bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lewis Acid Binding and Transfer as a Versatile Experimental Gauge of the Lewis Basicity of Fe0, Ru0, and Pt0Complexes
Authors: Braunschweig Holger , Brunecker Carina , Dewhurst Rian D. , Schneider Christoph , Wennemann Benedikt 
Published: November 2015

AbstractA number of zerovalent ruthenium tri‐ and tetracarbonyl complexes of the form [Ru(CO)5−nLn] (n=1, 2) with neutral phosphine or N‐heterocyclic carbene donor ligands have been treated with the Lewis acids GaCl3and Ag+to form a range of metal‐only Lewis pairs (MOLPs). The spectroscopic and structural parameters of the adducts are compared to each other and to related iron carbonyl based MOLPs. The Lewis basicity of the original Ru0complexes is gauged by transfer experiments, as well as through the degree of pyramidization of the bound GaCl3units and the RuM bond lengths. The work shows the benefits of the MOLP concept as one of the few direct experimental gauges of metal basicity, and one that can allow comparisons between metal complexes with different metal centers and ligand sets.
Steric Constraints Induced Frustrated Growth of Supramolecular Nanorods in Water
Authors: Appel Ralph , Fuchs Jonas , Tyrrell Sara M. , Korevaar Peter A. , Stuart Marc C. A. , Voets Ilja K. , Schönhoff Monika , Besenius Pol 
Published: November 2015

AbstractA unique example of supramolecular polymerisation in water based on monomers with nanomolar affinities, which yield rod‐like materials with extraordinarily high thermodynamic stability, yet of finite length, is reported. A small library of charge‐neutral dendritic peptide amphiphiles was prepared, with a branched nonaphenylalanine‐based core that was conjugated to hydrophilic dendrons of variable steric demand. Below a critical size of the dendron, the monomers assemble into nanorod‐like polymers, whereas for larger dendritic side chains frustrated growth into near isotropic particles is observed. The supramolecular morphologies observed by electron microscopy, X‐ray scattering and diffusion NMR spectroscopy studies are in agreement with the mechanistic insights obtained from fitting polymerisation profiles: non‐cooperative isodesmic growth leads to degrees of polymerisation that match the experimentally determined nanorod contour lengths of close to 70 nm. The reported designs for aqueous self‐assembly into well‐defined anisotropic particles has promising potential for biomedical applications and the development of functional supramolecular biomaterials, with emerging evidence that anisotropic shapes in carrier design outperform conventional isotropic materials for targeted imaging and therapy.
Host–Guest Strategy to Reversibly Control a Chloride Carrier Process with Cyclodextrins
Authors: Gravel Julien , Kempf Julie , Schmitzer Andreea 
Published: November 2015

AbstractHerein, we report a reversible modular chloride transport process based on host–guest competitive interactions between an imidazolium‐based chloride carrier and beta‐cyclodextrin. We report evidence for the formation of the supramolecular complex between 1,3‐bis(2‐(adamantan‐1‐yl)ethyl)imidazolium bis(trifluorometyl‐sulfonyl)imide with two β‐cyclodextrins. Through fluorescence assays in liposomes and black lipid membrane experiments, we demonstrate that the formation of the supramolecular complex results in the inhibition of the chloride transport. We show that the chloride transport process can be entirely restored in the presence of competitive adamantyl‐functionalized guests. This is the first example of an entirely reversible modular chloride transport process in phospholipid bilayers involving a mobile carrier transporter and cyclodextrin supramolecular complex.
Supramolecular Alternating Polymer from Crown Ether and Pillar[5]arene‐Based Double Molecular Recognition for Preparation of Hierarchical Materials
Authors: Li Hui , Fan Xiaodong , Qi Miao , Yang Zhen , Zhang Haitao , Tian Wei 
Published: November 2015

AbstractA novel supramolecular alternating polymer is constructed based on double molecular recognition events of benzo‐21‐crown‐7 with a secondary ammonium salt and of pillar[5]arene with a neutral guest. The resulting polymer is utilized to prepare hierarchical materials with different dimensionalities for the first time. These materials included zero‐dimensional spherical aggregates, one‐dimensional nanofibers, two‐dimensional microstructured films, and three‐dimensional ordered glue. This development will be helpful for designing and preparing supramolecular hierarchical materials with different dimensionalities.
Organocatalytic 1,4‐Addition Reaction of 2‐Formyl(thio)esters to Vinylketones: An Efficient Access to Acyclic Chiral Building Blocks with a Quaternary Carbon Stereocenter
Authors: Tatsumi Toshifumi , Misaki Tomonori , Sugimura Takashi 
Published: November 2015

