bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spectroscopic and Theoretical Identification of Two Thermal Isomerization Pathways for Bistable Chiral Overcrowded Alkenes
Authors: Kistemaker Jos C. M. , Pizzolato Stefano F. , van Leeuwen Thomas , Pijper Thomas C. , Feringa Ben L. 
Published: August 2016

AbstractChiroptical molecular switches play an important role in responsive materials and dynamic molecular systems. Here we present the synthesis of four chiral overcrowded alkenes and the experimental and computational study of their photochemical and thermal behavior. By irradiation with UV light, metastable diastereoisomers with opposite helicity were generated through high yielding E–Z isomerizations. Kinetic studies on metastable 1–4 using CD spectroscopy and HPLC analysis revealed two pathways at higher temperatures for the thermal isomerization, namely a thermal E–Z isomerization (TEZI) and a thermal helix inversion (THI). These processes were also studied computationally whereby a new strategy was developed for calculating the TEZI barrier for second‐generation overcrowded alkenes. To demonstrate that these overcrowded alkenes can be employed as bistable switches, photochromic cycling was performed, which showed that the alkenes display good selectivity and fatigue resistance over multiple irradiation cycles. In particular, switch 3 displayed the best performance in forward and backward photoswitching, while 1 excelled in thermal stability of the photogenerated metastable form. Overall, the alkenes studied showed a remarkable and unprecedented combination of switching properties including dynamic helicity, reversibility, selectivity, fatigue resistance, and thermal stability.
Alkyltelluro Substitution Improves the Radical‐Trapping Capacity of Aromatic Amines
Authors: Poon Jia‐fei , Yan Jiajie , Singh Vijay P. , Gates Paul J. , Engman Lars 
Published: August 2016

AbstractThe synthesis of a variety of aromatic amines carrying an ortho‐alkyltelluro group is described. The new antioxidants quenched lipidperoxyl radicals much more efficiently than α‐tocopherol and were regenerable by aqueous‐phase N‐acetylcysteine in a two‐phase peroxidation system. The inhibition time for diaryl amine 9 b was four‐fold longer than recorded with α‐tocopherol. Thiol consumption in the aqueous phase was found to correlate inversely to the inhibition time and the availability of thiol is the limiting factor for the duration of antioxidant protection. The proposed mechanism for quenching of peroxyl radicals involves O‐atom transfer from peroxyl to Te followed by H‐atom transfer from amine to alkoxyl radical in a solvent cage.
Shell Biorefinery: Dream or Reality?
Authors: Chen Xi , Yang Huiying , Yan Ning 
Published: August 2016

AbstractShell biorefinery, referring to the fractionation of crustacean shells into their major components and the transformation of each component into value‐added chemicals and materials, has attracted growing attention in recent years. Since the large quantities of waste shells remain underexploited, their valorization can potentially bring both ecological and economic benefits. This Review provides an overview of the current status of shell biorefinery. It first describes the structural features of crustacean shells, including their composition and their interactions. Then, various fractionation methods for the shells are introduced. The last section is dedicated to the valorization of chitin and its derivatives for chemicals, porous carbon materials and functional polymers.
Near‐Infrared Intraoperative Chemiluminescence Imaging
Authors: Büchel Gabriel E. , Carney Brandon , Shaffer Travis M. , Tang Jun , Austin Christine , Arora Manish , Zeglis Brian M. , Grimm Jan , Eppinger Jörg , Reiner Thomas 
Published: August 2016

