bluuebunny/crossref_metadata_2025 huggingface dataset:
Solvent‐Free Chemical Approach to Synthesize Co Nanoparticles Supported on N‐doped Porous Carbon for Efficient Electrocatalytic Oxygen Reduction
Authors: Chen Zixi , Li Yizhao , Liu Baolin , Wang Kun , Cao Yali
Published: February 2020

Transition metal/N‐doped carbon materials are the most promising alternative to expensive Pt‐based electrocatalysts for oxygen reduction reaction (ORR). In this paper, we design hierarchical three‐dimensional (3D) Co nanoparticles supported on N‐doped carbon (Co/N−C) with abundant defects using a simple solvent‐free strategy. With the help of templates, Co nanoparticles are embedded in the interconnected porous carbon network derived from phenolic resin, and Co/N−C is obtained after the introduction of N atoms. Benefitting from the coupling effect of Co and N in carbon matrix, Co/N−C exhibits better electrocatalytic performance than porous N‐doped carbon (N−C) for ORR in alkaline medium. The Co/N−C shows a dominant four‐electron transfer toward oxygen reduction with a rather high half‐wave potential of 0.82 V versus relative hydrogen electrode (vs. RHE), as well as good stability and methanol tolerance. The crumpled porous 3D structure of Co/N−C with a high specific surface area facilitates the formation of N‐contained defects as active sites, and boosts the transport of electrons and ions. Our work provides a feasible way to design non‐noble metal electrocatalysts with satisfied properties for ORR.
Hollow 3D Frame Structure Modified with NiCo2S4 Nanosheets and Spinous Fe2O3 Nanowires as Electrode Materials for High‐Performance All‐Solid‐State Asymmetric Supercapacitors
Authors: Yuan Zhen , Zhang Aitang , Jiang Degang , Mao Ning , Tian Jinmi , Huang Weiguo , Liu Rui , Liu Jingquan
Published: February 2020

Supercapacitors have attracted tremendous research interest, since they are expected to achieve battery‐level energy density, while having a long calendar life and short charging time. Herein, a novel asymmetric supercapacitor has been successfully assembled from NiCo2S4 nanosheets and spinous Fe2O3 nanowire modified hollow melamine foam decorated with polypyrrole as positive and negative electrodes, respectively. Owing to the well‐designed nanostructure and suitable matching of electrode materials, the assembled asymmetric supercapacitor (ASC) exhibits an extended operation voltage window of 1.6 V with an energy density of 20.1 Wh kg−1 at a power density of 159.4 kW kg−1. Moreover, the ASC shows stable cycling stability, with 81.3 % retention after 4000 cycles and a low internal resistance of 1.03 Ω. Additionally, a 2.5 V light‐emitting diode indicator can be lit up by three ASCs connected in series; this provides evidence of the practical application potential of the assembled energy‐storage system. The excellent electrochemical performances should be credited to the significant enhancement of the specific surface area, charge transport, and mechanical stability resulting from the unique 3D morphology.
A Novel [OSSO]‐Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides
Authors: Della Monica Francesco , Paradiso Veronica , Grassi Alfonso , Milione Stefano , Cavallo Luigi , Capacchione Carmine
Published: January 2020

A new chromium(III) complex, bearing a bis‐thioether‐diphenolate [OSSO]‐type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.
Highly Stable, Readily Reducible, Fluorescent, Trifluoromethylated 9‐Borafluorenes
Authors: Rauch Florian , Fuchs Sonja , Friedrich Alexandra , Sieh Daniel , Krummenacher Ivo , Braunschweig Holger , Finze Maik , Marder Todd B.
Published: January 2020

Three different perfluoroalkylated borafluorenes (FBf) were prepared and their electronic and photophysical properties were investigated. The systems have four trifluoromethyl moieties on the borafluorene moiety as well as two trifluoromethyl groups at the ortho positions of their exo‐aryl moieties. They differ with regard to the para substituents on their exo‐aryl moieties, being a proton (FXylFBf, FXyl: 2,6‐bis(trifluoromethyl)phenyl), a trifluoromethyl group (FMesFBf, FMes: 2,4,6‐tris(trifluoromethyl)phenyl) or a dimethylamino group (p‐NMe2‐FXylFBf, p‐NMe2‐FXyl: 4‐(dimethylamino)‐2,6‐bis(trifluoromethyl)phenyl), respectively. All derivatives exhibit extraordinarily low reduction potentials, comparable to those of perylenediimides. The most electron‐deficient derivative FMesFBf was also chemically reduced and its radical anion isolated and characterized. Furthermore, all compounds exhibit very long fluorescent lifetimes of about 250 ns up to 1.6 μs; however, the underlying mechanisms responsible for this differ. The donor‐substituted derivative p‐NMe2‐FXylFBf exhibits thermally activated delayed fluorescence (TADF) from a charge‐transfer (CT) state, whereas the FMesFBf and FXylFBf borafluorenes exhibit only weakly allowed locally excited (LE) transitions due to their symmetry and low transition‐dipole moments.
Organic Cage Dumbbells
Authors: Greenaway Rebecca L. , Santolini Valentina , Szczypiński Filip T. , Bennison Michael J. , Little Marc A. , Marsh Andrew , Jelfs Kim E. , Cooper Andrew I.
Published: February 2020

Molecular dumbbells with organic cage capping units were synthesised via a multi‐component imine condensation between a tri‐topic amine and di‐ and tetra‐topic aldehydes. This is an example of self‐sorting, which can be rationalised by computational modelling.
Building Knowledge Bridges through Effective Science Communication
Authors: Beardsworth Stuart J.
Published: January 2020

