bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultrasmall Zeolite L Crystals Prepared from Highly Interdispersed Alkali‐Silicate Precursors
Authors: Li Rui , Linares Noemi , Sutjianto James G. , Chawla Aseem , Garcia‐Martinez Javier , Rimer Jeffrey D.
Published: June 2018

The preparation of nanosized zeolites is critical for applications where mass‐transport limitations within microporous networks hinder their performance. Often the ability to generate ultrasmall zeolite crystals is dependent upon the use of expensive organics with limited commercial relevance. Herein, we report the generation of zeolite L crystals with uniform sizes less than 30 nm using a facile, organic‐free method. Time‐resolved analysis of precursor assembly and evolution during nonclassical crystallization highlights key differences among silicon sources. Our findings reveal that a homogenous dispersion of potassium ions throughout silicate precursors leads to the formation of a metastable nonporous phase, which undergoes an intercrystalline transformation to zeolite L. The generation of highly interdispersed alkali‐silicate precursors is seemingly critical to enhancing the rate of nucleation and facilitating the formation of ultrasmall crystal.
Purification of Uranium‐based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release
Authors: Fuertes‐Espinosa Carles , Gómez‐Torres Alejandra , Morales‐Martínez Roser , Rodríguez‐Fortea Antonio , García‐Simón Cristina , Gándara Felipe , Imaz Inhar , Juanhuix Judith , Maspoch Daniel , Poblet Josep M. , Echegoyen Luis , Ribas Xavi
Published: June 2018

Supramolecular nanocapsule 1⋅(BArF)8 is able to sequentially and selectively entrap recently discovered U2@C80 and unprecedented Sc2CU@C80, simply by soaking crystals of 1⋅(BArF)8 in a toluene solution of arc‐produced soot. These species, selectively and stepwise absorbed by 1⋅(BArF)8, are easily released, obtaining highly pure fractions of U2@C80 and Sc2CU@C80 in one step. Sc2CU@C80 represents the first example of a mixed metal actinide‐based endohedral metallofullerene (EMF). Remarkably, the host–guest studies revealed that 1⋅(BArF)8 is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations.
Organocatalytic Formation of Chiral Trisubstituted Allenes and Chiral Furan Derivatives
Authors: Poulsen Pernille H. , Li Yang , Lauridsen Vibeke H. , Jørgensen Danny K. B. , Palazzo Teresa A. , Meazza Marta , Jørgensen Karl Anker
Published: June 2018

A novel reaction that provides chiral allenes by amino catalytic activation of either aldehydes or α,β‐unsaturated aldehydes for reaction with alkynyl‐substituted enones is presented. The reaction forms a variety of trisubstituted allenes in high yields and with excellent stereoselectivities. The utility of the reaction concept is demonstrated by the synthesis of chiral furan derivatives in high yields and stereoselectivities.
Blood‐Catalyzed RAFT Polymerization
Authors: Reyhani Amin , Nothling Mitchell D. , Ranji‐Burachaloo Hadi , McKenzie Thomas G. , Fu Qiang , Tan Shereen , Bryant Gary , Qiao Greg G.
Published: June 2018

The use of hemoglobin (Hb) contained within red blood cells to drive a controlled radical polymerization via a reversible addition‐fragmentation chain transfer (RAFT) process is reported for the first time. No pre‐treatment of the Hb or cells was required prior to their use as polymerization catalysts, indicating the potential for synthetic engineering in complex biological microenvironments without the need for ex vivo techniques. Owing to the naturally occurring prevalence of the reagents employed in the catalytic system (Hb and hydrogen peroxide), this approach may facilitate the development of new strategies for in vivo cell engineering with synthetic macromolecules.
Thiourea‐Catalyzed Asymmetric Michael Addition of Carbazolones to 2‐Chloroacrylonitrile: Total Synthesis of 5,22‐Dioxokopsane, Kopsinidine C, and Demethoxycarbonylkopsin
Authors: Ni Dongshun , Wei Yi , Ma Dawei
Published: June 2018

A modified Takemoto catalyst enabled the asymmetric Michael addition of carbazolones to 2‐chloroacrylonitrile to afford 3,3‐disubstituted carbazolones with excellent enantioselectivity. This method was successfully applied to total syntheses of three Kopsia alkaloids which featured an unprecedented MnIII‐mediated oxidative cyclization to create the caged ring system and a SmI2‐mediated reductive coupling as key steps.
Competition between H and CO for Active Sites Governs Copper‐Mediated Electrosynthesis of Hydrocarbon Fuels
Authors: Schreier Marcel , Yoon Youngmin , Jackson Megan N. , Surendranath Yogesh
Published: June 2018

The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO2. Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface‐affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH4 and H2 production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate‐limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis.
Oxidative Stability of Papaya Seed Oil From Hainan/Eksotika Obtained by Subcritical and Supercritical Carbon Dioxide Extraction
Authors: Zhang Weimin , Xia Qiuqi , Ji Yanyu , Chen Haiming , Pan Yonggui , Chen Wenxue , Cao Jun , Yang Hong , Huang Wuyang , Wang Liling
Published: June 2018

