bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spectroscopic, Structural, and Kinetic Investigation of the Ultrafast Spin Crossover in an Unusual Cobalt(II) Semiquinonate Radical Complex
Authors: Rupp Fabian , Chevalier Katharina , Graf Michèle , Schmitz Markus , Kelm Harald , Grün Anneken , Zimmer Manuel , Gerhards Markus , van Wüllen Christoph , Krüger Hans‐Jörg , Diller Rolf 
Published: November 2016

AbstractA comprehensive spectroscopic and structural investigation of [CoII(l‐N4 tBu2)(dbsq)][B(p‐C6H4Cl)4] (1, l‐N4 tBu2=N,N′‐di‐tert‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, dbsq1−=3,5‐di‐tert‐butylsemiquinonate), the first known octahedral complex with a low‐spin (ls) CoII semiquinonate ground state, is reported. Above 200 K, solids as well as solutions of 1 exhibit thermally induced spin‐crossover (SCO) from the ls to the high‐spin (hs) CoII semiquinonate state instead of the frequently observed valence tautomerism from ls CoIII catecholate to hs CoII semiquinonate. DFT calculations demonstrate that the (closed shell) CoIII catecholate suffers from a triplet instability leading to the ls CoII semiquinonate ground state. The thorough temperature‐dependent spectroscopic study of the SCO enables a photophysical investigation. Thus, by selective photoexcitation of the ls fraction of 1 in solution at room temperature, ultrafast conversion to the hs state is observed using femtosecond electronic and IR‐vibrational (infrared) transient absorption spectroscopy. The kinetics of the photocycle is described by a stretched exponential with τ=3.3–3.6 ps and β=0.52–0.54, representing an upper limit for the hs–ls relaxation time. This is, to our knowledge, the fastest interconversion ever determined for a SCO complex, and is attributed to the special situation that in 1 a CoII complex is coordinated to a π‐radical ligand allowing very efficient coupling between the ls and hs spin states.
Quantitative Investigation of the Structural, Thermal, and Mechanical Properties of Polymorphs of a Fluorinated Amide
Authors: Mondal Pradip Kumar , Kiran M. S. R. N. , Ramamurty U. , Chopra Deepak 
Published: November 2016

AbstractThe discovery of three polymorphs of N‐(3,5‐difluorophenyl)‐2,4‐difluorobenzamide, of which two exist as concomitant polymorphs, highlights the significance of short, linear C−H⋅⋅⋅F intermolecular interactions in the solid state. The formation of these polymorphs can be regulated by monitoring the scan rate in differential scanning calorimetry. The phases have been characterized structurally and the investigation of the mechanical properties depicts that Form 1 is stiffer and harder than Form 2 by 50 % and 33 %, respectively.
Magnetic Tuning of an Anionic CoII‐MOF through Deionization of the Framework: Spin‐Canting, Spin‐Flop, and Easy‐Plane Magnetic Anisotropy
Authors: Tian Chong‐Bin , Han Yun‐Hu , He Zhang‐Zhen , Du Shao‐Wu 
Published: November 2016

AbstractAn anionic CoII‐MOF, (Me2NH2)[Co3(Me2NH)3(OH)(SDBA)3] (1) (H2SDBA=4,4′‐sulfonyldibenzoic acid) consisting of highly symmetric CoII3(μ3‐OH) triangles exhibits spin‐canting, spin‐flop, and easy‐plane magnetic anisotropy. Measurement on a single crystal shows that the ab plane of 1 is the easy magnetization plane. After structural modification through simultaneous removal of the coordinated dimethylamine (DMA) molecule at the Co center and the ionic groups DMA+ and OH−, the resulting neutral amorphous framework 2 displays an enhanced spin frustration effect. The deionization of 1 does not result in the collapse of the framework, showing the high stability of the backbone structure.
The Role of Coordination Environment and pH in Tuning the Oxidation Rate of Europium(II)
Authors: Ekanger Levi A. , Basal Lina A. , Allen Matthew J. 
Published: November 2016

