bluuebunny/crossref_metadata_2025_split huggingface dataset:
Transforming a Stable Amide into a Highly Reactive One: Capturing the Essence of Enzymatic Catalysis
Authors: Souza Bruno S. , Mora Jose R. , Wanderlind Eduardo H. , Clementin Rosilene M. , Gesser Jose C. , Fiedler Haidi D. , Nome Faruk , Menger Fredric M. 
Published: April 2017

AbstractAspartic proteinases, which include HIV‐1 proteinase, function with two aspartate carboxy groups at the active site. This relationship has been modeled in a system possessing an otherwise unactivated amide positioned between two carboxy groups. The model amide is cleaved at an enzyme‐like rate that renders the amide nonisolable at 35 °C and pH 4 owing to the joint presence of carboxy and carboxylate groups. A currently advanced theory attributing almost the entire catalytic power of enzymes to electrostatic reorganization is shown to be superfluous when suitable interatomic interactions are present. Our kinetic results are consistent with spatiotemporal concepts where embedding the amide group between two carboxylic moieties in proper geometries, at distances less than the diameter of water, leads to enzyme‐like rate enhancements. Space and time are the essence of enzyme catalysis.
Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac‐Lactide Polymerizations
Authors: Myers Dominic , White Andrew J. P. , Forsyth Craig M. , Bown Mark , Williams Charlotte K. 
Published: April 2017

AbstractPolylactide (PLA) is the leading bioderived polymer produced commercially by the metal‐catalyzed ring‐opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac‐lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m−1 min−1, THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (Pi=0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives.
Cyclische Alkylaminocarbene (CAACs): Neues von guten Bekannten
Authors: Melaimi Mohand , Jazzar Rodolphe , Soleilhavoup Michèle , Bertrand Guy 
Published: April 2017

AbstractEin Kennzeichen der seit 2005 bekannten cyclischen Alkylaminocarbene (CAACs) ist ihre ausgeprägte Nucleophilie (σ‐Donor) und zugleich Elektrophile (π‐Akzeptor). Diese Eigenschaften ermöglichen die Aktivierung einer Vielzahl kleiner Moleküle und starker Bindungen, die Stabilisierung hochreaktiver dia‐ und paramagnetischer Spezies der Haupt‐ und Nebengruppenelemente sowie die Bildung stabiler Bindungen mit Metallen, was zu robusten Katalysatoren führt. Dieser Aufsatz fasst die wichtigsten Ergebnisse vor 2014 kurz zusammen, wobei der Schwerpunkt jedoch auf den Erkenntnissen der vergangenen drei Jahre liegt.
Mixed‐Matrix Membranes
Authors: Dechnik Janina , Gascon Jorge , Doonan Christian J. , Janiak Christoph , Sumby Christopher J. 
Published: April 2017

AbstractResearch into extended porous materials such as metal‐organic frameworks (MOFs) and porous organic frameworks (POFs), as well as the analogous metal‐organic polyhedra (MOPs) and porous organic cages (POCs), has blossomed over the last decade. Given their chemical and structural variability and notable porosity, MOFs have been proposed as adsorbents for industrial gas separations and also as promising filler components for high‐performance mixed‐matrix membranes (MMMs). Research in this area has focused on enhancing the chemical compatibility of the MOF and polymer phases by judiciously functionalizing the organic linkers of the MOF, modifying the MOF surface chemistry, and, more recently, exploring how particle size, morphology, and distribution enhance separation performance. Other filler materials, including POFs, MOPs, and POCs, are also being explored as additives for MMMs and have shown remarkable anti‐aging performance and excellent chemical compatibility with commercially available polymers. This Review briefly outlines the state‐of‐the‐art in MOF‐MMM fabrication, and the more recent use of POFs and molecular additives.
Conjugated Polymer Nanoparticles to Augment Photosynthesis of Chloroplasts
Authors: Wang Yunxia , Li Shengliang , Liu Libing , Lv Fengting , Wang Shu 
Published: April 2017