Papaya seed is a good source of edible oil with considerable antioxidant activity. Here, papaya seed oil (PSO) of Hainan/Eksotika variety was obtained by subcritical butane extraction (SBE) and supercritical carbon dioxide extraction (SCDE), and its yields, physicochemical properties, oxidative and thermal stability, and chemical and microscopic structures were compared. The results showed that SBE‐PSO had a higher yield (25.88 ± 0.29% vs. 19.47 ± 0.92%), but a lower melting point compared to SCDE‐PSO. Molecular structures indicated that there was no oxidative degradation during SBE and SCDE. Both SBE and SCDE caused significant structural changes of seed tissues. In addition, aldehyde composition analysis using high performance liquid chromatography (HPLC) showed that SBE‐PSO had fewer octanal, nonanal, 2‐decenal, and 2‐undecenal contents than SCDE‐PSO. All these results proved that SBE‐PSO exhibited superiority on the oxidative stability compared to SCDE‐PSO. It indicated that SBE was a superior method to obtain antioxidant edible oil with good stability.
What happened after the Last Glacial Maximum? Transitions in site use on an arid inland island in north‐western Australia
Authors: REYNEN WENDY , VANNIEUWENHUYSE DORCAS , MORSE KATE , MONKS CARLY , BALME JANE
Published: June 2018

The presence of Aboriginal people in interior refuges as climate conditions deteriorated with the onset of glacial aridity is now well documented in the Australian arid zone. Further excavation at Yurlu Kankala, a large rock shelter located on an island of high land in the inland Pilbara, demonstrates repeated human occupation from at least 47–43 cal ka BP through the Last Glacial Maximum to the mid‐Holocene. Despite the continued presence of bone representing human food remains and an increased occurrence of hearths, after 18–17 cal ka BP there is a dramatic reduction in stone artefact numbers, suggesting that use of the site changed markedly. In exploring the drivers behind this change, we investigate the role of rock shelters in Aboriginal land‐use systems in the Pleistocene Pilbara. Yurlu Kankala makes a substantive contribution to answering questions on changing rock shelter and landscape use during the post‐LGM movement of people into the wider Pilbara uplands.
Hybridized Polyoxometalate‐Based Metal–Organic Framework with Ketjenblack for the Nonenzymatic Detection of H2O2
Authors: Wang Cong , Zhou Ming , Ma Yuanyuan , Tan Huaqiao , Wang Yonghui , Li Yangguang
Published: June 2018

The rational design and development of efficient and affordable enzyme‐free electrocatalysts for electrochemical detection are of great significance for the large‐scale applications of sensor materials, and have aroused increasing research interest. Herein, we report that a typical polyoxometalate (POM)‐based metal–organic framework (NENU5) that was hybridized with ketjenblack (KB) was a highly efficient electrochemical catalyst that could be used for the highly sensitive nonenzymatic detection of H2O2. The composite catalyst exhibited superb electrochemical detection performance towards H2O2, including a broad linear range from 10–50 mm, a low detection limit of 1.03 μm, and a high sensitivity of 33.77 μA mm−1, as well as excellent selectivity and stability. These excellent electrocatalytic properties should be attributed to the unique redox activity of the POM, the high specific surface area of the metal–organic framework (MOF), the strong conductivity of KB, and the synergistic effects of the multiple components in the composites during the electrolysis of H2O2. This work provides a new pathway for the exploration of nonenzymatic electrochemical sensors.
Neubau Übungshalle für die Staatliche Feuerwehrschule Würzburg
Authors: Stumpf Martin , Reinhardt Achim , Wörner Sven
Published: June 2018

Auf dem Gelände der Staatlichen Feuerwehrschule in Würzburg entstand eine neue Halle mit 77 m Länge und einer Breite von 40 m. Auf diesem „Spielplatz für große Jungs und starke Mädchen“ ist es künftig möglich, wetterunabhängig und realitätsnah Feuerwehreinsätze jeder Art zu üben. Innerhalb der 21 m hohen Halle sind vielfältige Übungsszenarien möglich. Im Halleninnenraum sind neben einer vierstöckigen Gebäudezeile, in der verschiedenste Nutzungen vom Mehrfamilienhaus über einen Einkaufsladen bis hin zu einem Labor simuliert werden, noch ein Hochregallager und ein Hochhaus mit acht Stockwerken enthalten. Dieses Hochhaus mit einer Höhe von fast 30 m ragt über das Hallendach hinaus und wird durch eine aufgesetzte Haube vor der Witterung geschützt.
Distributed Strain Sensing in der Geotechnik – Teil 2
Authors: Kindler Arne , Großwig Stephan , Pfeiffer Thomas
Published: June 2018

Mit der vorliegenden Abhandlung wird der erste Beitrag zum Distributed Strain Sensing in der Geotechnik in der Bautechnik ergänzt. Insbesondere zeigt die Vergangenheit, dass gerade beim planenden Ingenieur eine große Unsicherheit hinsichtlich der Ausschreibung besteht. Damit ist vor allem das „Was“ gemeint. Das Feld der ortsverteilten faseroptischen Sensortechnik ist, wie bereits beschrieben, ein weitgefächertes Gebiet. Die im Folgenden zusammengestellten Ausführungen gelten sowohl für das Distributed Temperature Sensing als auch für das Distributed Strain Sensing. Der zusammengetragene Ausschreibungsumfang basiert auf einer 25‐jährigen Tätigkeit auf dem Gebiet der faseroptischen Messtechnik in der Erdöl‐ und Erdgasindustrie, im Wasserbau und der Geotechnik. Die Ausführungen beziehen sich auf das Distributed Strain Sensing. Das beschriebene System wird kommerziell auf dem Markt vertrieben und unterliegt keiner ausschreibungsrelevanten Beschränkung. Der Beitrag umfasst eine kurze allgemeine Beschreibung der auszuschreibenden Leistungen in Verbindung mit Ausschreibungsbausteinen, welche die gewünschte Leistung derart beschreibt, dass der planende Ingenieur wirklich vergleichbare Angebote erhält. Der Beitrag schützt den Ausschreibenden jedoch nicht vor der eigenen Wertung der angebotenen Leistung hinsichtlich der Eignung und Leistungsfähigkeit des Bieters. Abschließend werden zwei nicht abschließende Wirtschaftlichkeitsbetrachtungen zwischen dem Distributed Sensing und konventionellen Messverfahren dargestellt.
Age differences in moral judgment: Older adults are more deontological than younger adults
Authors: McNair Simon , Okan Yasmina , Hadjichristidis Constantinos , de Bruin Wändi Bruine
Published: June 2018