Abstract2‐Formyl(thio)esters were utilized as pronucleophiles to obtain less‐accessible acyclic chiral building blocks bearing versatile functional groups on a quaternary carbon atom for enantioselective 1,4‐addition to vinylketones. To achieve high enantioselectivity in the present 1,4‐addition reaction, thiourea‐tertiary amines containing a bulky chiral backbone were developed as catalysts, and several derivatizations of the products were performed to demonstrate the synthetic utility of the products.
Circularly Polarized Luminescence from Helically Chiral N,N,O,O‐Boron‐Chelated Dipyrromethenes
Authors: Alnoman Rua B. , Rihn Sandra , O'Connor Daniel C. , Black Fiona A. , Costello Bernard , Waddell Paul G. , Clegg William , Peacock Robert D. , Herrebout Wouter , Knight Julian G. , Hall Michael J. 
Published: November 2015

AbstractHelically chiral N,N,O,O‐boron chelated dipyrromethenes showed solution‐phase circularly polarized luminescence (CPL) in the red region of the visible spectrum (λem(max) from 621 to 663 nm). The parent dipyrromethene is desymmetrised through O chelation of boron by the 3,5‐ortho‐phenolic substituents, inducing a helical chirality in the fluorophore. The combination of high luminescence dissymmetry factors (|glum| up to 4.7 ×10−3) and fluorescence quantum yields (ΦF up to 0.73) gave exceptionally efficient circularly polarized red emission from these simple small organic fluorophores, enabling future application in CPL‐based bioimaging.
Connectivity between the OFF bipolar type DB3a and six types of ganglion cell in the marmoset retina
Authors: Masri Rania A. , Percival Kumiko A. , Koizumi Amane , Martin Paul R. , Grünert Ulrike 
Published: November 2015

ABSTRACTParallel visual pathways originate at the first synapse in the retina, where cones make connections with cone bipolar cells that in turn contact ganglion cells. There are more ganglion cell types than bipolar types, suggesting that there must be divergence from bipolar to ganglion cells. Here we analyze the contacts between an OFF bipolar type (DB3a) and six ganglion cell types in the retina of the marmoset monkey (Callithrix jacchus). Ganglion cells were transfected via particle‐mediated gene transfer of an expression plasmid for the postsynaptic density 95‐green fluorescent protein (PSD95‐GFP), and DB3a cells were labeled via immunohistochemistry. Ganglion cell types that fully or partially costratified with DB3a cells included OFF parasol, OFF midget, broad thorny, recursive bistratified, small bistratified, and large bistratified cells. On average, the number of DB3a contacts to parasol cells (18 contacts per axon terminal) is higher than that to other ganglion cell types (between four and seven contacts). We estimate that the DB3a output to OFF parasol cells accounts for at least 30% of the total DB3a output. Furthermore, we found that OFF parasol cells receive approximately 20% of their total bipolar input from DB3a cells, suggesting that other diffuse bipolar types also provide input to OFF parasol cells. We conclude that DB3a cells preferentially contact OFF parasol cells but also provide input to other ganglion cell types. J. Comp. Neurol. 524:1839–1858, 2016. © 2015 Wiley Periodicals, Inc.
The anatomical basis for modulatory convergence in the antennal lobe of Manduca sexta
Authors: Lizbinski Kristyn M. , Metheny Jackie D. , Bradley Samual P. , Kesari Aditya , Dacks Andrew M. 
Published: November 2015

ABSTRACTThe release of neuromodulators by widely projecting neurons often allows sensory systems to alter how they process information based on the physiological state of an animal. Neuromodulators alter network function by changing the biophysical properties of individual neurons and the synaptic efficacy with which individual neurons communicate. However, most, if not all, sensory networks receive multiple neuromodulatory inputs, and the mechanisms by which sensory networks integrate multiple modulatory inputs are not well understood. Here we characterized the relative glomerular distribution of two extrinsic neuromodulators associated with distinct physiological states, serotonin (5‐HT) and dopamine (DA), in the antennal lobe (AL) of the moth Manduca sexta. By using immunocytochemistry and mass dye fills, we characterized the innervation patterns of both 5‐HT‐ and tyrosine hydroxylase‐immunoreactive processes relative to each other, to olfactory receptor neurons (ORNs), to projection neurons (PNs), and to several subsets of local interneurons (LNs). 5‐HT immunoreactivity had nearly complete overlap with PNs and LNs, yet no overlap with ORNs, suggesting that 5‐HT may modulate PNs and LNs directly but not ORNs. TH immunoreactivity overlapped with PNs, LNs, and ORNs, suggesting that dopamine has the potential to modulate all three cell types. Furthermore, the branching density of each neuromodulator differed, with 5‐HT exhibiting denser arborizations and TH‐ir processes being sparser. Our results suggest that 5‐HT and DA extrinsic neurons target partially overlapping glomerular regions, yet DA extends further into the region occupied by ORNs. J. Comp. Neurol. 524:1859–1875, 2016. © 2015 Wiley Periodicals, Inc.
1 D Hierarchical MnCo2O4 Nanowire@MnO2 Sheet Core–Shell Arrays on Graphite Paper as Superior Electrodes for Asymmetric Supercapacitors
Authors: Liu Shude , Hui Kwan San , Hui Kwun Nam 
Published: November 2015

