bluuebunny/crossref_metadata_2025_split huggingface dataset:
Disila‐Galaxolide and Derivatives: Synthesis and Olfactory Characterization of Silicon‐Containing Derivatives of the Musk Odorant Galaxolide
Authors: Dörrich Steffen , Bauer Jennifer B. , Lorenzen Sabine , Mahler Christoph , Schweeberg Sarah , Burschka Christian , Baus Johannes A. , Tacke Reinhold , Kraft Philip 
Published: July 2013

AbstractA series of silicon‐containing derivatives of the polycyclic musk odorant galaxolide (4 a) was synthesized, that is, disila‐galaxolide ((4RS,7SR)‐4 b/(4RS,7RS)‐4 b), its methylene derivative rac‐9, and its nor analogue rac‐10. The tricyclic title compounds with their 7,8‐dihydro‐6,8‐disila‐6 H‐cyclopenta[g]isochromane skeleton were prepared in multistep syntheses by using a cobalt‐catalyzed [2+2+2] cycloaddition of the mono‐ yne H2CCHCH2OCH2CCB(pin) (B(pin)=4,4,5,5‐tetramethyl‐1,3,2‐di‐ oxaborolan‐2‐yl) with the diynes H2CC[Si(CH3)2CCH]2 or H2C‐ [Si(CH3)2CCH]2 as the key step. Employing [Cr(CO)3(MeCN)3] as an auxiliary, the disila‐galaxolide diastereomers (4RS,7SR)‐4 b and (4RS,7RS)‐4 b could be chromatographically separated through their tricarbonylchromium(0) complexes, followed by oxidative decomplexation. The identity of the title compounds and their precursors was established by elemental analyses and multinuclear NMR spectroscopic studies and in some cases additionally by crystal structure analyses. Compounds (4RS,7SR)‐4 b, (4RS,7RS)‐4 b, rac‐9, and rac‐10 were characterized for their olfactory properties, including GC‐olfactory studies of the racemic compounds on a chiral stationary phase. As for the parent galaxolide stereoisomers 4 a, only one enantiomer of the silicon compounds (4RS,7SR)‐4 b, (4RS,7RS)‐4 b, rac‐9, and rac‐10, smelt upon enantioselective GC‐olfactometry, which according to the elution sequence is assumed to be also (4S)‐configured as in the case of the galaxolide stereoisomers. The disila‐analogues (4S,7R)‐4 b and (4S,7S)‐4 b were, however, about one order of magnitude less intense in terms of their odor threshold than their parent carbon compounds (4S,7R)‐4 a and (4S,7S)‐4 a. The introduction of a 7‐methylene group in disila‐galaxolide (4 b→rac‐9) improved the odor threshold by a factor of two. With the novel silicon‐containing galaxolide derivatives, the presumed hydrophobic bulk binding pocket of the corresponding musk receptor(s) could be characterized in more detail, which could be useful for the design of novel musk odorants with an improved environmental profile.
Formation and Evolution of Chain‐Propagating Species Upon Ethylene Polymerization with Neutral Salicylaldiminato Nickel(II) Catalysts
Authors: Soshnikov Igor E. , Semikolenova Nina V. , Zakharov Vladimir A. , Möller Heiko M. , Ölscher Franz , Osichow Anna , Göttker‐Schnettmann Inigo , Mecking Stefan , Talsi Evgenii P. , Bryliakov Konstantin P. 
Published: July 2013

