bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modes of stepwise eastward migration of the northern Tyrrhenian Sea back‐arc extension: Evidences from the northern Latium offshore (Italy)
Authors: Buttinelli M. , Scrocca D. , De Rita D. , Quattrocchi F. 
Published: January 2014

AbstractThe structural architecture of a portion of the eastern side of the Tyrrhenian Sea back‐arc basin has been defined reinterpreting a public data set made up by seismic reflection profiles. A detailed reconstruction of the extensional front migration trough time across the area has been achieved. Migration has been defined by identifying the generation of unconformities in the graben‐like basins developed in the area, as due to the activation and deactivation of normal faults. Such phenomena are part of a tectonic process that also involved blocks rotation, crustal thinning, and stretching. Syn‐rift extension affected the area since the early to middle Miocene (our estimate), principally interesting the north‐westernmost sectors. During late Miocene and throughout the Plio‐Quaternary the extensional front moved stepwise toward the southeastern and eastern sectors. Widespread postrift conditions established over the whole area since the late Pliocene to early Pleistocene. Since the Quaternary, the locus of active extension further migrated toward the present onshore area, where a pronounced volcanic phase developed. In this evolutionary framework the rates of observed migration could be correlated with the acceleration of Calabrian slab rollback since Pliocene. Furthermore, direct evidences of magmatism were not recognized in the offshore. Although the observed crustal thinning, the absence of volcanic bodies in the study area could be related to normal faults which were unable to sufficiently extend the crust, in association with lower crust and mantle processes unable to produce melts.
Defining quality metrics and improving safety and outcome in allergy care
Authors: Lee Stella , Stachler Robert J. , Ferguson Berrylin J. 
Published: January 2014

BackgroundThe delivery of allergy immunotherapy in the otolaryngology office is variable and lacks standardization. Quality metrics encompasses the measurement of factors associated with good patient‐centered care. These factors have yet to be defined in the delivery of allergy immunotherapy. We developed and applied quality metrics to 6 allergy practices affiliated with an academic otolaryngic allergy center.MethodsThis work was conducted at a tertiary academic center providing care to over 1500 patients. We evaluated methods and variability between 6 sites. Tracking of errors and anaphylaxis was initiated across all sites. A nationwide survey of academic and private allergists was used to collect data on current practice and use of quality metrics.ResultsThe most common types of errors recorded were patient identification errors (n = 4), followed by vial mixing errors (n = 3), and dosing errors (n = 2). There were 7 episodes of anaphylaxis of which 2 were secondary to dosing errors for a rate of 0.01% or 1 in every 10,000 injection visits/year. Site visits showed that 86% of key safety measures were followed. Analysis of nationwide survey responses revealed that quality metrics are still not well defined by either medical or otolaryngic allergy practices. Academic practices were statistically more likely to use quality metrics (p = 0.021) and perform systems reviews and audits in comparison to private practices (p = 0.005).ConclusionQuality metrics in allergy delivery can help improve safety and quality care. These metrics need to be further defined by otolaryngic allergists in the changing health care environment.
Supramolekulare Anordnungen mit Charge‐Transfer‐Wechselwirkungen zwischen Donor‐ und Akzeptor‐Chromophoren
Authors: Das Anindita , Ghosh Suhrit 
Published: January 2014

AbstractIn diesem Kurzaufsatz werden supramolekulare Anordnungen diskutiert, bei denen eine (nichtkovalente) Charge‐Transfer(CT)‐Wechselwirkung zwischen einem organischen Donor und Akzeptor genutzt wird, um Strukturen wie fibrilläre Gele, Micellen, Vesikel, Nanoröhren, Foldamere, konformativ eingeschränkte Makromoleküle und flüssigkristalline Phasen zu erzeugen. Nicht zuletzt auch nach dem Vorbild der Natur haben Chemiker die Wasserstoffbrücke als ein Hilfsmittel für die Herstellung von supramolekularen Anordnungen aus einer vielfältigen Auswahl an abiotischen Bausteinen umfassend genutzt. Als Strukturmotiv können CT‐Komplexe hinsichtlich ihrem gerichteten Charakter und ihrer Komplementarität mit Wasserstoffbrücken‐gebundenen Komplexen verglichen werden. Vorteile von CT‐Wechselwirkungen sind eine breite Lösungsmitteltoleranz und ihre einfache spektroskopische Messung. Ein potentieller Nachteil ist jedoch ihre geringe Assoziationskonstante. Um dieses Hindernis zu überwinden, wurden verschiedene Strategien entwickelt, z. B. die Verstärkung von CT‐Wechselwirkungen mit zusätzlichen nichtkovalenten Kräften, ohne dass die Art der Donor‐Akzeptor‐Stapelung beeinträchtigt wird. Ein besonders vielversprechendes Anwendungsfeld von Donor‐Akzeptor‐CT‐Komplexen ist die organische Elektronik.
TMEDA in der Eisen‐katalysierten Kumada‐Kupplung: homoleptische at‐Komplexe statt Diaminaddukte
Authors: Bedford Robin B. , Brenner Peter B. , Carter Emma , Cogswell Paul M. , Haddow Mairi F. , Harvey Jeremy N. , Murphy Damien M. , Nunn Joshua , Woodall Christopher H. 
Published: January 2014

