bluuebunny/crossref_metadata_2025_split huggingface dataset:
A life cycle energy use and greenhouse gas emissions analysis of the corn stover feedstock supply system for cellulosic biorefineries
Authors: Shah Ajay , Darr Matt 
Published: April 2017

AbstractCorn stover is the primary feedstock choice for most of the near‐term first‐generation cellulosic biorefineries in the Midwest with rated capacities between 76 and 114 million liters per year (MLPY). These biorefineries will require an annual feedstock supply of around 250–375 metric ton (t) to meet their feedstock demand. However, there is a dearth of studies based on sustainable ways to supply a vast quantity of feedstock to the biorefinery gate, thus this study focuses on stochastically evaluating the life‐cycle energy use and greenhouse gas emissions (GHGE) of the different components of corn stover based feedstock supply system of a 114 MLPY cellulosic biorefinery in the Midwest by using production‐scale experimental field data collected in Iowa. Different components of the supply chain considered includes corn stover harvesting in a large rectangular bale form, field collection, storage, handling and transportation. This study also evaluates the energy use and GHGE of nutrients removed from the field with collected stover. Average energy use, energy‐use ratio (EUR) and GHGE for this feedstock supply system of a Midwest‐based 114 MLPY biorefinery plant are estimated to be 1,502 MJ std. t−1, 21%, and 95.2 kg‐CO2e std. t−1, respectively. Nutrients removed during stover harvest shares 38 to 47% of the overall life‐cycle energy use and GHGE for the supply chain, followed by harvesting (~24–28%) and transportation (~23–27%). Life‐cycle GHGE and energy use are identified to be the most sensitive to the quantity of nitrogen removed, bale density, bale length, harvest rate, baler field efficiency and dry matter loss. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
On Narrow Norms of Rationality and Questionable Data Analyses: A Comment on Jekel and Glöckner
Authors: Rieskamp Jörg 
Published: April 2017

AbstractIn many areas of psychology, it has been argued that people are equipped with a repertoire of strategies to solve the problems they face. Past work has also shown that in situations in which people receive feedback about the correctness of their inferences, substantial learning effects occur, such that simple heuristics that perform well in an environment also do well in describing people's inferences (e.g., Rieskamp, 2006; Rieskamp & Otto, 2006). This work has been challenged by Jekel and Glöcker (2016), who argued that the simple heuristic was compared with a weak competitor. In this work, I reply to this challenge by showing that the competing compensatory strategy is not a weak competitor on either normative or descriptive empirical grounds. I show that the conclusions of past work also hold when including—as suggested—additional compensatory strategies as competing models. The theoretical and empirical analysis demonstrates that the conclusions of Jekel and Glöckner rely on narrow theoretical assumptions and questionable reanalyses of past results. Copyright © 2017 John Wiley & Sons, Ltd.
Safe driving communication: A regulatory focus perspective
Authors: Craciun Georgiana , Shin Dongwoo , Zhang Jason Q. 
Published: April 2017

AbstractThis research article examines the effects of self‐regulation on adolescents' aggressive driving tendencies and their attitudes toward safe driving communication. Two experimental studies demonstrate that an individual's regulatory orientation is a good predictor of aggressive driving tendencies and that self‐regulation plays a moderating role on the effects of safe driving messages on recipients' attitudes. Specifically, the findings reveal that promotion‐oriented (vs. prevention‐oriented) individuals are more likely to demonstrate aggressive driving tendencies. In addition, promotion‐oriented individuals show more favorable attitudes toward gain‐framed safe driving messages than loss‐framed messages. Prevention‐oriented individuals show the opposite pattern. Implications for theory and practice are discussed.
Biochemical Characterization and Analyses of Polysialic‐Acid‐Associated Carrier Proteins and Genes in Piglets during Neonatal Development
Authors: Chen Yue , Ren He , Zhang Nai , Troy Frederic A. , Wang Bing 
Published: April 2017