AbstractFormation of Ni–polymeryl propagating species upon the interaction of three salicylaldiminato nickel(II) complexes of the type [(N,O)Ni(CH3)(Py)] (where (N,O)=salicylaldimine ligands, Py=pyridine) with ethylene (C2H4/Ni=10:30) has been studied by 1H and 13C NMR spectroscopy. Typically, the ethylene/catalyst mixtures in [D8]toluene were stored for short periods of time at +60 °C to generate the [(N,O)Ni(polymeryl)] species, then quickly cooled, and the NMR measurements were conducted at −20 °C. At that temperature, the [(N,O)Ni(polymeryl)] species are stable for days; diffusion 1H NMR measurements provide an estimate of the average length of polymeryl chain (polymeryl=(C2H4)nH, n=6–18). At high ethylene consumptions, the [(N,O)Ni(polymeryl)] intermediates decline, releasing free polymer chains and yielding [(N,O)Ni(Et)(Py)] species, which also further decompose to form the ultimate catalyst degradation product, a paramagnetic [(N,O)2Ni(Py)] complex. In [(N,O)2Ni(Py)], the pyridine ligand is labile (with activation energy for its dissociation of (12.3±0.5) kcal mol−1, ΔH≠298=(11.7±0.5) kcal mol−1, ΔS≠298 =(−7±1) cal K−1 mol−1). Upon the addition of nonpolar solvent (pentane), the pyridine ligand is lost completely to yield the crystals of diamagnetic [(N,O)2Ni] complex. NMR spectroscopic analysis of the polyethylenes formed suggests that the evolution of chain‐propagating species ends up with formation of polyethylene with predominately internal and terminal vinylene groups rather than vinyl groups.
Fluorescent π‐Conjugated Polymer Dots versus Self‐Assembled Small‐Molecule Nanoparticles: What’s the Difference?
Authors: Fischer Irén , Kaeser Adrien , Peters‐Gumbs Mauraline A. M. , Schenning Albertus P. H. J. 
Published: July 2013

AbstractFluorescent nanoparticles based on π‐conjugated small molecules and polymers are two different classes of π‐conjugated systems that have attracted much interest. To date, both emerging classes have only been studied separately and showed no clear differences in their properties. Herein these nanoparticles are compared on the basis of a fluorene co‐polymer and its corresponding small molecule. Both systems formed nanoparticles with the same diameter, whereas the fluorescence properties clearly differed. In case of the polymer the fluorescence diminished, whereas for the small molecules the fluorescence increased. In addition, the capability of encapsulation and release of a hydrophobic dye from the fluorescent nanoparticles was studied. For the polymer system, encapsulation was highly efficient and no release was observed, whereas for the small molecule system encapsulation was less efficient and release of the dye was observed. These studies show a clear difference between small molecules and polymers which has important implications for the design of fluorescent nanoparticles.
Single Crystalline Na0.7MnO2 Nanoplates as Cathode Materials for Sodium‐Ion Batteries with Enhanced Performance
Authors: Su Dawei , Wang Chengyin , Ahn Hyo‐jun , Wang Guoxiu 
Published: July 2013

AbstractSingle crystalline rhombus‐shaped Na0.7MnO2 nanoplates have been synthesized by a hydrothermal method. TEM and HRTEM analyses revealed that the Na0.7MnO2 single crystals predominantly exposed their (100) crystal plane, which is active for Na+‐ion insertion and extraction. When applied as cathode materials for sodium‐ion batteries, Na0.7MnO2 nanoplates exhibited a high reversible capacity of 163 mA h g−1, a satisfactory cyclability, and a high rate performance. The enhanced electrochemical performance could be ascribed to the predominantly exposed active (100) facet, which could facilitate fast Na+‐ion insertion/extraction during the discharge and charge process.
Tetramethyl‐Bis(ethylenedithio)‐Tetrathiafulvalene (TM‐BEDT‐TTF) Revisited: Crystal Structures, Chiroptical Properties, Theoretical Calculations, and a Complete Series of Conducting Radical Cation Salts
Authors: Pop Flavia , Laroussi Steeve , Cauchy Thomas , Gomez‐Garcia Carlos J. , Wallis John D. , Avarvari Narcis 
Published: July 2013