AbstractEisenchloride bilden mit Mesityl‐Grignard‐Reagentien und Tetramethylethylendiamin (TMEDA) unter katalyserelevanten Bedingungen nicht den entsprechenden Diaminkomplex, sondern den homoleptischen at‐Komplex [Fe(mes)3]− (mes=Mesityl), der die katalytische Aktivität gewährleistet. Sowohl [Fe(mes)3]− als auch [Fe(Bn)3]− (Bn=Benzyl) reagieren mit repräsentativen Elektrophilen schneller als die entsprechenden neutralen [FeR2(TMEDA)]‐Komplexe. Mit Benzyl‐ oder kleineren Grignard‐Reagentien werden zudem FeI‐Spezies beobachtet. Die Festkörpermolekülstrukturen von [Fe(Bn)3]− und [Fe(Bn)4]− wurden bestimmt. [Fe(Bn)4]− ist der erste strukturell charakterisierte homoleptische Eisen(III)‐σ‐Organylkomplex.
Proximity‐Enabled Protein Crosslinking through Genetically Encoding Haloalkane Unnatural Amino Acids
Authors: Xiang Zheng , Lacey Vanessa K. , Ren Haiyan , Xu Jing , Burban David J. , Jennings Patricia A. , Wang Lei 
Published: January 2014

AbstractThe selective generation of covalent bonds between and within proteins would provide new avenues for studying protein function and engineering proteins with new properties. New covalent bonds were genetically introduced into proteins by enabling an unnatural amino acid (Uaa) to selectively react with a proximal natural residue. This proximity‐enabled bioreactivity was expanded to a series of haloalkane Uaas. Orthogonal tRNA/synthetase pairs were evolved to incorporate these Uaas, which only form a covalent thioether bond with cysteine when positioned in close proximity. By using the Uaa and cysteine, spontaneous covalent bond formation was demonstrated between an affibody and its substrate Z protein, thereby leading to irreversible binding, and within the affibody to increase its thermostability. This strategy of proximity‐enabled protein crosslinking (PEPC) may be generally expanded to target different natural amino acids, thus providing diversity and flexibility in covalent bond formation for protein research and protein engineering.
Induction of Electromotive Force by an Autonomously Moving Magnetic Bot
Authors: Sailapu Sunil Kumar , Chattopadhyay Arun 
Published: January 2014

AbstractWe report the observation of the induction of electromotive force (emf) into a Faraday coil by an autonomously moving composite magnetic particle in aqueous medium. The particle consisted of a micron‐sized polymer sphere, which was decorated with catalytic Pd nanoparticles (NPs) and attached to a micron‐scale (N‐42 grade) rare‐earth magnet. The Pd NPs catalytically decomposed H2O2 to generate O2, resulting in buoyancy‐driven vertical motion of the particle, while the micromagnet induced emf during the flight. Because a small volume of ethanol was layered on top of the liquid, the bubble burst when the particle ascended to the top and thus nearly continuous vertical motion was achieved. Spikes of alternating electrical signal could be observed up to 20 times per minute. The signal was sufficiently strong to illuminate light‐emitting diodes following appropriate amplification. This distinctive approach is expected to pave the way to developing synthetic bots which are autonomously propelled, generating their own signal for running complex circuitry.
Pd/C als Katalysator für die vollständig regioselektive und milde C‐H‐Funktionalisierung von Thiophenen
Authors: Tang Dan‐Tam D. , Collins Karl D. , Ernst Johannes B. , Glorius Frank 
Published: January 2014