AbstractPolysialic acid plays a key role in cancer metastasis and neurodevelopment. Our aim was to determine the developmental gene‐expression profiles for the two polysialyltransferases ST8Sia II and ST8Sia IV, neural cell‐adhesion molecules (NCAMs), SynCAM 1, neuropilin‐2 (NRP2) and their polysialylated cognate glycans in different regions of the piglet brain during postnatal development. Our findings show that: 1) the cellular levels of mRNA coding for ST8Sia II and ST8Sia IV, NCAMs, SynCAM 1, NRP2 and polySia are age‐dependent and cell‐type‐specific during neonatal brain development, 2) there was a lack of correlation between abundance level of mRNA coding for ST8Sia II and ST8Sia IV and the abundance level of the post‐translation expression of polySia in all nine brain regions, 3) expression levels of polySia did not correlate with the levels of the carrier proteins NCAM‐140, SynCAM 1 and NRP2 in nine brain regions, and 4) the cellular abundance of ST8Sia II and ST8Sia IV in nine subregions of piglet brain is regulated at the level of translation/post‐translation, and not at the level of transcription. Collectively, our findings suggest that neuronal and glial cells within different regions of the brain have different transcriptional programs that can direct cell division at different rates based on the activity levels of ST8Sia II and ST8Sia IV and the level of their carrier proteins during neurodevelopment.
Synthesis and Reactivity of 2‐Arylquinazoline Halidoruthenacycles in Arylation Reactions
Authors: Kuzman Petra , Požgan Franc , Meden Anton , Svete Jurij , Štefane Bogdan 
Published: April 2017

AbstractThe synthesis of a range of new cyclometallated organoruthenium(II) complexes through the ortho‐C−H activation of the aryl group in 2‐aryl‐substituted quinazolines with [RuX2(p‐cymene)]2 is described. The beneficial effect of the carboxylate ligand on both the cyclometallation and the further arylation reaction step was demonstrated. Mechanistic studies reveal that bromide and iodide anions decelerate the arylation process by an in situ ligand exchange reaction. Additionally, a detailed NMR spectroscopy investigation was performed to explain some elementary steps in the arylation of 2‐(aryl)quinazoline halidoruthenacycles.
Hydrothermal Carbonization of Lignin with Vanillin as a Model Component
Authors: Curtze Jan Henning , Bär Fabian , Steffan Jörg , Dörr Timo , Vogel Herbert 
Published: April 2017

AbstractHydrothermal carbonization (HTC) is one possibility to concentrate energy of wet biomass in so‐called hydrochar. To design technical HTC reactors in a rational way, the reaction kinetics of the four main components of biomass, i.e., carbohydrates, lignin, fats/oils, and proteins, should be known. To determine the kinetics of hydrochar functionalization, initially an appropriate analytical method must be developed. In the presented experiments, the hydrochar obtained by HTC of vanillin is investigated by diffuse reflectance infrared (IR) Fourier transform spectroscopy (DRIFTS). In order to assign the IR bands in the DRIFT spectra to different functional groups, temperature‐programmed desorption (TPD) experiments are conducted, followed by a combination of DRIFTS and TPD. This TPD/DRIFT combination is applied as an analytical method to investigate the kinetics of hydrochar functionalization during HTC.
Fluorescence‐Lifetime Imaging and Super‐Resolution Microscopies Shed Light on the Directed‐ and Self‐Assembly of Functional Porphyrins onto Carbon Nanotubes and Flat Surfaces
Authors: Mao Boyang , Calatayud David G. , Mirabello Vincenzo , Kuganathan Navaratnarajah , Ge Haobo , Jacobs Robert M. J. , Shepherd Ashley M. , Ribeiro Martins José A. , Bernardino De La Serna Jorge , Hodges Benjamin J. , Botchway Stanley W. , Pascu Sofia I. 
Published: April 2017

AbstractFunctional porphyrins have attracted intense attention due to their remarkably high extinction coefficients in the visible region and potential for optical and energy‐related applications. Two new routes to functionalised SWNTs have been established using a bulky ZnII‐porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this zinc(II)‐substituted, bulky aryl porphyrin and those of the corresponding new nano‐composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: i) the supramolecular interactions between the pristine SWNTs and ZnII‐porphyrin by virtue of π–π stacking, and ii) a novel covalent binding strategy based on the Bingel reaction. The functional porphyrins used acted as dispersing agent for the SWNTs and the resulting nanohybrids showed improved dispersibility in common organic solvents. The synthesized hybrid materials were probed by various characterisation techniques, leading to the prediction that supramolecular polymerisation and host–guest functionalities control the fluorescence emission intensity and fluorescence lifetime properties. For the first time, XPS studies highlighted the differences in covalent versus non‐covalent attachments of functional metalloporphyrins to SWNTs. Gas‐phase DFT calculations indicated that the ZnII‐porphyrin interacts non‐covalently with SWNTs to form a donor–acceptor complex. The covalent attachment of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalisation of the SWNTs. This represents a synthetic challenge as well as an opportunity in the design of functional nanohybrids for future sensing and optoelectronic applications.
Soluble Porous Coordination Frameworks Constructed from Inorganic Nanoparticles as Homogenized Heterogeneous Photocatalysts for Suzuki Coupling Reactions under Near‐Infrared Light
Authors: Luo Yuting , Peng Yong , Liu Weisheng , Chen Fengjuan , Wang Baodui 
Published: April 2017