In 2 studies, an older and a younger age group morally evaluated dilemmas contrasting a deontological judgment (do not harm others) against a utilitarian judgment (do what is best for the majority). Previous research suggests that deontological moral judgments are often underpinned by affective reactions and utilitarian moral judgments by deliberative thinking. Separately, research on the psychology of aging has shown that affect plays a more prominent role in the judgments and decision making of older (vs. younger) adults. Yet age remains a largely overlooked factor in moral judgment research. Here, we therefore investigated whether older adults would make more deontological judgments on the basis of experiencing different affective reactions to moral dilemmas as compared with younger adults. Results from 2 experiments indicated that older adults made significantly more deontological moral judgments. Mediation analyses revealed that the relationship between age and making more deontological moral judgments is partly explained by older adults exhibiting significantly more negative affective reactions and having more morally idealistic beliefs as compared with younger adults.
BRCA1 and BRCA2 gene variants and nonsyndromic cleft lip/palate
Authors: Rodriguez Nicholas , Maili Lorena , Chiquet Brett T. , Blanton Susan H. , Hecht Jacqueline T. , Letra Ariadne
Published: June 2018

Background

Nonsyndromic cleft lip with or without cleft palate (NSCL/P) is a debilitating condition that not only affects the individual, but the entire family. The purpose of this study was to investigate the association of BRCA1 and BRCA2 genes with NSCL/P.

Methods

Twelve polymorphisms in/nearby BRCA1 and BRCA2 were genotyped using Taqman chemistry. Our data set consisted of 3,473 individuals including 2,191 nonHispanic white (NHW) individuals (from 151 multiplex and 348 simplex families) and 1,282 Hispanic individuals (from 92 multiplex and 216 simplex families). Data analysis was performed using Family‐Based Association Test (FBAT), stratified by ethnicity and family history of NSCL/P.

Results

Nominal associations were found between NSCL/P and BRCA1 in Hispanics and BRCA2 in NHW and Hispanics (p < .05). Significant haplotype associations were found between NSCL/P and both BRCA1 and BRCA2 (p ≤ .004).

Conclusions

Our results suggest a modest association between BRCA1 and BRCA2 and NSCL/P. Further studies in additional populations and functional studies are needed to elucidate the role of these genes in developmental processes and signaling pathways contributing to NSCL/P.
Future of 3D printing: How 3D bioprinting technology can revolutionize healthcare?
Authors: Morris Steven
Published: June 2018

Currently there are more than 2,000 children on the transplant waiting list—and more than 100,000 Americans nationwide—awaiting a matching organ. Most children aged one through 10 are awaiting a kidney, liver, or heart. As with any transplant, there are two ways to find an organ—someone can donate or someone can die. Unfortunately, the supply falls far short of the demand, leaving people to die every day waiting for a second chance at life. Scientific and medical experts, however, continue to develop promising technology like 3D bioprinting that could save thousands of lives without the need of a donor.
CRISPR–Mediated Genome Editing and Gene Repression in Scheffersomyces stipitis
Authors: Cao Mingfeng , Gao Meirong , Ploessl Deon , Song Cunjiang , Shao Zengyi
Published: June 2018

Scheffersomyces stipitis, renowned for its native xylose‐utilizing capacity, has recently demonstrated its potential in producing health‐promoting shikimate pathway derivatives. However, its broader application is hampered by the low transformation efficiency and the lack of genetic engineering tools to enable sophisticated genomic manipulations. S. stipitis employs the predominant non‐homologous end joining (NHEJ) mechanism for repairing DNA double‐strand breaks (DSB), which is less desired due to its incompetence in achieving precise genome editing. Using CRISPR technology, here a ku70Δku80Δ deficient strain in which homologous recombination (HR)‐based genome editing appeared dominant for the first time in S. stipitis is constructed. To build all essential tools for efficiently manipulating this highly promising nonconventional microbial host, the gene knockdown tool is also established, and repression efficiency is improved by incorporating a transcriptional repressor Mxi1 into the CRISPR‐dCas9 platform. All these results are obtained with the improved transformation efficiency, which is 191‐fold higher than that obtained with the traditional parameters used in yeast transformation. This work paves the way for advancing a new microbial chassis and provides a guideline for developing efficient CRISPR tools in other nonconventional yeasts.
Microbial Methylotrophic Metabolism: Recent Metabolic Modeling Efforts and Their Applications In Industrial Biotechnology
Authors: Lieven Christian , Herrgård Markus J. , Sonnenschein Nikolaus
Published: June 2018