AbstractDie vollständig C3‐selektive Arylierung von Thiophenen und Benzo[b]thiophenen wurde unter Verwendung von Pd/C als Heterogenkatalysator ohne Ligand und Additive unter milden Reaktionsbedingungen erreicht. Die Praktikabilität dieser Transformation beruht auf ihrer bemerkenswerten Toleranz für funktionelle Gruppen und der Unempfindlichkeit gegen H2O und Luft. Die Methode ist ebenso anwendbar auf Benzofuran, 1H‐Indol und 2‐n‐Butylfuran und führt zu den entsprechenden C2‐arylierten Produkten. Drei‐Phasen‐, Hg‐Vergiftungs‐ und Filtrationstests deuten in hohem Maße auf eine heterogene katalytisch aktive Spezies hin.
Divergent Syntheses of Fused β‐Naphthol and Indene Scaffolds by Rhodium‐Catalyzed Direct and Decarbonylative Alkyne–Benzocyclobutenone Couplings
Authors: Chen Peng‐hao , Xu Tao , Dong Guangbin 
Published: January 2014

AbstractA tunable rhodium‐catalyzed intramolecular alkyne insertion reaction proceeding through the CC cleavage of benzocyclobutenones is described. Selective formation of either the direct or decarbonylative insertion product can be controlled by using different catalytic systems. A variety of fused β‐naphthol and indene scaffolds were obtained in good yields with high functional group tolerance. This work illustrates a divergent approach to synthesize fused‐ring systems by CC activation/functionalization.
Ligand Bite Angle‐Dependent Palladium‐Catalyzed Cyclization of Propargylic Carbonates to 2‐Alkynyl Azacycles or Cyclic Dienamides
Authors: Daniels David S. B. , Jones Alison S. , Thompson Amber L. , Paton Robert S. , Anderson Edward A. 
Published: January 2014

AbstractThe regioselectivity of the palladium‐catalyzed cyclization of propargylic carbonates with sulfonamide nucleophiles is critically dependent on the bite angle of the bidentate phosphine ligand. Ligands with small bite angles favor attack on the central carbon atom of an allenylpalladium intermediate to afford cyclic dienamide products, whereas the use of those with large bite angles leads to alkynyl azacycles, with high stereoselectivity. A computational analysis of the reaction pathway is also presented.
Pd/C as a Catalyst for Completely Regioselective CH Functionalization of Thiophenes under Mild Conditions
Authors: Tang Dan‐Tam D. , Collins Karl D. , Ernst Johannes B. , Glorius Frank 
Published: January 2014

AbstractThe completely C3‐selective arylation of thiophenes and benzo[b]thiophenes was achieved by using Pd/C as a heterogeneous catalyst without ligands or additives under mild reaction conditions. The practicability of this transformation is demonstrated by notable functional group tolerance and the insensitivity of the reaction to H2O and air. This method is also applicable to nitrogen‐ and oxygen‐containing heterocycles, yielding the corresponding C2‐arylated products. Three‐phase tests along with Hg‐poisoning and hot‐filtration tests suggest that the catalytically active species is heterogeneous in nature.
Bandgap Engineering through Controlled Oxidation of Polythiophenes
Authors: Wei Sujun , Xia Jianlong , Dell Emma J. , Jiang Yivan , Song Rui , Lee Hyunbok , Rodenbough Philip , Briseno Alejandro L. , Campos Luis M. 
Published: January 2014

AbstractThe use of Rozen’s reagent (HOF⋅CH3CN) to convert polythiophenes to polymers containing thiophene‐1,1‐dioxide (TDO) is described. The oxidation of polythiophenes can be controlled with this potent, yet orthogonal reagent under mild conditions. The oxidation of poly(3‐alkylthiophenes) proceeds at room temperature in a matter of minutes, introducing up to 60 % TDO moieties in the polymer backbone. The resulting polymers have a markedly low‐lying lowest unoccupied molecular orbital (LUMO), consequently exhibiting a small bandgap. This approach demonstrates that modulating the backbone electronic structure of well‐defined polymers, rather than varying the monomers, is an efficient means of tuning the electronic properties of conjugated polymers.
Synergistic Spin Transition between Spin Crossover and Spin‐Peierls‐like Singlet Formation in the Halogen‐Bonded Molecular Hybrid System: [Fe(Iqsal)2][Ni(dmit)2]⋅CH3CN⋅H2O
Authors: Fukuroi Kappei , Takahashi Kazuyuki , Mochida Tomoyuki , Sakurai Takahiro , Ohta Hitoshi , Yamamoto Takashi , Einaga Yasuaki , Mori Hatsumi 
Published: January 2014