AbstractHeterostructured metal oxide core–shell architectures have attracted considerable attention owing to their superior electrochemical performance in supercapacitors compared to a single structure. Here, we report a simple and effective synthesis of hierarchical MnCo2O4 nanowire@MnO2 sheet core–shell nanostructures anchored on graphite paper for use in supercapacitors. The proposed electrode exhibits a specific capacitance of 2262 F g−1 at 1 A g−1. In addition, good rate capability and excellent cycling performance are observed. An asymmetric supercapacitor with operating potential at 1.6 V is demonstrated using MnCo2O4@MnO2 as cathode and graphene/nickel foam (NF) as anode. The MnCo2O4@MnO2//graphene/NF asymmetric device shows a high energy density of 85.7 Wh kg−1 at a power density of 800 W kg−1 while maintaining a high energy density of 34.7 Wh kg−1 at 24 kW kg−1. Moreover, the device demonstrates a long‐term cycling stability of 81.6 % retention of its initial specific capacitance.
Organic Nanostructures for Photoacoustic Imaging
Authors: Kim Jeesu , Park Sungjo , Lee Changho , Kim Jin Young , Kim Chulhong 
Published: November 2015

AbstractPhotoacoustic imaging (PAI) has gained significant attention over the last two decades as a noninvasive, nonionizing, real‐time, and inexpensive medical imaging modality. By exploiting the low acoustic scattering compared to optical scattering in biological tissues, PAI can achieve high resolution while maintaining superior optical contrast in deep tissues. PAI can probe many endogenous chromophores based on their strong optical absorption contrast, including oxygenated hemoglobin, deoxygenated hemoglobin, melanin, water, and lipid. However, these intrinsic absorbers are typically activated by visible (e.g., wavelength 400≤λ≤700 nm) or infrared (λ>1000 nm) light, at which wavelengths light penetration is severely limited. Because the optimal spectral region is the near‐infrared (NIR, 700≤λ≤1000 nm) window for deep‐tissue imaging, additional contrast mechanisms for PAI should be found. So far, various exogenous contrast agents have been developed for this purpose including small monomers, inorganic nanoparticles (NPs), organic NPs, etc. For successful and fast clinical translation, the proposed contrast agents must be safe and degradable in vivo, and the organic nanostructures may be good candidates for this purpose. In this article, we review recent progress in developing organic nanoformulations as PAI contrast agents.
The Phenomenology and Generation of Positive Mental Imagery in Early Psychosis
Authors: Laing Jennifer , Morland Tristan , Fornells‐Ambrojo Miriam 
Published: November 2015

BackgroundTheoretical models of depression and bipolar disorder emphasise the importance of positive mental imagery in mood and behaviour. Distressing, intrusive images are common in psychosis; however, little is known about positive imagery experiences or their association with clinical symptoms. The aim of the current study was to examine the phenomenology of positive imagery in early psychosis and the relationship between the characteristics of positive, future‐oriented imagery and symptom severity.MethodCharacteristics, thematic content and appraisals of recent self‐reported images were examined in 31 people with early psychosis. The vividness and perceived likelihood of deliberately generated, future‐oriented images were investigated in relation to clinical symptoms.ResultsEighty‐four percent of participants reported experiencing a recent positive image. Themes included the achievement of personal goals, spending enjoyable time with peers and family, loving, intimate relationships and escape from current circumstances. The vividness and perceived likelihood of generated prospective imagery were negatively correlated with levels of depression and social anxiety.ConclusionsThe relationship between emotional problems and the ability to imagine positive, future events may have implications for motivation, mood and goal‐directed behaviour in psychosis. Everyday experiences of positive imagery may represent the simulation of future goals, attempts to cope or avoid aversive experiences or idealised fantasy. Copyright © 2015 John Wiley & Sons, Ltd.Key Practitioner Message