Developing methylotrophic bacteria into cell factories that meet the chemical demand of the future could be both economical and environmentally friendly. Methane is not only an abundant, low‐cost resource but also a potent greenhouse gas, the capture of which could help to reduce greenhouse gas emissions. Rational strain design workflows rely on the availability of carefully combined knowledge often in the form of genome‐scale metabolic models to construct high‐producer organisms. In this review, the authors present the most recent genome‐scale metabolic models in aerobic methylotrophy and their applications. Further, the authors present models for the study of anaerobic methanotrophy through reverse methanogenesis and suggest organisms that may be of interest for expanding one‐carbon industrial biotechnology. Metabolic models of methylotrophs are scarce, yet they are important first steps toward rational strain‐design in these organisms.
Live‐Cell Imaging by Confocal Raman and Fluorescence Microscopy Recognizes the Crystal Structure of Calcium Carbonate Particles in HeLa Cells
Authors: Abalymov Anatolii A. , Verkhovskii Roman A. , Novoselova Marina V. , Parakhonskiy Bogdan V. , Gorin Dmitry A. , Yashchenok Alexey M. , Sukhorukov Gleb B.
Published: June 2018

Porous calcium carbonate (CaCO3) vaterite particles are very attractive templates for the encapsulation of pharmaceuticals and for the construction of hollow polyelectrolyte capsules, sensors, and enzyme‐catalyzed reactors. Although CaCO3 is biocompatible and biodegradable, little is known about the intercellular behavior and properties of vaterite particles in the cytoplasm of cells. In this work, the authors combine confocal Raman and fluorescent microscopy for the imaging of porous CaCO3 vaterite particles in HeLa cells to study the uptake and status of the particles inside the cells in real time. Analysis of the fluorescence images shows that the particles penetrated the plasma membrane 3 h after being added to the cell culture and that the internalization of the particles continued up to 48 h. The crystal structure of individual vaterite particles in the cytoplasm of HeLa cells did not obviously change for 144 h. For clusters of particles, however, the authors identify Raman spectroscopic signatures of the stable calcite phase after 72 h of incubation, confirming an ion‐exchange mechanism of vaterite transformation to calcite. The results indicate that these imaging approach to examining inorganic particles in living cells may have theranostic applications.
Direct comparison of LC–MS/MS and RIA methods for the pharmacokinetics assessment of human insulin in preclinical development
Authors: Dong Shiqi , Gu Yuan , Wei Guangli , Si Duanyun , Liu Changxiao
Published: June 2018

Insulin is an effective therapeutic for diabetes, and the level of insulin in vivo is directly related to the health of diabetic patients. Traditionally, the concentrations of insulin in vivo are determined by the radioimmunoassay (RIA) method. In this study, we developed an LC–MS/MS method for the quantification of human insulin in dog plasma and directly compared the RIA and LC–MS/MS methods. Our LC–MS/MS method exhibited superior accuracy, efficiency and cost‐effective for the pharmacokinetic (PK) assessment of human insulin. The LC–MS/MS method can quantitate human insulin and canine insulin simultaneously without cross‐reactivity, making the analysis more efficient. The LLOQ of our LC–MS/MS method was 38.5 pg/mL, which was necessary to fully describe the PK profiles of endogenous and exogenous insulin in vivo. The direct comparison of PK data obtained from the two methods demonstrated that LC–MS/MS could be an alternative to the RIA method and should be widely used for the quantification of insulin drugs, especially in preclinical studies.
Physical fitness interventions for nonambulatory stroke survivors: A mixed‐methods systematic review and meta‐analysis
Authors: Lloyd Megan , Skelton Dawn A. , Mead Gillian E. , Williams Brian , van Wijck Frederike
Published: June 2018

Introduction

Physical fitness training after stroke is recommended in guidelines across the world, but evidence pertains mainly to ambulatory stroke survivors. Nonambulatory stroke survivors (FAC score ≤2) are at increased risk of recurrent stroke due to limited physical activity. This systematic review aimed to synthesize evidence regarding case fatality, effects, experiences, and feasibility of fitness training for nonambulatory stroke survivors.

Methods

Eight major databases were searched for any type of study design. Two independent reviewers selected studies, extracted data, and assessed study quality, using published tools. Random‐effects meta‐analysis was used. Following their separate analysis, qualitative and quantitative data were synthesized using a published framework.

Results

Of 13,614 records, 33 studies involving 910 nonambulatory participants met inclusion criteria. Most studies were of moderate quality. Interventions comprised assisted walking (25 studies), cycle ergometer training (5 studies), and other training (3 studies), mainly in acute settings. Case fatality did not differ between intervention (1.75%) and control (0.88%) groups (95% CI 0.13–3.78, p = 0.67). Compared with control interventions, assisted walking significantly improved: fat mass, peak heart rate, peak oxygen uptake and walking endurance, maximum walking speed, and mobility at intervention end, and walking endurance, balance, mobility, and independent walking at follow‐up. Cycle ergometry significantly improved peak heart rate, work load, peak ventilation, peak carbon dioxide production, HDL cholesterol, fasting insulin and fasting glucose, and independence at intervention end. Effectiveness of other training could not be established. There were insufficient qualitative data to draw conclusions about participants' experiences, but those reported were positive. There were few intervention‐related adverse events, and dropout rate ranged from 12 to 20%.

Conclusions

Findings suggest safety, effectiveness, and feasibility of adapted fitness training for screened nonambulatory stroke survivors. Further research needs to investigate the clinical and cost‐effectiveness as well as experiences of fitness training—especially for chronic stroke survivors in community settings.
Neural bases of enhanced attentional control: Lessons from action video game players
Authors: Föcker Julia , Cole Daniel , Beer Anton L. , Bavelier Daphne
Published: June 2018

Objectives

The ability to resist distraction and focus on‐task‐relevant information while being responsive to changes in the environment is fundamental to goal‐directed behavior. Such attentional control abilities are regulated by a constant interplay between previously characterized bottom‐up and top‐down attentional networks. Here we ask about the neural changes within these two attentional networks that may mediate enhanced attentional control.

