bluuebunny/crossref_metadata_2025_split huggingface dataset:
New RuII(arene) Complexes with Halogen‐Substituted Bis‐ and Tris(pyrazol‐1‐yl)borate Ligands
Authors: Orbisaglia Serena , Di Nicola Corrado , Marchetti Fabio , Pettinari Claudio , Pettinari Riccardo , Martins Luísa M. D. R. S. , Alegria Elisabete C. B. A. , Guedes da Silva M. Fátima C. , Rocha Bruno G. M. , Kuznetsov Maxim L. , Pombeiro Armando J. L. , Skelton Brian W. , Sobolev Alexandre N. , White Allan H. 
Published: February 2014

Abstract[RuCl(arene)(μ‐Cl)]2 dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis‐ and tris(pyrazolyl)borate ligands [Na(Bp)], [Tl(Tp)], and [Tl(TpiPr, 4Br)]. Mononuclear neutral complexes [RuCl(arene)(κ2‐Bp)] (1: arene=p‐cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)(κ2‐Tp)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)(κ2‐TpiPr, 4Br)] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru2(hmb)2(μ‐Cl)3][Tp] (5′), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)(κ2‐Bp)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)(κ2‐Bp)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1–12 have been characterized by analytical and spectroscopic data (IR, ESI‐MS, 1H and 13C NMR spectroscopy). The structures of the thallium and calcium derivatives of ligand Tp, [Tl(Tp)] and [Ca(dmso)6][Tp]2⋅2 DMSO, of the complexes 1, 4, 5′, 6, 11, and of the decomposition product [RuCl(cym)(HpziPr, 4Br)2][Cl] (7′) have been confirmed by using single‐crystal X‐ray diffraction. Electrochemical studies showed that 1–9 and 11 undergo a single‐electron RuII→RuIII oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron‐donor characters of the bis‐ and tris(pyrazol‐1‐yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever EL ligand parameter for Bp, Tp, and TpiPr, 4Br. Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal‐centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the μ3‐binuclear complex 5′ (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.
Low‐LUMO Pyrene‐Fused Azaacenes
Authors: More Sandeep , Bhosale Rajesh , Mateo‐Alonso Aurelio 
Published: February 2014

AbstractA series of pyrene‐fused azaacenes with four and six linearly fused rings that possess LUMO levels between −3.7 and −4.3 eV is reported. These LUMO values are remarkably lower than those typically observed for pyrene‐fused azaacenes, even for systems with sixteen linearly fused rings, and are comparable to those observed for state‐of‐the‐art n‐azaacenes.
Thiazolidinones Derived from Dynamic Systemic Resolution of Complex Reversible‐Reaction Networks
Authors: Zhang Yan , Ramström Olof 
Published: February 2014

AbstractA complex dynamic system based on a network of multiple reversible reactions has been established. The network was applied to a dynamic systemic resolution protocol based on kinetically controlled lipase‐catalyzed transformations. This resulted in the formation of cyclized products, where two thiazolidinone compounds were efficiently produced from a range of potential transformations.
A Reevaluation of the Costs of Heart Failure and Its Implications for Allocation of Health Resources in the United States
Authors: Voigt Jeff , John M. Sasha , Taylor Andrew , Krucoff Mitchell , Reynolds Matthew R. , Michael Gibson C. 
Published: February 2014

AbstractThe annual cost of heart failure (HF) is estimated at $39.2 billion. This has been acknowledged to underestimate the true costs for care. The objective of this analysis is to more accurately assess these costs. Publicly available data sources were used. Cost calculations incorporated relevant factors such as Medicare hospital cost‐to‐charge ratios, reimbursement from both government and private insurance, and out‐of‐pocket expenditures. A recently published Atherosclerosis Risk in Communities (ARIC) HF scheme was used to adjust the HF classification scheme. Costs were calculated with HF as the primary diagnosis (HF in isolation, or HFI) or HF as one of the diagnoses/part of a disease milieu (HF syndrome, or HFS). Total direct costs for HF were calculated at $60.2 billion (HFI) and $115.4 billion (HFS). Indirect costs were $10.6 billion for both. Costs attributable to HF may represent a much larger burden to US health care than what is commonly referenced. These revised and increased costs have implications for policy makers.
Species‐specific differences in the medial prefrontal projections to the pons between rat and rabbit
Authors: Moya Maria V. , Siegel Jennifer J. , McCord Eedann D. , Kalmbach Brian E. , Dembrow Nikolai , Johnston Daniel , Chitwood Raymond A. 
Published: February 2014