The majority of participants experienced a recent positive image with themes related to goal attainment and social relationships.
Depression and social anxiety levels were correlated with the vividness of intentionally generated positive future‐oriented images and their perceived likelihood.
The assessment of positive imagery in early psychosis appears warranted and may provide insights regarding individual coping strategies, values and goals.
Enhancing the Performance of Amorphous‐Silicon Photoanodes for Photoelectrocatalytic Water Oxidation
Authors: Qin Wei , Wang Nan , Yao Tingting , Wang Shubo , Wang Hui , Cao Yuexian , Liu Shengzhong (Frank) , Li Can 
Published: November 2015

AbstractHerein, hydrogenated amorphous Si (a‐Si:H) covered with a thin layer of CoOx is applied as photoanode for PEC water splitting. The thin layer of CoOx effectively protects a‐Si:H from the corrosive electrolyte and quantitative oxidation of water to oxygen was observed. A high applied bias photon‐to‐current efficiency of 2.34 % was achieved using an intrinsic absorber and an additional p‐type layer. This work shows that a‐Si:H with a sandwich‐like structure, in which each layer has its own functionality, can be applied as an efficient and stable photoanode for PEC water oxidation.
Characterization of Quinoxolinol Salen Ligands as Selective Ligands for Chemosensors for Uranium
Authors: DeVore II Michael A. , Kerns Spencer A. , Gorden Anne E. V. 
Published: November 2015

AbstractQuinoxalinol salen ligands have been characterized as selective ligands for the rapid identification of uranyl. The absorption maximum of ligand 1 presented a hypsochromic (blue) shift with the addition of UO22+ (as the acetate salt), and a bathochromic (red) shift in the presence of Cu2+ or Co2+ acetate salts, resulting in distinct, visible color changes for all three metal ions. The absorption maximum of ligand 2 was not observed to change with the addition of UO22+; however, it does present a bathochromic shift with the addition of Cu2+, and a hypsochromic shift with Co2+ added. Using TDDFT calculations, it was demonstrated that the hypsochromic shift for UO22+ ion complexation with ligand 1 is caused by a ligand‐to‐metal charge transfer, while the bathochromic shift observed with Cu2+ ion addition was caused by a metal‐to‐ligand charge transfer. Finally, it was found that the addition of Cu2+ (as metal salts) to either ligand resulted in rapid, complete quenching of the ligand fluorescence.
A free surface flow solver for complex three‐dimensional water impact problems based on the VOF method
Authors: Nguyen Van‐Tu , Park Warn‐Gyu 
Published: November 2015

SummaryA three‐dimensional numerical model is developed to analyze free surface flows and water impact problems. The flow of an incompressible viscous fluid is solved using the unsteady Navier–Stokes equations. Pseudo‐time derivatives are introduced into the equations to improve computational efficiency. The interface between the two phases is tracked using a volume‐of‐fluid interface tracking algorithm developed in a generalized curvilinear coordinate system. The accuracy of the volume‐of‐fluid method is first evaluated by the multiple numerical benchmark tests, including two‐dimensional and three‐dimensional deformation cases on curvilinear grids. The performance and capability of the numerical model for water impact problems are demonstrated by simulations of water entries of the free‐falling hemisphere and cone, based on comparisons of water impact loadings, velocities, and penetrations of the body with experimental data. For further validation, computations of the dam‐break flows are presented, based on an analysis of the wave front propagation, water level, and the dynamic pressure impact of the waves on the downstream walls, on a specific container, and on a tall structure. Extensive comparisons between the obtained solutions, the experimental data, and the results of other numerical simulations in the literature are presented and show a good agreement. Copyright © 2015 John Wiley & Sons, Ltd.
Development and preliminary validation of an Observation List for detecting mental disorders and social Problems in the elderly in primary and home care (OLP)
Authors: Tak Erwin C. P. M. , van Hespen Ariëtte T. H. , Verhaak Peter F. M. , Eekhof Just , Hopman‐Rock Marijke 
Published: November 2015