AbstractTo introduce halogen‐bond interactions between a cation and an anion, a novel FeIII complex from iodine‐substituted ligands involving a paramagnetic nickel dithiolene anion was prepared and characterized. The compound exhibited the synergy between a spin‐crossover transition and a spin‐Peierls‐like singlet formation. The halogen‐bond interactions between the iodine and the sulfur atoms stabilized the paramagnetic state of π‐spins and played a crucial role in the synergistic magnetic transition between d‐ and π‐spins. In addition, the compound showed the light‐induced excited spin state trapping effect.
Modeling of gas–liquid separation through stacked neural network
Authors: Qazi Nadeem , Yeung Hoi 
Published: January 2014

ABSTRACTIn recent years, few mechanistic models have been proposed for design optimization and predicting the performance of reserve flow cyclonic separators. However, there is not much literature available on design and performance evaluation of axial flow compact separator. The work presented in this paper demonstrates the use of stacked neural network to model the nonlinear process of gas–liquid separation through a novel designed axial flow compact separator (called as I‐SEP in this study). We trained several standard back propagation training algorithms to predict the separation efficiency of the I‐SEP; these base models are then combined to form a single composite model. Principle component regression techniques are used to estimate the weight of the participant trained neural networks in the composite model. It has shown in this work that combination of trained neural networks improves prediction accuracy of gas–liquid separation as compared with that of participant individual neural network models. The stacked neural network model produced satisfactory prediction on unseen experimental data and may be helpful to the operators in effectively controlling the separator by predicting the separation efficiency at the changing operating inlet condition. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Modeling and CFD‐PBE simulation of an airlift bioreactor for PHB production
Authors: Mavaddat Poorya , Mousavi Seyyed Mohammad , Amini Ershad , Azargoshasb Hamidreza , Shojaosadati Seyed Abbas 
Published: January 2014

ABSTRACTIn the present attempt, a 3D simulation using a commercially available computational fluid dynamics package (FLUENT 6.3.26), and a metabolic model were used to investigate hydrodynamics and production of polyhydroxybutyrate (PHB) in an airlift bioreactor, performed by Tavares et al. (L. Z. Tavares, E. S. da Silva, J. G. C. Pradella. Biochem. Eng. J., 2004; 18, 21–31). An Eulerian approach was applied to model the gas–liquid interactions. In order to account for the combined effect of bubble breakup and coalescence in the bioreactor, a population balance model implemented in the software was used. Biosynthesis of PHB in the bioreactor was examined and maximum forward reaction rate values of thiolase, reductase, and synthase steps were determined as V1(thiolase) = 1.8 mM/min, V1(reductase) = 400 mM/min, and V1(synthase) = 380 mM/min to predict the experimental PHB production rate by Tavares et al. suitably. A simplified reaction was considered for PHB production. Moreover, gas holdup, liquid velocity vectors, shear stress, and volumetric oxygen transfer coefficient were investigated. Also, molar concentration profiles of PHB and glucose within the bioreactor were obtained. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Molecular, rheological, and thermal study of long‐chain branched polypropylene obtained by esterification of anhydride grafted polypropylene
Authors: Guapacha Jorge , Failla Marcelo D. , Vallés Enrique M. , Quinzani Lidia M. 
Published: January 2014

ABSTRACTLong‐chain branched polypropylene was prepared using reaction in the molten state in the presence of glycerol and a linear polypropylene functionalized with maleic anhydride (PPg). The concentration of glycerol in the melt was varied in the range from 0.1 to 5 wt % to obtain different levels of branching. FTIR spectroscopy results indicate that the OH groups of glycerol react with the anhydrides on the PPg chains giving place to ester groups. The presence of long‐chain branches in the molecular structure of PPg was confirmed using multiple‐detection size‐exclusion chromatography and rheology. These techniques demonstrate that the level of branching increases with glycerol concentration and that the modification of PPg produces materials with a bimodal distribution of polymer species. Moreover, some of the highly modified materials display gel‐like behavior. The materials also display thermo‐rheological complexity and enhanced activation energy at low frequencies. The crystallization study shows that both the anhydride groups in PPg and the LCBs have opposite nucleating effects. PPg presents the largest activation energy of crystallization and its value decreases with the concentration of glycerol for a given level of crystallization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40357.
Effect of polymer chain scission on photodegradation behavior of polystyrene/multi‐wall carbon nanotube composite
Authors: Hamadate Masato , Sato Ryousaku , Miyazaki Kensuke , Okazaki Noriyasu , Nakatani Hisayuki 
Published: January 2014

