bluuebunny/crossref_metadata_2025_split huggingface dataset:
Beyond Skills and Structure: Justice Dispositions as Antecedents of Young Citizens' Volunteering and Political Participation
Authors: Neufeind Max , Jiranek Patrick , Wehner Theo 
Published: October 2013

ABSTRACTCommunity involvement is usually attributed to opportunity structures and individuals' ability to be involved. Building on psychological justice research, this paper proposes that justice dispositions add to explaining why young citizens become active in their communities or not. Furthermore, it is argued that justice dispositions help to understand why most studies find only moderate relationships between youth volunteering and forms of political involvement. In a sample of 321 young Swiss volunteers, this study shows justice centrality and belief in a just world to predict the extent of volunteering and political participation, even after controlling for civic skills and opportunity structures. However, scrutinising the motivations to volunteer, self‐oriented motivations (enhancement, social, career and understanding) more strongly affected the level of volunteering than motivations related to justice dispositions (political responsibility and social responsibility). These findings have implications for the attraction and retention of volunteers as well as for the politics of volunteering and community development in general. Copyright © 2013 John Wiley & Sons, Ltd.
Small‐Molecule Mechanism of Action Studies in Caenorhabditis elegans
Authors: Zlotkowski Katherine , Eliasen Anders M. , Mitra Aurpon , Siegel Dionicio 
Published: October 2013

AbstractA general protocol for exogenous small‐molecule pull‐down experiments with Caenorhabditis elegans is described; it provides a link between small‐molecule screens in worms and existing mutant and RNAi technologies, thereby enabling organismal mechanism of action studies for the natural product clovanemagnolol. Forward chemical genetic screens followed by mechanism of action studies with C. elegans, when coupled with genetic validation of identified targets to reproduce the small molecule's phenotypic effects, provide a unique platform for discovering the biological targets of compounds that affect multicellular processes. First, the use of an immobilized FK506 derivative and soluble competition experiments with optimally prepared soluble C. elegans proteome successfully identified interactions with FK506 binding proteins 1 to 6. This approach was used to determine an unknown mechanism of action for clovanemagnolol, a small molecule that promotes axonal branching in both primary neuronal cultures and in vivo in C. elegans. Following the synthesis of an appropriately functionalized solid‐phase reagent bearing a clovanemagnolol analogue pull‐down experiments employing soluble competition identified kinesin light chain‐1 (KLC‐1), a protein involved in axonal cargo transport, as a putative target. This was corroborated through the use of mutant worms lacking klc‐1 and possessing GFP neuronal labeling, reproducing the axonal branching phenotype induced by the small molecule clovanemagnolol.
Cytoplasmic extension peptide of Pichia pastoris glucose sensor Gss1 is not compulsory for glucose signalling
Authors: Polupanov Andriy S. , Sibirny Andriy A. 
Published: October 2013

AbstractIn the methylotrophic yeast, Pichia pastoris, Gss1 protein is a glucose sensor involved in pexophagy, glucose utilization and glucose catabolite repression. This study identifies that deletion of 150 residues of Gss1 affects slightly glucose catabolite repression and pexophagy, while maintaining signalling function of Gss1. Substitution of one conserved amino acid R180K of Gss1 protein has no visible phenotype, in contrast to corresponding changes in glucose sensors from other yeast species. We suggest that C‐terminal cytoplasmic extension of PpGss1plays different role to that of its homologs in Saccharomyces cerevisiae and Hansenula polymorpha.
Complex cytogenetic rearrangements at the DURS1 locus in syndromic Duane retraction syndrome
Authors: Baris Hagit N. , Chan Wai‐Man , Andrews Caroline , Behar Doron M. , Donovan Diana J. , Morton Cynthia C. , Ranells Judith , Pal Tuya , Ligon Azra H. , Engle Elizabeth C. 
Published: October 2013

Key Clinical MessageA patient with syndromic Duane retraction syndrome harbors a chromosome 811.1q13.2 inversion and 8p11.1‐q12.3 marker chromosome containing subregions with differing mosaicism and allele frequencies. This case highlights the potential requirement for multiple genetic methods to gain insight into genotype–phenotype correlation, and ultimately into molecular mechanisms that underlie human disease.
Prenatal diagnosis of complex rearrangement of chromosome 21: The significance of interphase and metaphase fluorescence in situ hybridization and comparative genomic hybridization
Authors: Namba Akira , Nishiyama Miyuki , Weiser Joseph J , Wyatt Phillip , Kimura Machiko , Niizawa Rei , Miki Akinori , Ishihara Osamu , Itakura Atsuo , Kamei Yoshimasa 
Published: October 2013