AbstractBy coating chloroplasts with conjugated polymer nanoparticles (CPNs), a new bio‐optical hybrid photosynthesis system (chloroplast/CPNs) is developed. Since CPNs possess unique light harvesting ability, including the ultraviolet part that chloroplasts absorb less, chloroplast/CPN complexes can capture broader range of light to accelerate the electron transport rates in photosystem II (PS II), the critical protein complex in chloroplasts, and augment photosynthesis beyond natural chloroplasts. The degree of spectral overlay between emission of CPNs and absorption of chloroplasts is critical for the enhanced photosynthesis. This work exhibits good potential to explore new and facile nanoengineering strategy for reforming chloroplast with light‐harvesting nanomaterials to enhance solar energy conversion.
Synthesis of N,N′,X‐tridentate 2‐iminomethylpyrrole‐coordinated palladium(II) complexes via N─H bond activation of pyrrole moiety
Authors: Kim Dongil , Seo Jaeyoung , Nayab Saira , Lee Hyosun 
Published: April 2017

The reaction of [Pd(CH3CN)2Cl2] with N‐functional group‐substituted 2‐iminomethylpyrrole‐based ligands, namely N1‐((1H‐pyrrol‐2‐yl)methylene)‐N3,N3‐dimethylpropane‐1,3‐diamine (LA), N1‐((1H‐pyrrol‐2‐yl)methylene)‐N3‐methyl‐N3‐phenylpropane‐1,3‐diamine (LB), N‐((1H‐pyrrol‐2‐yl)methylene)‐3‐(methylthio)propan‐1‐amine (LC) and N‐((1H‐pyrrol‐2‐yl)methylene)‐3‐methoxypropan‐1‐amine (LD), resulted in [LnPdCl] (Ln = LA–LD) complexes in high yield via N─H bond activation of pyrrole moiety without use of base. [LnPdCl] existed as monomeric four‐coordinated complexes with slightly distorted square planar geometries around the palladium metal center. The ligands show N,N′,X‐tridentate binding mode to the palladium metal center to give two fused ring metallacycles. [LBPdCl] gave the highest activity (3.29 × 105 g PMMA (mol Pd)−1 h−1) for a methyl methacrylate (MMA) polymerization in the presence of modified methylaluminoxane at 60 °C compared to the other Pd(II) analogues, and resulted in PMMA with higher molecular weight (Mw = 7.16 × 105 g mol−1) and narrower polydispersity index. Syndiotactic‐enriched PMMA resulted in all cases.
Study on droplet entrainment in the composite scrubbing–cooling chamber
Authors: Wang Y. , Yan L. , Guo Q. , Wang F. , Yu G. 
Published: April 2017

AbstractA cold model experimental device was established for studying droplet entrainment in the composite scrubbing–cooling chamber. The effect of the superficial gas velocity, the initial liquid flow velocity of the nozzle, and the radial position of nozzles on droplet entrainment was investigated. The experimental results show that the droplet entrainment increases with the increase of the superficial gas velocity and the flow rate of falling film, but its profile is quite mean in the radial direction in the chamber. The droplet entrainment decreases by about 40% when the number of nozzles increases from two to four. Increasing the nozzle number can make the droplet well distributed and reduce droplet entrainment. Based on the experiment data, an empirical correlation for droplet entrainment fraction is also obtained, as E ∝ Re1.92·We0.52. The optimization study for the structure of the scrubbing–cooling chamber can provide some guidance for the industrial application. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Polycarbonate/1‐(2‐hydroxyethyl)‐2,3‐dimethylimidazolium chloride composite membranes and short‐range chain mobility analysis
Authors: Mendonça da Rocha Oliveira Lucas , Vedovello Priscila , Paranhos Caio Marcio 
Published: April 2017

ABSTRACTIn this investigation, the incorporation of imidazolium salt, 1‐(2‐hydroxehtyl)‐2,3‐dimethylimidazolium chloride [hydemmim][Cl] within bisphenol A polycarbonate (PC) matrix and the subsequent formation of membranes via casting were studied. Characterizations that aimed to establish structure‐property correlations by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and water vapor transport (WVT) were performed. The results indicated that the presence of ionic liquid (IL) within the PC matrix significantly alter the local and macromolecular structure. The thermal stability is increased for all levels of incorporation. The plasticizing and antiplasticizing effects were observed due to the influence of the proportions of IL incorporated and of the cation's substituent chain of this IL. Distinct mechanisms of WVT were also observed in the presence of IL. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45117.
Plasticized thermoplastic polyurethanes for dielectric elastomers with improved electromechanical actuation
Authors: Renard Christophe , Wang Dongrui , Yang Yu , Xiong Silai , Shi Chang‐Yong , Dang Zhi‐Min 
Published: April 2017