ABSTRACTThe (S,S,S,S) and (R,R,R,R) enantiomers of tetramethyl‐bis(ethylenedithio)‐tetrathiafulvalene (TM‐BEDT‐TTF) show equatorial conformation for the four methyl groups in the solid state, according to the single‐crystal X‐ray analyses. Theoretical calculations at the Density Functional Theory (DFT) and time‐dependent (TD) DFT levels indicate higher gas phase stability for the axial conformer than the equatorial one by 1.25 kcal · mole‐1 and allow the assignment of the UV–vis and circular dichroism transitions. A complete series of radical cation salts of 1:1 stoichiometry with the triiodide anion I3‐ was obtained by electrocrystallization of both enantiopure and racemic forms of the donor. In the packing the donors are organized in dimers that further interact through S · · · S intermolecular contacts and the triiodide anions lie parallel to pairs of oxidized donors. The conductivity of the racemate, which adopts the same, but disordered, structural type, is considerably lower, with much higher activation energy. Chirality 25:466–474, 2013.© 2013 Wiley Periodicals, Inc.
Simulation of Bubble Size Distribution in a Square Cross‐Sectioned Bubble Column: A Study of Modeling the Inlet Condition
Authors: Ryll Marco , Nold Michael 
Published: July 2013

AbstractDie Simulation dreidimensionaler Gas/flüssig‐Strömungen in quadratischen Blasensäulen unter Verwendung des Euler‐Euler‐Verfahrens und des k‐ϵ‐Mixture‐Turbulenzmodells wird untersucht. Die Populationsbilanz basiert auf dem homogenen MUSIG‐Modell und der Zerfall bzw. die Koaleszenz wird nach Luo beschrieben. Das Hauptaugenmerk der Arbeit galt der Modellierung des Gaseinlasses und deren Einfluss auf die Blasengrößenverteilung. Radiale und vertikale Profile des Sauter‐Durchmessers wurden berechnet und mit experimentellen Werten aus der Literatur verglichen.
Clinical Characteristics of Lower‐Extremity Edema in Stage A Cardiovascular Disease Status Defined by the ACC/AHA 2001 Chronic Heart Failure Guidelines
Authors: Kataoka Hajime 
Published: July 2013

AbstractBackgroundChecking for lower‐extremity edema is important for diagnosing, monitoring, and managing heart failure (HF). However, the characteristics of this sign in the early stages of cardiovascular disease (stage A, as defined by the American College of Cardiology/American Heart Association 2001 chronic HF guidelines) have not been adequately explored.HypothesisWe hypothesized that stage A HF patients (at risk for HF) are free from leg edema.MethodsAfter the exclusion of patients with high serum creatinine levels (≥1.2 mg/dL), abnormal electrocardiogram rhythm, and/or comorbid critical disease(s), we studied the prevalence and predictors for leg edema in 274 subjects at risk for heart failure but without structural heart disease or symptoms of HF.ResultsThe overall prevalence of lower‐extremity edema was 33 of 274 patients (12.0%; 95% confidence interval: 8.2%‐15.9%). In most patients (29/33, 88%), the leg edema involved only the ankle and foot. Compared with patients without leg edema (n = 241), those with leg edema (n = 33) were older (age, 74 ± 11 7 vs 69 ± 12 years, P = 0.006), more likely to present with pulmonary crackles (52% vs 31%, P < 0.03), and more likely to have varicose veins (55% vs 15%, P < 0.001). Leg edema and varicose veins coexisted in 19 (58%) patients, of whom 16 patients were women. On multivariate analysis, the presence of varicose veins was the only independent predictor of the appearance of bilateral leg edema (odds ratio: 8.18, 95% confidence interval: 3.92‐17.1, P < 0.001).ConclusionsA mild degree of leg edema is not uncommon in patients at risk for HF. Recognition of this phenomenon might be important for evaluation, monitoring, and self‐care of HF patients.
Neural convergence and divergence in the mammalian cerebral cortex: From experimental neuroanatomy to functional neuroimaging
Authors: Man Kingson , Kaplan Jonas , Damasio Hanna , Damasio Antonio 
Published: July 2013