The ability to communicate is fundamental to life as we know it and the key to success in many cases is based on having good communication skills. Be it written, spoken, visual, auditory or otherwise, effective communication can open many doors to hidden knowledge that can benefit the world. Science as an entity, which itself stems from the Latin word Scientia, (Engl. “knowledge”), has a tradition of not being particularly well communicated, with long words, vast and confusing concepts, and information overloads. However, as good as communication between scientists has generally become, there is still room for improvement. This article hopes to inform and inspire scientists to lead by example, to educate and advise in the best ways that we can, not just for non‐experts, but for the interest of everyone.
Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation
Authors: Vanagas Nicole A. , Higgins Robert F. , Wacker Jennifer N. , Asuigui Dane Romar C. , Warzecha Evan , Kozimor Stosh A. , Stoll Sarah L. , Schelter Eric J. , Bertke Jeffery A. , Knope Karah E.
Published: January 2020

Uranium(IV) complexation by 2‐furoic acid (2‐FA) was examined to better understand the effects of ligand identity and reaction conditions on species formation and stability. Five compounds were isolated: [UCl2(2‐FA)2(H2O)2]n (1), [U4Cl10O2(THF)6(2‐FA)2]⋅2 THF (2), [U6O4(OH)4(H2O)3(2‐FA)12]⋅7 THF⋅H2O (3), [U6O4(OH)4(H2O)2(2‐FA)12]⋅8.76 H2O (4), and [U38Cl42O54(OH)2(H2O)20]⋅m H2O⋅n THF (5). The structures were determined by single‐crystal X‐ray diffraction and further characterized by Raman, IR, and optical absorption spectroscopy. The thermal stability and magnetic behavior of the compounds were also examined. Variations in the synthetic conditions led to notable differences in the structural units observed in the solid state. At low H2O/THF ratios, a tetranuclear oxo‐bridged [U4O2] core was isolated. Aging of this solution resulted in the formation a U38 oxo cluster capped by chloro and water ligands. However, at increasing water concentrations only hexanuclear units were observed. In all cases, at temperatures of 100–120 °C, UO2 nanoparticles formed.
Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation
Authors: da Silva Amanda F. , Afonso Marco A. S. , Cormanich Rodrigo A. , Jurberg Igor D.
Published: January 2020

A visible‐light‐promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction‐evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.
Solvophobically Driven Complexation of Adamantyl Mannoside with β‐Cyclodextrin in Water and Structured Organic Solvents
Authors: Leko Katarina , Hanževački Marko , Brkljača Zlatko , Pičuljan Katarina , Ribić Rosana , Požar Josip
Published: January 2020

The effects of solvent and temperature on the complexation of adamantyl mannoside with β‐cyclodextrin and 6‐O‐monotosyl‐6‐deoxy‐β‐cyclodextrin were explored experimentally and by means of molecular dynamics simulations. Efficient binding was observed only in hydrogen‐bonded solvents, which indicated solvophobically driven complexation. The stability of the inclusion complex was considerably higher in aqueous media. A pronounced temperature dependence of ΔrH○ and ΔrS○, resulting in perfect enthalpy–entropy compensation, was observed in water. The complexation thermodynamics was in line with classical rationale for the hydrophobic effect at lower temperatures and the nonclassical explanation at higher temperatures. This finding linked cyclodextrin complexation thermodynamics with insights regarding the effect of temperature on the hydration water structure. The complexation enthalpies and entropies were weakly dependent on temperature in organic media. The signs of ΔrH○ and ΔrS○ were in accordance with the nonclassical hydrophobic (solvophobic) effect. The structures of the optimized product corresponded to those deduced spectroscopically, and the calculated and experimentally obtained values of ΔrG○ were in very good agreement. This investigation clearly demonstrated that solvophobically driven formation of cyclodextrin complexes could be anticipated in structured solvents in general. However, unlike in water, adamantane and the host cavity behaved solely as structure breakers in the organic media explored so far.
Metallation‐Induced Heterogeneous Dynamics of DNA Revealed by Single‐Molecule FRET
Authors: Berrocal‐Martin Raul , Sanchez‐Cano Carlos , Chiu Cookson K. C. , Needham Russell J. , Sadler Peter J. , Magennis Steven W.
Published: January 2020

The metallation of nucleic acids is key to wide‐ranging applications, from anticancer medicine to nanomaterials, yet there is a lack of understanding of the molecular‐level effects of metallation. Here, we apply single‐molecule fluorescence methods to study the reaction of an organo‐osmium anticancer complex and DNA. Individual metallated DNA hairpins are characterised using Förster resonance energy transfer (FRET). Although ensemble measurements suggest a simple two‐state system, single‐molecule experiments reveal an underlying heterogeneity in the oligonucleotide dynamics, attributable to different degrees of metallation of the GC‐rich hairpin stem. Metallated hairpins display fast two‐state transitions with a two‐fold increase in the opening rate to ≈2 s−1, relative to the unmodified hairpin, and relatively static conformations with long‐lived open (and closed) states of 5 to ≥50 s. These studies show that a single‐molecule approach can provide new insight into metallation‐induced changes in DNA structure and dynamics.
Early noncardiovascular organ failure and mortality in the cardiac intensive care unit
Authors: Jentzer Jacob C. , Wiley Brandon , Bennett Courtney , Murphree Dennis H. , Keegan Mark T. , Gajic Ognjen , Kashani Kianoush B. , Barsness Gregory W.
Published: January 2020

Background

Noncardiac organ failure has been associated with worse outcomes among a cardiac intensive care unit (CICU) population.