Key Clinical MessageMaternal serum screening–positive patient had prenatal diagnosis with amniotic fluid, which showed inconsistent results between interphase fluorescence in situ hybridization (three signals of 21q22.13‐21q22.2) and G‐banding analysis (46,XY). Further analyses proved that the fetus had extremely complex rearrangements of chromosome 21, including the interstitial duplication of Down syndrome critical region.
Confinement of Metal Nanoparticles in Carbon Nanotubes
Authors: Trang Nguyen T. , Serp Philippe 
Published: October 2013

AbstractThe effect of several parameters that include carbon nanotube (CNT) pretreatment and diameter, and the nature of the metal (Co, Ru, Pd), the metal precursor (nitrate, chloride, organometallic complexes), and the solvent on the filling yield of metallic nanoparticles in CNT channels is reported. The obtained results show that it is possible to modulate the filling yield between 10 and 80 % by controlling the CNT opening and playing on the molecular recognition of the inner/outer surfaces by the metal molecular precursor. Interestingly, the best filling yields have been obtained on nitric acid oxidized nanotubes; a treatment often used for the preparation of most CNT‐supported metal catalysts. The confined nanoparticles systematically show a smaller particle size than those supported on the external surface. All the prepared samples were tested for the selective hydrogenation of cinnamaldehyde, and clear correlations were established between the catalytic performances and the filling yields.
Oxidative Additions of Aryl Halides to Palladium Proceed through the Monoligated Complex
Authors: Vikse Krista , Naka Tsuki , McIndoe J. Scott , Besora Maria , Maseras Feliu 
Published: October 2013

AbstractPalladium(0) complexes facilitate many catalytic transformations that begin with the oxidative addition of a halobenzene. The ligation state of the palladium during this reaction is a vexing issue, owing to the inherent difficulty of isolating reactive, coordinatively unsaturated metal complexes. By isolating them in the gas phase in an ion‐trap mass spectrometer, the reactivity of mono‐ and bisligated palladium complexes can be directly compared, and the former proved to be several orders of magnitude more reactive towards halobenzenes. Calculations of barrier heights for the oxidative addition led to additional experiments, which demonstrated that although the reaction proceeded to completion for iodobenzene, the reaction was slower for bromobenzene and progressed only as far as an ion–molecule adduct for chloro‐ and fluorobenzene.
Difference spectra for the reduction of the feasible bands of response profiles of multivariate curve resolution: comparison of the feasible bands of difference spectra and ordinary data
Authors: Bahram Morteza , Beth‐Moushoul Elsie 
Published: October 2013

In multivariate curve resolution (MCR) methods, a bilinear decomposition of the experimental data matrix (D) is performed to estimate, for example, the concentration profiles (C) and the spectra (S) using the model equation, D = CST + E, where E is the error or noise matrix. The main limitation of all soft‐modeling methods is the fact that there is often no unique solution and sometimes a range of feasible solutions that fit the data equally well (while fulfilling the applied constraint) is obtained. This fact is known as rotational ambiguity. In the present work, the effect of differencing the spectra as a preprocessing method on the feasible bands of response profiles of the MCR results is investigated. The feasible band of several simulated ordinary and difference data sets of pH titration of a diprotic acid as a three‐component system was analyzed and compared. Also, a real experimental data were studied by the proposed method. The results showed that by using this pretreatment strategy, the feasible bands of MCR results are reduced.Actually, the reason is the fact of reducing the number of compounds in one and, hence, reducing the compounds overlapping. For analyzing the data with high degree of overlapping, this effect is very obvious. Copyright © 2013 John Wiley & Sons, Ltd.
Theoretical Modelling of Photoswitching of Hyperpolarisabilities in Ruthenium Complexes
Authors: Coe Benjamin J. , Avramopoulos Aggelos , Papadopoulos Manthos G. , Pierloot Kristine , Vancoillie Steven , Reis Heribert 
Published: October 2013