ABSTRACTThe medial prefrontal cortex (mPFC) of both rats and rabbits has been shown to support trace eyeblink conditioning, presumably by providing an input to the cerebellum via the pons that bridges the temporal gap between conditioning stimuli. The pons of rats and rabbits, however, shows divergence in gross anatomical organization, leaving open the question of whether the topography of prefrontal inputs to the pons is similar in rats and rabbits. To investigate this question, we injected anterograde tracer into the mPFC of rats and rabbits to visualize and map in 3D the distribution of labeled terminals in the pons. Effective mPFC injections showed labeled axons in the ipsilateral descending pyramidal tract in both species. In rats, discrete clusters of densely labeled terminals were observed primarily in the rostromedial pons. Clusters of labeled terminals were also observed contralateral to mPFC injection sites in rats, appearing as a less dense "mirror‐image" of ipsilateral labeling. In rabbits, mPFC labeled corticopontine terminals were absent in the rostral pons, and instead were restricted to the intermediate pons. The densest terminal fields were typically observed in association with the ipsilateral pyramidal tract as it descended ventromedially through the rabbit pons. No contralateral terminal labeling was observed for any injections made in the rabbit mPFC. The results suggest the possibility that mPFC inputs to the pons may be integrated with different sources of cortical inputs between rats and rabbits. The resulting implications for mPFC or pons manipulations for studies of trace eyeblink in each species are discussed. J. Comp. Neurol. 522:3052–3074, 2014. © 2014 Wiley Periodicals, Inc.
A meshless point collocation treatment of transient bioheat problems
Authors: Bourantas G. C. , Loukopoulos V. C. , Burganos V. N. , Nikiforidis G. C. 
Published: February 2014

SUMMARYA meshless numerical method is proposed for the solution of the transient bioheat equation in two and three dimensions. The Pennes bioheat equation is extended in order to incorporate water evaporation, tissue damage, and temperature‐dependent tissue properties during tumor ablation. The conductivity of the tissue is not assumed constant but is treated as a local function to simulate local variability due to the existence of usually unclear interfacing of healthy and pathological segments. In this way, one avoids the need for accurate identification of the boundaries between pathological and healthy regions, which is a typical problem in medical practice, and sidesteps, evidently, the corresponding mathematical treatment of such boundaries, which is usually a tedious procedure with some inevitable degree of approximation. The numerical results of the new method for test applications of the bioheat transfer equation are validated against analytical predictions and predictions of other numerical methods. 3D simulations are presented that involve the modeling of tumor ablation and account for metabolic heat generation, blood perfusion, and heat ablation using realistic values for the various parameters. An evaluation of the effective medium approximation to homogenize conductivity fields for use with the bioheat equation is also provided. Copyright © 2014 John Wiley & Sons, Ltd.
Clusters of Ammonium Cation—Hydrogen Bond versus σ‐Hole Bond
Authors: Grabowski Sławomir J. 
Published: February 2014

AbstractMP2/6‐311++G(d,p) calculations were performed on the NH4+⋅⋅⋅(HCN)nand NH4+⋅⋅⋅(N2)nclusters (n=1–8), and interactions within them were analyzed. It was found that for molecules of N2and HCN, the N centers play the role of the Lewis bases, whereas the ammonium cation acts as the Lewis acid, as it is characterized by sites of positive electrostatic potential, that is, H atoms and the sites located at the N atom in the extension of the HN bonds. Hence, the coordination number for the ammonium cation is eight, and two types of interactions of this cation with the Lewis base centers are possible: NH⋅⋅⋅N hydrogen bonds and HN⋅⋅⋅N interactions that are classified as σ‐hole bonds. Redistribution of the electronic charge resulting from complexation of the ammonium cation was analyzed. On the one hand, the interactions are similar, as they lead to electronic charge transfer from the Lewis base (HCN or N2in this study) to NH4+. On the other hand, the hydrogen bond results in the accumulation of electronic charge on the N atom of the NH4+ion, whereas the σ‐hole bond results in the depletion of the electronic charge on this atom. Quantum theory of “atoms in molecules” and the natural bond orbital method were applied to deepen the understanding of the nature of the interactions analyzed. Density functional theory/natural energy decomposition analysis was used to analyze the interactions of the ammonium ion with various types of Lewis bases. Different correlations between the geometrical, energetic, and topological parameters were found and discussed.
Superior Pseudocapacitive Behavior of Confined Lignin Nanocrystals for Renewable Energy‐Storage Materials
Authors: Kim Sung‐Kon , Kim Yun Ki , Lee Hyunjoo , Lee Sang Bok , Park Ho Seok 
Published: February 2014

