bluuebunny/crossref_metadata_2025_split huggingface dataset:
Active Nanointerface‐Assisted Co‐Assembly to Yolk–Shell Au@Ordered Mesoporous Carbon Nanospheres
Authors: Zhang Weicai , Peng Jing , Zheng Mingtao , Dong Hanwu , Hu Hang , Xiao Yong , Liu Yingliang , Liang Yeru 
Published: December 2019

AbstractAssembling of well‐orientated mesopores and 0D substance into an orchestrate architecture for constructing advanced carbon‐based composites is highly attractive. Currently, this nanofabrication method is facing challenges, because of the difficulty in the co‐assembly of the building blocks is very hard to perform onto a high‐curvature and heterogeneous 0D substrate. Here, an efficient active nanointerface‐assisted co‐assembly approach for design and fabrication of a novel class of yolk–shell Au@ordered mesoporous carbon nanosphere is reported. The key point to this preparation strategy is construction of reactive aldehyde functional groups on the surface of Au@SiO2 nanospheres, which can react with the carbon source to in situ form a stable covalent bond at their nanointerface. The as‐synthesized yolk–shell Au@ordered mesoporous carbon nanosphere not only exhibits uniform spherical morphology and robust porosity but also possesses a totally new ordered mesoporous and fast permeable shell structure, providing a chance for greatly broadening their application scope.
Enantioenriched Methylene‐Bridged Benzazocanes Synthesis by Organocatalytic and Superacid Activations
Authors: Beaud Rodolphe , Michelet Bastien , Reviriot Yasmin , Martin‐Mingot Agnès , Rodriguez Jean , Bonne Damien , Thibaudeau Sébastien 
Published: December 2019

AbstractAchieving in a straightforward way the synthesis of enantioenriched elaborated three‐dimensional molecules related to bioactive natural products remains a long‐standing quest in organic synthesis. Enantioselective organocatalysis potentially offers a unique opportunity to solve this problem, especially when combined with complementary modes of activation. Here, we report the sequential association of organocatalytic and superacid activations of simple linear achiral readily available precursors to promote the formation of unique highly elaborated chiral methylene‐bridged benzazocanes exhibiting three to five fully‐controlled stereocenters. This peculiar backbone, difficult to assemble by standard synthetic approaches, is closely related to bioactive natural and synthetic morphinans and benzomorphans. The formation of a highly reactive chiral 7‐membered ring N‐acyl iminium superelectrophilic ion, evidenced by low‐temperature in situ NMR experiments, triggers a challenging stereoselective Friedel–Crafts‐type cyclization.
On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts
Authors: Kumar Kavita , Dubau Laetitia , Mermoux Michel , Li Jingkun , Zitolo Andrea , Nelayah Jaysen , Jaouen Frédéric , Maillard Frédéric 
Published: December 2019

AbstractFe‐N‐C catalysts containing atomic FeNx sites are promising candidates as precious‐metal‐free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The durability of Fe‐N‐C catalysts in fuel cells has been extensively studied using accelerated stress tests (AST). Herein we reveal stronger degradation of the Fe‐N‐C structure and four‐times higher ORR activity loss when performing load cycling AST in O2‐ vs. Ar‐saturated pH 1 electrolyte. Raman spectroscopy results show carbon corrosion after AST in O2, even when cycling at low potentials, while no corrosion occurred after any load cycling AST in Ar. The load‐cycling AST in O2 leads to loss of a significant fraction of FeNx sites, as shown by energy dispersive X‐ray spectroscopy analyses, and to the formation of Fe oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O2 is due to reactive oxygen species produced between H2O2 and Fe sites via Fenton reactions.
Synthesis of Biaryl‐Bridged Cyclic Peptides via Catalytic Oxidative Cross‐Coupling Reactions
Authors: Ben‐Lulu Mor , Gaster Eden , Libman Anna , Pappo Doron 
Published: December 2019