Materials and Methods

To address this question, we contrasted action video game players (AVGPs) and nonvideo game players (NVGPs) in a Posner‐cueing paradigm, building on studies documenting enhanced attentional control in AVGPs.

Results

Behavioral results indicated a trend for more efficient target processing in AVGPs, and better suppression in rare catch trials for which responses had to be withheld. During the cue period, AVGPs recruited the top‐down network less than NVGPs, despite showing comparable validity effects, in line with a greater efficiency of that network in AVGPs. During target processing, as previously shown, recruitment of top‐down areas correlated with greater processing difficulties, but only in NVGPs. AVGPs showed no such effect, but rather greater activation across the two networks. In particular, the right temporoparietal junction, middle frontal gyrus, and superior parietal cortex predicted better task performance in catch trials. A functional connectivity analysis revealed enhanced correlated activity in AVGPs compared to NVGPs between parietal and visual areas.

Conclusions

These results point to dynamic functional reconfigurations of top‐down and bottom‐up attentional networks in AVGPs as attentional demands vary. Aspects of this functional reconfiguration that may act as key signatures of high attentional control are discussed.
Sleep‐disordered breathing, brain volume, and cognition in older individuals with heart failure
Authors: Moon Chooza , Melah Kelsey E. , Johnson Sterling C. , Bratzke Lisa C.
Published: June 2018

Background and purpose

Sleep‐disordered breathing is common in individuals with heart failure and may contribute to changes in the brain and decreased cognition. However, limited research has explored how the apnea‐hypopnea index contributes to brain structure and cognition in this population. The aims of this study were to explore how the apnea‐hypopnea index is associated with brain volume and cognition in heart failure patients.

Methods

Data of 28 heart failure patients (mean age = 67.93; SD = 5.78) were analyzed for this cross‐sectional observational study. We evaluated the apnea‐hypopnea index using a portable multichannel sleep‐monitoring device. All participants were scanned using 3.0 Tesla magnetic resonance imaging and neuropsychological tests. Brain volume was evaluated using a voxel‐based morphometry method with T1‐weighted images. We used multiple regressions to analyze how the apnea‐hypopnea index is associated with brain volume and cognition.

Results

We found an inverse association between apnea‐hypopnea index scores and white matter volume (β = −0.002, p = 0.026), but not in gray matter volume (β = −0.001, p = 0.237). Higher apnea‐hypopnea index was associated with reduced regional gray and white matter volume (p < 0.001, uncorrected). Cognitive scores were not associated with the apnea‐hypopnea index (p‐values were >0.05).

Conclusion

Findings from this study provide exploratory evidence that higher apnea‐hypopnea index may be associated with greater brain volume reduction in heart failure patients. Future studies are needed to establish the relationship between sleep‐disordered breathing, brain volume, and cognition in heart failure samples.
Psychology, community, and the recovering racist
Authors: Tuffin Keith , Brittain Eleanor , Maydell Elena
Published: June 2018

This study adds to the tradition of studying race talk in the context of a flash point in biculturalism in Aotearoa New Zealand. The research examined constructions of the Mayor of New Plymouth (Andrew Judd) following his advocacy for extended Māori representation on the New Plymouth District Council. Data comprised reports, editorials, opinion pieces, and letters to the local newspaper immediately after Judd's appearance on a nationally broadcast current affairs television show when he announced the end of his mayoralty. The analysis considered constructions of Judd as both hero and anti‐hero, with complimentary constructions of the local community as racist, or not. In subscribing to the view for extended representation on the grounds of cultural constituency, Judd was variously positioned as culturally and politically naïve, as a hero for the cause for greater political representation for Māori, and an anti‐hero responsible for letting his own community down and bringing negative publicity to the town he was meant to serve. Judd was the target of abuse that prompted him to end his mayoralty, and this abuse stimulated constructions of widespread community racism. The discussion includes an interrogation of what it means to be a recovering racist, and finally, it is argued that the analysis provides further evidence of the sinuousness of racism.
Roles of Albumin‐Binding Proteins in Cancer Progression and Biomimetic Targeted Drug Delivery
Authors: Zhao Pengfei , Wang Yonghui , Wu Aihua , Rao Yuefeng , Huang Yongzhuo
Published: June 2018

Nutrient transporters have attracted significant attention for their promising application in biomimetic delivery. Due to the active consumption of nutrients, cancer cells generally overexpress nutrient transporters to meet their increased need for energy and materials. For example, albumin‐binding proteins (ABPs) are highly overexpressed in malignant cells, stromal cells, and tumor vessel endothelial cells responsible for albumin uptake. ABP (e.g., SPARC) is a promising target for tumor‐specific drug delivery, and albumin has been widely used as a biomimetic delivery carrier. Apart from the transportation function, ABPs are closely associated with neoplasia, invasion, and metastasis. Herein, a summary of the roles of ABP in cancer progression and the application of albumin‐based biomimetic tumor‐targeted delivery through the ABP pathway is presented.
Contribution of cooking and drying to the structure of couscous grains made from durum wheat semolina
Authors: Bellocq Bettina , Ruiz Thierry , Cuq Bernard
Published: June 2018

Background and objectives

During the processing of couscous grains of durum wheat semolina, the steam cooking and the drying stage helps strengthen the structure and reaches the end‐properties of the product. The objective of the present work was to investigate the physicochemical mechanisms generated during the steam cooking stage, under different water contents, and the drying stage, under different temperatures.