AbstractStrong demand for high‐performance energy‐storage devices has currently motivated the development of emerging capacitive materials that can resolve their critical challenge (i.e., low energy density) and that are renewable and inexpensive energy‐storage materials from both environmental and economic viewpoints. Herein, the pseudocapacitive behavior of lignin nanocrystals confined on reduced graphene oxides (RGOs) used for renewable energy‐storage materials is demonstrated. The excellent capacitive characteristics of the renewable hybrid electrodes were achieved by synergizing the fast and reversible redox charge transfer of surface‐confined quinone and the interplay with electron‐conducting RGOs. Accordingly, pseudocapacitors with remarkable rate and cyclic performances (∼96 % retention after 3000 cycles) showed a maximum capacitance of 432 F g−1, which was close to the theoretical capacitance of 482 F g−1 and sixfold higher than that of RGO (93 F g−1). The chemical strategy delineated herein paves the way to develop advanced renewable electrodes for energy‐storage applications and understand the redox chemistry of electroactive biomaterials.
Adaptive latitudinal variation in Common Blackbird Turdus merula nest characteristics
Authors: Mainwaring Mark C. , Deeming D. Charles , Jones Chris I. , Hartley Ian R. 
Published: February 2014

AbstractNest construction is taxonomically widespread, yet our understanding of adaptive intraspecific variation in nest design remains poor. Nest characteristics are expected to vary adaptively in response to predictable variation in spring temperatures over large spatial scales, yet such variation in nest design remains largely overlooked, particularly amongst open‐cup‐nesting birds. Here, we systematically examined the effects of latitudinal variation in spring temperatures and precipitation on the morphology, volume, composition, and insulatory properties of open‐cup‐nesting Common Blackbirds’ Turdus merula nests to test the hypothesis that birds living in cooler environments at more northerly latitudes would build better insulated nests than conspecifics living in warmer environments at more southerly latitudes. As spring temperatures increased with decreasing latitude, the external diameter of nests decreased. However, as nest wall thickness also decreased, there was no variation in the diameter of the internal nest cups. Only the mass of dry grasses within nests decreased with warmer temperatures at lower latitudes. The insulatory properties of nests declined with warmer temperatures at lower latitudes and nests containing greater amounts of dry grasses had higher insulatory properties. The insulatory properties of nests decreased with warmer temperatures at lower latitudes, via changes in morphology (wall thickness) and composition (dry grasses). Meanwhile, spring precipitation did not vary with latitude, and none of the nest characteristics varied with spring precipitation. This suggests that Common Blackbirds nesting at higher latitudes were building nests with thicker walls in order to counteract the cooler temperatures. We have provided evidence that the nest construction behavior of open‐cup‐nesting birds systematically varies in response to large‐scale spatial variation in spring temperatures.
Does seasonality drive spatial patterns in demography? Variation in survival in African reed warblersAcrocephalus baeticatusacross southern Africa does not reflect global patterns
Authors: Jansen Dorine Y.M. , Abadi Fitsum , Harebottle Doug , Altwegg Res 
Published: February 2014

