bluuebunny/crossref_metadata_2025_split huggingface dataset:
Substitution and Catalytic Chemistry of Gyroscope‐Like Complexes Derived from Cl–Rh–CO Rotators and Triply trans Spanning Di(trialkylphosphine) Ligands
Authors: Estrada Alexander L. , Jia Tiezheng , Bhuvanesh Nattamai , Blümel Janet , Gladysz John A. 
Published: October 2015

AbstractReactions of trans‐[Rh(CO)(Cl){P{(CH2)14}3P2(Rh–P2)}] (1) with ZnPh2, MeLi, or NaBH4 give the chloride‐substitution products trans‐[Rh(CO)(Ph){P{(CH2)14}3P2(Rh–P2)}] (3, 89 %), trans‐[Rh(CO)(Me){P{(CH2)14}3P2(Rh–P2)}] (94 %, 92 % purity), and trans‐[Rh(CO)(H2BH2){P{(CH2)14}3P2(Rh–P2)}] (5, 99 %). The crystal structures of 3, 5, and the corresponding (fortuitously obtained) bromide complex are determined, and the ability of the X–Rh–CO moieties to rotate is interpreted in terms of their effective radii and the void space within the dibridgehead diphosphine cage. Reaction of 1 and excess PMe3 gives the diphosphine substitution product trans‐[Rh(CO)(Cl)(PMe3)2] (89 %) and the dibridgehead diphosphine P[(CH2)14]3P (58 %). Complex 5 serves as a catalyst precursor for the hydroformylation of 1‐octene (neat or THF, 60 °C, 75 psig 1:1 CO/H2). The locus of catalysis with respect to the diphosphine cage is discussed.
PEGylated DOTA‐AHA‐Based GdIII Chelates: A Relaxometric Study
Authors: Fontes André , Karimi Shima , Helm Lothar , Ferreira Paula M. , André João P. 
Published: October 2015

AbstractInvited for the cover of this issue are Dr. João Paulo André, Dr. Paula Margarida Ferreira, and Dr. André Fontes at the University of Minho, Braga, Portugal, and Prof. Lothar Helm at the EPFL, Lausanne, Switzerland. The cover image shows the general structure of PEGylated DOTA‐based GdIII chelates developed as potential contrast agents for magnetic resonance imaging. The rotating arrow illustrates the importance of the tumbling behavior of the chelates for their relaxivity.
Conjugation of Bioactive Molecules to a Fluorescent Dithiomaleimide by Photoin­duced and BEt3‐Initiated Thio‐Click Reactions
Authors: Lázár László , Nagy Miklós , Borbás Anikó , Herczegh Pál , Zsuga Miklós , Kéki Sándor 
Published: October 2015

AbstractTwo versions of the free‐radical thiol–ene addition, a photoinduced reaction in the presence of 2,2‐dimethoxy‐2‐phenylacetophenone, and a UV‐light‐free hydrothiolation using triethylborane as the initiator, were studied for the conjugation of fluorescent dithiomaleimide to biologically active compounds. A dithiomaleimide derivative bearing a vinyl ether functionality was prepared as the alkene partner. This was coupled with a range of thiols, including thiosugars, captopril, N‐acetyl‐L‐cysteine, and sodium 2‐sulfonatoethanethiol. The Et3B‐initiated method was superior to the photoinduced reaction, as it minimized decomposition of the sensitive maleimide group. The vinyl ether derivative and the addition products showed green light emission in tetrahydrofuran. The compounds all showed almost identical absorption and emission spectra, proving that the structure of the thiols has no influence on the fluorescence properties of the maleimide part of the molecules. The hydrothiolation products showed relatively high quantum yields.
Banking carbon: a review of organic carbon storage and physical factors influencing retention in floodplains and riparian ecosystems
Authors: Sutfin Nicholas A. , Wohl Ellen E. , Dwire Kathleen A. 
Published: October 2015