ABSTRACTTo clarify an effect of polymer chain scission on a polystyrene (PS)/multi‐wall carbon nanotube (MWNT) composite photodegradation, a relationship between the change of molecular weight and photodegradation behavior was studied. The MWNT loading brought about severe PS chain scission and led to the increase of the low molecular weight (less than 105) fraction. The increase of the fraction was not proportional to the loading amount and showed the minimum at the 2% loading. The strange behavior was due to a rheological effect bringing about a decrease of shear stress in the composite preparation. An unsaturated end group was produced by the chain scission and became the photodegradation initiator leading to auto‐oxidation and crosslink reactions. The MWNT scavenged radical species and worked as an antioxidant. The coexistence of the unsaturated end group and MWNT made the photodegradation behavior complicated. However, the MWNT radical scavenging ability was considerably poor, and the MWNT had little ability to inhibit the photodegradation initiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40362.
Isothermal and non‐isothermal crystallization of poly(L‐lactic acid)/poly(butylene terephthalate) blends
Authors: Di Lorenzo Maria Laura , Rubino Paolo , Cocca Mariacristina 
Published: January 2014

ABSTRACTIsothermal and non‐isothermal crystallization kinetics of poly(l‐lactic acid)/poly(butylene terephthalate) (PLLA/PBT) blends containing PLLA as major component is detailed in this contribution. PLLA and PBT are not miscible, but compatibility of the polymer pair is ensured by interactions between the functional groups of the two polyesters, established upon melt mixing. Crystal polymorphism of the two polyesters is not influenced by blending, as probed by wide‐angle X‐ray analysis. The addition of PLLA does not affect the temperature range of crystallization kinetics of PBT, nor the crystallinity level attained when the blends are cooled from the melt at constant rate. Conversely, PBT favors crystallization of the biodegradable polyester. The addition of PBT results in an anticipated onset of crystallization of PLLA during cooling at a fixed rate, with a sizeable enhancement of the crystal fraction. Isothermal crystallization analysis confirmed the faster crystallization rate of PLLA in the presence of PBT. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40372.
Highly Crystallized Nanometer‐Sized Zeolite A with Large Cs Adsorption Capability for the Decontamination of Water
Authors: Torad Nagy L. , Naito Masanobu , Tatami Junichi , Endo Akira , Leo Sin‐Yen , Ishihara Shinsuke , Wu Kevin C.‐W. , Wakihara Toru , Yamauchi Yusuke 
Published: January 2014

AbstractNanometer‐sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post‐milling recrystallization method. This method is suitable for producing nanometer‐sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer‐sized zeolite A, nanometer‐sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer‐sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future.
An Efficient Probe for Rapid Detection of Cyanide in Water at Parts per Billion Levels and Naked‐Eye Detection of Endogenous Cyanide
Authors: Kumari Namita , Jha Satadru , Bhattacharya Santanu 
Published: January 2014

AbstractA new molecular probe based on an oxidized bis‐indolyl skeleton has been developed for rapid and sensitive visual detection of cyanide ions in water and also for the detection of endogenously bound cyanide. The probe allows the “naked‐eye” detection of cyanide ions in water with a visual color change from red to yellow (Δλmax=80 nm) with the immediate addition of the probe. It shows high selectivity towards the cyanide ion without any interference from other anions. The detection of cyanide by the probe is ratiometric, thus making the detection quantitative. A Michael‐type addition reaction of the probe with the cyanide ion takes place during this chemodosimetric process. In water, the detection limit was found to be at the parts per million level, which improved drastically when a neutral micellar medium was employed, and it showed a parts‐per‐billion‐level detection, which is even 25‐fold lower than the permitted limits of cyanide in water. The probe could also efficiently detect the endogenously bound cyanide in cassava (a staple food) with a clear visual color change without requiring any sample pretreatment and/or any special reaction conditions such as pH or temperature. Thus the probe could serve as a practical naked‐eye probe for “in‐field” experiments without requiring any sophisticated instruments.