AbstractThe EuII/III redox couple offers metal‐based oxidation‐sensing with magnetic resonance imaging making the study of EuII oxidation chemistry important in the design of new probes. Accordingly, we explored oxidation reactions with a set of EuII‐containing complexes. Superoxide formation from the reaction between EuII and dioxygen was observed using electron paramagnetic resonance spectroscopy. Additionally, oxidation kinetics of three EuII‐containing complexes with bromate and glutathione disulfide at pH values, including 5 and 7, is reported. In the reaction with bromate, the oxidation rate of two of the complexes increased by 7.3 and 6.7 times upon decreasing pH from 7 to 5, but the rate increased by 17 times for a complex containing amide functional groups over the same pH range. The oxidation rate of a fluorobenzo‐functionalized cryptate was relatively slow, indicating that the ligand used to impart thermodynamic oxidative stability might also be useful for controlling oxidation kinetics.
Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons
Authors: Miletić Tanja , Fermi Andrea , Orfanos Ioannis , Avramopoulos Aggelos , De Leo Federica , Demitri Nicola , Bergamini Giacomo , Ceroni Paola , Papadopoulos Manthos G. , Couris Stelios , Bonifazi Davide 
Published: November 2016

AbstractThe synthesis of O‐doped polyaromatic hydro‐ carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high‐yield ring‐closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C−O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron‐donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third‐order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices.
Adsorption and Reactive Desorption on Metal–Organic Frameworks: A Direct Strategy for Lactic Acid Recovery
Authors: Stassin Timothée , Reinsch Helge , Van de Voorde Ben , Wuttke Stefan , Medina Dana D. , Stock Norbert , Bein Thomas , Ameloot Rob , De Vos Dirk 
Published: November 2016

AbstractBiomass‐derived lactic acid (LA) is an important platform chemical towards the sustainable production of numerous materials. However, the fermentation process currently in use is limited by the difficult recovery of the LA product from the fermentation broth and results in the generation of stoichiometric amounts of gypsum waste. Herein, we show that metal–organic frameworks (MOFs) of the UiO‐66(Zr) type are effective adsorbents for the separation of LA from aqueous (buffer) solutions. These frameworks based on zirconium clusters and terephthalic acid derivatives display a tremendous uptake (up to 42 wt %) and a high affinity for LA. The latter can further be tuned by changing the hydrogen‐bonding properties of the functional groups present on the organic ligand. A Rietveld refinement disclosed the specific interaction of LA with the clusters of UiO‐66(Zr) and a preferential adsorption on open zirconium sites. Taking advantage of the catalytic activity of UiO‐66(Zr), desorption of LA was performed in alcohols to recover up to 73 % as ester. Applied to the recovery of LA, adsorption and reactive desorption offer a direct and gypsum‐free strategy as an alternative for the current multi‐step process.
Biorefining of Lignocellulosic Feedstock by a Modified Ammonia Fiber Expansion Pretreatment and Enzymatic Hydrolysis for Production of Fermentable Sugars
Authors: Kamm Birgit , Leiß Sebastian , Schönicke Petra , Bierbaum Matthias 
Published: November 2016

AbstractWheat straw was pretreated and afterwards enzymatically hydrolyzed using a modified ammonia fiber expansion (AFEX) process under different reaction conditions to produce fermentable sugars. Instead of liquid ammonia, aqueous ammonia (25 % w/v) was used to test its influence on the sugar concentration and yield of the sugars. It is shown that a protein extraction after the pretreatment can distinctly improve the result obtained for the enzymatic hydrolysis. This modified AFEX process using aqueous ammonia represents a simpler and less expensive variant of the AFEX process usually described in literature. Thus, the described process can be used for the primary refining of lignocellulosic feedstocks in the sense of a roadmap for biorefinery.
Efficacy, acceptability and safety of guided imagery/hypnosis in fibromyalgia – A systematic review and meta‐analysis of randomized controlled trials
Authors: Zech N. , Hansen E. , Bernardy K. , Häuser W. 
Published: November 2016