AbstractRivers are dynamic components of the terrestrial carbon cycle and provide important functions in ecosystem processes. Although rivers act as conveyers of carbon to the oceans, rivers also retain carbon within riparian ecosystems along floodplains, with potential for long‐term (> 102 years) storage. Research in ecosystem processing emphasizes the importance of organic carbon (OC) in river systems, and estimates of OC fluxes in terrestrial freshwater systems indicate that a significant portion of terrestrial carbon is stored within river networks. Studies have examined soil OC on floodplains, but research that examines the potential mechanistic controls on OC storage in riparian ecosystems and floodplains is more limited. We emphasize three primary OC reservoirs within fluvial systems: (1) standing riparian biomass; (2) dead biomass as large wood (LW) in the stream and on the floodplain; (3) OC on and beneath the floodplain surface, including litter, humus, and soil organic carbon (SOC). This review focuses on studies that have framed research questions and results in the context of OC retention, accumulation and storage within the three primary pools along riparian ecosystems. In this paper, we (i) discuss the various reservoirs for OC storage in riparian ecosystems, (ii) discuss physical conditions that facilitate carbon retention and storage in riparian ecosystems, (iii) provide a synthesis of published OC storage in riparian ecosystems, (iv) present a conceptual model of the conditions that favor OC storage in riparian ecosystems, (v) briefly discuss human impacts on OC storage in riparian ecosystems, and (vi) highlight current knowledge gaps. Copyright © 2015 John Wiley & Sons, Ltd.
Do Jumps Matter for Volatility Forecasting? Evidence from Energy Markets
Authors: Prokopczuk Marcel , Symeonidis Lazaros , Wese Simen Chardin 
Published: October 2015

AbstractThis paper characterizes the dynamics of jumps and analyzes their importance for volatility forecasting. Using high‐frequency data on four prominent energy markets, we perform a model‐free decomposition of realized variance into its continuous and discontinuous components. We find strong evidence of jumps in energy markets between 2007 and 2012. We then investigate the importance of jumps for volatility forecasting. To this end, we estimate and analyze the predictive ability of several Heterogenous Autoregressive (HAR) models that explicitly capture the dynamics of jumps. Conducting extensive in‐sample and out‐of‐sample analyses, we establish that explicitly modeling jumps does not significantly improve forecast accuracy. Our results are broadly consistent across our four energy markets, forecasting horizons, and loss functions. © 2015 Wiley Periodicals, Inc. Jrl Fut Mark 36:758–792, 2016
Identifying the causes, prevention and management of crises in dementia. An online survey of stakeholders
Authors: Ledgerd Ritchard , Hoe Juanita , Hoare Zoë , Devine Mike , Toot Sandeep , Challis David , Orrell Martin 
Published: October 2015

BackgroundCrisis situations in dementia can lead to hospital admission or institutionalisation. Offering immediate interventions may help avoid admission, whilst stabilising measures can help prevent future crises.ObjectiveOur objective was to identify the main causes of crisis and interventions to treat or prevent crisis in persons with dementia based on different stakeholder perspectives.MethodsAn online questionnaire was developed to identify the causes of crisis and appropriate interventions in a crisis. Participants included people with dementia, family carers and staff working in health and social care, including emergency and voluntary sectors, and academia.ResultsThe results ranked the main causes of crisis, interventions that can prevent a crisis and interventions that can be useful in a crisis. Wandering, falls and infection were highly rated as risk factors for crises across all stakeholder groups. Consumers rated aggression as less important but severity of memory impairment as much more important than the other groups did. Education and support for family carers and home care staff were highly valued for preventing crises. Well‐trained home care staff, communication equipment, emergency contacts and access to respite were highly valued for managing crises.ConclusionsWe identified triggers and interventions that different stakeholders see as important for crisis in dementia. Recognition of these may be critical to planning effective and accepted support and care for people with dementia. Copyright © 2015 John Wiley & Sons, Ltd.
Cost‐effectiveness of exercise as a therapy for behavioural and psychological symptoms of dementia within the EVIDEM‐E randomised controlled trial
Authors: D'Amico Francesco , Rehill Amritpal , Knapp Martin , Lowery David , Cerga‐Pashoja Arlinda , Griffin Mark , Iliffe Steve , Warner James 
Published: October 2015