Findings

The physicochemical characteristics of couscous grains (size, shape, compactness, water content, extent of starch gelatinization, microstructure, and texture) were measured during processing. These mechanisms are promoted by high temperatures during processing under different conditions of water contents and by water transfer. The mechanisms were discussed in regard to the state diagram of the wheat components and the hydrotextural diagram.

Conclusions

During the steam cooking and the drying stages, the grains remain saturated by interstitial water, which means that the deformation mechanisms of the grains compensated the variations of the water content.

Significance and novelty

An analytical drying model describes the kinetics of average water contents during the first part of the drying stage and allows modelling the changes in compactness and the subsequent changes in diameter for the agglomerates of couscous grains.
Microwave‐Promoted ortho‐C−H Bond (Hetero)arylation of Arylpyrimidines in Water Catalyzed by Ruthenium(II)−Carboxylate
Authors: Drev Miha , Grošelj Uroš , Ledinek Bine , Perdih Franc , Svete Jurij , Štefane Bogdan , Požgan Franc
Published: June 2018

Efficient diarylation of ortho‐C−H bonds of 2‐arylpyrimidines was achieved by Ru(II)−carboxylate‐catalyzed reaction with aryl bromides in water, whereas meta‐substituted phenylpyrimidines selectively led to monoarylation. The reaction is strongly accelerated under microwave irradiation, and is compatible with various functional groups on both coupling partners. As established from Hammett plots, electron‐withdrawing groups on the pyrimidine substrates facilitate the arylation, while both, electron‐withdrawing and electron‐donating groups on the aryl bromides lead to a faster reaction. The C−H functionalization of 2‐arylpyrimidines with heteroaryl halides provides potential multidentate ligands.
Role of the Strong Lewis Base Sites on Glucose Hydrogenolysis
Authors: Yazdani Parviz , Wang Bo , Gao Feng , Kawi Sibudjing , Borgna Armando
Published: June 2018

This work reports the individual role of strong Lewis base sites on catalytic conversion of glucose hydrogenolysis to acetol/lactic acid, including glucose isomerisation to fructose and pyruvaldehyde rearrangement/hydrogenation to acetol/lactic acid. La2O3, Nd2O3, Sm2O3, and Pr6O11 were selected as representative oxides consisting of different base sites. The basicity of these lanthanide oxides was characterised by CO2‐TPD and DRIFT spectroscopy. It was found that lanthanide cation‐oxygen pairs, Brønsted OH group coordinated with one Lanthanide cation, and lanthanide cation near lanthanide cation‐oxygen pairs are the dominant base sites as compared to the other base sites on La2O3, Nd2O3, Sm2O3 and Pr6O11. In addition, the relative concentration of the base sites is different over the examined lanthanide oxides. These unique properties of lanthanide oxides are used to understand the individual role of base sites on the reactions mentioned above. Then, the catalytic results were correlated with the base properties of these lanthanide oxides. Based on this correlation, the base site requirements for each reaction were identified. In this regard, Brønsted OH group coordinated with one Lanthanide cation over Nd2O3 is found to be the suitable base site for glucose isomerisation. On the other hand, lactic acid is produced as the main product in glucose hydrogenolysis over lanthanide cation near lanthanide‐oxygen pairs on Pr6O11. Finally, lanthanide‐oxygen pairs over La2O3 are suitable base sites for retro‐aldol condensation of fructose to C3 chemicals.
Additive‐free Semihydrogenation of an Alkynyl Group to an Alkenyl Group over Pd−TiO2 Photocatalyst Utilizing Temporary In‐situ Deactivation
Authors: Kojima Yasumi , Fukui Makoto , Tanaka Atsuhiro , Hashimoto Keiji , Kominami Hiroshi
Published: June 2018

Lindlar's catalyst, i. e., calcium carbonate‐supported palladium (Pd) modified with lead, has been used for semihydrogenation of an alkynyl group in the presence of hydrogen gas (H2). We examined hydrogenation of an alkynyl group in organosilane and hydrocarbon in methanolic suspensions of a Pd‐loaded titanium(IV) oxide (Pd−TiO2) photocatalyst without the use of additives and H2. In the photocatalytic reaction, Pd particles worked as co‐catalysts for hydrogenation and alkyne hydrogenation had priority to alkene hydrogenation. Since the Pd co‐catalyst was temporarily deactivated during the reaction owing to accumulation of the oxidized product(s) of methanol, the capacity of hydrogenation of the unsaturated C−C bond was limited. By optimizing the capacity and amount of alkynes, almost complete semihydrogenation of alkynes was achieved under a poison‐free condition. Pd−TiO2 can be regenerated by very simple treatments, i. e., washing and drying at room temperature.
Mono‐Atomic Fe Centers in Nitrogen/Carbon Monolayers for Liquid‐Phase Selective Oxidation Reaction
Authors: Lv Li‐Bing , Yang Shi‐Ze , Ke Wen‐Yu , Wang Hong‐Hui , Zhang Bing , Zhang Pengfei , Li Xin‐Hao , Chisholm Matthew F. , Chen Jie‐Sheng
Published: June 2018