AbstractThis systematic review aimed at evaluating the efficacy, acceptability and safety of guided imagery/hypnosis (GI/H) in fibromyalgia.
Cochrane Library, MEDLINE, PsycINFO and SCOPUS were screened through February 2016. Randomized controlled trials (RCTs) comparing GI/H with controls were analysed. Primary outcomes were ≥50% pain relief, ≥20% improvement of health‐related quality of life, psychological distress, disability, acceptability and safety at end of therapy and 3‐month follow‐up. Effects were summarized by a random effects model using risk differences (RD) or standardized mean differences (SMD) with 95% confidence intervals (CI).Seven RCTs with 387 subjects were included into a comparison of GI/H versus controls. There was a clinically relevant benefit of GI/H compared to controls on ≥50% pain relief [RD 0.18 (95% CI 0.02, 0.35)] and psychological distress [SMD −0.40 (95% CI −0.70, −0.11)] at the end of therapy. Acceptability at the end of treatment for GI/H was not significantly different to the control. Two RCTs with 95 subjects were included in the comparison of hypnosis combined with cognitive behavioural therapy (CBT) versus CBT alone. Combined therapy was superior to CBT alone in reducing psychological distress at the end of therapy [SMD −0.50 (95% CI −0.91, −0.09)]. There were no statistically significant differences between combined therapy and CBT alone in other primary outcomes at the end of treatment and follow‐up. No study reported on safety.
GI/H hold promise in a multicomponent management of fibromyalgia.SignificanceWe provide a systematic review with meta‐analysis on guided imagery and hypnosis for fibromyalgia. Current analyses endorse the efficacy and tolerability of guided imagery/hypnosis and of the combination of hypnosis with cognitive–behavioural therapy in reducing key symptoms of fibromyalgia.
Carbon Foam Decorated with Silver Nanoparticles for Electrochemical CO2 Conversion
Authors: Ma Sichao , Liu Jianfeng , Sasaki Kazunari , Lyth Stephen M. , Kenis Paul J. A. 
Published: November 2016

AbstractElectrochemistry is a promising method to recycle CO2 into useful carbon feedstock and for storing intermittent renewable energy. To date, Au and Ag nanoparticles are the most active catalysts for electrochemical conversion of CO2 to CO. However, agglomeration reduces the activity and the high cost slows widespread commercialization. Suitable support materials are thus needed to improve catalyst utilization. We explore carbon foam (CF) as a catalyst support. Compared with carbon black or graphene nanoplatelets, CF has higher surface area, larger pores, and more defects, resulting in improved uniformity of Ag nanoparticle distribution as well as higher activity and efficiency for CO2 conversion to CO.
Estimation of lateral force contribution of boundary elements in steel plate shear wall systems
Authors: Verma Abhishek , Sahoo Dipti Ranjan 
Published: November 2016

SummarySteel plate shear walls (SPSWs) are used as lateral force‐resisting systems in new and retrofitted structures in high‐seismic regions. Various international codes recommend the design of SPSWs assuming the entire lateral load to be resisted by the infill plates. Such a design procedure results in significant overstrength leading to uneconomical and inefficient use of materials. This study is focused on the estimation of contribution of boundary elements in resisting the lateral force considering their interaction with the web plates of SPSW systems. Initially, the relative contribution of web plates and boundary frames is computed for a single‐bay single‐story frame with varying rigidity and end connections of boundary elements. Nonlinear static analyses are carried out for the analytical models inOpenSeesplatform to quantify this contribution. Later, this study is extended to the code‐based designed three‐story, six‐story, and nine‐story SPSWs of varying aspect ratios. Based on the results obtained, a new design procedure is proposed taking the lateral strengths of the boundary frames into account. Nonlinear time‐history analyses are conducted for 40 recorded ground motions representing the design basis earthquake and maximum considered earthquake hazard levels to compare the interstory and residual drift response and yield mechanisms of SPSWs designed as per current practice and the proposed methodology. Finally, an expression has been proposed to predict the lateral force contribution of the infill plate and the boundary frame of SPSWs. Copyright © 2016 John Wiley & Sons, Ltd.
Dynamic laser speckle angiography achieved by eigen‐decomposition filtering
Authors: Li Chenxi , Wang Ruikang 
Published: November 2016