AbstractAmong birds, northern temperate species generally have larger clutches, shorter development periods and lower adult survival than similarly‐sized southern and tropical species. Even though this global pattern is well accepted, the driving mechanism is still not fully understood. The main theories are founded on the differing environmental seasonality of these zones (higher seasonality in the North). These patterns arise in cross‐species comparisons, but we hypothesized that the same patterns should arise among populations within a species if different types of seasonality select for different life histories. Few studies have examined this. We estimated survival of an azonal habitat specialist, the African reed warbler, across the environmentally diverse African subcontinent, and related survival to latitude and to the seasonality of the different environments of their breeding habitats. Data (1998–2010) collected through a public ringing scheme were analyzed with hierarchical capture‐mark‐recapture models to determine resident adult survival and its spatial variance across sixteen vegetation units spread across four biomes. The models were defined as state‐space multi‐state models to account for transience and implemented in a Bayesian framework. We did not find a latitudinal trend in survival or a clear link between seasonality and survival. Spatial variation in survival was substantial across the sixteen sites (spatial standard deviation of the logit mean survival: 0.70, 95% credible interval (CRI): 0.33–1.27). Mean site survival ranged from 0.49 (95% CRI: 0.18–0.80) to 0.83 (95% CRI: 0.62–0.97) with an overall mean of 0.67 (95% CRI: 0.47–0.85). A hierarchical modeling approach enabled us to estimate spatial variation in survival of the African reed warbler across the African subcontinent from sparse data. Although we could not confirm the global pattern of higher survival in less seasonal environments, our findings from a poorly studied region contribute to the study of life‐history strategies.
Endemicity and evolutionary value: a study of Chilean endemic vascular plant genera
Authors: Scherson Rosa A. , Albornoz Abraham A. , Moreira‐Muñoz Andrés S. , Urbina‐Casanova Rafael 
Published: February 2014

AbstractThis study uses phylogeny‐based measures of evolutionary potential (phylogenetic diversity and community structure) to evaluate the evolutionary value of vascular plant genera endemic to Chile. Endemicity is regarded as a very important consideration for conservation purposes. Taxa that are endemic to a single country are valuable conservation targets, as their protection depends upon a single government policy. This is especially relevant in developing countries in which conservation is not always a high resource allocation priority. Phylogeny‐based measures of evolutionary potential such as phylogenetic diversity (PD) have been regarded as meaningful measures of the “value” of taxa and ecosystems, as they are able to account for the attributes that could allow taxa to recover from environmental changes. Chile is an area of remarkable endemism, harboring a flora that shows the highest number of endemic genera in South America. We studied PD and community structure of this flora using a previously available supertree at the genus level, to which we added DNA sequences of 53 genera endemic to Chile. Using discrepancy values and a null model approach, we decoupled PD from taxon richness, in order to compare their geographic distribution over a one‐degree grid. An interesting pattern was observed in which areas to the southwest appear to harbor more PD than expected by their generic richness than those areas to the north of the country. In addition, some southern areas showed more PD than expected by chance, as calculated with the null model approach. Geological history as documented by the study of ancient floras as well as glacial refuges in the coastal range of southern Chile during the quaternary seem to be consistent with the observed pattern, highlighting the importance of this area for conservation purposes.
Electron Transfer from Excited [Ir(2‐phenylpyridyl)3] through a Coexisting Electron Relay in Zeolite
Authors: Xu Chen , Mochizuki Dai , Maitani Masato M. , Wada Yuji 
Published: February 2014

AbstractPhotoinduced electron transfer was investigated between an ortho‐metalated IrIII complex encapsulated in the supercage of faujasite zeolite dispersed in solution and viologen derivatives dissolved in the solution. The electron‐transfer rate across the zeolite solution interface was 310 times slower than that between the free molecules in solution. To facilitate electron transfer, 1,1′‐ethylene‐2,2′‐bipyridyldiylium (diquat = 2DQ2+) was introduced as an electron relay into the zeolite by ion exchange. When triethanolamine (TEOA) was added as a sacrificial electron donor into the dispersion solution, the 2DQ2+ in the supercages was reduced to 2DQ·+ radical cation under light irradiation, which can be explained as the electron transfer from the excited state of the IrIII complex to 2DQ2+, and the regeneration of the complex through the reduction of the resulting oxidized complex by the electron donor TEOA in the solution through the zeolite solution interface. An electron is transferred through the zeolite framework from the 2DQ·+ radical cation formed in the supercage to propyl viologen sulfonate in the solution. This system demonstrates controllability of the electron transfer by solid host materials such as zeolites.
Planar Binuclear Phthalocyanine‐Containing Sandwich‐Type Rare‐Earth Complexes: Synthesis, Spectroscopy, Electrochemistry, and NLO Properties
Authors: Huang Chunhua , Wang Kang , Sun Junshang , Jiang Jianzhuang 
Published: February 2014