AbstractStatic excited‐state polarisabilities and hyperpolarisabilities of three RuII ammine complexes are computed at the density functional theory (DFT) and several correlated ab initio levels. Most accurate modelling of the low energy electronic absorption spectrum is obtained with the hybrid functionals B3LYP, B3P86 or M06 for the complex [RuII(NH3)5(MeQ+)]3+ (MeQ+=N‐methyl‐4,4′‐bipyridinium, 3) in acetonitrile. The match with experimental data is less good for [RuII(NH3)5L]3+ (L=N‐methylpyrazinium, 2; N‐methyl‐4‐{E,E‐4‐(4‐pyridyl)buta‐1,3‐dienyl}pyridinium, 4). These calculations confirm that the first dipole‐ allowed excited state (FDAES) has metal‐to‐ligand charge‐transfer (MLCT) character. Both the solution and gas‐phase results obtained for 3 by using B3LYP, B3P86 or M06 are very similar to those from restricted active‐space SCF second‐order perturbation theory (RASPT2) with a very large basis set and large active space. However, the time‐dependent DFT λmax predictions from the long‐range corrected functionals CAM‐B3LYP, LC‐ωPBE and wB97XB and also the fully ab initio resolution of identity approximate coupled‐cluster method (gas‐phase only) are less accurate for all three complexes. The ground state (GS) two‐state approximation first hyperpolarisability β2SA for 3 from RASPT2 is very close to that derived experimentally via hyper‐Rayleigh scattering, whereas the corresponding DFT‐based values are considerably larger. The β responses calculated by using B3LYP, B3P86 or M06 increase markedly as the π‐conjugation extends on moving along the series 2→4, for both the GS and FDAES species. All three functionals predict substantial FDAES β enhancements for each complex, increasing with the π‐conjugation, up to about sevenfold for 4. Also, the computed second hyperpolarisabilities γ generally increase in the FDAES, but the results vary between the different functionals.
Group Additive Values for the Gas‐Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
Authors: Paraskevas Paschalis D. , Sabbe Maarten K. , Reyniers Marie‐Françoise , Papayannakos Nikos , Marin Guy B. 
Published: October 2013

AbstractA complete and consistent set of 60 Benson group additive values (GAVs) for oxygenate molecules and 97 GAVs for oxygenate radicals is provided, which allow to describe their standard enthalpies of formation, entropies and heat capacities. Approximately half of the GAVs for oxygenate molecules and the majority of the GAVs for oxygenate radicals have not been reported before. The values are derived from an extensive and accurate database of thermochemical data obtained by ab initio calculations at the CBS‐QB3 level of theory for 202 molecules and 248 radicals. These compounds include saturated and unsaturated, α‐ and β‐branched, mono‐ and bifunctional oxygenates. Internal rotations were accounted for by using one‐dimensional hindered rotor corrections. The accuracy of the database was further improved by adding bond additive corrections to the CBS‐QB3 standard enthalpies of formation. Furthermore, 14 corrections for non‐nearest‐neighbor interactions (NNI) were introduced for molecules and 12 for radicals. The validity of the constructed group additive model was established by comparing the predicted values with both ab initio calculated values and experimental data for oxygenates and oxygenate radicals. The group additive method predicts standard enthalpies of formation, entropies, and heat capacities with chemical accuracy, respectively, within 4 kJ mol−1 and 4 J mol−1 K−1 for both ab initio calculated and experimental values. As an alternative, the hydrogen bond increment (HBI) method developed by Lay et al. (T. H. Lay, J. W. Bozzelli, A. M. Dean, E. R. Ritter, J. Phys. Chem.­ 1995, 99, 14514) was used to introduce 77 new HBI structures and to calculate their thermodynamic parameters (ΔfH°, S°, Cp°). The GAVs reported in this work can be reliably used for the prediction of thermochemical data for large oxygenate compounds, combining rapid prediction with wide‐ranging application.
Porphyrins Fused to N‐Heterocyclic Carbenes (NHCs): Modulation of the Electronic and Catalytic Properties of NHCs by the Central Metal of the Porphyrin
Authors: Lefebvre Jean‐François , Lo Mamadou , Gisselbrecht Jean‐Paul , Coulembier Olivier , Clément Sébastien , Richeter Sébastien 
Published: October 2013