AbstractSelf‐assembly has emerged as a promising method to control the structure and properties of ensembles of inorganic nanoparticles (NPs) for exploiting their collective effects. However, the rational assembly of inorganic NPs into soluble porous architectures for use as homogenized heterogeneous catalysts has been less studied. Herein, it is shown that inorganic NPs can be used for the assembly of soluble porous coordination frameworks (PCFs) by atom‐scale interfacial coordination‐driven assembly. Owing to their large pore size, high dispersity in solution, strong absorption in the near‐infrared (NIR) range, and long‐lived electron–hole pair, the obtained soluble frameworks could serve as a platform for homogenized heterogeneous photocatalysts, which exhibited excellent activity, high apparent quantum efficiency, and recyclability in the catalysis of the noble‐metal‐free Suzuki coupling reactions under NIR light at room temperature. Moreover, PCF catalysts can be reused more than five times without significant loss of activity, which indicates long‐term stability. The present strategy to fabricate soluble porous nanostructures opens a new chemical toolbox for homogenized heterogeneous catalysts and may bring new inspiration to photocatalysis.
Dynamic Iminoboronate‐Based Boroxine Chemistry for the Design of Ambient Humidity‐Sensitive Self‐Healing Polymers
Authors: Delpierre Sébastien , Willocq Bertrand , De Winter Julien , Dubois Philippe , Gerbaux Pascal , Raquez Jean‐Marie 
Published: April 2017

AbstractDeveloping intrinsic self‐healing polymeric materials is of great interest nowadays to extend material lifetime and/or prevent the replacement of damaged pieces. Spontaneously humidity‐sensitive healable polymer network built around dynamic covalent B−O bonds was templated by using iminoboronate‐based boroxine derivatives. Taking advantage of the dynamic boroxine/boronic acid equilibrium and iminoboronate chemistry, it is possible to construct polymeric materials able to self‐heal without requiring any energy‐demanding external activation. Interestingly, this novel family of iminoboronate adduct‐based materials can be readily produced by a relatively simple and straightforward synthesis between boronic acid and diamine‐based compounds, paving the way to coatings that are self‐healable at ambient humidity.
N‐Acetonitrile Functionalized Nitropyrazoles: Precursors to Insensitive Asymmetric N‐Methylene‐C Linked Azoles
Authors: Kumar Dheeraj , Imler Gregory H. , Parrish Damon A. , Shreeve Jean'ne M. 
Published: April 2017

AbstractProperties of energetic compounds obtained by linking energetic pyrazoles to tetrazoles by means of N‐methylene‐C bridges can be fine‐tuned. Reactions of pyrazole derivatives with chloroacetonitrile followed by conversion of the cyano group to tetrazole using click reactions in the presence of zinc chloride result in asymmetric N‐methylene‐C bridged azole‐based energetic compounds. All the compounds were thoroughly characterized by IR and NMR [1H, 13C {1H}, 15N] spectroscopy, elemental analysis, and differential scanning calorimetry (DSC), and for two compounds, further supported by single‐crystal X‐ray diffraction studies. Heats of formation and detonation performances were calculated using Gaussian 03 and EXPLO5 v6.01 programs, respectively. Initial studies show that this new approach is promising for synthesizing less sensitive energetic compounds with fine‐tuned properties.
Thiocarbohydrates on Gold Nanoparticles: Strong Influence of Stereocenters on Binding Affinity and Interparticle Forces
Authors: Fudickar Werner , Pavashe Prashant , Linker Torsten 
Published: April 2017

