bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Modular Access to Divinyldiphosphenes with a Strikingly Small HOMO–LUMO Energy Gap
Authors: Rottschäfer Dennis , Sharma Mahendra K. , Neumann Beate , Stammler Hans‐Georg , Andrada Diego M. , Ghadwal Rajendra S. 
Published: May 2019

AbstractThe olefinic C−H bond functionalization of (NHC)CHPh (NHC=IPr=C{(NAr)CH}2 1; SIPr=C{(NAr)CH2}2 2; Ar=2,6‐iPr2C6H3), derived from classical N‐heterocyclic carbenes (NHCs), with PCl3 affords the dichlorovinylphosphanes {(NHC)C(Ph)}PCl2 (NHC=IPr 3, SIPr 4). Two‐electron reduction of 3 and 4 with magnesium leads to the formation of the divinyldiphosphenes [{(NHC)C(Ph)}P]2 (NHC=IPr 5, SIPr 6) as crystalline solids. Unlike literature‐known diphosphenes, which are mostly yellow or orange, 5 is a green whereas 6 is a purple solid. Although the P=P bond lengths of 5 (2.062(1)) and 6 (2.055(1) Å) are comparable to those of the known diphosphenes (2.02–2.08 Å), the C−P bond lengths of 5 (1.785(1)) and 6 (1.797(1) Å) are, however, considerably shorter than a C
−P single bond length (1.85 Å), indicating a considerable π‐conjugation between C=C and P=P moieties. The HOMO–LUMO energy gap for 5 (4.15) and 6 (4.52 eV) is strikingly small and thus the narrowest among the diphosphenes (>4.93 eV) reported as yet. Consequently, 5 readily undergoes P=P bond cleavage at room temperature on treatment with sulfur to form the unique dithiophosphorane {(IPr)C(Ph)}P(S)2 7. Interestingly, reaction of 5 with selenium gives the selenadiphosphirane [{(IPr)C(Ph)}P]2Se 8 with an intact P−P bond.
Brodie's or Hummers’ Method: Oxidation Conditions Determine the Structure of Graphene Oxide
Authors: Feicht Patrick , Biskupek Johannes , Gorelik Tatiana E. , Renner Julian , Halbig Christian E. , Maranska Maria , Puchtler Florian , Kaiser Ute , Eigler Siegfried 
Published: May 2019

AbstractSynthesis and studies of graphite oxide started more than 150 years ago and turned into a boom by the measurements of the outstanding physical properties of graphene. A series of preparation protocols emanated trying to optimize the synthesis of graphene oxide in order to obtain a less defective material, as source for graphene. However, over‐oxidation of the carbon framework hampered establishing structure‐property relationships. Here, the fact that two different synthetic methods for graphene oxide preparation lead to very similar types of graphene oxide with a preserved graphene lattice is demonstrated. Either sodium chlorate in nitric acid (similar to Brodie's method) or potassium permanganate in sulfuric acid (similar to Hummers’ method) treatment are possible; however, reaction conditions must be controlled. With a preserved carbon lattice analytical differences between the samples relate to the altered on‐plane functionality. Consequently, terming preparation protocols “according to Brodie's/Hummers’ method” is not sufficient.
Strategien zur gezielten Verbesserung des anodenseitigen Elektronentransfers in mikrobiellen Brennstoffzellen
Authors: Heydorn Raymond Leopold , Engel Christina , Krull Rainer , Dohnt Katrin 
Published: May 2019

AbstractDas Konzept der mikrobiellen Brennstoffzelle (microbial fuel cell, MFC) existiert seit über 100 Jahren, doch erst im letzten Jahrzehnt ist deren praktische Anwendung in der Abwasseraufbereitung auch in Maßstäben bis 1000 L realisiert worden. In diesem Beitrag werden verfügbare Strategien vorgestellt, um den bislang noch limitierenden extrazellulären Elektronentransfer (EET) im Anodenraum von MFCs zu erhöhen. Dafür werden Organismen‐basierte Ansätze sowie der Einfluss von (Bio‐)Polymeren und Redox‐Mediatoren auf den EET vorgestellt.
Does social support reduce distress and worry among Aboriginal and Torres Strait Islander people with cancer?
Authors: Bernardes Christina Maresch , Langbecker Danette , Beesley Vanessa , Garvey Gail , Valery Patricia Casarolli 
Published: May 2019