Two‐dimensional catalyst supports with mono‐atomic transition metals stabilized in special surface pockets conceptually promise excellent catalytic activity. Similar heterogenized mono‐atomic metal‐based catalysts usually suffer from poor stability in liquid‐phase reaction system, whilst highly ligand‐stabilized metal‐centers are less accessible for reactions. We report a two‐dimensional mono‐atomic Fe/N/C layered nanostructure (2D‐FeNC), generated through the direct polycondensation of C,N‐containing molecules and Fe salts. With a 2D structure similar to graphene, the ultrathin CN support act as a solid ligand, leaving the z‐direction open at molecular scale. This approach significantly promotes reactivity and the mass transfer to the Fe centers, here exemplified by the selective oxidation of alcohols using molecular oxygen. The catalysts show also high mechanical and chemical stability for good to excellent reusability.
Electrophile, Substrate Functionality, and Catalyst Effects in the Synthesis of α‐Mono and Di‐Substituted Benzylamines via Visible‐Light Photoredox Catalysis in Flow
Authors: Vilé Gianvito , Richard‐Bildstein Sylvia , Lhuillery Arnaud , Rueedi Georg
Published: June 2018

We report herein the facile and one‐pot synthesis of α‐mono‐ and di‐substituted benzylamines from cheap and readily available α‐amino acids, via photocatalytic decarboxylative arylation in flow. This enables to access intermediates and building blocks that are difficult to obtain via other synthetic routes, but are key for the manufacture of pharmaceuticals, agrochemicals, and fine chemicals. The optimal decarboxylative conditions were identified through a high‐throughput evaluation of catalysts, organic or inorganic bases, ligands, and reaction parameters (i. e., contact time, temperatures, and photoelectron power). The reaction turned out to be electronically controlled as the yields increased with increasing electron‐density on the aryl moiety. The results were correlated with the redox properties of the photocatalysts, deriving catalyst structure‐performance relationships which can facilitate the future identification of even better materials. In addition, compared to traditional batch chemistry, the use of a flow protocol led to quicker reactions (30 min instead of 12–72 h) and ensured more predictable reaction scale‐ups.
Structural Advantage Induced by Sulfur to Boost the Catalytic Performance of FeNC Catalyst towards the Oxygen Reduction Reaction
Authors: Luo Ergui , Xiao Meiling , Wang Yuemin , Ge Junjie , Liu Changpeng , Xing Wei
Published: June 2018

Among various replacement candidates for precious‐metal catalysts towards the cathodic oxygen reduction reaction (ORR) of fuel cells, FeNC material has been perceived as the most promising one. Herein, we report an FeNC catalyst featured with highly uniform texture and high BET specific surface area. This catalyst was synthesized by a facile one‐step pyrolysis process accompanied by the sulfur‐induced in situ delamination effect, using glucose, trithiocyanuric acid and ferrous gluconate as precursors. The structural characteristics led to increased exposed active sites, which may be responsible for the dramatically improved activity of the final S‐doped FeNC catalyst with elevated half‐wave potentials in both acid (0.76 V vs. 0.68 V) and alkaline (0.87 V vs. 0.84 V) media compared to the sulfur‐free control sample.
Theoretical Insights into the Nature of Oxidant and Mechanism in the Regioselective Syn‐dihydroxylation of an Alkene with a Rieske oxygenase inspired Iron Catalyst
Authors: Roy Lisa
Published: June 2018

Selective C=C bond oxidation is a fundamental process in Nature and has potential utility in organic synthesis. Herein, ab initio and density functional techniques are employed to investigate the nature of the oxidant and mechanism in alkene oxidation by two H2O2 activating Rieske oxygenase inspired iron catalysts, one of which is more sterically encumbered. Electronic structure analysis reveals that the mechanism involves a water‐assisted homolytic O−O bond cleavage of the peroxide moiety to generate an FeIV(O.)OH radical intermediate, followed by epoxidation or syn‐dihydroxylation of the alkene substrate. Furthermore, it is shown that a greater degree of structural reorganization due to higher steric repulsion between the substrate and bulky substituents selectively avoids epoxidation in one of the complexes, thus directing it towards exclusive hydroxylation. Additionally, the rate‐determining barrier for cis‐diol release is curtailed by ∼14 kcal/mol due to synergistic assistance from Lewis acid. Our study therefore highlights the crucial role of ligand modification and additives which can be further engineered to achieve enzyme‐like optimum activity.
Assessment of a Thermally Modified Cellulose Acetate Forward‐Osmosis Membrane Using Response Surface Methodology
Authors: Zyaie Javad , Sheikhi Mohammad , Baniasadi Javad , Sahebi Soleyman , Mohammadi Toraj
Published: June 2018

Cellulose acetate (CA) flat sheet membranes were fabricated and evaluated in a forward‐osmosis process. Effects of CA concentration, coagulation bath temperature, and annealing thermal treatment on both membrane structure and performance were investigated. NaCl rejection of the optimum membrane was determined utilizing a reverse‐osmosis setup based on conductivity measurements. Two validated models were obtained by means of response surface methodology based on Box‐Behnken design. The optimum operating pressure, temperature, and draw solution concentration were assessed as well.
CuCo2S4 Nanosheets Coupled With Carbon Nanotube Heterostructures for Highly Efficient Capacitive Energy Storage
Authors: Li Mei‐Ling , Xiao Kang , Su Hang , Li Nan , Cai Yue‐Peng , Liu Zhao‐Qing
Published: June 2018