ABSTRACTIn this article, four different plasticizers are blended in thermoplastic polyurethane (PU) to improve its electromechanical actuation performance. The selected plasticizers include dibutyl phthalate, triphenyl phosphate, polyethylene glycol (PEG), and an unsaturated polyester PMG. The plasticization effect of various plasticizers on the mechanical properties, dielectric properties, and the electromechanical actuation of PU films is carefully characterized and compared. Results demonstrate that the actuated strain under low electric fields and the electromechanical coupling efficiency of PU can be substantially improved by blending with appropriate type and amount of plasticizers. The oligomer‐type plasticizers, PEG and PMG, act more efficiently in the improvement of actuation. An actuated strain in thickness of 1.54%, 140 times higher than that of pure PU, along with an electromechanical coupling efficiency of 0.60 under a low electric field of 5 V/μm was achieved for the PU plasticized with PMG suggesting an attractive approach toward advanced dielectric elastomer actuators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45123.
Influence of model parameter estimation methods and regression algorithms on curing kinetics and rheological modelling
Authors: Abliz Dilmurat , Artys Tatjana , Ziegmann Gerhard 
Published: April 2017

ABSTRACTThe accuracy of the phenomenological curing and rheological models are strongly related to the estimated start parameters and selected regression algorithms. Considering the versatile methods for model start parameter estimation (model‐free vs. model‐fitting, dynamic vs. isothermal) and regression analysis algorithm (linear vs. nonlinear, single‐target vs. multi‐target), this paper investigates the theoretical basis and influence of these aspects on the model development process and model quality. The curing kinetics is modelled by model‐free and model‐fitting start parameters and different regression algorithms, followed by cross model validation at the final. The results showed that the different parameter estimation methods and evaluation algorithms have a remarkable influence on the final model parameters and its quality. The study shows the correlation between the different aspects and provides a basis for better selection of model parameter evaluation methods and regression algorithms for model development with improved quality and accuracy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45137.
Extracellular Assembly of the Elastin Cable Line Element in the Developing Lung
Authors: Valenzuela Cristian D. , Wagner Willi L. , Bennett Robert D. , Ysasi Alexandra B. , Belle Janeil M. , Molter Karin , Straub Beate K. , Wang Dong , Chen Zi , Ackermann Maximilian , Tsuda Akira , Mentzer Steven J. 
Published: April 2017

ABSTRACTIn the normal lung, a dominant structural element is an elastic “line element” that originates in the central bronchi and inserts into the distal airspaces. Despite its structural importance, the process that leads to development of the cable line element is unknown. To investigate the morphologic events contributing to its development, we used optical clearing methods to examine the postnatal rat lung. An unexpected finding was numerous spheres, with a median diameter of 1–2 µm, within the primary septa of the rat lung. The spheres demonstrated green autofluorescence, selective fluorescent eosin staining, reactivity with carboxyfluorescein succinimidyl ester, and specific labeling with anti‐tropoelastin monoclonal antibody—findings consistent with tropoelastin. The sphere number peaked on rat postnatal day 4 (P4) and were rare by P14. The disappearance of the spheres was coincident with the development of the cable line element in the rat lung. Transmission electron microscopy demonstrated no consistent association between parenchymal cells and sphere alignment. In contrast, the alignment of tropoelastin spheres appeared to be the direct result of interactions of scaffold proteins including collagen fibers and fibrillin microfibrils. We conclude that the spatial organization of the cable line element appears to be independent of tropoelastin deposition, but dependent on crosslinking to scaffold proteins within the primary septa. Anat Rec, 300:1670–1679, 2017. © 2017 Wiley Periodicals, Inc.
Mycophenolate Mofetil Versus Placebo for Systemic Sclerosis–Related Interstitial Lung Disease: An Analysis of Scleroderma Lung Studies I and II
Authors: Volkmann Elizabeth R. , Tashkin Donald P. , Li Ning , Roth Michael D. , Khanna Dinesh , Hoffmann‐Vold Anna‐Maria , Kim Grace , Goldin Jonathan , Clements Philip J. , Furst Daniel E. , Elashoff Robert M. 
Published: April 2017