A new approach is proposed for statistically analysis of laser speckle signals emerged from a living biological tissue based on eigen‐decomposition to separate the dynamic speckle signals due to moving blood cells from the static speckle signals due to static tissue components, upon which to achieve angiography of the interrogated tissue in vivo. The proposed approach is tested by imaging mouse ear pinna in vivo, demonstrating its capability of providing detailed microvascular networks with high contrast, and high temporal and spatial resolutions. It is expected to provide further opportunities for laser speckle imaging in the biomedical and clinical applications where microvascular response to certain stimulus or tissue injury is of interest.
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Predictors of bystander behaviors and sexual assertiveness among college women attending a sexual assault prevention program
Authors: Hahn Christine K. , Morris Jill M. , Jacobs Gerard A. 
Published: November 2016

AbstractIdentifying predictors of bystander behaviors and sexual assertiveness can help to inform sexual assault prevention programs on college campuses. College sorority members (N = 141) completed measures of sexual assault history, rape myth acceptance, bystander self‐efficacy, sexual assertiveness, and bystander behaviors before attending The Women's Program, which is a bystander‐based sexual assault prevention program. Regression analyses were conducted. Lower rape myth acceptance and greater bystander self‐efficacy predicted more engagement in bystander behaviors and higher sexual assertiveness. A total of 28 participants completed a 2‐week follow‐up survey that included measures of rape myth acceptance, bystander self‐efficacy, and sexual assertiveness. T‐test analyses were conducted. Rape myth acceptance was significantly lower among participants at 2‐week follow‐up compared to baseline. Implications for sexual assault prevention on college campuses are discussed.
Radiosynthesis and biological evaluation of the new PDE10A radioligand [18F]AQ28A
Authors: Wagner Sally , Teodoro Rodrigo , Deuther‐Conrad Winnie , Kranz Mathias , Scheunemann Matthias , Fischer Steffen , Wenzel Barbara , Egerland Ute , Hoefgen Norbert , Steinbach Jörg , Brust Peter 
Published: November 2016

Cyclic nucleotide phosphodiesterase 10A (PDE10A) regulates the level of the second messengers cAMP and cGMP in particular in brain regions assumed to be associated with neurodegenerative and psychiatric diseases. A better understanding of the pathophysiological role of the expression of PDE10A could be obtained by quantitative imaging of the enzyme by positron emission tomography (PET). Thus, in this study we developed, radiolabeled, and evaluated a new PDE10A radioligand, 8‐bromo‐1‐(6‐[18F]fluoropyridin‐3‐yl)‐3,4‐dimethylimidazo[1,5‐a]quinoxaline ([18F]AQ28A). [18F]AQ28A was radiolabeled by both nucleophilic bromo‐to‐fluoro or nitro‐to‐fluoro exchange using K[18F]F‐K2.2.2‐carbonate complex with different yields. Using the superior nitro precursor, we developed an automated synthesis on a Tracerlab FX F‐N module and obtained [18F]AQ28A with high radiochemical yields (33 ± 6%) and specific activities (96‐145 GBq·μmol−1) for further evaluation. Initially, we investigated the binding of [18F]AQ28A to the brain of different species by autoradiography and observed the highest density of binding sites in striatum, the brain region with the highest PDE10A expression. Subsequent dynamic PET studies in mice revealed a region‐specific accumulation of [18F]AQ28A in this region, which could be blocked by preinjection of the selective PDE10A ligand MP‐10. In conclusion, the data suggest [18F]AQ28A is a suitable candidate for imaging of PDE10A in rodent brain by PET.
Air temperature in Novaya Zemlya Archipelago and Vaygach Island from 1832 to 1920 in the light of early instrumental data
Authors: Przybylak Rajmund , Wyszyński Przemysław 
Published: November 2016