Highly efficient electrode materials with high specific capacitance, good rate capability, and durable cycling stability are of great importance for supercapacitors (SCs). Herein, we report a highly active electrode material based on carbon nanotubes (CNTs) as the supporter and copper cobalt bimetallic sulfide as the active material. The CuCo2S4/CNTs electrode exhibits a good electrochemical performance with a high specific capacity of 1690.3 F g−1 at 1 A g−1, good rate capability with 62.6 % capacitance retention at 50 A g−1, and good cycling stability that retains about 95.5 % of the capacitance after 10 000 cycles. The asymmetric supercapacitors (ACS) are self‐assembled by using CuCo2S4/CNTs as the positive electrode and CNTs as the negative electrode, exhibiting a high energy density of 37.32 Wh kg−1 at a power density of 800.7 W kg−1. This work provides directly empirical evidence for the design and optimization of the supercapacitive performance of transition‐metal compounds.
High Performance N‐Doped Carbon Electrodes Obtained via Hydrothermal Carbonization of Macroalgae for Supercapacitor Applications
Authors: Ren Meng , Jia Ziyang , Tian Zhongwei , Lopez Diana , Cai Jinjun , Titirici Maria‐Magdalena , Jorge A. Belen
Published: June 2018

The conversion of bio‐waste into useful porous carbons constitutes a very attractive approach to contribute to the development of sustainable energy economy, even more as they can be used in energy storage devices. Here we report the synthesis of N‐doped carbons from hydrothermal carbonization of macroalgae, Enteromorpha prolifera (EP), followed by a mild KOH activation step. The obtained N‐doped carbons exhibited surface areas of up to ∼2000 m2/g with N‐loadings varied in the range of 1.4∼2.9 at %. By modifying activation temperature, we were able to tune the surface chemistry and porosity, achieving excellent control of their properties. The specific capacitance reached values of up to 200 F/g at 1 A/g in 6 M KOH for the sample obtained at activation temperature of 700 °C (AHC‐700). The symmetric supercapacitor using the sample activated at 800 °C (AHC‐800) as electrodes exhibited the highest cycling stability of the samples studied in this work, with capacitance retention of up to 96 % at 10 A/g, even after 10,000 cycles, constituting the highest reported for biomass‐derived carbon electrodes. These results show the great potential of N‐doped carbons as electrodes for supercapacitors and confirm the excellent electrochemical properties of biomass‐derived carbons in energy storage technologies.
Towards polypotent natural products: The Derringer desirability approach and nonparametric ranking for multicriteria evaluation of essential oils
Authors: Andrić Filip Lj.
Published: June 2018

Chemical complexity of natural products often results in their pharmacological polypotency. However, selecting a natural product with desirable activity profile is not a straightforward task, especially if optimization of one feature results in deterioration of other facets.

Recently, in the field of multiobjective optimization, the sum of ranking differences (SRD) has emerged as a simple and statistically sound method for fusion of multiple criteria. However, the data pretreatment seems to strongly influence the ranking outcome, which may lead to ambiguous or even false interpretations. Therefore, in the present study, the data of 55 essential oils originated from different plant species and tested on multiple bacterial and fungal strains as well as 4 antioxidative assays were studied. Essential oils were ranked using the classical Deringer desirability approach, and results were compared with the SRD analysis of primary activity data as well as the previously row‐wise standardized data, normalized data, and the data scaled to fit the preferences. Ultimately, the most promising candidate (polypotent) essential oils, as well as the most resilient and most sensitive bacterial and fungal strains, and antioxidative assays were identified. Data transformation based on the Deringer desirability approach, compared with the data that have not been previously transformed or those that transformed using a row‐wise standardization or normalization to the unit length vector, seemed to be the crucial step providing the sound and meaningful SRD ranking.
High Throughput Experimentation and Continuous Flow Validation of Suzuki–Miyaura Cross‐Coupling Reactions
Authors: Jaman Zinia , Mufti Ahmed , Sah Samyukta , Avramova Larisa , Thompson David H.
Published: June 2018

Traditional methods to discover optimal reaction conditions for small molecule synthesis is a time‐consuming effort that requires large quantities of material and a significant expenditure of labor. High‐throughput techniques are a potentially transformative approach for reaction condition screening, however, rapid validation of the reaction hotspots under continuous flow conditions remains necessary to build confidence in high throughput screening hits. Continuous flow technology offers the opportunity to upscale the screening hotspots and optimize their output of the target compounds due to the exceptional heat and mass transfer ability of flow reactions that are conducted in a smaller and safer reaction volume. We report a robotic high throughput technique to execute reactions in multi‐well plates that were coupled with fast mass spectrometric analysis using an autosampler to accelerate the reaction screening process. Palladium‐catalyzed Suzuki–Miyaura cross‐coupling reactions were screened in this system and a heat map was generated to identify the best reaction conditions for downstream scale‐up under continuous flow. Here, high throughput experimentation reactions in 96‐well plates were performed for 1 h at 50 °C, 100 °C, 150 °C, and 200 °C before diluting them into 384‐well plates for mass analysis. With the aid of high throughput tools, 648 unique experiments were conducted in duplicate. The cross‐coupling reactions were evaluated as a function of stoichiometry, temperature, concentration, order of addition, and substrate type. The hotspots from high throughput experimentation were examined using a microfluidic Chemtrix system that confirmed the positive reaction leads as true positives. Negative outcomes identified by these experiments were found to be true negatives by microfluidic reaction evaluation. Quantitation of product yields was performed using high‐performance liquid chromatography‐mass spectrometry (HPLC/MS‐MS).