Hypothesis

We hypothesized that early organ failure based on the sequential organ failure assessment (SOFA) score would be associated with mortality in CICU patients.

Methods

Adult CICU patients from 2007 to 2015 were reviewed. Organ failure was defined as any SOFA organ subscore ≥3 on the first CICU day. Organ failure was evaluated as a predictor of hospital mortality and postdischarge survival after adjustment for illness severity and comorbidities.

Results

We included 10 004 patients with a mean age of 67 ± 15 years (37% female). Admission diagnoses included acute coronary syndrome in 43%, heart failure in 46%, cardiac arrest in 12%, and cardiogenic shock in 11%. Organ failure was present in 31%, including multiorgan failure in 12%. Hospital mortality was higher in patients with organ failure (22% vs 3%, adjusted OR 3.0, 95% CI 2.5‐3.7, P < .001). After adjustment, each failing organ system predicted twofold higher odds of hospital mortality (adjusted OR 1.9, 95% CI 1.1‐2.1, P < .001). Mortality risk was highest with cardiovascular, coagulation and liver failure. Among hospital survivors, organ failure was associated with higher adjusted postdischarge mortality risk (P < .001); multiorgan failure did not confer added long‐term mortality risk.

Conclusions

Early noncardiovascular organ failure, especially multiorgan failure, is associated with increased hospital mortality in CICU patients, and this risk continues after hospital discharge, emphasizing the need to promote early recognition of organ failure in CICU patients.
Long‐term results of a phase 2 trial of nilotinib 400 mg twice daily in newly diagnosed patients with chronic‐phase chronic myeloid leukemia
Authors: Masarova Lucia , Cortes Jorge E. , Patel Keyur P. , O’Brien Susan , Nogueras‐Gonzalez Graciela M. , Konopleva Marina , Verstovsek Srdan , Garcia‐Manero Guillermo , Ferrajoli Alessandra , Kadia Tapan M. , Ravandi‐Kashani Farhad , Borthakur Gautam , DellaSala Sara , Estrov Zeev , Jabbour Elias J. , Kantarjian Hagop M.
Published: January 2020

Background

Nilotinib is a potent, second‐generation inhibitor of BCR‐ABL1 tyrosine kinase and has been approved as frontline and salvage therapy for patients with chronic‐phase chronic myeloid leukemia (CP‐CML).

Methods

In this single‐institution, phase 2 study, 122 patients with newly diagnosed CP‐CML received nilotinib 400 mg twice daily. The median follow‐up on study was 78.3 months (interquartile range, 58.4‐96.5 months).

Results

Fifty‐six percent of patients remained on therapy at the last follow‐up. Both the complete cytogenetic response rate and the major molecular response (MR) rate were 91%. Seventy‐five percent and 59% of patients achieved a ≥4.5‐log reduction in BCR‐ABL1 transcripts (MR4.5) and a sustained MR4.5 beyond 2 years, respectively. The estimated event‐free survival and overall survival rates at 5 years were 89% and 93%, respectively, and the corresponding rates at 10 years were 85% and 88%, respectively. Treatment discontinuation due to toxicity occurred in 19% of patients, mostly because of cardiovascular events (10%) and biochemical abnormalities (6%). The top 3 nonhematologic toxicities were rash (55%), elevated bilirubin (57%), and elevated aminotransferases (48%). Hematologic toxicity was transient and mild. Ischemic cardiovascular adverse events occurred in 8% of patients. Four patients (3%) progressed to accelerated or blast phase while on therapy, and 7 patients (6%) died on study.

Conclusions

The current data confirm the long‐term efficacy of nilotinib 400 mg twice daily in patients with CP‐CML. A majority of patients can achieve sustained MR4.5.
An Approach to the Synthesis of a Two‐Dimensional Polymer Using a Preorganized Host‐Guest Network by Self‐Assembly at the Liquid/Solid Interface
Authors: Iritani Kohei , Kaneko Kyohei , Tahara Kazukuni , De Feyter Steven , Tobe Yoshito
Published: January 2020

An approach to synthesize a two‐dimensional polymer (2DP) using a preorganized host‐guest network at the liquid/solid interface is presented. As a host network, we used a self‐assembled monolayer of a dehydrobenzo[12]annulene derivative having aminophenyl groups at three alkoxy chain ends and, as a guest, a hexakis(phenylethynyl)benzene derivative having six formyl groups, aiming to connect the host to the guest embedded in the host matrix by imine bond formation. STM observations of host‐guest mixtures with trifluoroacetic acid at the 1‐phenyloctane/highly oriented pyrolytic graphite interface revealed that the guest was observed as a spoke‐like feature in the nanowells. Based on the STM image analysis, short distances between the diagonal phenyl groups in the nanowells are detected, indicating that the imine bonds are formed. However, the small abundance and random distribution of the short phenyl‐phenyl distance indicate that the periodically ordered 2DP structure is not formed, probably because the network cannot tolerate the structural change due to partial bond formation.
Tuning Solid‐State Luminescence in Conjugated Organic Materials: Control of Excitonic and Excimeric Contributions through π Stacking and Halogen Bond Driven Self‐Assembly
Authors: Majumdar Prabhat , Tharammal Fazil , Gierschner Johannes , Varghese Shinto
Published: January 2020