AbstractBiaryl‐bridged cyclic peptides comprise an intriguing class of structurally diverse natural products with significant biological activity. Especially noteworthy are the antibiotics arylomycin and its synthetic analogue G0775, which exhibits potent activity against Gram‐negative bacteria. Herein, we present a simple, flexible, and reliable strategy based on activating‐group‐assisted catalytic oxidative coupling for assembling biaryl‐bridged cyclic peptides from natural amino acids. The synthetic approach was utilized for preparing a number of natural and unnatural biaryl‐bridged cyclic peptides, including arylomycin/G0775 and RP 66453 cyclic cores.
Acyclic Branched α‐Fluoro Ketones for the Direct Asymmetric Mannich Reaction Leading to the Synthesis of β‐Tetrasubstituted β‐Fluoro Amines
Authors: Trost Barry M. , Tracy Jacob S. , Yusoontorn Tas , Hung Chao‐I Joey 
Published: December 2019

AbstractThe preparation of acyclic β‐fluoro amines bearing tetrasubstituted fluorine stereocenters is described via a direct Zn/ProPhenol‐catalyzed Mannich reaction. The reaction utilizes branched vinyl or alkynyl α‐fluoro ketones that can be coupled with a range of aryl, heteroaryl, vinyl, or cyclopropyl aldimines in high yield and with excellent diastereo‐ (up to >20:1) and enantioselectivity (up to 99 %). The use of readily cleaved tert‐butoxycarbonyl (Boc) or carboxybenzyl (Cbz) imine protecting groups adds utility to the reaction by allowing for easy access to the free amine products under mild and chemoselective reaction conditions.
Visible‐Light‐Excited Room‐Temperature Phosphorescence in Water by Cucurbit[8]uril‐Mediated Supramolecular Assembly
Authors: Wang Jie , Huang Zizhao , Ma Xiang , Tian He 
Published: December 2019

AbstractSolid‐state materials with efficient room‐temperature phosphorescence (RTP) emissions have found widespread applications in materials science, while liquid or solution‐phase pure organic RTP emission systems has been rarely reported, because of the nonradiative decay and quenchers from the liquid medium. Reported here is the first example of visible‐light‐excited pure organic RTP in aqueous solution by using a supramolecular host‐guest assembly strategy. The unique cucurbit[8]uril‐mediated quaternary stacking structure allows tunable photoluminescence and visible‐light excitation, enabling the fabrication of multicolor hydrogels and cell imaging. The present assembly‐induced emission approach, as a proof of concept, contributes to the construction of novel metal‐free RTP systems with tunable photoluminescence in aqueous solution, providing broad opportunities for further applications in biological imaging, detection, optical sensors, and so forth.
The Mutation of the “Nobel Prize in Chemistry” into the “Nobel Prize in Chemistry or Life Sciences”: Several Decades of Transparent and Opaque Evidence of Change within the Nobel Prize Program
Authors: Seeman Jeffrey I. , Restrepo Guillermo 
Published: December 2019

AbstractOver the past several decades, the Nobel Prize program has slowly but steadily been modified in both transparent and opaque ways. A transparent change has been the creation of the Nobel Prize in Economic Sciences, officially known as the Sveriges Riksbank Prize in Economic Sciences in Memory of Alfred Nobel. An opaque change has been the mutation of the Nobel Prize in Chemistry into what is effectively the “Nobel Prize in Chemistry or Life Sciences.” This paper presents a detailed study of this opaque change, including evidence that the disciplines of chemistry and biochemistry cover, today, intellectually quite distinct and generally scientifically‐unrelated intellectual territory. This paper supports the evolution of the Nobel Prizes, and encourages the Nobel Prize program to move from opaque to transparent change processes for the next generations of achievement in the sciences.
Rhodium‐Catalyzed Remote C(sp3)−H Borylation of Silyl Enol Ethers
Authors: Li Jie , Qu Shuanglin , Zhao Wanxiang 
Published: December 2019

AbstractA rhodium‐catalyzed remote C(sp3)−H borylation of silyl enol ethers (SEEs, E/Z mixtures) by alkene isomerization and hydroboration is reported. The reaction exhibits mild reaction conditions and excellent functional‐group tolerance. This method is compatible with an array of SEEs, including linear and branched SEEs derived from aldehydes and ketones, and provides direct access to a broad range of structurally diverse 1,n‐borylethers in excellent regioselectivities and good yields. These compounds are precursors to various valuable chemicals, such as 1,n‐diols and aminoalcohols.
Difunctionalization of Alkenes Involving Metal Migration
Authors: Li Yuqiang , Wu Dong , Cheng Hong‐Gang , Yin Guoyin 
Published: December 2019

AbstractThe direct difunctionalization of alkenes, a cheap and abundant feedstock, represents one of the most attractive strategies for increasing molecular complexity in synthetic organic chemistry. In contrast with the 1,2‐difunctionalization of alkenes, recent advances showcase alkene 1,n‐difunctionalizations (n≠2) involving metal migration is an emerging and rapidly growing area of research. This promising strategy not only opens a novel avenue for future development of alkene transformations, but also significantly expands upon the bond disconnections available in modern organic synthesis. This Minireview summarizes recent progress in the migratory difunctionalization of alkenes, with an emphasis on the driving force for metal migration.
Well‐defined PEPPSI‐themed palladium–NHC complexes: synthesis, and catalytic application in the direct arylation of heteroarenes
Authors: Kaloğlu Murat , Gürbüz Nevin , Yıldırım İlkay , Özdemir Namık , Özdemir İsmail 
Published: December 2019

In this study, a series of benzimidazolium salts were synthesized as unsymmetrical N‐heterocyclic carbene (NHC) precursors. Benzimidazolium salts were used for synthesis of the PEPPSI (pyridine enhanced precatalyst preparation stabilization and initiation)‐themed, six new Pd‐complexes with the general formula [PdX2(NHC)(pyridine)]. The structures of all compounds were characterized by various spectroscopic techniques such as 1H NMR, 13C NMR and FT‐IR. The more detailed structural characterization of four of the complexes was determined by single‐crystal X‐ray diffraction study. The catalytic activities of all Pd‐complexes were evaluated in the direct arylation of the 2‐acetylfuran and 2‐acetylthiophene with aryl bromides in the presence of 1 mol% catalyst loading.
Creating and renewing identity and value through the use of non‐invasive archaeological methods: Mapoon unmarked graves, potential burial mounds and cemeteries project, western Cape York peninsula, Queensland
Authors: SUTTON MARY‐JEAN , CONYERS LAWRENCE B. , PEARCE SIMON , PIERRE EMMA ST , NICHOLLS PITT DIANE 
Published: December 2019

ABSTRACTIn 2010, Elders from Mapoon watched “Time Team” and saw ground‐penetrating radar (GPR) and other non‐invasive scientific methods being used to identify cultural features on archaeological sites. This led Elders to express their desire for such techniques, particularly GPR, to be brought on country to assist with documenting and protecting cultural heritage sites. This paper explores how Mapoon families have employed these techniques in archaeological settings to reconnect and reimagine specific features in their cultural landscape, as well as to explore, create and renew narratives from their interpretations of the results from the project. We also investigate the nature of Traditional Owner interactions with these technologies in archaeological settings to understand their impact on how cultural identity and value are recreated and renewed, on “caring for country” programmes, and on modernising culturally appropriate forms of engagement with ancestors’ remains. We apply these findings to a discussion of how Mapoon people think about their cultural history, identity and connections to country, particularly in relation to mortuary practices and settlement patterns from pre‐contact to the “mission time”.
Artemisinin‐derived dimers as potential anticancer agents: Current developments, action mechanisms, and structure–activity relationships
Authors: Zhang Bo 
Published: December 2019

AbstractAnticancer agents play a pivotal role in cancer treatment. However, most of the anticancer drugs currently used in the clinics have a severe anticancer scenario, as well as low specificity and fatal side effects. Thus, there is an urgent demand to develop novel drugs with great efficacy, high specificity, and low side effects. Artemisinin and its semisynthetic derivatives are mainstays of chemotherapy against malaria, and artemisinin‐based compounds, especially artemisinin‐derived dimers, also exhibit excellent in vitro and in vivo anticancer activity. The structure–activity relationship (SAR) demonstrated that the linker between the two artemisinin moieties influenced the anticancer activity significantly; so, the rational design of the linker may provide valuable therapeutic intervention for the treatment of cancer. This review outlines the potential anticancer activity of artemisinin‐derived dimers tethered by different linkers. The SARs, as well as mechanisms of action, are discussed to provide insights for the rational design of more effective dimers.
Diffraction stack imaging as a potential tool for detecting underground voids – the case of the ancient copper mines of Timna Valley (Israel)
Authors: Wechsler Neta , Shustak Matan , Ben‐Yosef Erez 
Published: December 2019

AbstractDetection of subsurface features using geophysical methods is an important component of archaeological research. Most geophysical methods suffer from loss of resolution with depth and are most successful when employed on hyper‐shallow targets. We present a novel imaging method that utilizes summation of diffracted seismic energy in the depth domain to image the subsurface and detect areas of material contrasts, which is especially useful for detecting subsurface voids. The diffraction imaging (DI) method was validated in a synthetic case and in two archaeological sites where known ancient tunnels exist and then employed in the ancient copper ore district of Timna Valley (southern Israel). The results demonstrate the feasibility of the DI method to detect ancient underground mining galleries that connected between (now blocked) mining shafts, which in turn constitutes a significant contribution to the study of ancient prospection and mining technologies and related social and historical aspects.
Co‐contributorship network and division of labor in individual scientific collaborations
Authors: Lu Chao , Zhang Yingyi , Ahn Yong‐Yeol , Ding Ying , Zhang Chenwei , Ma Dandan 
Published: December 2019

AbstractCollaborations are pervasive in current science. Collaborations have been studied and encouraged in many disciplines. However, little is known about how a team really functions from the detailed division of labor within. In this research, we investigate the patterns of scientific collaboration and division of labor within individual scholarly articles by analyzing their co‐contributorship networks. Co‐contributorship networks are constructed by performing the one‐mode projection of the author–task bipartite networks obtained from 138,787 articles published in PLoS journals. Given an article, we define 3 types of contributors: Specialists, Team‐players, and Versatiles. Specialists are those who contribute to all their tasks alone; team‐players are those who contribute to every task with other collaborators; and versatiles are those who do both. We find that team‐players are the majority and they tend to contribute to the 5 most common tasks as expected, such as “data analysis” and “performing experiments.” The specialists and versatiles are more prevalent than expected by our designed 2 null models. Versatiles tend to be senior authors associated with funding and supervision. Specialists are associated with 2 contrasting roles: the supervising role as team leaders or marginal and specialized contributors.
Social and Object Attention Is Influenced by Biological Sex and Toy Gender‐Congruence in Children With and Without Autism
Authors: Harrop Clare , Jones Desiree R. , Sasson Noah J. , Zheng Shuting , Nowell Sallie W. , Parish‐Morris Julia 
Published: December 2019

Emerging research suggests social attention in autism spectrum disorder (ASD) girls is enhanced relative to ASD boys but may also be affected by the type of social and nonsocial content presented. This study examined how biological sex and gender norms interact to influence visual attention in 79 school‐aged children observing scenes that included gender‐associated toys and actors of both sexes. Attention to social (faces) and object activity (hands with toys) stimuli was measured. Previously described distinctions between social attention in ASD boys and girls were replicated, with ASD girls looking more at faces than ASD boys. Irrespective of diagnosis, males and females attended more to actors that shared their same sex, and attended more to toys with gender‐associations that were consistent with their own sex, suggesting that social and object salience increases for children under sex‐consistent conditions. Importantly, ASD and typically developing (TD) children increased their gaze to faces when male actors were shown playing with female‐associated toys, suggesting that both groups of children are sensitive to societal messages about the acceptability of males playing with female‐associated toys. Our findings provide further evidence of heightened attention to faces in ASD girls relative to ASD boys, and indicate that social attention in ASD and TD children is influenced by who (male or female actor) and what (male‐ or female‐associated toy) is being observed. Collectively, these results present a nuanced profile of attention in ASD that adds to a growing body of research indicating subtle phenotypic differences in ASD girls that may impact identification, assessment, and intervention. Autism Res 2020, 13: 763–776.. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.Lay SummarySex differences observed in typical development may also be present in individuals with autism. In this study, we developed an eye‐tracking paradigm featuring videos of boys and girls playing with toys that varied in their gender associations. Attention to faces differed between autistic and non‐autistic children but was also influenced by the sex of the actor and gender‐association of toys. Autistic females demonstrated subtle attention differences that distinguished them from autistic males and may influence referral, diagnosis, and intervention.
Systematic review of the introduction and evaluation of magnetic augmentation of the lower oesophageal sphincter for gastro-oesophageal reflux disease
Authors: Kirkham E N , Main B G , Jones K J B , Blazeby J M , Blencowe N S 
Published: December 2019

Abstract

Background
Magnetic sphincter augmentation (MSA) is reported to be an innovative alternative to antireflux surgery for patients with gastro-oesophageal reflux disease. Although used in practice, little is known about how it has been evaluated. This study aimed to systematically summarize and appraise the reporting of MSA and its introduction into clinical practice, in the context of guidelines (such as IDEAL) for evaluating innovative surgical devices.