ObjectiveAlthough available evidence is modest, exercise could be beneficial in reducing behavioural and psychological symptoms of dementia. We aim to evaluate the cost‐effectiveness of a dyadic exercise regimen for individuals with dementia and their main carer as therapy for behavioural and psychological symptoms of dementia.MethodsCost‐effectiveness analysis within a two‐arm, pragmatic, randomised, controlled, single‐blind, parallel‐group trial of a dyadic exercise regimen (individually tailored, for 20–30 min at least five times per week). The study randomised 131 community‐dwelling individuals with dementia and clinically significant behavioural and psychological symptoms with a carer willing and able to participate in the exercise regimen; 52 dyads provided sufficient cost data for analyses.ResultsMean intervention cost was £284 per dyad. For the subsample of 52 dyads, the intervention group had significantly higher mean cost from a societal perspective (mean difference £2728.60, p = 0.05), but costs were not significantly different from a health and social care perspective. The exercise intervention was more cost‐effective than treatment as usual from both societal and health and social care perspectives for the measure of behavioural and psychological symptoms (Neuropsychiatric Inventory). It does not appear cost‐effective in terms of cost per quality‐adjusted life year gain.ConclusionsThe exercise intervention has the potential to be seen as cost‐effective when considering behavioural and psychological symptoms but did not appear cost‐effective when considering quality‐adjusted life year gains. Copyright © 2011 John Wiley & Sons, Ltd.
Bioethanol production from biomass: carbohydrate vs syngas fermentation
Authors: Kennes David , Abubackar Haris Nalakath , Diaz Marío , Veiga María C , Kennes Christian 
Published: October 2015

AbstractEnvironmental problems associated with the use of fossil fuels as well as their expected scarcity in the near future requires a search for new alternative fuels produced from renewable sources. Bioethanol is a biofuel that can be obtained from biomass and waste as feedstocks through fermentation. Two major routes allow conversion of the feedstocks to fermentable substrates, i.e. the hydrolytic route and the thermochemical route. In the hydrolytic route, the feedstock undergoes a pretreatment stage first, aimed at facilitating the subsequent hydrolytic treatment. Chemical, physical or biological pretreatments can be applied. Lignocellulosic feedstocks are mainly composed of cellulose, hemicellulose and lignin. The pretreatment attacks the lignin and hemicellulose polymers and makes cellulose more accessible in the next, hydrolytic, stage. The hydrolytic treatment uses enzymes to convert the cellulose polymer to simple, fermentable, sugars, mainly glucose. Simple sugars obtained from hemicellulose and cellulose are then fermented by yeasts to bioethanol. In the thermochemical alternative, the feedstock is gasified, yielding syngas – a mixture largely composed of CO, CO2 and H2 – which can be fermented anaerobically, usually by clostridia, to ethanol or other products. In both cases, downstream processes are then applied to recover and purify the biofuel. The different stages involved in both alternatives are described, and both processes are compared in terms of their main characteristics and development stage. © 2015 Society of Chemical Industry
Subsoil rhizosphere modification by chickpea under a dry topsoil: implications for phosphorus acquisition
Authors: Kabir Md. Enamul , Johansen Chris , Bell Richard W. 
Published: October 2015

AbstractChickpea (Cicer arietinum L.) roots exude carboxylates. While chickpea commonly grows where the topsoil dries out during crop growth, the importance of carboxylate exudation by the roots and mobilization of soil P from below the dry topsoil has not been examined. The study investigates the response of carboxylate exudation and soil P mobilization by this crop to subsoil P fertilizer rate. In constructed soil columns in the glasshouse, the P levels (high, low, and nil P) were varied in the well‐watered subsoil (10–30 cm), while a low level of P in the dry topsoil (0–10 cm) was maintained. At flowering, rhizosphere carboxylates and rhizosphere soil from topsoil and subsoil roots were collected separately and analyzed. The concentration of total carboxylates per unit rhizosphere mass in the subsoil was nearly double that of the topsoil. Plants depleted sparingly soluble inorganic P (Pi), NaOH‐Pi, and HCl‐Pi, along with the labile Pi (water soluble and NaHCO3‐Pi). The P depletion by plants was greater from the subsoil than the topsoil. The study concluded that depletion of sparingly soluble P from the chickpea rhizosphere in the subsoil was linked with the greater levels of carboxylates in the rhizosphere. These findings indicate that chickpea, with its deep rooting pattern, can increase its access to subsoil P when the topsoil dries out during crop growth by subsoil rhizosphere modification.
Phosphate fertilizer form and application strategy affect phosphorus mobility and transformation in a drip‐irrigated calcareous soil
Authors: Wang Jing , Chu Guixin 
Published: October 2015

