysis. Thoracotomy patients (N = 85) were compared with VATS patients (N = 15) using paired t‐tests and analysis of variance tests.

Results

Multivariate analyses indicated no differences in QoL change between the two groups from pre‐ to post‐surgery. Physical and emotional role functioning significantly improved among VATS patients and worsened among thoracotomy patients. Among thoracotomy patients, a significant decrease in post‐surgical physical QoL was observed only in those who underwent lobectomy (−3.3; 95% CI: −5.1,−1.5), not limited resection.

Conclusions

Although the sample size is small, preliminary findings underscore that changes in overall QoL are similar in VATS and thoracotomy stage IA lung cancer patients. Extension of the resection may be a more relevant factor on QoL post‐surgery. J. Surg. Oncol. 2017;115:173–180. © 2016 Wiley Periodicals, Inc.
Differentiation of essential oils in Atractylodes lancea and Atractylodes koreana by gas chromatography with mass spectrometry
Authors: Liu Qiutao , Zhang Shanshan , Yang Xihui , Wang Ruilin , Guo Weiying , Kong Weijun , Yang Meihua
Published: October 2016

Atractylodes rhizome is a valuable traditional Chinese medicinal herb that comprises complex several species whose essential oils are the primary pharmacologically active component. Essential oils of Atractylodes lancea and Atractylodes koreana were extracted by hydrodistillation, and the yield was determined. The average yield of essential oil obtained from A. lancea (2.91%) was higher than that from A. koreana (2.42%). The volatile components of the essential oils were then identified by a gas chromatography with mass spectrometry method that demonstrated good precision. The method showed clear differences in the numbers and contents of volatile components between the two species. 41 and 45 volatile components were identified in A. lancea and A. koreana, respectively. Atractylon (48.68%) was the primary volatile component in A. lancea, while eudesma‐4(14)‐en‐11‐ol (11.81%) was major in A. koreana. However, the most significant difference between A. lancea and A. koreana was the major component of atractylon and atractydin. Principal component analysis was utilized to reveal the correlation between volatile components and species, and the analysis was used to successfully discriminate between A. lancea and A. koreana samples. These results suggest that different species of Atractylodes rhizome may yield essential oils that differ significantly in content and composition.