ObjectiveTo compare mycophenolate mofetil (MMF) with placebo for the treatment of systemic sclerosis (SSc)–related interstitial lung disease (ILD).MethodsWe included participants enrolled in the placebo arm of Scleroderma Lung Study (SLS) I and the MMF arm of SLS II. SLS I randomized participants to receive either oral cyclophosphamide (CYC) or placebo for 1 year, while SLS II randomized participants to receive either MMF for 2 years or oral CYC for 1 year followed by 1 year of placebo. Eligibility criteria for SLS I and SLS II were nearly identical. The primary outcome was % predicted forced vital capacity (FVC), and key secondary outcomes included % predicted diffusing capacity for carbon monoxide (DLco), the modified Rodnan skin thickness score (MRSS), and dyspnea. Joint models were created to evaluate the treatment effect on the course of these outcomes over 2 years.ResultsAt baseline, the MMF‐treated group in SLS II (n = 69) and the placebo‐treated group in SLS I (n = 79) had similar percentages of men and women and similar disease duration, SSc subtype, extent of skin disease, and % predicted FVC. MMF‐treated patients in SLS II were slightly older (mean ± SD age 52.6 ± 9.7 years versus 48.1 ± 12.4 years; P = 0.0152) and had higher % predicted DLco (mean ± SD 54.0 ± 11.1 versus 46.2 ± 13.3; P = 0.0002) than placebo‐treated patients in SLS I. After adjustment for baseline disease severity, treatment with MMF in comparison with placebo was associated with improved % predicted FVC (P < 0.0001), % predicted DLco (P < 0.0001), MRSS (P < 0.0001), and dyspnea (P = 0.0112) over 2 years.ConclusionAlthough there are inherent limitations in comparing participants from different trials, treatment with MMF was associated with improvements in physiologic outcomes and dyspnea compared with placebo, even after accounting for baseline disease severity. These results further substantiate the use of MMF for the treatment of SSc‐related ILD.
A Stimuli‐Responsive Metallohydrogel Exhibiting Cyclohexane‐Like Hydrophobicity
Authors: Laishram Raju , Maitra Uday 
Published: April 2017

AbstractSilver(I) forms a hydrogel in the presence of cholate with unusual properties, which are not observed with other cations. Polarity‐sensitive probes have shown that the spherical aggregates observed in the gel have ‘pockets’ with hydrophobicity comparable to that of degassed cyclohexane. The gel exhibited thermo‐ and mechanoresponsive properties. Color tunability from blue to cyan and green was observed with prodan. The two sol phases of the gel formed by applying stress and temperature showed very different properties.
CO2 Fixation with Epoxides under Mild Conditions with a Cooperative Metal Corrole/Quaternary Ammonium Salt Catalyst System
Authors: Tiffner Maximilian , Gonglach Sabrina , Haas Michael , Schöfberger Wolfgang , Waser Mario 
Published: April 2017

AbstractThe cooperative catalytic activity of several metal corrole complexes in combination with tetrabutyl‐ammonium bromide (TBAB) has been investigated for the reaction of epoxides with CO2 leading to cyclic carbonates. It was found that the use of just 0.05 mol % of a manganese(III)corrole with 2 mol % TBAB exhibits excellent catalytic activity under an atmosphere of CO2.
Stability Analysis in a Curved Road Traffic Flow Model Based on Control Theory
Authors: Meng Xiang Pei , Yan Li Ying 
Published: April 2017

AbstractIn the paper, a novel traffic flow model is proposed to describe the behavior of vehicles moving on a curved road with a slope. We investigate the related influences on uniform traffic jam analytically and numerically. Based on control theory, the condition for no traffic jam is obtained analytically. Finally, simulations are carried out to verify the new traffic flow model. The theoretical and numerical results show that the related factors including the friction coefficient, radius of curvature, slope of the curved road and the parameter λ have major effects on the stability of traffic flow respectively.
Der Wärmedurchgang bei Doppelfenstern – Konzept zur In‐situ‐Bewertung historischer Konstruktionen
Authors: Kain Günther , Gschwandtner Florian , Idam Friedrich 
Published: April 2017