ObjectiveEven though the prevalence of mental disorders and social problems is high among elderly patients, it is difficult to detect these in a primary (home) care setting. Goal was the development and preliminary validation of a short observation list to detect six problem areas: anxiety, depression, cognition, suspicion, loneliness, and somatisation.MethodsA draft list of indicators identified from a short review of the literature and the opinions of 22 experts was evaluated by general practitioners (GPs) and home care organisations for feasibility. It was then used by GPs and home care personnel to observe patients, who also completed validated tests for psychological disorders (General Health Questionnaire 12 item version (GHQ‐12)), depression (Geriatric Depression Scale 15‐item version (GDS‐15)), anxiety and suspicion (Symptom Checklist‐90 (SCL‐90)), loneliness (University of California, Los Angeles (UCLA)), somatisation (Illness Attitude Scale (IAS)), and cognition (Mini‐Mental State Examination (MMSE)).ResultsGPs and home care personnel observed 180 patients (mean age 78.4 years; 66% female) and evaluated the draft list during a regular visit. Cronbach's α was 0.87 for the draft list and ≥0.80 for the draft problem areas (loneliness and suspicion excepted). Principal component analysis identified six components (cognition, depression + loneliness, somatisation, anxiety + suspicion, depression (other signs), and an ambiguous component). Convergent validity was shown for the indicators list as a whole (using the GHQ‐12), and the subscales of depression, anxiety, loneliness, cognition, and somatisation. Using pre‐set agreed criteria, the list was reduced to 14 final indicators divided over five problem areas.ConclusionThe Observation List for mental disorders and social Problems (OLP) proved to be preliminarily valid, reliable, and feasible for use in primary and home care settings. Copyright © John Wliey & Sons, Ltd.
In vitro model for gastroduodenal reflux–induced nuclear factor‐kappaB activation and its role in hypopharyngeal carcinogenesis
Authors: Sasaki Clarence T. , Issaeva Natalia , Vageli Dimitra P. 
Published: November 2015

AbstractBackgroundThe purpose of this study was to investigate whether gastroduodenal reflux can play a role in the pathogenesis of hypopharyngeal cancer; therefore, we assessed its effect on the nuclear factor‐kappa B (NF‐κB) pathway, as similarly noted in the esophagus.MethodsWe exposed human cells derived from the hypopharyngeal epithelium to bile acids or deoxycholic acid. We centered our study on the transcriptional activation of NF‐κB pathway, previously linked to head and neck squamous cell carcinoma (HNSCC).ResultsWe show that acidic‐bile salts induce: (1) NF‐κB activation with high cytoplasmic Bcl‐2 expression; (2) significant increase in expression v‐rel avian reticuloendotheliosis viral oncogene homolog A (RELA(p65)), v‐rel avian reticuloendotheliosis viral oncogene homolog (c‐REL) signal transducer and activator of transcription 3 (STAT3), isoform of transformation related protein p63 (ΔNp63), B‐cell lymphoma 2 (Bcl‐2), tumor necrosis factor alpha (TNF‐α), epidermal growth factor receptor (EGFR), and wingless type MMTV integration site family member 5A (WNT5A) and a decrease in tumor protein p53 (Tp53); and (3) phenotypic changes that are similar to the phenotype of the untreated hypopharyngeal cancer cell line, University of Michigan squamous cell carcinoma (UMSCC)‐11B. These changes are not seen when cells were exposed to neutral control or acid alone.ConclusionOur findings in vitro are consistent with the hypothesis that gastroduodenal reflux plays a role in hypopharyngeal carcinogenesis and its effect is mediated through activation of NF‐κB pathway. © 2015 Wiley Periodicals, Inc. Head Neck 38: E1381–E1391, 2016
Disease‐free survival after salvage therapy for recurrent oropharyngeal squamous cell carcinoma
Authors: Joseph Andrew W. , Guo Theresa , Hur Kevin , Xie Yanjun , Yin Linda , Califano Joseph A. , Ha Patrick K. , Quon Harry , Richmon Jeremy D. , Eisele David W. , Agrawal Nishant , Fakhry Carole 
Published: November 2015

AbstractBackgroundFactors associated with disease‐free survival (DFS) after salvage therapy for recurrent oropharyngeal squamous cell carcinoma (SCC) in the context of human papillomavirus (HPV) are poorly understood.MethodsA retrospective cohort analysis was conducted of patients with recurrent oropharyngeal SCC with known HPV tumor status who received salvage therapy.ResultsEighty‐six patients were eligible for analysis. Sixty‐four patients (74%) were HPV‐positive. In multivariable analysis, HPV‐positive tumor status (hazard ratio [HR] = 0.30; 95% confidence interval [CI] = 0.13–0.71; p = .007), clinical response to any salvage therapy (HR = 0.29; 95% CI = 0.11–0.77; p = .01), and surgical salvage (HR = 0.38; 95% CI = 0.16–0.88; p = .02) were associated with improved overall survival (OS). Positive surgical margin was associated with worse DFS after salvage (HR = 8.43; 95% CI = 1.99–35.70; p = .004).ConclusionFor recurrent oropharyngeal SCC, HPV‐positive tumor status, surgical salvage, and clinical response to salvage therapy are independently associated with improved OS, but not DFS after salvage. Surgical margin is the only independent predictor of DFS. © 2015 Wiley Periodicals, Inc. Head Neck 38: E1501–E1509, 2016