AbstractThe mixed cyclic tetramerization of 4,5‐bis(hexylthio)phthalonitrile and bis(diiminoisoindoline) with [M(acac)3]·nH2O (M = Pr, Eu, Lu) as template in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in n‐pentanol at reflux has provided binuclear phthalocyanine‐containing sandwich‐type rare‐earth complexes [{Pc(SC6H13)8}M{BiPc(SC6H13)12}M(SC6H13)8] (M = Pr, Eu, Lu; 1–3). These new binuclear phthalocyanine‐containing sandwich compounds have been characterized by a series of spectroscopic methods including mass spectrometry and 1H NMR, electronic absorption, and IR spectroscopy in addition to elemental analysis. Their electrochemical data have also been obtained by cyclic voltammetry. In addition, the third‐order nonlinear optical properties of [{Pc(SC6H13)8}Pr{BiPc(SC6H13)12}Pr(SC6H13)8] (1) and [Pr{Pc(SC6H13)8}2] in toluene solution were studied comparatively by using the Z‐scan technique; effective imaginary third‐order molecular hyperpolarizabilities of 1.86 × 10–11 and 1.56 × 10–11 esu, respectively, were obtained, which indicates their potential application in the optical‐limiting field.
Copper‐Mediated 1,4‐Diamination of 1,3‐Butadienes
Authors: Martínez Claudio , Martínez Luis , Kirsch Jonathan , Escudero‐Adán Eduardo C. , Martin Eddy , Muñiz Kilian 
Published: February 2014

AbstractA copper(II)‐mediated diamination of 1,3‐butadienes is reported. The reaction employs an inorganic base, copper dibromide as a reagent, and saccharin as the nitrogen source. The diamination proceeds for a series of 1,3‐butadienes under relatively mild conditions with complete selectivity in favor of the 1,4‐oxidation products.
Total Synthesis and Structural Revision of (–)‐Protubonine A and (–)‐Protubonine B
Authors: Lorenzo Paula , Álvarez Rosana , de Lera Ángel R. 
Published: February 2014

AbstractThe proposed structures of (–)‐protubonine A and (–)‐protubonine B, which are pyrrolidinoindoline diketopiperazine alkaloids that were isolated from the marine‐derived fungus Aspergillus sp. SF‐5044, have been synthesized and correspond to diastereomers of the natural isolates. The total syntheses, herein, established the stereostructures of the alkaloids as the C‐11 epimers of the purported structures.
Palladium‐Catalyzed C–H Acylation of Arenes Using Thioethers as Directing Groups
Authors: Xu Bo , Liu Wei , Kuang Chunxiang 
Published: February 2014

AbstractA highly efficient protocol for regioselective synthesis of diaryl ketones by palladium‐catalyzed direct acylation of arenes using thioethers as directing groups is reported. The possible pathway of direct acylation between thioethers and α‐oxocarboxylic acids is discussed.
Supercapacitors Based on Flexible Substrates: An Overview
Authors: Dubal Deepak P. , Kim Jong Guk , Kim Youngmin , Holze Rudolf , Lokhande Chandrakant D. , Kim Won Bae 
Published: February 2014

AbstractRecently our modern society is demanding flexible, low‐cost, and lightweight electrochemical energy storage systems, which are very important in variety of applications ranging from portable consumer electronics to large industrial‐scale power and energy management. Among different energy storage systems, flexible supercapacitors have been considered as one of the most promising candidates due to their significant merits such as high power density along with the unique properties of being flexible, lightweight, shape versatile, and eco‐friendly in comparison to other energy storage systems. In this regard, this review article describes the principles of supercapacitors and the recent research progress on flexible supercapacitor electrodes, for which metal substrates, carbon‐based paper, conventional paper, textiles, sponges, and cables are used as substrates to fabricate high‐performance flexible supercapacitors. Finally, the future challenges and perspectives for the development of flexible supercapacitors based on bendable substrates and their applications are discussed.