AbstractHistorische Kastenfenster stehen noch immer in Verwendung, werden aber seit den 1980er Jahren vermehrt durch sogenannte Thermofenster aus Holz, Metall oder Kunststoff ersetzt. Als Hauptargument für den Fenstertausch wird neben der Haltbarkeit der Oberflächenbeschichtung vor allem der hohe Wärmedurchgang bei Kastenfenstern ins Treffen geführt. Dabei werden aber für diese historischen Fenster nicht Messergebnisse am realen Bestand, sondern normativ festgelegte Default‐Werte herangezogen. Diese Default‐Werte betragen allerdings das Drei‐ bis Vierfache der Laborwerte der industriell gefertigten Thermofenster. Um den tatsächlichen Wärmedurchgang bei Kastenfenstern bestimmen zu können, wurde an der Höheren Technischen Bundeslehranstalt (HTBLA) in Hallstatt/Oberösterreich die Entwicklung eines Messverfahrens in Angriff genommen, das an Ort und Stelle am realen Objekt einsetzbar ist. Die erste Messreihe legt den Schluss nahe, dass der reale Wärmedurchgang bei Kastenfenstern deutlich niedriger liegt, als die Default‐Werte vorgeben.
On the Counterfactual Nature of Gambling Near‐misses: An Experimental Study
Authors: Wu Yin , van Dijk Eric , Li Hong , Aitken Michael , Clark Luke 
Published: April 2017

AbstractResearch on gambling near‐misses has shown that objectively equivalent outcomes can yield divergent emotional and motivational responses. The subjective processing of gambling outcomes is affected substantially by close but non‐obtained outcomes (i.e. counterfactuals). In the current paper, we investigate how different types of near‐misses influence self‐perceived luck and subsequent betting behavior in a wheel‐of‐fortune task. We investigate the counterfactual mechanism of these effects by testing the relationship with a second task measuring regret/relief processing. Across two experiments (Experiment 1, n = 51; Experiment 2, n = 104), we demonstrate that near‐wins (neutral outcomes that are close to a jackpot) decreased self‐perceived luck, whereas near‐losses (neutral outcomes that are close to a major penalty) increased luck ratings. The effects of near‐misses varied by near‐miss position (i.e. whether the spinner stopped just short of, or passed through, the counterfactual outcome), consistent with established distinctions between upward versus downward, and additive versus subtractive, counterfactual thinking. In Experiment 1, individuals who showed stronger counterfactual processing on the regret/relief task were more responsive to near‐wins and near‐losses on the wheel‐of‐fortune task. The effect of near‐miss position was attenuated when the anticipatory phase (i.e. the spin and deceleration) was removed in Experiment 2. Further differences were observed within the objective gains and losses, between “clear” and “narrow” outcomes. Taken together, these results help substantiate the counterfactual mechanism of near‐misses. © 2017 The Authors Journal of Behavioral Decision Making Published by John Wiley & Sons Ltd.
Challenging the knowledge‐transfer orthodoxy: Knowledge co‐construction in technology‐enhanced learning for children with autism
Authors: Guldberg Karen , Parsons Sarah , Porayska‐Pomsta Kaśka , Keay‐Bright Wendy 
Published: April 2017

Experimental intervention studies constitute the current dominant research designs in the autism education field. Such designs are based on a ‘knowledge‐transfer’ model of evidence‐based practice in which research is conducted by researchers, and is then ‘transferred’ to practitioners to enable them to implement evidence‐based interventions. While these research designs contribute important knowledge, they lead to a gap between what the research evidence may prescribe and what happens in practice, with a concomitant disparity between the priorities of researchers and practitioners. This paper discusses findings from the ESRC‐funded ‘SHAPE’ project, which adopted a different model of evidence‐based practice, focusing on knowledge co‐construction. Pupils (N = 8), teachers (N = 10), a speech and language therapist and a parent in three different school communities investigated creative ways in which children's social communication skills could be enhanced through technology use. Through a participatory methodology, digital stories were used as a method to enable engagement with the practical realities of the classroom and empower practitioners to construct and share their own authentic narratives. Participants articulated precise knowledge about the learning opportunities afforded to them and their pupils through quality interactions that were mediated by the technologies, as evidenced through digital stories. The SHAPE project shows that it is feasible to develop methodologies that enable genuine knowledge co‐construction with school practitioners, parents and pupils. Such co‐construction could offer realistic opportunities for pedagogical emancipation and innovation in evidence‐based practice as an alternative to the currently dominant and narrow model of knowledge transfer.