ABSTRACTIn this article, the results of an investigation into the air temperature conditions in Novaya Zemlya Archipelago and Vaygach Island (NZR) from 1832 to 1920, on the basis of all available early instrumental data gathered during exploratory and scientific expeditions, are presented. Traditional analysis based on mean monthly data was supplemented by an approach less popular in the scientific literature, i.e. the additional use of daily data. Moreover, the daily data used were not limited only to mean daily air temperature, but include also maximum daily temperature, minimum daily temperature and diurnal temperature range. Such rich sets of data allowed for more comprehensive and precise recognition of air temperature conditions in the NZR. Based on these kinds of daily data, it was also possible to calculate the number of so‐called ‘characteristic days’ (i.e. the number of days with temperatures exceeding specified thresholds) and day‐to‐day temperature variability and, for the first time, to determine different characteristics of thermal seasons (duration, onset and end dates) according to Baranowski's (1968) proposition. The results were compared with contemporary temperature conditions (1981–2010) to estimate the range of their changes between historical and present times.Analysis reveals that in 1832–1920, the NZR was markedly colder than today in all seasons. Coldest was autumn (on average by ca 5 °C), and least – summer (by 1.6 °C). Mean annual air temperature was colder than today by about 3 °C. The majority of mean monthly air temperatures in historical times lie within two standard deviations from the modern mean. This means that values of air temperature in historical times lie within the range of contemporary air temperature variability. Different air temperature characteristics calculated on the basis of daily data for the NZR for historical/contemporary periods also confirm the occurrence of climate warming between the studied periods.
The importance of electrode location in cochlear implantation
Authors: O'Connell Brendan P. , Hunter Jacob B. , Wanna George B. 
Published: November 2016

ObjectivesAs indications for cochlear implantation have expanded to include patients with more residual hearing, increasing emphasis has been placed on minimally traumatic electrode insertion. Histopathologic evaluation remains the gold standard for evaluation of cochlear trauma, but advances in imaging techniques have allowed clinicians to determine scalar electrode location in vivo. This review will examine the relationship between scalar location of electrode arrays and audiologic outcomes. In addition, the impact that surgical approach, electrode design, and insertion depth have on scalar location will be evaluated.Data Sources: PubMed literature reviewReview Methods: A review of the current literature was conducted to analyze the relationship between scalar location of cochlear implant electrode arrays and speech perception outcomes. Further, data were reviewed to determine the impact that surgical variables have on scalar electrode location.ResultsElectrode insertions into the scala tympani are associated with superior speech perception and higher rates of hearing preservation. Lateral wall electrodes, and round window/extended round window approaches appear to maximize the likelihood of a scala tympani insertion. It does not appear that deeper insertions are associated with higher rates of scalar translocation.ConclusionSuperior audiologic outcomes are observed for electrode arrays inserted entirely within the scala tympani. The majority of clinical data demonstrate that lateral wall design and a round window approach increase the likelihood of a scala tympani insertion.Level of EvidenceN/A.
Two‐in‐One: λ‐Orthogonal Photochemistry on a Radical Photoinitiating System
Authors: Hurrle Silvana , Lauer Andrea , Gliemann Hartmut , Mutlu Hatice , Wöll Christof , Goldmann Anja S. , Barner‐Kowollik Christopher 
Published: November 2016

An alkyne functional radical photoinitiator, 2‐(4‐(2‐hydroxy‐2‐methylpropanoyl)phenoxy)ethyl hex‐5‐ynoate, and evidence that both reactive moieties – the alkyne and the photoinitiator terminus – can be independently addressed with light of disparate wavelength (λ‐orthogonality) are introduced. The alkyne functionality is subjected to a visible light (420 nm) induced copper‐catalyzed Huisgen reaction, which is employed for the selective functionalization of the initiator with a poly(ethylene glycol) (PEG) chain. This reaction proceeds completely λ‐orthogonal in the presence of the UV‐reactive photoinitiating moiety. Conversely, it is demonstrated that the alkyne functionality of the photoinitiator is quantitatively orthogonal to UV irradiation emitted by the pulsing action of an excimer laser (351 nm, pulsed‐laser polymerization, PLP) and the generated radical species. In turn, the PEGylated initiator can readily be employed as a macrophotoinitiator during PLP. The introduced λ‐orthogonally addressable dual functional initiator can be used in a wide range of applications, including surface lithography and post‐synthetic modification of photocured materials.
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