Two polymorphs with distinctly different fluorescence emission (green and yellow; G, Y) emanating from excitonic and excimeric contributions were prepared from solution as well as by using physical vapour transport. Based on crystal structure investigations, the vibrationally‐resolved excitonic emission is found to originate from a β‐Sheet arrangement (G), whereas a sandwich herringbone structure is responsible for the excimer emission (Y). The intermolecular interactions and energies were quantified to have a complete picture of the decisive factors that controls the self‐assembly. Halogen‐bond directed self‐assembly was explored to fine‐tune the intermolecular interactions through co‐crystallization as well as a commercially viable liquid assisted grinding method. A smooth fluorescence shift from G to Y was achieved by co‐assembly due to substantial differences in the π orbital overlap in the molecular packing. Our investigation provides a comprehensive understanding of the origin of excitonic and excimeric contributions of emission behaviour in conjunction with the molecular packing and π–π orbital overlap, and might provide a directive towards the engineering of fluorescent functional molecular materials.
Turkish adaptation of the Short Schema Mode Inventory
Authors: Aytaç Mert , Köse Karaca Bahar , Karaosmanoğlu Alp
Published: January 2020

The purpose of the current study is to present the psychometric properties of the Short Schema Mode Inventory in the Turkish culture. The study sample comprised 1,287 participants, including both clinical and nonclinical participants. The age of the participants ranged between 18 and 48 years. The construct validity of the scale was tested using confirmatory factor analysis. The internal (Cronbach's alpha) and test–retest reliability coefficients were used to examine the reliability of the scale. Discriminant validity was investigated by comparing the nonclinical and clinical participants. Concurrent validity was tested via the Splitting Scale. The results of the study showed that the tested model had good data‐model fit statistics. Additionally, the reliability analyses revealed that the scales had good internal and test–retest reliability coefficients. A significant association was found between the subscales of the Schema Mode Inventory. Furthermore, the scores of the clinical participants were significantly higher compared with the scores of the nonclinical participants for the maladaptive schema modes. Nonetheless, the participants in the nonclinical group had significantly higher levels of the healthy schema modes than individuals in the clinical group. The results of this study demonstrated that the Schema Mode Inventory was a reliable and valid instrument to measure schema modes in the Turkish population.
Ru‐Catalyzed Switchable N‐Hydroxyethylation and N‐Acetonylation with Crude Glycerol
Authors: Xin Zhuo , Jia Le , Huang Yuxing , Du Chen‐Xia , Li Yuehui
Published: February 2020

Highly efficient Ru‐catalyzed selective C−C or C−O bond cleavage of polyols (e.g., crude glycerol) for N‐hydroxyethylation or N‐acetonylation of amines was achieved through the hydrogen‐borrowing approach. A variety of amines were transformed to the desired amino alcohols/ketones in moderate‐to‐excellent yields, opening up new avenues for generation of oxygenated pharmaceuticals and fine chemicals from renewable raw materials. The use of new redox‐active catalysts containing bisphosphine/thienylmethylamine ligands allows this hydrogen‐borrowing system to be operated selectively under both basic and acidic conditions.
Associations between empathy, inhibitory control, and physical aggression in toddlerhood
Authors: Noten Malou M. P. G. , Van der Heijden Kristiaan B. , Huijbregts Stephan C. J. , Van Goozen Stephanie H. M. , Swaab Hanna
Published: January 2020

Impaired empathy has been associated with aggression in children, adolescents and adults, but results have been contradictory for the preschool period. Impaired inhibitory control also increases the risk of aggression, and possibly moderates empathy‐aggression associations. The current study investigated whether empathy and inhibitory control are associated with aggression in toddlerhood. Furthermore, we aimed to clarify the role of inhibitory control in empathy and aggression, specifically, whether inhibitory control moderates the association between empathy and aggression. During a laboratory visit at age 30 months (N = 103), maternal reports of physical aggression were obtained and child inhibitory control was examined using a gift delay task. Empathy was examined by obtaining behavioral observations and recording physiological responses (heart rate response and respiratory sinus arrhythmia response) to an empathy‐eliciting event (i.e., simulated distress). Reduced inhibitory control was associated with more aggression. Behavioral and physiological indicators of empathy were not associated with aggression. Hierarchical regression analyses revealed an interaction effect of heart rate response to distress simulation with inhibitory control in the prediction of aggression. Post hoc analyses indicated a negative association between heart rate response and aggression when inhibitory control was high, but a positive association was found in toddlers who demonstrated low inhibitory control. These results suggest that children are less aggressive when they have both high levels of empathy and inhibitory control. Therefore, both empathy and inhibition are important targets for interventions aiming to reduce or prevent aggression at a young age.
A machine learning approach for handling big data produced by high resolution mass spectrometry after data independent acquisition of small molecules – Proof of concept study using an artificial neural network for sample classification
Authors: Streun Gabriel L. , Elmiger Marco P. , Dobay Akos , Ebert Lars , Kraemer Thomas
Published: January 2020

Liquid chromatography coupled to high‐resolution mass spectrometry (HRMS) enables data independent acquisition (DIA) and untargeted screening. However, to avoid the handling of the resulting large dataset, most laboratories in that field still use targeted screening methods, which offer good sensitivity and specificity but are limited to known compounds. The promising field of machine learning offers new possibilities such as artificial neural networks that can be trained to classify large amounts of data. In this proof of concept study, we exemplify such a machine learning approach for raw HRMS‐DIA data files. We evaluated a machine learning model using training, validation, and test sets of solvent and whole blood samples containing drugs (of abuse) common in forensic toxicology. For that purpose, different platforms were used. With a feedforward neural network model architecture, a category prediction (blank sample vs. drug containing sample) was aimed for. With the applied machine learning approaches, the sensitivity and specificity, of the validation and test set, for the prediction of sample classes were in a suitable range for an actual use in a (routine) laboratory (e.g. workplace drug testing). In conclusion, this proof of concept study clearly demonstrated the huge potential of machine learning in the analysis of HRMS‐DIA data.
Boreal predator co‐occurrences reveal shared use of seismic lines in a working landscape
Authors: Tattersall Erin R. , Burgar Joanna M. , Fisher Jason T. , Burton A. Cole
Published: January 2020