AbstractWe report herein a detailed study of the use of porphyrins fused to imidazolium salts as precursors of N‐heterocyclic carbene ligands 1 M. Rhodium(I) complexes 6 M–9 M were prepared by using 1 M ligands with different metal cations in the inner core of the porphyrin (M=NiII, ZnII, MnIII, AlIII, 2H). The electronic properties of the corresponding N‐heterocyclic carbene ligands were investigated by monitoring the spectroscopic changes occurring in the cod and CO ancillary ligands of [(1 M)Rh(cod)Cl] and [(1 M)Rh(CO)2Cl] complexes (cod=1,5‐cyclooctadiene). Porphyrin–NHC ligands 1 M with a trivalent metal cation such as MnIII and AlIII are overall poorer electron donors than porphyrin–NHC ligands with no metal cation or incorporating a divalent metal cation such as NiII and ZnII. Imidazolium salts 3 M (M=Ni, Zn, Mn, 2H) have also been used as NHC precursors to catalyze the ring‐opening polymerization of L‐lactide. The results clearly show that the inner metal of the porphyrin has an important effect on the reactivity of the outer carbene.
Visualizing Lithium‐Ion Migration Pathways in Battery Materials
Authors: Filsø Mette Ø. , Turner Michael J. , Gibbs Gerald V. , Adams Stefan , Spackman Mark A. , Iversen Bo B. 
Published: October 2013

AbstractThe understanding of lithium‐ion migration through the bulk crystal structure is crucial in the search for novel battery materials with improved properties for lithium‐ion conduction. In this paper, procrystal calculations are introduced as a fast, intuitive way of mapping possible migration pathways, and the method is applied to a broad range of lithium‐containing materials, including the well‐known battery cathode materials LiCoO2, LiMn2O4, and LiFePO4. The outcome is compared with both experimental and theoretical studies, as well as the bond valence site energy approach, and the results show that the method is not only a strong, qualitative visualization tool, but also provides a quantitative measure of electron‐density thresholds for migration, which are correlated with theoretically obtained activation energies. In the future, the method may be used to guide experimental and theoretical research towards materials with potentially high ionic conductivity, reducing the time spent investigating nonpromising materials with advanced theoretical methods.
Thermal Cyclization of Phenylallenes That Contain ortho‐1,3‐Dioxolan‐2‐yl Groups: New Cascade Reactions Initiated by 1,5‐Hydride Shifts of Acetalic H Atoms
Authors: Alajarin Mateo , Bonillo Baltasar , Marin‐Luna Marta , Sanchez‐Andrada Pilar , Vidal Angel 
Published: October 2013

AbstractA series of 2‐(1,3‐dioxolan‐2‐yl)phenylallenes that contained a range of substituents (alkyl, aryl, phosphinyl, alkoxycarbonyl, sulfonyl) at the cumulenic C3 position were prepared by using a diverse range of synthetic strategies and converted into their respective 1‐(2‐hydroxy)‐ethoxy‐2‐substituted naphthalenes by smooth thermal activation in toluene solution. Electron‐withdrawing groups at the C3 position accelerated these tandem processes, which consisted of 1) an initial hydride‐like [1,5]‐H shift of the acetalic H atom onto the central cumulene carbon atom; 2) a subsequent 6π‐electrocyclic ring‐closure of the resulting reactive ortho‐xylylenes; and 3) a final aromatization step with concomitant ring‐opening of the 1,3‐dioxolane fragment. If the 1,3‐dioxolane ring of the starting allenes was replaced by a dimethoxymethyl group, the reactions led to mixtures of two disubstituted naphthalenes, which were formed by the migration of either the acetalic H atom or the methoxy group, with the latter migration occurring to a lesser extent. Two of the final 1,2‐disubstituted naphthalenes were converted into their corresponding naphtho‐fused dioxaphosphepine or dioxepinone through an intramolecular transesterification reaction. A DFT computational study accounted for the beneficial influence of the 1,3‐dioxolane fragment on the carbon atom from which the H‐shift took place and also of the electron‐withdrawing substituents on the allene terminus. Remarkably, in the processes that contained a sulfonyl substituent, the conrotatory 6π‐electrocyclization step was of lower activation energy than the alternative disrotatory mode.
Antifreeze Protein‐Induced Selective Crystallization of a New Thermodynamically and Kinetically Less Preferred Molecular Crystal
Authors: Wang Sen , Wen Xin , Golen James A. , Arifin Josh F. , Rheingold Arnold L. 
Published: October 2013