AbstractIntraoperative imaging technologies recently entered the operating room, and their implementation is revolutionizing how physicians plan, monitor, and perform surgical interventions. In this work, we present a novel surgical imaging reporter system: intraoperative chemiluminescence imaging (ICI). To this end, we have leveraged the ability of a chemiluminescent metal complex to generate near‐infrared light upon exposure to an aqueous solution of Ce4+ in the presence of reducing tissue or blood components. An optical camera spatially resolves the resulting photon flux. We describe the construction and application of a prototype imaging setup, which achieves a detection limit as low as 6.9 pmol cm−2 of the transition‐metal‐based ICI agent. As a proof of concept, we use ICI for the in vivo detection of our transition metal tracer following both systemic and subdermal injections. The very high signal‐to‐noise ratios make ICI an interesting candidate for the development of new intraoperative imaging technologies.
Performance analysis of the Kahan‐enhanced scalar product on current multi‐core and many‐core processors
Authors: Hofmann Johannes , Fey Dietmar , Riedmann Michael , Eitzinger Jan , Hager Georg , Wellein Gerhard 
Published: August 2016

SummaryWe investigate the performance characteristics of a numerically enhanced scalar product (dot) kernel loop that uses the Kahan algorithm to compensate for numerical errors, and describe efficient single instruction multiple data‐vectorized implementations on recent multi‐core and many‐core processors. Using low‐level instruction analysis and the execution‐cache‐memory performance model, we pinpoint the relevant performance bottlenecks for single‐core and thread‐parallel execution and predict performance and saturation behavior. We show that the Kahan‐enhanced scalar product comes at almost no additional cost compared with the naive (non‐Kahan) scalar product if appropriate low‐level optimizations, notably single instruction multiple data vectorization and unrolling, are applied. The execution‐cache‐memory model is extended appropriately to accommodate not only modern Intel multicore chips but also the Intel Xeon Phi ‘Knights Corner’ coprocessor and an IBM POWER8 CPU. This allows us to discuss the impact of processor features on the performance across four modern architectures that are relevant for high performance computing. Copyright © 2016 John Wiley & Sons, Ltd.
Misclassification of Self‐Directed Violence
Authors: Cwik Jan Christopher , Teismann Tobias 
Published: August 2016

BackgroundInconsistent nomenclature and classification of suicidal behaviour have plagued the field of suicidology for a long time. Recently, the United States Centers for Disease Control (CDC) advocated for the usage of a specific classification system. Aim of the current study was to determine the extent of misdiagnosed acts of self‐directed violence—controlling for the level of expertise in psychology/psychotherapy. Additionally, the effect of gender and diagnosis on misclassifications was assessed.MethodA total of 426 participants (laypersons, psychology students, psychotherapists‐in‐training, licensed psychotherapists) were presented with an array of case vignettes describing different acts of self‐directed violence (e.g., non‐suicidal self‐directed violence, suicide attempt, suicide ideation) and were asked to make a classification. Gender and given diagnosis were varied systematically in two vignettes.ResultsOverall 51.6% of the cases were misclassified (according to the Self‐Directed Violence Classification System). The level of expertise was almost unrelated to classification correctness. Yet, psychotherapists were more confident about their judgments. Female gender of the character described in the vignette and an ascribed diagnosis of Borderline Personality Disorder were associated with higher misclassification rates.LimitationsThe validity of case vignettes is discussible.ConclusionsThe results highlight the importance of more methodological and diagnostic training of psychologists regarding suicidal issues. Copyright © 2016 John Wiley & Sons, Ltd.Key Practitioner Message

Misclassification of non‐suicidal and suicidal events is common.
Expertise is only weakly associated with classification correctness.
Misclassification of suicide attempts occurs more often in women.
Misclassification of suicide attempts occurs more often in Borderline Personality Disorder.
The use of standardized diagnostic tools in relation to self-directed violence is highly recommended.
Early‐Stage Capital Cost Estimation of Biorefinery Processes: A Comparative Study of Heuristic Techniques
Authors: Tsagkari Mirela , Couturier Jean‐Luc , Kokossis Antonis , Dubois Jean‐Luc 
Published: August 2016