Interspecific interactions are an integral aspect of ecosystem functioning that may be disrupted in an increasingly anthropocentric world. Industrial landscape change creates a novel playing field on which these interactions take place, and a key question for wildlife managers is whether and how species are able to coexist in such working landscapes. Using camera traps deployed in northern Alberta, we surveyed boreal predators to determine whether interspecific interactions affected occurrences of black bears (Ursus americanus), coyotes (Canis latrans), and lynx (Lynx canadensis) within a landscape disturbed by networks of seismic lines (corridors cut for seismic exploration of oil and gas reserves). We tested hypotheses of species interactions across one spatial‐only and two spatiotemporal (daily and weekly) scales. Specifically, we hypothesized that (1) predators avoid competition with the apex predator, gray wolf (Canis lupus), (2) they avoid competition with each other as intraguild competitors, and (3) they overlap with their prey. All three predators overlapped with wolves on at least one scale, although models at the daily and weekly scale had substantial unexplained variance. None of the predators showed avoidance of intraguild competitors or overlap with prey. These results show patterns in predator space use that are consistent with both facilitative interactions or shared responses to unmeasured ecological cues. Our study provides insight into how predator species use the working boreal landscape in relation to each other, and highlights that predator management may indirectly influence multiple species through their interactions.
Complete tag loss in capture–recapture studies affects abundance estimates: An elephant seal case study
Authors: Malcolm‐White Emily , McMahon Clive R. , Cowen Laura L. E.
Published: January 2020

In capture–recapture studies, recycled individuals occur when individuals lose all of their tags and are recaptured as though they were new individuals. Typically, the effect of these recycled individuals is assumed negligible.

Through a simulation‐based study of double‐tagging experiments, we examined the effect of recycled individuals on parameter estimates in the Jolly–Seber model with tag loss (Cowen & Schwarz, 2006). We validated the simulation framework using long‐term census data of elephant seals.

Including recycled individuals did not affect estimates of capture, survival, and tag‐retention probabilities. However, with low tag‐retention rates, high capture rates, and high survival rates, recycled individuals produced overestimates of population size. For the elephant seal case study, we found population size estimates to be between 8% and 53% larger when recycled individuals were ignored.

Ignoring the effects of recycled individuals can cause large biases in population size estimates. These results are particularly noticeable in longer studies.
The Transition Metal Chemistry of PGeP and PSnP Pincer Heavier Tetrylenes
Authors: Cabeza Javier A. , García‐Álvarez Pablo , Laglera‐Gándara Carlos J.
Published: January 2020

This review article collects and discusses the syntheses of the currently known metal‐free heavier tetrylenes having a PEP pincer topology (E = tetrel atom) as well as their transition metal derivative chemistry. To date, only five PGeP germylenes and two PSnP stannylenes have been isolated. These compounds have been successfully synthesized by treating GeCl2(diox) (diox = 1,4‐dioxane), GeCl2(NHC) (NHC = N‐heterocyclic carbene) or SnCl2 with two equivalents of an appropriate lithiated phosphine. Their transition metal chemistry is dominated by processes in which, in addition to the coordination of one or both phosphane groups, the E atom ends inserted into M–M or M–X (X = anionic group) bonds. Only in a few occasions a simple coordination of the tetrylene fragment (as a neutral two‐electron‐donor ligand) has been observed. The structural and bonding characteristics of the metal‐free PEP tetrylenes and of relevant examples of their transition metal derivatives are also surveyed.
Profile of Triacylglycerols, Phenols, and Vitamin E of Manjari Medika Grape Seed Oil and Cake: Introducing a Novel Indian Variety
Authors: Khan Zareen S. , Chatterjee Niladri S. , Shabeer T.P. Ahammed , Shaikh Shamim , Banerjee Kaushik
Published: January 2020

The aim of the study is to investigate the biochemical composition of grapeseed oil and cake from an unexplored Indian grape‐juice cultivar, Manjari Medika (MM). The composition of oil and residual seed cake is evaluated using various chromatographic and spectroscopic techniques. The findings demonstrate that the vitamin E content of MM‐seed oil (1.15–1.35 g kg−1) is distinctively higher than the Codex standard, suggesting its superior quality as an edible oil. The predominant triacylglycerols include trilinolein (LLL, 43%), dilinoleoyl‐stearylglycerol (LSL, 19%), and dilinoleoyl‐palmitoylglycerol (LLP, 11%), which are earlier recognized as natural antioxidants. The seed‐cake is rich in polyphenols including acylated anthocyanins (e.g., pelargonidin‐3‐O‐coumaroyl glucoside) and certain other flavonoids (e.g., catechin). The profile of phytonutrients in MM seed‐oil and cake is significantly superior to its seeded female parent and two other widely cultivated wine‐grape varieties. In brief, the studied by‐products of this new grape‐juice cultivar can be an important source of high‐value ingredients for use in food supplements, nutraceuticals, and functional foods.