AbstractBackgroundConnections to people and place are particularly important for Indigenous Australians. It is currently unknown what role social support plays in helping this population cope with a diagnosis of cancer.AimsThis study describes components of social support available for Indigenous Australians with cancer and investigates its association with distress and/or worry.Methods and resultsSecondary data of a cross‐sectional study involving 248 Aboriginal and Torres Strait Islander cancer patients was used to map out social support dimensions (structural, functional, and appraisal) using Cheng et al's27 social support framework. Distress was measured by the distress thermometer and worry by the worry chart. Overall, 67% of participants reported significant distress, and 49% worry about their cancer. In the functional dimension of social support, participants who had someone caring for them during diagnosis and treatment had increased odds of reporting worry. In the appraisal dimension, participants with unmet social support needs had significantly increased odds of reporting distress and worry compared with participants who were satisfied with the support received. Components in the structural dimension were not associated with distress or worry.ConclusionWhile many aspects of social support did not appear to affect cancer distress or worry, having a carer or having unmet social support needs had a negative impact on these outcomes. Health professionals should consider the worries of the bonded relationship and monitor patients' needs and their satisfaction with the support provided as an integral part of cancer care.
Cationic Gold(I) Diarylallenylidene Complexes: Bonding Features and Ligand Effects
Authors: Sorbelli Diego , Nunes dos Santos Comprido Laura , Knizia Gerald , Hashmi A. Stephen K. , Belpassi Leonardo , Belanzoni Paola , Klein Johannes E. M. N. 
Published: May 2019

AbstractUsing computational approaches, we qualitatively and quantitatively assess the bonding components of a series of experimentally characterized Au(I) diarylallenylidene complexes (N.Kim, R.A.Widenhoefer, Angew. Chem. Int. Ed. 2018, 57, 4722–4726). Our results clearly demonstrate that Au(I) engages only weakly in π‐backbonding, which is, however, a tunable bonding component. Computationally identified trends in bonding are clearly correlated with the substitution patterns of the aryl substituents in the Au(I) diarylallenylidene complexes and good agreement is found with the previously reported experimental data, such as IR spectra, 13C NMR chemical shifts and rates of decomposition together with their corresponding barrier heights, further substantiating the computational findings. The description of the bonding patterns in these complexes allow predictions of their spectroscopic features, their reactivity and stability.
Fabrication and Characterization of Hollow Microcapsules from Polyelectrolytes Bearing Thymine Pendant Groups for Ultraviolet‐B (UVB)‐Induced Crosslinking
Authors: Giménez Rodrigo E. , Serrano Mariana P. , Álvarez Rosa María S. , Martino Débora M. , Borsarelli Claudio D. 
Published: May 2019

AbstractDNA – bioinspired polyelectrolytes poly[vinylbenzylthymine (VBT)‐4‐vinylbenzyltriethylammonium chloride (VBA)] and poly[vinylbenzylthymine (VBT)‐4‐vinylphenylsufonate (VPS)] were used for the preparation of hollow microcapsules (HMC) using the layer‐by‐layer method and CaCO3 microspheres as removable molds. Stable aqueous suspensions of spherical‐shaped HMCs with a shell composed of six layers of VBA‐based polyelectrolytes were obtained, of approximately (7.0±1.5) μm diameter and a shell thickness of 1 μm. Ultraviolet‐B irradiation of the HMC suspensions induces an efficient crosslinking between adjacent polyelectrolyte chains through the formation of thymine photodimers, such as the cyclobutane pyrimidine dimer (CPD) and the (6–4) pyrimidine–pyrimidone photoproduct (6–4PP). This process resulted in a reduction of the average interstitial mesh size of the HMC shells, modulating their permeability properties and increasing the mechanical stability of the HMC without a noticeable modification of size and shape. Thus, the DNA‐bioinspired polyelectrolytes are promising materials for the preparation of UVB‐responsive HMCs.
Immobilization of DNA on Biosensing Devices with Nitrogen Mustard–Modified Linkers
Authors: Kurinomaru Takaaki , Kojima Naoshi , Kurita Ryoji 
Published: May 2019