AbstractBiorefineries offer a promising alternative to fossil‐based processing industries and have undergone rapid development in recent years. Limited financial resources and stringent company budgets necessitate quick capital estimation of pioneering biorefinery projects at the early stages of their conception to screen process alternatives, decide on project viability, and allocate resources to the most promising cases. Biorefineries are capital‐intensive projects that involve state‐of‐the‐art technologies for which there is no prior experience or sufficient historical data. This work reviews existing rapid cost estimation practices, which can be used by researchers with no previous cost estimating experience. It also comprises a comparative study of six cost methods on three well‐documented biorefinery processes to evaluate their accuracy and precision. The results illustrate discrepancies among the methods because their extrapolation on biorefinery data often violates inherent assumptions. This study recommends the most appropriate rapid cost methods and urges the development of an improved early‐stage capital cost estimation tool suitable for biorefinery processes.
A Unique Hybrid Quasi‐Solid‐State Electrolyte for Li–O2 Batteries with Improved Cycle Life and Safety
Authors: Yi Jin , Zhou Haoshen 
Published: August 2016

AbstractIn the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li–O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li–O2 batteries. To overcome this issue, rechargeable solid‐state Li–O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi‐solid‐state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li–O2 batteries. The proposed rechargeable solid‐state Li–O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi‐solid‐state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li–O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid‐state electrolytes for Li–O2 batteries upon future application.
Solar‐Driven H2O2 Generation From H2O and O2 Using Earth‐Abundant Mixed‐Metal Oxide@Carbon Nitride Photocatalysts
Authors: Wang Ruirui , Pan Kecheng , Han Dandan , Jiang Jingjing , Xiang Chengxiang , Huang Zhuangqun , Zhang Lu , Xiang Xu 
Published: August 2016

AbstractLight‐driven generation of H2O2 only from water and molecular oxygen could be an ideal pathway for clean production of solar fuels. In this work, a mixed metal oxide/graphitic‐C3N4 (MMO@C3N4) composite was synthesized as a dual‐functional photocatalyst for both water oxidation and oxygen reduction to generate H2O2. The MMO was derived from a NiFe‐layered double hydroxide (LDH) precursor for obtaining a high dispersion of metal oxides on the surface of the C3N4 matrix. The C3N4 is in the graphitic phase and the main crystalline phase in MMO is cubic NiO. The XPS analyses revealed the doping of Fe3+ in the dominant NiO phase and the existence of surface defects in the C3N4 matrix. The formation and decomposition kinetics of H2O2 on the MMO@C3N4 and the control samples, including bare MMO, C3N4 matrix, Ni‐ or Fe‐loaded C3N4 and a simple mixture of MMO and C3N4, were investigated. The MMO@C3N4 composite produced 63 μmol L−1 of H2O2 in 90 min in acidic solution (pH 3) and exhibited a significantly higher rate of production for H2O2 relative to the control samples. The positive shift of the valence band in the composite and the enhanced water oxidation catalysis by incorporating the MMO improved the light‐induced hole collection relative to the bare C3N4 and resulted in the enhanced H2O2 formation. The positively shifted conduction band in the composite also improved the selectivity of the two‐electron reduction of molecular oxygen to H2O2.
Assessing mechanisms of climate change impact on the upland forest water balance of the Willamette River Basin, Oregon
Authors: Turner David P. , Conklin David R. , Vache Kellie B. , Schwartz Cynthia , Nolin Anne W. , Chang Heejun , Watson Eric , Bolte John P. 
Published: August 2016