Practical applications: This study reports the phytochemical profile of the seed‐oil and seed cake derived from a newly developed grape variety, Manjari Medika. High contents of selective antioxidants: lipids, vitamin E, and phenols in the seed‐oil and cake with health benefits suggest their potential for use in nutraceutical and functional foods. These byproducts can be utilised as ingredients of functional foods and nutraceuticals (e.g., grape seed oil capsule) and also as raw materials in food supply chains (e.g., for production of grape cookies or cake). MM can also be utilized as a colorant in the food industry.
A Route to 1‐Deoxynojirimycin and 1‐Deoxymannojirimycin Derivatives with Quaternary Centers Adjacent to the Ring Nitrogen from Methyl α‐d‐Mannopyranoside
Authors: Chadda Rekha , Murphy Paul V.
Published: February 2020

6‐Alkylated‐8‐azido‐1,6‐octadiene derivatives were prepared from methyl α‐d‐mannopyranoside. The sequence to allylic azide precursors included a Horner–Wadsworth‐Emmons reaction with a concomitant epimerization that ultimately enabled synthesis of 1‐deoxynojirimycin as well as 1‐deoxymannojirimycin derivatives. Thermally promoted allylic acid rearrangement followed by triazoline formation, then decomposition to aziridine and finally reaction with acetic acid was used to generate products that have quaternary anomeric centers adjacent to the piperidine ring nitrogen atom (cyclic α‐tertiary amines). The stereoselectivity is accounted for based on minimization of steric interactions in the transition state structure, favoring the product where the methyl substituent is equatorial and the vinyl group prefers to be axial.
Synthesis of Sulfonyl Fluorides from Sulfonamides
Authors: Pérez‐Palau Marina , Cornella Josep
Published: January 2020

A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry‐BF4and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late‐stage formation of sulfonyl fluorides from densely functionalized molecules.
Mathematical Modelling of a Non‐enzymatic Amperometric Electrochemical Biosensor for Cholesterol
Authors: Goyal Arpit , Bairagi Pallab Kumar , Verma Nishith
Published: February 2020

Thickness of the electro‐polymerized layer grown on a substrate and used as the recognition element for the analyte is critical to measuring the response of a biosensor, with high sensitivity and accuracy. However, it is difficult to control the thickness during synthesis. A mathematical model is developed in this study that considers thickness of the electro‐polymerized layer in simulating the electrochemical response of a non‐enzymatic biosensor for cholesterol in blood. The model includes transient kinetics and one‐dimensional diffusion of the analyte in the poly‐methyl orange (PMO) recognition layer electrochemically grown on the electrode. The governing partial differential equations resulting from the species conservation balances in the PMO layer are numerically solved. Time and spatial concentration profiles of the analyte in the PMO layer are determined. Model predictions are calibrated with the experimental data for different PMO thicknesses. Interestingly, model predictions show a linear response over the calibrated concentration range of cholesterol for all PMO layer thicknesses. Based on the chronoamperometry measurements, the model predictions for the cholesterol concentrations measured in the laboratory samples were also found to be remarkably accurate. This is the first mathematical model developed to understand the transport and kinetics of an analyte in the electro‐polymerized layer used as the recognition element of a non‐enzymatic biosensor.
Synergistic Enhancement Effects of Carbon Quantum Dots and Au Nanoclusters for Cathodic ECL and Non‐enzyme Detections of Glucose
Authors: Han Shuang , Gao Yuan , Li Lin , Lu Beibei , Zou Yongxing , Zhang Ling , Zhang Jiaheng
Published: February 2020

In this study, we found that glucose enhance electrochemiluminescence (ECL) intensity of both Au nanoclusters (Au NCs) and carbon quantum dots (CQDs) with K2S2O8 as the co‐reactants. The enhancing effects by Au NCs and CQDs were overlapped, enabling the detection of glucose. The increased ECL intensity of glucose was linear with the logarithm of concentrations of glucose in the range of 50 μM–3.0 mM, and the limit of detection is 20 μM. Anti‐interruption ability was achieved, and ascorbic acid, urea, and uric acid had little influence to glucose detection. This method realized the direct detection of glucose by enhancing ECL of Au NCs and CQDs, which was fast and economic, possessing potential applications for glucose detection in human serum.
A small NGS–SNP panel of ancestry inference designed to distinguish African, European, East, and South Asian populations
Authors: Guo Yu‐Xin , Jin Xiao‐Ye , Xia Zhi‐Yu , Chen Chong , Cui Wei , Zhu Bo‐Feng
Published: February 2020

In this study, a small set of ancestry informative SNPs was selected to differentiate African, European, East and South Asian samples, which was detected by the next‐generation sequencing technology. A total of 127 Chinese Shaanxi Han individuals were collected as test samples. No statistically significant linkage disequilibrium of any pair of loci or departure from Hardy–Weinberg equilibrium of each locus was observed in the test population. To evaluate the performance of ancestry assignment using this panel, admixture analysis, principal component analysis, and likelihood ratio calculations were conducted based on the 1000 genome data and test samples. All populations were clustered into four groups, African, European, South and East Asian populations, which were consistent with their geographical origins. The pairwise fixation index (FST) between populations from different continental groups ranged from 0.140 to 0.621 with average 0.415, and the pairwise FST between populations from the same continent ranged from 0.000 to 0.056 with average 0.012. The likelihood ratio results of 125 test individuals indicated that their ancestry components were highly possible from East Asia. In conclusion, this small set of ancestry informative SNPs can be used as a reliable tool to identify and quantify ancestry components of unknown samples.
Pricing VIX options with volatility clustering
Authors: Jing Bo , Li Shenghong , Ma Yong
Published: January 2020