ABSTRACTA development essential for understanding the neural basis of complex behavior and cognition is the description, during the last quarter of the twentieth century, of detailed patterns of neuronal circuitry in the mammalian cerebral cortex. This effort established that sensory pathways exhibit successive levels of convergence, from the early sensory cortices to sensory‐specific and multisensory association cortices, culminating in maximally integrative regions. It was also established that this convergence is reciprocated by successive levels of divergence, from the maximally integrative areas all the way back to the early sensory cortices. This article first provides a brief historical review of these neuroanatomical findings, which were relevant to the study of brain and mind–behavior relationships and to the proposal of heuristic anatomofunctional frameworks. In a second part, the article reviews new evidence that has accumulated from studies of functional neuroimaging, employing both univariate and multivariate analyses, as well as electrophysiology, in humans and other mammals, that the integration of information across the auditory, visual, and somatosensory–motor modalities proceeds in a content‐rich manner. Behaviorally and cognitively relevant information is extracted from and conserved across the different modalities, both in higher order association cortices and in early sensory cortices. Such stimulus‐specific information is plausibly relayed along the neuroanatomical pathways alluded to above. The evidence reviewed here suggests the need for further in‐depth exploration of the intricate connectivity of the mammalian cerebral cortex in experimental neuroanatomical studies. J. Comp. Neurol. 521:4097–4111, 2013. © 2013 Wiley Periodicals, Inc.
Developmental changes in the spatial organization of neurons in the neocortex of humans and common chimpanzees
Authors: Teffer Kate , Buxhoeveden Daniel P. , Stimpson Cheryl D. , Fobbs Archibald J. , Schapiro Steven J. , Baze Wallace B. , McArthur Mark J. , Hopkins William D. , Hof Patrick R. , Sherwood Chet C. , Semendeferi Katerina 
Published: July 2013

ABSTRACTIn adult humans the prefrontal cortex possesses wider minicolumns and more neuropil space than other cortical regions. These aspects of prefrontal cortex architecture, furthermore, are increased in comparison to chimpanzees and other great apes. In order to determine the developmental appearance of this human cortical specialization, we examined the spatial organization of neurons in four cortical regions (frontal pole [Brodmann's area 10], primary motor [area 4], primary somatosensory [area 3b], and prestriate visual cortex [area 18]) in chimpanzees and humans from birth to approximately the time of adolescence (11 years of age). Horizontal spacing distance (HSD) and gray level ratio (GLR) of layer III neurons were measured in Nissl‐stained sections. In both human and chimpanzee area 10, HSD was significantly higher in the postweaning specimens compared to the preweaning ones. No significant age‐related differences were seen in the other regions in either species. In concert with other recent studies, the current findings suggest that there is a relatively slower maturation of area 10 in both humans and chimpanzees as compared to other cortical regions, and that further refinement of the spatial organization of neurons within this prefrontal area in humans takes place after the postweaning periods included here. J. Comp. Neurol. 521:4249–4259, 2013. © 2013 Wiley Periodicals, Inc.
Effects of Esomeprazole on the Pharmacokinetics of Lapatinib in Breast Cancer Patients
Authors: Koch Kevin M. , Im Young‐Hyuck , Kim Sung‐Bae , Urruticoechea Ribate Ander , Stephenson Joe , Botbyl Jeffrey , Cartee Leanne , Holshouser Jane , Ridgway Derry 
Published: July 2013

AbstractThe aqueous solubility of lapatinib declines significantly at pH >4, suggesting that its bioavailability might be lowered by acid‐reducing drugs. A study was therefore conducted to assess the effects of esomeprazole on lapatinib pharmacokinetics (PK). Women with metastatic human epidermal growth factor receptor 2 positive (HER2+) breast cancer were enrolled. Patients received 1,250 mg lapatinib once daily (QD) in the morning on Days 1–7 (Period 1) and Days 8–14 (Period 2) with 40 mg esomeprazole QD at bedtime 3 hours after dinner on Days 8–14. Lapatinib PK sampling occurred during the 24‐hour steady‐state dosing intervals on Day 7 (lapatinib alone) and Day 14 (lapatinib with esomeprazole). Esomeprazole treatment resulted in decreased lapatinib bioavailability (mean 26%, range 6–49%) that was inversely associated with patient age as a significant covariate.
Force Distribution Analysis of Mechanochemically Reactive Dimethylcyclobutene
Authors: Li Wenjin , Edwards Scott A. , Lu Lanyuan , Kubar Tomas , Patil Sandeep P. , Grubmüller Helmut , Groenhof Gerrit , Gräter Frauke 
Published: July 2013