AbstractCarbohydrates carrying thiol groups at the C‐2 position have been attached to gold nanoparticles (AuNPs) with stereocenters in close proximity to the surface for the first time. Their configurations can be clearly distinguished by the tendency of particle aggregation. AuNP surface plasmon resonance (SPR), X‐ray photoelectron spectroscopy (XPS), and IR spectroscopy indicate that the thiocarbohydrates replace citrate molecules at different rates, causing aggregation and eventually precipitation. A quantitative formulation of this aggregation process shows that reactivities can vary by several magnitudes. Adsorption isotherms and kinetics also demonstrate that the number of thiocarbohydrates varies by a factor of two. Molecular mechanics force field (MMFF) calculations reveal their relative orientations. Based on these models, the different binding behavior can be ascribed to attractive van der Waals forces and hydrogen bonds. Such interactions occur either between the carbohydrate and AuNPs, by lateral intermolecular forces at the surface, or by interparticle attraction, in analogy to cell‐surface carbohydrates of biological recognition systems. Aggregation of NPs therefore act as an indicator to differentiate between various carbohydrates with defined configurations.
Catalytic Mechanism of Salicylate Dioxygenase: QM/MM Simulations Reveal the Origin of Unexpected Regioselectivity of the Ring Cleavage
Authors: Roy Subhendu , Kästner Johannes 
Published: April 2017

AbstractSalicylate 1,2‐dioxygenase (SDO) was the first enzyme discovered, in the family of iron dioxygenases, to catalyze the ring cleavage of a monohydroxylated aromatic compound, salicylate, without a proton donor. Salicylate is not electron‐rich like the familiar dihydroxy or aromatic substrates with an electron‐donating group that are utilized in the well‐known dioxygenases. SDO carries out the intramolecular C−C bond cleavage in salicylate bearing the OH and COOH groups with high regioselectivity in comparison with the extradiol and intradiol dioxygenases. The catalytic cleavage of a nonactivated substrate like salicylate that lacks an electron‐donating group, also in the absence of a proton source, raises many puzzling questions about the oxy intermediates in the reaction pathway of dioxygenase enzymes in general. To answer these fundamental queries, we have investigated the full catalytic mechanism of SDO by a combination of quantum mechanics and molecular mechanics (QM/MM) calculations. Herein, our QM/MM study has several unexpected and interesting implications for the mechanistic pathway of SDO in comparison to the experimental observations. Importantly, it unravels the basis for the unexpected “intra”‐cleavage regioselectivity in SDO. Ostensibly a similar alkylperoxo intermediate is formed in SDO much like in the extradiol and intradiol dioxygenases. In stark contrast to the two diol enzymes, the O−O bond breaking leads to an unprotonated gem‐hydroxy carboxylate intermediate, a paradigm analogue of the elusive gem diol intermediate. This unprotonated gem‐hydroxy carboxylate intermediate exclusively dictates the C−C cleavage regiospecificity in SDO, which is unprecedented in the family of dioxygenases. It forms a seven‐membered lactone species, which eventually forms the ring‐cleavage final product by incorporation of two oxygen atoms in the salicylate. Thus, our computational study unravels a detailed reaction pathway of the oxidative cleavage of salicylate without a proton source by identifying the hitherto elusive intermediates in the catalytic cycle of SDO with testable predictions. Moreover, we describe the atomistic origin of the new catalytic role of Arg127 in the catalysis and regioselectivity of SDO. It also rationalizes the formation of a side product without invoking a dioxetane intermediate. This study is important from a fundamental perspective and opens up a new window in the mechanism of the family of dioxygenase enzymes.
Indium(III)‐catalyzed Aza‐Conia‐Ene Reaction for the Synthesis of Indolizines
Authors: Meazza Marta , Leth Lars A. , Erickson Jeremy D. , Jørgensen Karl Anker 
Published: April 2017

AbstractA new indium(III)‐catalyzed reaction for the synthesis of a series of indolizine scaffolds has been developed. This methodology was highly efficient, allowing a low catalyst loading of 2 mol % (down to 0.5 mol %) and rendering the products in high yields through a 5‐exo‐dig aza‐Conia‐ene reaction. Furthermore, the possibility of incorporating an electrophile into the generated pyrrolidone ring in a one‐pot synergistic fashion was demonstrated. Finally, based on experimental observations, a mechanism proposal was outlined.
High‐throughput cell mechanical phenotyping for label‐free titration assays of cytoskeletal modifications
Authors: Golfier Stefan , Rosendahl Philipp , Mietke Alexander , Herbig Maik , Guck Jochen , Otto Oliver 
Published: April 2017