We investigate the valuation of volatility index (VIX) options by developing a model with a self‐exciting Hawkes process that allows for clustering in the VIX. In the proposed framework, we find semianalytical expressions for the characteristic function and forward characteristic function, and then we solve the pricing problem of standard‐start and forward‐start options via the fast Fourier transform. The empirical results provide evidence to support the significance of accounting for volatility clustering when pricing VIX options.
Inferring information from the S&P 500, CBOE VIX, and CBOE SKEW indices
Authors: Cao Jiling , Ruan Xinfeng , Zhang Wenjun
Published: January 2020

This paper compares the information extracted from the S&P 500, CBOE VIX, and CBOE SKEW indices for the S&P 500 index option pricing. Based on our empirical analysis, VIX is a very informative index for option prices. Whether adding the SKEW or the VIX term structure can improve the option pricing performance depends on the model we choose. Roughly speaking, the VIX term structure is informative for some models, while the SKEW is very noisy and does not contain much important information for option prices. This paper also extends Zhang et al. (2017, J Futures Markets, 37, 211–237) into three typical affine models.
Does corporate hedging affect firm valuation? Evidence from the IPO market
Authors: Qiao Zheng , Xia Chongwu , Zhang Lei
Published: January 2020

Focusing on the IPO market, we examine the influence of corporate hedging on firm valuation. Consistent with the argument that hedging reduces information asymmetry, we find that hedging IPO firms are associated with lower price revisions and underwriting fees. More important, hedging reduces IPO underpricing, especially for informationally opaque firms. This provides strong evidence that corporate hedging increases firm valuation. We also show that corporate hedging lowers aftermarket idiosyncratic volatility, enhances aftermarket liquidity, and improves the long‐term performance of IPO firms. We use both an instrumental variable approach and a regulation change on derivatives supply to address endogeneity concerns.
Prospective evaluation of XRCC‐1 Arg194Trp polymorphism as bio‐predictor for clinical outcome in locally advanced laryngeal cancer undergoing cisplatin‐based chemoradiation
Authors: Raturi Vijay , Hojo Hidehiro , Bhatt M. L. B. , Suhel Mohammad , Wu Chen‐Ta , Bei Yanping , Nakamura Masaki , Okumura Masayuki , Zhang Haiqin , Parmar Devendra , Badajena Avinash , Singh Rahul , Kumar Saurabh , Katiyar Tridev , Gaur Jalaj
Published: January 2020

Background

To determine X‐ray repair cross‐complementing 1 gene (XRCC‐1) Arg194Trp polymorphism as bio‐predictor for clinical outcome in advanced laryngeal squamous cell carcinoma undergoing cisplatin‐based chemoradiation (CRT).

Methods

A total of 150 patients were enrolled in this prospective study. XRCC‐1 Arg194Trp genotyping categorized patients as wild (C/C) and polymorphic (C/T or T/T). The primary endpoint was to assess acute radiation‐induced toxicity (ARIT).

Results

A significant correlation of skin (P‐ .04) and oral mucosal ARIT (P‐ .01) was noticed in the XRCC‐1 polymorphic variant. A higher treatment response was noted in the polymorphic variant, and it shows a trend toward significance (P‐ .08). With 33 months of median follow‐up, 2‐year progression‐free survival (PFS) and overall survival (OS) of wild vs polymorphic variant were 34.6% vs 46.9% (P‐ .066) and 50.6% vs 62.2% (P‐ .12).

Conclusion

XRCC‐1 polymorphic variants have significantly higher oral mucositis and skin ARIT and may have improved trend for treatment response and PFS.
Adjuvant external beam radiotherapy for surgically resected, nonmetastatic anaplastic thyroid cancer
Authors: Saeed Nadia A. , Kelly Jacqueline R. , Deshpande Hari A. , Bhatia Aarti K. , Burtness Barbara A. , Judson Benjamin L. , Mehra Saral , Edwards Heather A. , Yarbrough Wendell G. , Peter Patricia R. , Holt Elizabeth H. , Decker Roy H. , Husain Zain A. , Park Henry S.
Published: February 2020

Background

EBRT in resected, nonmetastatic anaplastic thyroid cancer (ATC) remains undefined. We evaluated patterns/outcomes with EBRT and chemotherapy in this setting.

Methods

This retrospective analysis included patients identified from the National Cancer Database with nonmetastatic ATC from 2004 to 2014 who underwent non‐palliative resection.

Results

Our analysis included 496 patients, including 375 who underwent adjuvant EBRT (among whom 198 received concurrent chemotherapy). The median age was 68 years. On MVA, EBRT was associated with sex (OR 0.5, 95% CI 0.3‐0.8, P = .002) and income (OR 2.2, 95% CI 1.4‐3.3, P < .001). EBRT was associated with longer OS on UVA (12.3 vs 9.1 months, P = .004) and MVA (HR 0.7 [CI 0.6‐0.9], P = .004). Concurrent chemoradiation was associated with longer OS on UVA (14.0 vs 9.1 months, P = .003) and MVA (HR 0.6 [CI 0.5‐0.8], P < .001).

Conclusion

Adjuvant EBRT is associated with longer OS in resected, nonmetastatic ATC, with additional improved survival with concurrent chemotherapy.
‘Not everybody is an internet person’: Barriers for menopause‐related health literacy among immigrant women from the Horn of Africa nations
Authors: Stanzel Karin A. , Hammarberg Karin , Fisher Jane
Published: February 2020

Issue addressed

Changes in health require new learning. There are increased risks of chronic noncommunicable diseases after menopause and positive health behaviour during the peri‐menopausal years and beyond are crucial for a healthy postmenopausal life. In order to implement health promotion messages, women require adequate health literacy skills in order to achieve better health and access to appropriate health care.