AbstractImmobilization of DNA is an important step in relation to DNA‐based biosensors and bioassays with multiple applications. This unit describes synthesis and applications of novel bifunctional linker molecules containing nitrogen mustard and one of two types of functional groups: cyclic disulfide or biotin. Two ways of immobilizing DNA on a surface are described. With the first method, a bifunctional alkylating linker molecule is first reacted with the target DNA to form alkylated DNA and then immobilized on a specific surface. With the second method, the bifunctional alkylating linker molecule is first attached to the surface, and then the target DNA is immobilized through an alkylating reaction with a nitrogen mustard moiety. We have also achieved immunochemical detection and quantification of 5‐methylcytosine in a target DNA immobilized by the above methods. The methods for immobilization of intact DNA using novel bifunctional linker molecules are applicable to a wide range of biological analysis techniques. © 2019 by John Wiley & Sons, Inc.
Highly Selective Single‐Component Formazanate Ferrate(II) Catalysts for the Conversion of CO2 into Cyclic Carbonates
Authors: Kamphuis Aeilke J. , Milocco Francesca , Koiter Luuk , Pescarmona Paolo P. , Otten Edwin 
Published: May 2019

AbstractThe development of new families of active and selective single‐component catalysts based on earth‐abundant metal is of interest from a sustainable chemistry perspective. In this context, anionic mono(formazanate) iron(II) complexes bearing labile halide ligands, which possess both Lewis acidic and nucleophilic functionalities, have been developed as novel single‐component homogeneous catalysts for the reaction of CO2 with epoxides to produce cyclic carbonates. The influence of the halide ligand and the electronic properties of the formazanate ligand backbone on the catalytic activity are investigated by employing the iron(II) complexes with and without an additional nucleophile. Very high selectivity is achieved towards the formation of the cyclic carbonate products from various terminal and internal epoxides without the need of a cocatalyst.
A charge sharing–based switching scheme for SAR ADCs
Authors: Akbari Meysam , Hashemipour Omid , Nazari Masoud , Moradi Farshad 
Published: May 2019

SummaryThis paper presents an energy‐efficient switching scheme for successive approximation register (SAR) analogue‐to‐digital converter (ADC). The proposed scheme employs charge recycling method to keep the capacitor arrays free of transitional energy between bit generations except reset phase. In comparison with the conventional switching scheme, the proposed one achieves 100% transitional energy saving without considering reset phase. In addition, configuration of a 10‐bit SAR ADC shows that the proposed switching scheme reduces the capacitor area by 25% compared with the conventional switching scheme.
Ultrasound‐guided fine‐needle aspiration of axillary lymph nodes in breast cancer: Diagnostic accuracy and role in surgical management
Authors: Iwamoto Naoko , Aruga Tomoyuki , Horiguchi Shinichiro , Asami Hidekazu , Saita Chiaki , Onishi Mai , Goto Risa , Ishiba Toshiyuki , Honda Yayoi , Miyamoto Hiromi , Kuroi Katsumasa 
Published: May 2019

AbstractBackgroundThe objective of this study was to evaluate the accuracy of fine needle aspiration cytology (FNAC) of axillary lymph nodes (LN) in breast cancer, to compare the results of FNAC and pathological examination, and to distinguish patients with 1 to 2 metastatic LNs from those with ≥3 metastatic LNs in patients with FNAC‐positive patients.Patients and MethodsThis study included 198 breasts of 196 patients with breast cancer who underwent FNAC and surgery for the primary and axilla without neoadjuvant chemotherapy from January 2010 to August 2016. Axillary nodal status was assessed by ultrasound (US), and whether FNAC‐positive had three or more suspicious LNs on US imaging was examined.ResultsThe results of FNAC were positive in 75 (38%), negative in 97 (49%), suspicious in 2 (1%), indeterminate in 5 (2.5%), and insufficient in 19 patients (9.5%). FNAC sensitivity, specificity, positive predictive value, and negative predictive value were 62.6%, 100%, 100%, and 62.0%, respectively. Whereas 53% (18/34) of patients with false‐negative FNAC had one metastatic LN on final pathology, 61% (47/77) patients who were FNAC‐positive had three or more metastatic LNs. In the FNAC‐positive patients, all patients had ≥3 metastatic LNs if they had ≥3 suspicious LNs on US imaging.ConclusionPatients with positive cytology were more likely to have ≥3 positive LNs compared to false‐negative cytology patients. Patients with ≥3 abnormal LNs on US and positive FNAC might require axillary dissection.
Zebrafish mab21l2 mutants possess severe defects in optic cup morphogenesis, lens and cornea development
Authors: Gath Natalie , Gross Jeffrey M. 
Published: May 2019