AbstractThe mechanical fingerprint of cells is inherently linked to the structure of the cytoskeleton and can serve as a label‐free marker for cell homeostasis or pathologic states. How cytoskeletal composition affects the physical response of cells to external loads has been intensively studied with a spectrum of techniques, yet quantitative and statistically powerful investigations in the form of titration assays are hampered by the low throughput of most available methods. In this study, we employ real‐time deformability cytometry (RT‐DC), a novel microfluidic tool to examine the effects of biochemically modified F‐actin and microtubule stability and nuclear chromatin structure on cell deformation in a human leukemia cell line (HL60). The high throughput of our method facilitates extensive titration assays that allow for significance assessment of the observed effects and extraction of half‐maximal concentrations for most of the applied reagents. We quantitatively show that integrity of the F‐actin cortex and microtubule network dominate cell deformation on millisecond timescales probed with RT‐DC. Drug‐induced alterations in the nuclear chromatin structure were not found to consistently affect cell deformation. The sensitivity of the high‐throughput cell mechanical measurements to the cytoskeletal modifications we present in this study opens up new possibilities for label‐free dose‐response assays of cytoskeletal modifications.
Neuronal distribution of tyramine and the tyramine receptor AmTAR1 in the honeybee brain
Authors: Thamm Markus , Scholl Christina , Reim Tina , Grübel Kornelia , Möller Karin , Rössler Wolfgang , Scheiner Ricarda 
Published: April 2017

AbstractTyramine is an important neurotransmitter, neuromodulator, and neurohormone in insects. In honeybees, it is assumed to have functions in modulating sensory responsiveness and controlling motor behavior. Tyramine can bind to two characterized receptors in honeybees, both of which are coupled to intracellular cAMP pathways. How tyramine acts on neuronal, cellular and circuit levels is unclear. We investigated the spatial brain expression of the tyramine receptor AmTAR1 using a specific antibody. This antibody detects a membrane protein of the expected molecular weight in western blot analysis. In honeybee brains, it labels different structures which process sensory information. Labeling along the antennal nerve, in projections of the dorsal lobe and in the gnathal ganglion suggest that tyramine receptors are involved in modulating gustatory and tactile perception. Furthermore, the ellipsoid body of the central complex and giant synapses in the lateral complex show AmTAR1‐like immunoreactivity (AmTAR1‐IR), suggesting a role of this receptor in modulating sky‐compass information and/or higher sensor‐motor control. Additionally, intense signals derive from the mushroom bodies, higher‐order integration centers for olfactory, visual, gustatory and tactile information. To investigate whether AmTAR1‐expressing brain structures are in vicinity to tyramine releasing sites, a specific tyramine antibody was applied. Tyramine‐like labeling was observed in AmTAR1‐IR positive structures, although it was sometimes weak and we did not always find a direct match of ligand and receptor. Moreover, tyramine‐like immunoreactivity was also found in brain regions without AmTAR1‐IR (optic lobes, antennal lobes), indicating that other tyramine‐specific receptors may be expressed there.
Effect of Donor Strength and Bulk on Thieno[3,4‐b]‐pyrazine‐Based Panchromatic Dyes in Dye‐Sensitized Solar Cells
Authors: Liyanage Nalaka P. , Cheema Hammad , Baumann Alexandra R. , Zylstra Alexa R. , Delcamp Jared H. 
Published: April 2017

AbstractNear‐infrared‐absorbing organic dyes are critically needed in dye‐sensitized solar cells (DSCs). Thieno[3,4‐b]pyrazine (TPz) based dyes can access the NIR spectral region and show power conversion efficiencies (PCEs) of up to 8.1 % with sunlight being converted at wavelengths up to 800 nm for 17.6 mA cm−2 of photocurrent in a co‐sensitized DSC device. Precisely controlling dye excited‐state energies is critical for good performances in NIR DSCs. Strategies to control TPz dye energetics with stronger donor groups and TPz substituent choice are evaluated here. Additionally, donor size influence versus dye loading on TPz dyes is analyzed with respect to the TiO2 surface protection designed to prevent recombination of electrons in TiO2 with the redox shuttle. Importantly, the dyes evaluated were demonstrated to work well with low Li+ concentration electrolytes, with iodine and cobalt redox shuttle systems, and efficiently as part of co‐sensitized devices.