AbstractThe formation of a new, dihydrate crystalline form of 5‐methyluridine (m5U) was selectively induced by a protein additive, antifreeze protein (AFP) in a highly efficient manner (in 10−6 molar scale, whereas known kinetic additives need 0.1 molar scale). The hemihydrate form (form I, the only previously known crystalline form of m5U) and the dihydrate form of m5U (form II) obtained herein were characterized using X‐ray crystallography and differential scanning calorimetry (DSC). Compared to form I, remarkably, form II is thermodynamically and kinetically less preferred. The presence of AFP can selectively inhibit the appearance of form I and hence allows the growth of form II, the pure form of which cannot grow directly from m5U supersaturated solutions under the same conditions. An explanation supported by both experimental and theoretical results is provided for the AFP‐induced selection process. Implications on AFP‐induced ice shape changes are also discussed. Control of crystallization from supersaturated solutions is of great interest in both fundamental research and practical applications in fields like chemistry, pharmacology and materials science. These findings suggest that crystallization processes with AFPs could be valuable for selective growth of hydrates and polymorphs of important pharmaceutical compounds.
Grignard Reagent/CuI/LiCl‐Mediated Stereoselective Cascade Addition/Cyclization of Diynes: A Novel Pathway for the Construction of 1‐Methyleneindene Derivatives
Authors: Li De‐Yao , Wei Yin , Shi Min 
Published: October 2013

AbstractDiynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1‐methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments.
Modular Total Synthesis of Rhizopodin: A Highly Potent G‐Actin Dimerizing Macrolide
Authors: Kretschmer Manuel , Dieckmann Michael , Li Pengfei , Rudolph Sven , Herkommer Daniel , Troendlin Johannes , Menche Dirk 
Published: October 2013

AbstractA highly convergent total synthesis of the potent polyketide macrolide rhizopodin has been achieved in 29 steps by employing a concise strategy that exploits the molecule′s C2 symmetry. Notable features of this convergent approach include a rapid assembly of the macrocycle through a site‐directed sequential cross‐coupling strategy and the bidirectional attachment of the side chains by means of Horner–Wadsworth–Emmons (HWE) coupling reactions. During the course of this endeavor, scalable routes for synthesis of three main building blocks of similar complexity were developed that allowed for their stereocontrolled construction. This modular route will be amenable to the development of syntheses of other analogues of rhizopodin.
Organogelation‐Controlled Topochemical [2+2] Cycloaddition and Morphological Changes: From Nanofiber to Peculiar Coaxial Hollow Toruloid‐Like Nanostructures
Authors: Wang Xiufeng , Duan Pengfei , Liu Minghua 
Published: October 2013

AbstractNovel amphiphilic molecules composed of naphthylacryl and L‐glutamide moieties (1‐NA and 2‐NA) have been designed and their organogel formation in various organic solvents as well as their self‐assembled nanostructures have been investigated. Both compounds formed organogels in many organic solvents, ranging from nonpolar to polar, and self‐assembled into essentially nanofiber structures, although some twist or belt structures could be observed in certain solvents. A gel of compound 2‐NA in ethanol initially self‐assembled into nanofibers and then these were transformed into a family of coaxial hollow toruloid‐like (CHTL) nanostructures under irradiation, in which various toroids and disks of different sizes were stacked coaxially. We have established that a topochemical [2+2] cycloaddition in the organogel triggers this transformation. When the gel was fabricated into xerogels in which no ethanol remained, such morphological changes could not happen. This might be the first report of an organogel, in which both organized nanofibers and solvent coexist, controlling a topochemical reaction as well as the self‐assembled nanostructures formed. Due to the formation of the toruloid‐like nanostructures, the gel collapsed to a precipitate. However, upon heating this precipitate with ethanol, it redissolved and then formed a gel and self‐assembled into nanofibers once more. Thus, a reversible morphological transformation between nanofibers and an unprecedented series of toruloid‐like nanostructures can be induced by alternately heating and irradiating the gel.
Pestalotiopens A and B: Stereochemically Challenging Flexible Sesquiterpene‐Cyclopaldic Acid Hybrids from Pestalotiopsis sp.
Authors: Hemberger Yasmin , Xu Jing , Wray Victor , Proksch Peter , Wu Jun , Bringmann Gerhard 
Published: October 2013

AbstractFrom the endophytic fungus Pestalotiopsis sp. isolated from the leaves of the Chinese mangrove, Rhizophora mucronata, two novel hybrid sesquiterpene‐cyclopaldic acid metabolites with an unusual carbon skeleton, named pestalotiopens A and B, were obtained, together with the already known phytotoxin altiloxin B. Pestalotiopen B even contains a third, triketide‐derived module. The constitutions and the absolute configurations of the new metabolites and of altiloxin B were unambiguously determined by a combination of spectroscopic methods and quantum‐chemical optical‐rotatory dispersion (ORD) and circular dichroism (CD) calculations. A biosynthetic pathway to pestalotiopens A and B is proposed with altiloxin B as one of the suggested precursors. Pestalotiopen A shows moderate antimicrobial activity against Enterococcus faecalis.