Methods

This qualitative study explored menopause‐related health literacy and experiences of menopause‐related health care using semi‐structured interviews with women from the Horn of Africa nations who had migrated to Melbourne, Australia.

Results

Participants viewed menopause as a normal life phase and did not see the need for accessing menopause‐related information and care. Limited education, low literacy and being unfamiliar with the internet were barriers to health literacy. Participants' preferred health care providers who could converse in their first language, but regretted their lack of proactive engagement in providing menopause‐related information.

Conclusion

Primary health care providers need to be aware that immigrant women from the Horn of Africa nations have poor health literacy and may be unaware of the benefits of positive health behaviours during and after menopause. Offering menopause‐related health promotion opportunistically may lead to better postmenopausal health for this group of women.

So what?

Health promotion and education programs codesigned with community stakeholders may be effective in engaging immigrant communities to improve menopause‐related health literacy.
Serum levels of hsa‐miR‐16‐5p, hsa‐miR‐29a‐3p, hsa‐miR‐150‐5p, hsa‐miR‐155‐5p and hsa‐miR‐223‐3p and subsequent risk of chronic lymphocytic leukemia in the EPIC study
Authors: Casabonne Delphine , Benavente Yolanda , Seifert Julia , Costas Laura , Armesto María , Arestin María , Besson Caroline , Hosnijeh Fatemeh S. , Duell Eric J. , Weiderpass Elisabete , Masala Giovanna , Kaaks Rudolf , Canzian Federico , Chirlaque María‐Dolores , Perduca Vittorio , Mancini Francesca R. , Pala Valeria , Trichopoulou Antonia , Karakatsani Anna , La Vecchia Carlo , Sánchez Maria‐Jose , Tumino Rosario , Gunter Marc J. , Amiano Pilar , Panico Salvatore , Sacerdote Carlotta , Schmidt Julie A. , Boeing Heiner , Schulze Matthias B. , Barricarte Aurelio , Riboli Elio , Olsen Anja , Tjønneland Anne , Vermeulen Roel , Nieters Alexandra , Lawrie Charles H. , de Sanjosé Silvia
Published: February 2020

Chronic lymphocytic leukemia (CLL) is an incurable disease accounting for almost one‐third of leukemias in the Western world. Aberrant expression of microRNAs (miRNAs) is a well‐established characteristic of CLL, and the robust nature of miRNAs makes them eminently suitable liquid biopsy biomarkers. Using a nested case–control study within the European Prospective Investigation into Cancer and Nutrition (EPIC), the predictive values of five promising human miRNAs (hsa‐miR‐16‐5p, hsa‐miR‐29a‐3p, hsa‐miR‐150‐5p, hsa‐miR‐155‐5p and hsa‐miR‐223‐3p), identified in a pilot study, were examined in serum of 224 CLL cases (diagnosed 3 months to 18 years after enrollment) and 224 matched controls using Taqman based assays. Conditional logistic regressions were applied to adjust for potential confounders. The median time from blood collection to CLL diagnosis was 10 years (p25–p75: 7–13 years). Overall, the upregulation of hsa‐miR‐150‐5p, hsa‐miR‐155‐5p and hsa‐miR‐29a‐3p was associated with subsequent risk of CLL [OR1∆Ct‐unit increase (95%CI) = 1.42 (1.18–1.72), 1.64 (1.31–2.04) and 1.75 (1.31–2.34) for hsa‐miR‐150‐5p, hsa‐miR‐155‐5p and hsa‐miR‐29a‐3p, respectively] and the strongest associations were observed within 10 years of diagnosis. However, the predictive performance of these miRNAs was modest (area under the curve <0.62). hsa‐miR‐16‐5p and hsa‐miR‐223‐3p levels were unrelated to CLL risk. The findings of this first prospective study suggest that hsa‐miR‐29a, hsa‐miR‐150‐5p and hsa‐miR‐155‐5p were upregulated in early stages of CLL but were modest predictive biomarkers of CLL risk.
Germline variant burden in multidrug resistance transporters is a therapy‐specific predictor of survival in breast cancer patients
Authors: Xiao Qingyang , Zhou Yitian , Winter Stefan , Büttner Florian , Schaeffeler Elke , Schwab Matthias , Lauschke Volker M.
Published: February 2020

Multidrug resistance due to facilitated drug efflux mediated by ATP‐binding cassette (ABC) transporters is a main cause for failure of cancer therapy. Genetic polymorphisms in ABC genes affect the disposition of chemotherapeutics and constitute important biomarkers for therapeutic response and toxicity. Here we correlated germline variability in ABC transporters with disease‐specific survival (DSS) in 960 breast cancer (BRCA), 314 clear cell renal cell carcinoma and 325 hepatocellular carcinoma patients. We find that variant burden in ABCC1 is a strong predictor of DSS in BRCA patients, whereas candidate polymorphisms are not associated with DSS. This association is highly drug‐specific for subgroups treated with the MRP1 substrates cyclophosphamide (log‐rank p = 0.0011) and doxorubicin (log‐rank p = 0.0088) independent of age and tumor stage, whereas no association was found in individuals treated with tamoxifen (log‐rank p = 0.13). Structural mapping of significant variants revealed multiple variants at residues involved in protein stability, cofactor stabilization or substrate binding. Our results demonstrate that BRCA patients with high variant burden in ABCC1 are less prone to respond appropriately to pharmacological therapy with MRP1 substrates, thus incentivizing the consideration of genomic germline data for precision cancer medicine.