AbstractProjected changes in air temperature, precipitation, and vapor pressure for the Willamette River Basin (Oregon, USA) over the next century will have significant impacts on the river basin water balance, notably on the amount of evapotranspiration (ET). Mechanisms of impact on ET will be both direct and indirect, but there is limited understanding of their absolute and relative magnitudes. Here, we developed a spatially explicit, daily time‐step, modeling infrastructure to simulate the basin‐wide water balance that accounts for meteorological influences, as well as effects mediated by changing vegetation cover type, leaf area, and ecophysiology. Three CMIP5 climate scenarios (Lowclim, Reference, and HighClim) were run for the 2010–2100 period. Besides warmer temperatures, the climate scenarios were characterized by wetter winters and increasing vapor pressure deficits. In the mid‐range Reference scenario, our landscape simulation model (Envision) projected a continuation of forest cover on the uplands but a threefold increase in area burned per year. A decline (12–30%) in basin‐wide mean leaf area index (LAI) in forests was projected in all scenarios. The lower LAIs drove a corresponding decline in ET. In a sensitivity test, the effect of increasing CO2 on stomatal conductance induced a further substantial decrease (11–18%) in basin‐wide mean ET. The net effect of decreases in ET and increases in winter precipitation was an increase in annual streamflow. These results support the inclusion of changes in land cover, land use, LAI, and ecophysiology in efforts to anticipate impacts of climate change on basin‐scale water balances.
The Governance of Climate Change Adaptation Through Urban Policy Experiments
Authors: Chu Eric K. 
Published: August 2016

AbstractClimate change is increasingly posing risks to infrastructure and public services in cities across the global South. Building on ideas of policy experimentation at the nexus of institutional and transition theories, this paper assesses six climate change adaptation experiments across the cities of Surat, Indore and Bhubaneswar in India to uncover the politics behind how experiments are conceived of, implemented, and supported in light of local development needs. Through employing both embedded and cross‐case comparative methods, I argue that policy experiments are often framed around achieving tangible urban economic benefits and maximizing specific project complementarities, which allow emerging adaptation priorities access to established policy directives and funding streams. However, I conclude that despite being arenas for testing new ideas, quantifying climate and development co‐benefits, and engaging private and civil society actors, adaptation policy experiments must be coherent with urban political economic contexts in order for them to affect sustained, equitable and transformative programmatic change. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
‘Frame Conflicts’ in Natural Resource Use: Exploring Framings Around Arctic Offshore Petroleum Using Q‐Methodology
Authors: Davies William , Van Alstine James , Lovett Jon C. 
Published: August 2016

AbstractEnvironmental and natural resource issues are often framed in multiple ways by different stakeholders. Given their complexity, how these issues are framed can diverge significantly, leading to ‘frame conflicts’. Frame conflicts have implications for decision makers when addressing socio‐ecological problems; this is especially the case for Arctic offshore petroleum. Q‐methodology is used to explore framings found across a group of stakeholders on the issue of Arctic offshore petroleum development, to empirically demonstrate the extent of frame conflicts and to explore possible bridges for consensus between these framings. The issue was framed in various ways: a global sustainability concern, a development panacea for Arctic communities, an issue where economic reality clashes with environmental idealism and an issue centred on local sustainability concerns. Despite significant divergence across framings, some potential bridges of consensus were evident, centring on ideas of traditional livelihoods, the importance of emphasizing ‘human’ aspects of the debate and the inherent risks involved in Arctic offshore petroleum. The implications and challenges of frame conflicts around Arctic offshore petroleum are discussed. Copyright © 2016 John Wiley & Sons, Ltd and ERP Environment
Heart failure epidemiology and novel treatments in Japan: facts and numbers
Authors: Konishi Masaaki , Ishida Junichi , Springer Jochen , von Haehling Stephan , Akashi Yoshihiro J. , Shimokawa Hiroaki , Anker Stefan D. 
Published: August 2016