AbstractBackgroundMutations in MAB21L2 result in severe ocular defects including microphthalmia, anophthalmia, coloboma, microcornea, and cataracts. The molecular and cellular underpinnings of these defects are unknown, as is the normal cellular function of MAB21L2. Zebrafish mab21l2
au10 mutants possess ocular defects resembling those in humans with MAB21L2 mutations, providing an excellent model to characterize mab21l2 functions during eye development.Results
mab21l2
−/− mutants possessed a host of ocular defects including microphthalmia and colobomas as well as small, disorganized lenses and cornea dysgenesis. Decreased proliferation, increased cell death, and defects in marker gene expression were detected in the lens. Cell death in the optic stalk was elevated in mab21l2
−/− mutants and the basement membrane between the edges of the choroid fissure failed to break down. Neuronal differentiation in the retina was normal, however. mab21l2
−/− mutant corneas were disorganized, possessed an increased number of cells, some of which proliferated ectopically, and failed to differentiate the corneal stroma.Conclusionsmab21l2 function is required for morphogenesis and cell survival in the lens and optic cup, and basement membrane breakdown in the choroid fissure. mab21l2 function also regulates proliferation in the lens and cornea; in its absence, the lens is small and mispatterned, and corneal morphogenesis and patterning are also disrupted.
Conditioning pain modulation reduces pain only during the first stimulation of the temporal summation of pain paradigm in healthy participants
Authors: Holden Sinead , Petersen Kristian Kjær , Arendt‐Nielsen Lars , Graven‐Nielsen Thomas 
Published: May 2019

AbstractBackgroundPro‐nociceptive and anti‐nociceptive mechanisms are commonly assessed in clinical and experimental pain studies, but their potential interaction is not well understood.ObjectivesInvestigate the effect of conditioning pain modulation (CPM) on temporal summation of pain (TSP).MethodsTwenty healthy participants underwent cuff algometry assessment on the lower legs to establish the pressure pain tolerance threshold (PTT). For the TSP assessment, ten stimuli at the level of the PTT were delivered by computerised cuff inflations (1‐s stimulation, 1‐s break) while participants rated pain intensity on a 10‐cm electronic visual analogue scale (VAS). This TSP paradigm was then repeated with a simultaneous conditioning stimulus induced by a cuff on the contralateral leg, inflated to a constant pressure corresponding to 30% (mild), 70% (moderate) or 100% (severe) of the PTT. These were assessed in a randomised order, with a fifteen‐minute break between tests. A final TSP test without conditioning was reassessed at the end (post‐recording).ResultsAn interaction between stimuli (1–10) and repetition (p < 0.05) was found for VAS scores. VAS scores for the first stimulus were decreased during 30%, 70%, and 100% conditioning intensities, compared to baseline and post‐recordings (p < 0.05). There was a significant increase in TSP during conditioning (p < 0.05). There were no significant differences between baseline and post‐recordings for any stimuli (p > 0.05).ConclusionsThe current study indicates that mild to severe stimuli administered by cuff algometry does not modulate summation effect of temporal summation of pain, which could indicate that pain facilitatory mechanisms are more potent compared with pain inhibitory mechanisms.SignificanceCurrent knowledge on the interaction effect of pro and anti‐nociceptive paradigms are the lacking. The current study indicates that conditioning pain modulation does not modulate the summation effect of temporal summation of pain, when evaluated by computerized pressure algometry. This finding was independent of the mild, moderate and severe painful conditioning intensities.
The European epidemic: Pain prevalence and socioeconomic inequalities in pain across 19 European countries
Authors: Todd Adam , McNamara Courtney L. , Balaj Mirza , Huijts Tim , Akhter Nasima , Thomson Katie , Kasim Adetayo , Eikemo Terje A. , Bambra Clare 
Published: May 2019

AbstractBackgroundUsing data from the European Social Survey (ESS) 2014, this study presents an update of pain prevalence amongst men and women across Europe and undertakes the first analysis of socioeconomic inequalities in pain.MethodsData from the ESS 2014 survey were analysed for three pain variables: back/neck pain (n = 11,032), hand/arm pain (n = 5,954) and foot/leg pain (n = 6,314). Education was used as the indicator of socioeconomic status (SES). Age‐adjusted risk differences and age‐adjusted risk ratios were calculated from predicted probabilities generated by means of binary logistic regression. These analyses compared the lower education group with the higher education group (the socioeconomic gap), and the medium education group with the higher education group (the gradient).ResultsHigh prevalence rates were reported for all three types of pain across European countries. At a pan‐European level, back/neck pain was the most prevalent with 40% of survey participants experiencing pain; then hand/arm pain at 22%, and then foot/leg pain at 21%. There was considerable cross‐national variation in pain across European counties, as well as significant socioeconomic inequalities in the prevalence of pain—with social gradients or socioeconomic gaps evident for both men and women; socioeconomic inequalities were most pronounced for hand/arm pain, and least pronounced for back/neck pain. The magnitudes of the socioeconomic pain inequalities differed between countries, but were generally higher for women.ConclusionsFuture strategies to reduce the burden of pain should acknowledge and consider the associated socioeconomic inequalities of pain to ensure the “pain gap” does not widen.SignificanceThis is a pan European study that has explored socioeconomic inequalities in pain. Across Europe, pain is more prevalent in people of lower socioeconomic position; these pain inequalities were most significant for hand/arm pain, and least significant for back/neck pain.
A realistic expectation of electricity production from current design concentrated solar power solar tower with thermal energy storage
Authors: Boretti Alberto 
Published: May 2019