AbstractInternal molecular forces can guide chemical reactions, yet are not straightforwardly accessible within a quantum mechanical description of the reacting molecules. Here, we present a force‐matching force distribution analysis (FM‐FDA) to analyze internal forces in molecules. We simulated the ring opening of trans‐3,4‐dimethylcyclobutene (tDCB) with on‐the‐fly semiempirical molecular dynamics. The self‐consistent density functional tight binding (SCC‐DFTB) method accurately described the force‐dependent ring‐opening kinetics of tDCB, showing quantitative agreement with both experimental and computational data at higher levels. Mechanical force was applied in two different ways, namely, externally by a constant pulling force and internally by embedding tDCB within a strained macrocycle‐containing stiff stilbene. We analyzed the distribution of tDCB internal forces in the two different cases by FM‐FDA and found that external force gave rise to a symmetric force distribution in the cyclobutene ring, which also scaled linearly with the external force, indicating that the force distribution was uniquely determined by the symmetric architecture of tDCB. In contrast, internal forces due to stiff stilbene resulted in an asymmetric force distribution within tDCB, which indicated a different geometry of force application and supported the important role of linkers in the mechanochemical reactivity of tDCB. In addition, three coordinates were identified through which the distributed forces contributed most to rate acceleration. These coordinates are mostly parallel to the coordinate connecting the two CH3 termini of tDCB. Our results confirm previous observations that the linker outside of the reactive moiety, such as a stretched polymer or a macrocycle, affects its mechanochemical reactivity. We expect FM‐FDA to be of wide use to understand and quantitatively predict mechanochemical reactivity, including the challenging cases of systems within strained macrocycles.
Camphoric Carbon‐Grafted Ni/NiO Nanowire Electrodes for High‐Performance Energy‐Storage Systems
Authors: Paravannoor Anjali , Nair Appukuttan S. , Ranjusha Rajagopal , Praveen Pattathil , Subramanian Kavassery R. V. , Sivakumar Nagarajan , Nair Shantikumar V. , Balakrishnan Avinash 
Published: July 2013

AbstractThe present study provides the first report on the preparation and utilization of camphoric carbon nanobeads grafted onto Ni/NiO nanowires for rechargeable electrodes for energy‐storage applications. These functionally graded nanowires were electrophoretically deposited onto nickel foils and processed into high‐surface‐area electrodes. A detailed study has been performed to elucidate the effect of carbon content, different electrolytes, and their concentrations on these nanowires. BET surface area analysis revealed that these grafted nanowires could exhibit a high surface area of about 106 m2 g−1, compared with pristine nanowires, which exhibited a surface area of about 45 m2 g−1. From the analysis of relevant electrochemical parameters, an intrinsic correlation between the capacitance, internal resistance, and the surface morphology has been deduced. Relative contributions of capacitive and diffusion‐controlled processes underlying these thin‐film electrodes have been mathematically modeled. These thin‐film electrodes exhibited specific mass capacitance values as high as (1950±80) and (1140±60) F g−1, as determined from cyclic voltammetry and charge discharge curves, respectively; these values were 30–50 % higher than that of a pristine nanowire electrode. Furthermore, a working model button cell employing these rechargeable electrodes is also described, which exhibited energy and power densities of 83 and 75 Wh kg−1, respectively. This study shows that electrodes based on such nanowire/carbon nanobead configurations can allow significant room for improvement in energy density, power density, and cyclic stability of supercapacitor/battery systems.
Energy Storage on Ultrahigh Surface Area Activated Carbon Fibers Derived from PMIA
Authors: Castro‐Muñiz Alberto , Suárez‐García Fabián , Martínez‐Alonso Amelia , Tascón Juan M. D. , Kyotani Takashi 
Published: July 2013