AbstractThe objective was to increase understanding about how P fertilizer form and application strategy affect P mobility and use efficiency in a drip‐irrigated calcareous soil. The study used two P forms (granular or liquid P) and two application methods (single or repeated application). Phosphorus uptake by roots was simulated by using diffusive gradients in thin films (DGT). Six fractions of inorganic P were obtained using the Jiang‐Gu sequential fractionation scheme. Mobility of P was greater when the fertilizer was applied in liquid rather than granular form. Depending on the fertilizer application rate, Olsen P concentrations 13.5–43 mm from the application point were larger by 22–96% in the liquid P treatment than in the granular P treatment. Liquid P increased DGT‐absorbed P by 29% and Ca2‐P by 17% compared with granular P averagely. The P uptake and PUE were averagely larger by 32 and 121%, respectively, in the liquid P treatment than in the granular P treatment. In conclusion, liquid P fertilization reduces P fixation and increases P diffusion, availability, and bioavailability in calcareous soil. Phosphorus mobility is greater when the fertilizer is applied in a single rather than repeated application.
Increased utilization of postmastectomy radiotherapy in the United States from 2003 to 2011 in patients with one to three tumor positive nodes
Authors: Yao Katharine , Liederbach Erik , Lutfi Waseem , Wang Chi‐Hsiung , Hou Ningqi , Karrison Theodore , Huo Dezheng 
Published: October 2015

Background and ObjectivesThere have been few recent studies that have examined the use of postmastectomy radiotherapy (PMRT) for patients with 1–3 positive nodes.MethodsWe utilized the National Cancer Data Base to examine trends in PMRT for 346,218 patients with Stage I–III breast cancer from 2003 to 2011. Neoadjuvant therapy cases were excluded. Log linear models examined trends in PMRT and logistic regressions were used to examine factors related to PMRT.ResultsThe proportion of pT1‐2N1 patients receiving PMRT increased from 23.9% in 2003 to 36.4% in 2011 with an annual percent change (APC) of 6.2% (P < 0.001). There were significant increases in the use of PMRT amongst patients with one (APC = 7.7%), two (APC = 6.7%), and three (APC = 4.2%) positive nodes. In 2011, 27.8%, 43.8%, and 57.8% of patients with one, two or three positive nodes underwent PMRT, respectively. The number of positive nodes and tumor size were the strongest independent predictors of PMRT in the 1–3 node group; lymphovascular invasion, invasive lobular histology, and triple negative phenotypes were also associated with PMRT use.ConclusionPMRT for patients with pT1‐2N1 disease has increased with the greatest increase seen in those with one tumor positive node. Tumor factors remain strong independent predictors of PMRT. J. Surg. Oncol. 2015;112:809–814. © 2015 Wiley Periodicals, Inc.
The Camphorquinone/Amine and Camphorquinone/Amine/Phosphine Oxide Derivative Photoinitiating Systems: Overview, Mechanistic Approach, and Role of the Excitation Light Source
Authors: Morlet‐Savary Fabrice , Klee Joachim E. , Pfefferkorn Frank , Fouassier Jean Pierre , Lalevée Jacques 
Published: October 2015

The camphorquinone (CQ)/amine and CQ/diphenyl (2,4,6‐trimethylbenzoyl)‐phosphine oxide (TPO)/amine photoinitiating systems (PISs) are largely used in the area of dental resins, but the role of the light source in connection with the excited state processes has not been deeply investigated so far. Here, a state‐of‐the‐art analysis on the photochemistry of these PISs is provided. Novel experiments using electron spin resonance spin trapping, cyclic voltammetry, photolysis as well as the recording of film polymerization profiles (by real time Fourier transform infrared (FTIR) measurements) of a trifunctional low molecular weight acrylate and a more viscous bisphenol A‐glycidyl methacrylate/triethyleneglycol dimethacrylate blend under well‐defined irradiation conditions (dental light‐emitting diode (LED) and monochromatic laser diode; this has not been done before) are carried out. Although a noticeable improvement under a polychromatic Xe lamp is clearly obtained in the literature when using CQ/TPO/amine compared to CQ/amine, the polymerization profiles of the representative (meth)acrylate monomers are only slightly better under a dental blue LED irradiation (band spectrum centred at 477 nm) and not affected under a laser diode at 473 nm. This work allows a complete and final description of the overall initiation mechanisms in these PISs.
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Molecular and Thermal Characterization of a Nearly Perfect Isotactic Poly(propylene)
Authors: Tranchida Davide , Mileva Daniela , Resconi Luigi , Rieger Bernhard , Schöbel Alexander 
Published: October 2015