Methods
Systematic searches were used to identify all published studies reporting MSA insertion. Data collected included patient selection, governance arrangements, surgeon expertise, technique description and outcome reporting.

Results
Searches identified 587 abstracts; 39 full-text papers were included (1 RCT 5 cohort, 3 case–control, 25 case series, 5 case reports). Twenty-one followed US Food and Drug Administration eligibility criteria for MSA insertion. Twenty-six documented that ethical approval was obtained. Two reported that participating surgeons received training in MSA; 18 provided information about how MSA insertion was performed, although techniques varied between studies. Follow-up ranged from 4 weeks to 5 years; in 14 studies, it was less than 1 year.

Conclusion
Most studies on MSA lacked information about patient selection, governance, expertise, techniques and outcomes, or varied between studies. Currently, MSA is being used despite a lack of robust evidence for its effectiveness.
Identification of Vaccinia‐H1 Related Phosphatase as an Anticancer Target for 1,2,3,4,6‐O‐Pentagalloylglucose
Authors: Yoon Sun‐Young , Kim Do‐Hwi , Min Roh Kyung , Ahn Dohee , Jin Kang Hyo , Chung Sang J. 
Published: December 2019

AbstractProtein tyrosine phosphatases are involved in diverse human diseases, including cancer, diabetes and inflammatory disorders. Loss of Vaccinia‐H1 related phosphatase (VHR) has been shown to arrest at the G1‐S and G2‐M transitions of the cell cycle, and to increases cell death of prostate cancer cells through JNK activation, suggesting that VHR can be considered as an anticancer target. In this study, 658 natural products were screened through in vitro enzyme assay to identify VHR inhibitor. Among the VHR‐inhibitory compounds, 1,2,3,4,6‐O‐pentagalloylglucose (PGG) was selected for further study as it has been reported to show antitumor effects against tumor model mice, but its direct target has not been identified. PGG inhibited the catalytic activity of VHR (Ki=53 nm) in vitro. Furthermore, the incubation of HeLa cervical cancer cells with PGG dramatically decreased cell viability and markedly increased the protein levels of the cleaved PARP, a hallmark of apoptosis. In addition, treatment of HeLa cells with PGG significantly reduced the protein levels of cyclin D1, Bcl‐2 and STAT3 phosphorylation. Taken together, these results suggest that PGG could be a potential therapeutic candidate for the treatment of cervical cancer through VHR inhibition.
Barriers to use of radial access for percutaneous coronary intervention
Authors: Riangwiwat Tanawan , Mumtaz Tayebah , Blankenship James C. 
Published: December 2019

AbstractObjectivesThe aim of this study was to identify barriers to transradial access percutaneous coronary intervention (PCI).BackgroundTransradial access yields fewer vascular complications, earlier ambulation, and more patient comfort. However, the adoption to practice is slow, and transfemoral access is still commonly used.MethodsWe identified all PCIs done by one operator in a radial‐first trainee‐driven practice. The individual charts were reviewed for all PCIs using femoral access. Reasons for not using radial access were identified. Descriptive statistics were used to report reasons for not using transradial access. Analyses were performed on a per‐procedure basis.ResultsOf 1,948 PCIs, 1,790 (92%) were via radial access and 158 (8%) via femoral access. Femoral access was used to bail out unsuccessful radial access in 21 PCIs (13% of all femoral PCIs, 1% of all PCIs). Radial access was unsuccessful due to failure to cannulate radial artery, radial artery spasm, and radial loop in majority of radial access failure PCIs (n = 13). Femoral access was used as a primary strategy in 137 PCIs (87% of all femoral PCIs, 7% of all PCIs), mostly due to undetectable radial artery pulse (both left and right) (n = 40).ConclusionsRadial access can be used for PCI safely and effectively. Inadequate radial pulse is the main barrier. Adjunctive strategies such as ulnar access and use of ultrasound may further increase the success rate of arterial access from the upper extremities.