AbstractHigh‐performance carbon materials for energy storage applications have been obtained by using poly(m‐phenylene isophthalamide), PMIA, as a precursor through the chemical activation of the carbonized aramid fiber by using KOH. The yield of the process of activation was remarkably high (25–40 wt %), resulting in activated carbon fibers (ACFs) with ultrahigh surface areas, over 3000 m2 g−1, and pore volumes exceeding 1.50 cm3 g−1, keeping intact the fibrous morphology. The porous structure and the surface chemical properties could easily be controlled through the conditions of activation. The PMIA‐derived ACFs were tested in two types of energy storage applications. At −196 °C and 1 bar, H2 uptake values of approximately 3 wt % were obtained, which, in combination with the textural properties, rendered it a good candidate for H2 adsorption at high pressure and temperature. The performance of the ACFs as electrodes for electrochemical supercapacitors was also investigated. Specific capacitance values between 297 and 531 F g−1 at 50 mA g−1 were obtained in aqueous electrolyte (1 M H2SO4), showing different behaviors depending on the surface chemical properties.
Adolescent brain maturation is necessary for adult‐typical mesocorticolimbic responses to a rewarding social cue
Authors: Bell Margaret R. , Meerts Sarah H. , Sisk Cheryl L. 
Published: July 2013

ABSTRACTThe interpretation of social cues must change during adolescence in order to promote appropriate social interactions in adulthood. For example, adult, but not juvenile, male Syrian hamsters find female pheromones contained in vaginal sections (VS) rewarding, and only adult hamsters engage in sexual behavior with a receptive female. We previously demonstrated that the rewarding value of VS is both testosterone‐ and dopamine‐dependent. Additionally, VS induces Fos expression throughout the mesocorticolimbic circuit in adult but not juvenile hamsters. In this study, we determined whether or not treatment of juvenile male hamsters with testosterone is sufficient to promote adult‐like neural responses to VS. Juvenile and adult male hamsters were gonadectomized and given empty or testosterone‐filled subcutaneous capsules for 1 week. Hamsters were then exposed to either clean or VS‐containing mineral oil on their nares, and brains were collected 1 h later for immunohistochemistry to visualize Fos and tyrosine hydroxylase immunoreactive cells. Testosterone treatment failed to promote adult‐typical patterns of Fos expression in juvenile hamsters; indeed, in some brain regions, juveniles exposed to VS expressed less Fos compared to age‐matched controls while, as expected, adults exposed to VS expressed greater Fos compared to age‐matched controls. Age‐related changes in tyrosine hydroxylase expression were also observed. These data indicate that testosterone cannot activate the adult‐typical pattern of Fos expression in response to female social cues in prepubertal males, and that additional neural maturation during adolescence is required for adult‐typical mesocorticolimbic responses to female pheromones. © 2013 Wiley Periodicals, Inc. Develop Neurobiol 73:856–869, 2013
An Object‐Coordinate‐Based Bilateral Control System Using Visual Information
Authors: Nakajima Yu , Nozaki Takahiro , Oyamada Yuji , Ohnishi Kouhei 
Published: July 2013

SUMMARYIn the field of teleoperation, visual or tactile information obtained by the operators is restricted (e.g., limited or delayed sight) because of communication constraints. Therefore, it is difficult for the operators to operate the system. In this paper, a bilateral control system using environmental information about the position and posture of a target as obtained by a camera is proposed. The proposed method reduces the workload of the operators by assuming some of their tasks. An experiment is conducted to demonstrate the benefit of the proposed method using a 1‐DOF master robot and a 2‐DOF slave robot. © 2013 Wiley Periodicals, Inc. Electron Comm Jpn, 96(8): 41–49, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ecj.11464