AbstractJapan has the highest proportion of older people in the world, 25.9% of the population were aged 65 or above in 2014. Although there have been no population‐based studies that precisely examined the prevalence of heart failure in Japan, one report estimated the number of Japanese outpatients with left ventricular dysfunction was 979, 000 (0.8% of total population), which was projected to increase gradually as the population ages, reaching 1.3 million by 2030. Ischemic etiology was less frequently observed in Japan (31–47%) than in western population (54–57%). The prevalence of HF with preserved ejection fraction was similar between Japan (34–68%) and western countries (34–51%). Non‐cardiac co‐morbidities such as chronic obstructive pulmonary diseases and anemia were observed in 6–9% in Japan and 19–31% in western countries, and 35–58% in Japan and 37–56% in western countries, respectively. The definition of chronic kidney disease widely differed among studies. A relatively good survival prognosis in Japanese patients has been discussed. One‐year mortality after discharge from initial hospitalization was 9–12%, which seems to be better than the western cohort. Although length of stay was remarkably longer in Japan (15–21 days) than western countries (4–9 days), it will have to be shortened, as Japan is now being faced with an upcoming HF pandemic. Some treatments in Japan are not approved outside Japan. Such treatments include carperitide infusion (used in 58% of hospitalized HF), nicorandil infusion (9.6%), and oral pimobendan (5%). More recently, landiolol and tolvaptan have been approved. Although these drugs might have a potential to be an effective therapeutic option, lack of corroborating evidence in many of such treatments would emphasize the need for larger clinical trials.
Electroanalytical Approach for Quantification of Pesticide Maneb
Authors: Stanković Dalibor M. 
Published: August 2016

AbstractFor the first time, in this study electrochemical oxidation behavior of pesticide maneb is evaluated. Due to the structure electroanalytical quantification of maneb has not been exploited enough. Maneb electrochemical behavior was investigated using glassy carbon (GC), graphene modified glassy carbon (GR/GC) and boron doped diamond (BDD) electrodes. It is shown that only BDD shows satisfactory results toward maneb detection. Based on this, a simple, sensitive and selective electroanalytical method for determination of pesticide maneb using differential pulse voltammetry (DPV) is proposed, with a working linear range of 80–3000 nM and the limit of detection of 24 nM. The developed methodology has been applied for the determination of maneb in river water samples with satisfactory recovery. Additionally, this green method, being simple, fast, and free of chemical‐reduction reagents, offers several advantages over modified electrodes and expands the scope of BDD based electrochemical sensing devices, with promise for wider applications in environmental analysis.
Cyclical hydrogen storage and retention in polyaniline
Authors: Ebrahim Rabi , Zomorrodian Ali , Attia Nour , Geckeler Kurt , Ignatiev Alex 
Published: August 2016

AbstractHydrogen adsorption in porous nanostructured polyaniline (PANI) has been investigated to determine its potential as a hydrogen storage media. Residual gas analysis and thermogravimetric analysis were used to investigate the cyclical hydrogen adsorption in PANI. A hydrogen storage capacity of up to 3 wt % was obtained by charging the polymers at up to 3.0 × 106 Pa hydrogen at elevated temperature. Multiple charge and discharge cycles have been shown, with good retention beyond 106 sec.
Patch‐scale representation of vegetation within hydraulic models
Authors: Marjoribanks Timothy I. , Hardy Richard J. , Lane Stuart N. , Tancock Matthew J. 
Published: August 2016

AbstractSubmerged aquatic vegetation affects flow, sediment and ecological processes within rivers. Quantifying these effects is key to effective river management. Despite a wealth of research into vegetated flows, the detailed flow characteristics around real plants in natural channels are still poorly understood. Here we present a new methodology for representing vegetation patches within computational fluid dynamics (CFD) models of vegetated channels. Vegetation is represented using a Mass Flux Scaling Algorithm (MFSA) and drag term within the Reynolds‐averaged Navier–Stokes Equations, which account for the mass and momentum effects of the vegetation, respectively. The model is applied using three different grid resolutions (0.2, 0.1 and 0.05 m) using time‐averaged solution methods and compared to field data. The results show that the model reproduces the complex spatial flow heterogeneity within the channel and that increasing the resolution leads to enhanced model accuracy. Future applications of the model to the prediction of channel roughness, sedimentation and key eco‐hydraulic variables are presented, likely to be valuable for informing effective river management. © 2016 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.