AbstractThe costs and electricity production of concentrated solar power (CSP) solar tower (ST) with molten salt (MS) thermal energy storage (TES) technology are here analyzed for the latest, recently dismissed, Aurora project. For a 135 MW net nominal capacity, the likely electricity production is less than the planned 495 GWh/year, corresponding to a capacity factor (CF) of 42%. The dispatchability of this electricity production is also less than the expected. The costs of the electricity produced by this technology are larger than the AU$ 78/MWh of the power purchase agreement (PPA). The larger costs are due to the large‐scale generation certificates (LGCs), valued at around AU$80/MWh, the low‐interest loan of 110 m$AU, and the indirect costs of the larger share of intermittent and unreliable electricity. In a state with peak power prices already up to AU$14000/MWh, the peak power costs are indeed expected to rise further, if the PPA does not specify any minimum amount of electricity to be produced. Given the electricity production of the similar plant of Crescent Dunes, one‐third of the planned, despite more than double the cost, it has been impossible to secure the investments needed even at a cost of AU$ 158/MWh.
The involvement of astrocytes in early‐life adversity induced programming of the brain
Authors: Abbink Maralinde R. , van Deijk Anne‐Lieke F. , Heine Vivi M. , Verheijen Mark H. , Korosi Aniko 
Published: May 2019

AbstractEarly‐life adversity (ELA) in the form of stress, inflammation, or malnutrition, can increase the risk of developing psychopathology or cognitive problems in adulthood. The neurobiological substrates underlying this process remain unclear. While neuronal dysfunction and microglial contribution have been studied in this context, only recently the role of astrocytes in early‐life programming of the brain has been appreciated. Astrocytes serve many basic roles for brain functioning (e.g., synaptogenesis, glutamate recycling), and are unique in their capacity of sensing and integrating environmental signals, as they are the first cells to encounter signals from the blood, including hormonal changes (e.g., glucocorticoids), immune signals, and nutritional information. Integration of these signals is especially important during early development, and therefore we propose that astrocytes contribute to ELA induced changes in the brain by sensing and integrating environmental signals and by modulating neuronal development and function. Studies in rodents have already shown that ELA can impact astrocytes on the short and long term, however, a critical review of these results is currently lacking. Here, we will discuss the developmental trajectory of astrocytes, their ability to integrate stress, immune, and nutritional signals from the early environment, and we will review how different types of early adversity impact astrocytes.
Axoglial interactions in myelin plasticity: Evaluating the relationship between neuronal activity and oligodendrocyte dynamics
Authors: Foster Antoinette Y. , Bujalka Helena , Emery Ben 
Published: May 2019

AbstractMyelin is a critical component of the vertebrate nervous system, both increasing the conduction velocity of myelinated axons and allowing for metabolic coupling between the myelinating cells and axons. An increasing number of studies demonstrate that myelination is not simply a developmentally hardwired program, but rather that new myelinating oligodendrocytes can be generated throughout life. The generation of these oligodendrocytes and the formation of myelin are influenced both during development and adulthood by experience and levels of neuronal activity. This led to the concept of adaptive myelination, where ongoing activity‐dependent changes to myelin represent a form of neural plasticity, refining neuronal functioning, and circuitry. Although human neuroimaging experiments support the concept of dynamic changes within specific white matter tracts relevant to individual tasks, animal studies have only just begun to probe the extent to which neuronal activity may alter myelination at the level of individual circuits and axons. Uncovering the role of adaptive myelination requires a detailed understanding of the localized interactions that occur between active axons and myelinating cells. In this review, we focus on recent animal studies that have begun to investigate the interactions between active axons and myelinating cells and review the evidence for—and against—the ability of neuronal activity to alter myelination at an axon‐specific level.