The structure formation upon cooling of the quiescent melt of a nearly defect‐free isotactic poly(propylene) (iPP) homopolymer is investigated in this study. This iPP, having a molecular weight of 1 × 106 g mol−1 and a narrow molecular weight distribution, has been produced with a C2 symmetric hafnocene complex. Information about the crystallization kinetics is collected in a broad range of cooling rates. Standard differential scanning calorimetry is used for cooling rates in the range 3–100 °C min−1 and FSC is employed to analyze the solidification process at cooling rates larger than 100 °C s−1. The near absence of regio‐ and stereo‐defects allows this iPP to crystallize at significantly high temperatures and to form crystals at cooling rates higher than commonly observed for standard Ziegler–Natta iPP. The data reveal that the iPP homopolymer with close‐to‐perfect stereo‐regularity form crystals at high cooling rates as, e.g., α‐nucleated iPP. The defect‐free polymer chain allows the formation of relatively thick lamellar crystals which resulted in a relatively high tensile modulus of 2088 ± 8 MPa.
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The Virtual Element Method for large scale Discrete Fracture Network simulations: fracture‐independent mesh generation
Authors: Berrone Stefano , Benedetto Matìas Fernando , Borio Andrea , Pieraccini Sandra , Scialò Stefano 
Published: October 2015

AbstractWe consider the problem of underground flow simulations in fractured media. This is a large scale, heterogeneous multi‐scale phenomenon involving very complex geological configurations. Within the Discrete Fracture Network (DFN) model, we focus on the resolution of the steady‐state flow in large fracture networks. Exploiting the peculiarity of the Virtual Element Method (VEM), which allows the use of rather general polygonal mesh elements, we propose an approach for building a suitable mesh for representing the solution on DFNs. (© 2015 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Investigation of optimal bipedal walking gaits subject to different energy‐based objective functions
Authors: Römer Ulrich , Fidlin Alexander , Seemann Wolfgang 
Published: October 2015

AbstractOptimal bipedal walking gaits subject to different energy‐based objective functions are investigated using a simple planar rigid body model of a bipedal robot with upper body, thighs and shanks. The robot's segments are connected by revolute joints actuated by electric motors. The actuators' torques are generated by a trajectory tracking controller to produce periodic walking gaits. A numerical optimization routine is used to find optimal reference trajectories for average speeds in the range of 0.3 – 2.3 m/s to investigate the influence of different objective functions. (© 2015 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Theoretical and numerical aspects in the multiphasic modelling of human brain tissue
Authors: Wagner Arndt , Ehlers Wolfgang 
Published: October 2015

AbstractA surgical intervention is often required if the functionality of the sensitive human brain tissue is seriously compromised, e. g., due to the occurrence of malignant brain tumours. A promising method for an effective tumour‐treatment procedure is given by the so‐called convection‐enhanced drug delivery (CED), cf. [1]. In this regard, the aim of this contribution is to simulate the expected effects as well as coupled impacts of a (scheduled) CED‐procedure with the help of numerical computations, which base on a sophisticated multiphasic and multi‐physical modelling strategy applied to human brain tissue. In particular, a quaternary porous‐media model, cf. [3–5], is used for the discussion of selected numerical examples and demonstrates the applicability of the model. In detail, the optimal catheter placement and the application of multiple infusion catheters are studied in terms of the occurring anisotropic therapeutic spreading of the infused drug. (© 2015 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Phase‐Field Modeling of Hydraulic Fracture
Authors: Mauthe Steffen , Miehe Christian 
Published: October 2015

AbstractHydraulically driven fracture has gained more and more research activity in the last few years, especially due to the growing interest of the petroleum industry. Key challenge for a powerful simulation of this scenario is an effective modeling and numerical implementation of the behavior of the solid skeleton and the fluid phase, the mechanical coupling between the two phases as well as the incorporation of the fracture process. Existing models for hydraulic fracturing can be found for example in [1], where the crack path is predetermined, or in [2] who use a phase field fracture model in an elastic framework, however without incorporating the fluid flow. In this work we propose a new compact model structure for the Biot‐type fluid transport in porous media at finite strains based on only two constitutive functions, that is the free energy function ψ and a dissipation potential ϕ that includes the incorporation of an additional Poiseuille‐type fluid flow in cracks. This formulation is coupled to a phase field approach for fracture and is fully variational in nature, as shown in [3]. In contrast to formulations with a sharp‐crack discontinuity, the proposed regularized approach has the main advantage of a straight‐forward modeling of complex crack patterns including branching. (© 2015 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim)