bluuebunny/crossref_metadata_2025_split huggingface dataset:
ImprovedBayesian multimodeling: Integration of copulas andBayesian model averaging
Authors: Madadgar Shahrbanou , Moradkhani Hamid 
Published: November 2014

AbstractBayesian model averaging (BMA) is a popular approach to combine hydrologic forecasts from individual models and characterize the uncertainty induced by model structure. In the original form of BMA, the conditional probability density function (PDF) of each model is assumed to be a particular probability distribution (e.g., Gaussian, gamma, etc.). If the predictions of any hydrologic model do not follow certain distribution, a data transformation procedure is required prior to model averaging. Moreover, it is strongly recommended to apply BMA on unbiased forecasts, whereas it is sometimes difficult to effectively remove bias from the predictions of complex hydrologic models. To overcome these limitations, we develop an approach to integrate a group of multivariate functions, the so‐called copula functions, into BMA. Here we introduce a copula‐embedded BMA (Cop‐BMA) method that relaxes any assumption on the shape of conditional PDFs. Copula functions have a flexible structure and do not restrict the shape of posterior distributions. Furthermore, copulas are effective tools in removing bias from hydrologic forecasts. To compare the performance of BMA with Cop‐BMA, they are applied to hydrologic forecasts from different rainfall‐runoff and land‐surface models. We consider the streamflow observation and simulations for 10 river basins provided by the Model Parameter Estimation Experiment (MOPEX) project. Results demonstrate that the predictive distributions are more accurate and reliable, less biased, and more confident with small uncertainty after Cop‐BMA application. It is also shown that the postprocessed forecasts have better correlation with observation after Cop‐BMA application.
Development and Evaluations of Aceclofenac Microcapsules for Colon‐Targeted Delivery: An In Vitro Study
Authors: Farooq Muhammad , Ahmad Mahmood , Madni Asadullah , Hanif Muhammad , Khan Muhammad Rizwan 
Published: November 2014

ABSTRACTMicrocapsules of aceclofenac with pH‐dependent release properties for achieving targeted delivery to colon were developed. A solvent evaporation technique was adopted for microcapsules preparation using Eudragit RS 100 as a retardant polymer. The microcapsules were found free flowing, whitish, and spherical in shape. The entrapment efficacies of microcapsules were 95.73, 85.67, and 84% for F1 (1:1), F2 (1:2), and F3 (1:3), respectively. The particle size was in the range of 12 ± 2.48 to 32 ± 2.20 μm. The X‐ray diffraction and Fourier transforms infrared (FTIR) studies of prepared microcapsules illustrated that there was no interaction between drug and polymer. The dissolution performed in three different pH media (1.2, 6.8, and 7.4) at 37 ± 0.5°C elucidates negligible release at pH 1.2 for 2 h but changing the pH from 1.2 to 6.8, showed burst release after 4 h and then demonstrated a constant release rate at 7.4 pH. The time for half‐life of microcapsules showed that drug release from F1 microcapsules was quicker than F2 and F3. The time for half‐life of capsule filled microcapsules was 15.54, 17.40, and 20.08 h, respectively. The formulated microcapsules do not show the release in gastric medium but released at phosphate buffer pH 6.8 and 7.4.
Origins of marronage: Mitochondrial lineages ofJamaica'sAccompongTownMaroons
Authors: Madrilejo Nicole , Lombard Holden , Torres Jada Benn 
Published: November 2014

ObjectivesThe Accompong Town Maroons are descendants of enslaved Africans who successfully waged war against British colonial rule and established an independent community in western Jamaica. There are discrepancies regarding Accompong Town Maroon ancestry with some scholars noting ancestry from both Africans and Taínos, Jamaica's indigenous population, while other scholars only acknowledge African ancestry. We considered the mitochondrial lineages of contemporary Accompong Town Maroons to address the question of ancestral origins.MethodsWe sequenced a section of the mitochondrial DNA control region (np 16,024–16,569) and genotyped a panel of hierarchically selected haplogroup diagnostic SNPs for 50 individuals with genealogical ties to Accompong Town. Mitochondrial haplotypes were also compared with publically available Jamaican mitochondrial haplotypes using an exact test as well as haplotypes within the EMPOP public database to further access biogeographic origins.ResultsL‐type mitochondrial haplogroups were observed in 96% of samples, and the remaining 4% belonged to haplogroup B2. Haplotype diversity was 0.922 (SD = 0.024) and not significantly different than the comparable Jamaican population. Of the two B2 haplotypes, one matched haplotypes throughout the Americas and East Asia and the other matched only in East Asia. These results suggest both African and indigenous American maternal ancestries within Accompong Town.ConclusionsOur data suggested that the maternal ancestry of contemporary Accompong Town Maroons is predominantly African and, despite claims to suggest otherwise, also indigenous American. Our study complemented Maroon oral histories, archeological data, and illuminated how colonization shaped human genetic variation within the Caribbean. Am. J. Hum. Biol. 27:432–437, 2015. © 2014 Wiley Periodicals, Inc.
Dreidimensionale Tomographie im mittleren Infrarotbereich von endogenen und exogenen Molekülen in einer einzelnen Zelle mit subzellulärer Auflösung
Authors: Quaroni Luca , Obst Martin , Nowak Marcus , Zobi Fabio 
Published: November 2014

AbstractMikroskopie im mittleren infraroten Spektralbereich liefert detaillierte chemische Informationen über eine Probe bei moderater Ortsauflösung und wird daher immer häufiger für die Charakterisierung von biologischen Proben wie etwa einzelnen Zellen verwendet. Aufgrund der Komplexität der Probentopographie sind konventionelle 2D‐Bildgebungen jedoch in ihren Möglichkeiten limitiert, spezifische Informationen zur Probenzusammensetzung mit subzellulären Strukturen in Verbindung zu bringen. Wir stellen hier eine Methode und detaillierte Versuchsbeschreibungen vor, welche es ermöglichen, diese Einschränkungen durch Kippserientomographie mit einem konventionellen Infrarot‐Labormikroskop zu umgehen. Basierend auf dem intrinsischen IR‐Absorptionskontrast ermöglicht dieser Ansatz, quantitative 3D‐Verteilungen von molekularen Komponenten zu erstellen. Wir demonstrieren die Methode anhand der Quantifizierung der Verteilung eines exogenen Metallcarbonyl‐Komplexes innerhalb einer Zelle sowie durch die Darstellung der Veränderungen der Koordinationsumgebung des Komplexes in verschiedenen Zellkompartimenten.
The Catalytic Asymmetric Abramov Reaction
Authors: Guin Joyram , Wang Qinggang , van Gemmeren Manuel , List Benjamin 
Published: November 2014

AbstractThe first catalytic enantioselective Abramov reaction is described. The process is based on the utilization of a chiral disulfonimide catalyst, which efficiently avoids the difficulties encountered with metal‐based catalysts. Several functionalized α‐hydroxy phosphonates were synthesized in good yields and with excellent enantiomeric ratios of up to >99:1. The process was shown to be scalable and up to 1 g of starting material could be employed under mild reaction conditions.
Structure of Framework Aluminum Lewis Sites and Perturbed Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR (3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics
Authors: Brus Jiří , Kobera Libor , Schoefberger Wolfgang , Urbanová Martina , Klein Petr , Sazama Petr , Tabor Edyta , Sklenak Stepan , Fishchuk Anna V. , Dědeček Jiří 
Published: November 2014

AbstractZeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H‐forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors—“perturbed” AlFR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad 27Al NMR resonance (δi=59–62 ppm, CQ=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the 27Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad 27Al NMR resonance (δi≈67 ppm, CQ≈20 MHz, and η≈0.1).
Synthesis of nanostructure hydroxy sodalite composite membranes via hydrothermal method: support surface modification and synthesis method effects
Authors: Kalantari Neda , Vaezi Mohammad Javad , Yadollahi Mostafa , Babaluo Ali Akbar , Bayati Behruz , Kazemzadeh Akram 
Published: November 2014

AbstractMultilayer hydroxy sodalite zeolite membranes were synthesized on the outer surface of support with and without modification via in situ and secondary growth hydrothermal synthesis methods. The synthesized zeolite membranes were characterized by X‐ray diffraction, scanning electron microscopy, and single gas (H2, N2, and n‐pentane) permeation measurements at different pressure differences. The membranes synthesized by secondary growth method on the modified support were found to be highly intergrown, but the permeation results for hydrogen and n‐pentane at a temperature of 323 K were not repeatable, which can be related to the weak interaction between zeolite layer and substrate. High performance hydroxy sodalite zeolite membrane was successfully formed on a nonmodified α‐Al2O3 support by in situ hydrothermal synthesis method. No permeance of n‐pentane was measured for this membrane at 323 K and 2 bar so that infinite permselectivity of H2/n‐C5H12 could be obtained for the four‐layer synthesized membrane on the nonmodified support, verifying the synthesis of a good quality hydroxy sodalite zeolite membrane. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Hybrid biomimetic electrospun fibrous mats derived from poly(ε‐caprolactone) and silk fibroin protein for wound dressing application
Authors: Chutipakdeevong Jesada , Ruktanonchai Uracha , Supaphol Pitt 
Published: November 2014

ABSTRACTTo achieve excellent biofunctionality of Bombyx mori silk fibroin (SF), we explored a novel hybridization method to combine the unique properties of SF with poly(ε‐caprolactone) (PCL) electrospun fibers. The hybrid electrospun fibers demonstrate excellent hydrophilicity and biocompatibility that are important to tissue engineering applications. The biomimetic fibrous structure was fabricated by conventional electrospinning of PCL. The individual surfaces of PCL electrospun fibers were coated with silk fibroin protein using a lyophilization technique. The SF coating layers were durable which were further developed by surface modification with fibronectin to improve their biological function. The hybrid electrospun fibers show excellent support for normal human dermal fibroblast (NHDF) cells adhesion and proliferation than neat PCL fibers, while the surface‐modified hybrid electrospun fibers show significantly enhanced proliferation of NHDF cells on their surface. This study indicates the new opportunity of fabrication technique that can construct a biomimetic fibrous structure while the original function as a biomaterial remained existing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41653.
Marine protected areas management in the Caribbean and Mediterranean seas: making them more than paper parks
Authors: Bustamante Georgina , Canals Purificación , Di Carlo Giuseppe , Gomei Marina , Romani Marie , Souan Helene , Vanzella‐Khouri Alessandra 
Published: November 2014

ABSTRACTThe paper comprises recommendations presented and discussed at several workshops of the 3rd International Marine Protected Areas Congress (Marseille, France, 21–27, October, 2013) to achieve effective management of marine protected areas in the Caribbean and Mediterranean Seas.It highlights the similarities but also differences between the two areas as a result of their distinct biogeographic and cultural characteristics.The biophysical setting, socioeconomic scenario and issues related to marine protected areas in the Caribbean and Mediterranean Seas are summarized and case studies from both regions are presented that illustrate the level of success thus far achieved by MPAs.Factors contributing to MPA success are related to ecological conditions, the involvement of stakeholders in decision‐making processes, and to better governance, as well as improved communication and training.The SPAW and SPA regional environmental agreements administered by the UNEP Regional Seas Programmes in collaboration with government and non‐government partners and the MPA managers' networks have provided technical assistance that has led to improved management.The experience of the last 3 years of contacts between both regional networks of MPA scientists and practitioners (i.e. MedPAN and CaMPAM) highlights the benefits of such an initiative and suggests the need to develop a robust transoceanic Exchange Programme to facilitate knowledge transfer. Copyright © 2014 John Wiley & Sons, Ltd.
Governance challenges in scaling up from individual MPAs to MPA networks
Authors: Solandt Jean‐Luc , Jones Peter , Duval‐Diop Dominique , Kleiven Alf Ring , Frangoudes Katia 
Published: November 2014

ABSTRACTWith the drive for greater numbers and areas of MPAs to be put in place to meet national and international targets, challenges have emerged in both the establishment and development of sustainable governance of the networks of sites that are emerging.Using 12 presentations given in a workshop on ‘Improving participation for better governance of MPAs’ at the 3rd International Marine Protected Areas Congress in October 2013, this paper reviews a range of top‐down, bottom‐up and collaborative approaches to governance, looking at all phases in the process from design of an MPA network to its implementation, as well as considering individual MPAs.Designation of MPA networks requires significant investment of resources to engage local stakeholders in discussions over potential site location and management measures.Scaling‐up from individual MPAs to networks of MPAs will often also require a scaling‐up of governance approaches, including top‐down approaches.Balancing the need to provide for the participation of local users in each constituent MPA with the need to address a variety of challenges, whilst achieving wider‐scale objectives through the inclusion of top‐down governance approaches is an important but neglected challenge in discussions concerning MPA networks.These case studies indicate that there are various ways in which this challenge can be addressed in different contexts and point to potential ‘good practice’ for other MPAs in similar scenarios. Copyright © 2014 John Wiley & Sons, Ltd.
A Chemoenzymatic and Fully Stereocontrolled Total Synthesis of the Antibacterial Natural Product (−)‐Platencin
Authors: Chang Ee Ling , Schwartz Brett D. , Draffan Alistair G. , Banwell Martin G. , Willis Anthony C. 
Published: November 2014

AbstractThe natural product (−)‐platencin is a potent antibacterial agent that exerts its effects through a novel mode of action. As such, it is an important lead in the development of next‐generation antibacterials that are urgently needed because of the rapidly developing resistance to current therapies. The work reported here concerns the development of a convergent and chemoenzymatic total synthesis of (−)‐platencin by methods that should provide access to a range of biologically relevant analogues. The key step involves a thermally promoted and facially selective intramolecular Diels–Alder (IMDA) cycloaddition reaction to give an adduct that embodies the tricarbocyclic core of (−)‐platencin. This adduct was elaborated over thirteen steps to the natural product. The substrate for the IMDA reaction was prepared by Stille cross‐coupling of a Z‐configured alkenylstannane with an iodinated diene obtained in an enantiomerically pure form through the whole‐cell biotransformation of iodobenzene.
A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media
Authors: Cornut Damien , Moerkerke Steven , Wouters Johan , Bruylants Gilles , Jabin Ivan 
Published: November 2014

AbstractThe efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two‐step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β‐alanine betaine G5, which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea‐based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen‐bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self‐associate. Remarkably, host 6 is able to perform solid–liquid as well as liquid–liquid extraction of G5. Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.
Copper‐Catalyzed Aerobic CC Bond Cleavage of Lactols with N‐Hydroxy Phthalimide for Synthesis of Lactones
Authors: Tnay Ya Lin , Chiba Shunsuke 
Published: November 2014

AbstractThe transformation of cyclic hemiacetals (lactols) into lactones has been achieved by Cu‐catalyzed aerobic CC bond cleavage in the presence of N‐hydroxy phthalimide (NHPI). The present process is composed of a multistep sequence including a) formation of exo‐cyclic enol ethers by dehydration; b) addition of phthalimide N‐oxyl radical to the enol ethers followed by trapping of the resulting C‐radicals with molecular oxygen to form peroxy radicals; c) reductive generation of oxy radicals and subsequent β‐radical fragmentation to generate lactones.
N‐Heterocyclic Carbenes Supported on Vinylic Addition Polynorbornene: A Recyclable and Recoverable Organocatalyst
Authors: Molina de la Torre Jesús A. , Albéniz Ana C. 
Published: November 2014

AbstractA bromoalkyl functionalized vinylic addition polynorbornene has been used as an inert new scaffold to support imidazolium salts by straightforward nucleophilic substitution using different imidazoles ImR (R=Me, mesityl, 2,6‐iPr2C6H3). These polymers, VA‐PNB‐(CH2)4ImRBr, are precursors of N‐heterocyclic carbenes which are useful as heterogeneous organocatalysts. The polymeric carbenes have been tested in two model reactions: The synthesis of saturated esters from α,β‐unsaturated aldehydes and the conjugate umpolung reaction of α,β‐unsaturated aldehydes for the synthesis of γ‐butyrolactones. The supported catalyst (R=mesityl) is fully recyclable and can be recovered as an imidazolium salt and stored for further use.
Deciphering Ligands’ Interaction with Cu and Cu2O Nanocrystal Surfaces by NMR Solution Tools
Authors: Glaria Arnaud , Cure Jérémy , Piettre Kilian , Coppel Yannick , Turrin Cédric‐Olivier , Chaudret Bruno , Fau Pierre 
Published: November 2014

AbstractThe hydrogenolysis of [Cu2{(iPrN)2(CCH3)}2] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6–9 nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface CuI sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re‐dissolution of CuII species at the expense of the nanocrystals.
Strong Interplay between the Electron Spin Lifetime in Chemically Synthesized Graphene Multilayers and Surface‐Bound Oxygen
Authors: Náfrádi Bálint , Choucair Mohammad , Southon Peter D. , Kepert Cameron J. , Forró László 
Published: November 2014

AbstractThe electron spin lifetime in an assembly of chemically synthesized graphene sheets was found to be extremely sensitive to oxygen. Introducing small concentrations of physisorbed O2 onto the graphene surface reduced the exceptionally long 140 ns electron spin lifetime by an order of magnitude. This effect was completely reversible: Removing the O2 by using a dynamic vacuum restored the spin lifetime. The presence of covalently bound oxygen also decreased the electron spin lifetime in graphene, although to a far lesser extent compared to physisorbed O2. The conduction electrons in graphene were found to play a significant role by counter‐balancing the spin depolarization caused by oxygen molecules. Our results highlight the importance of chemical environment control and device packing in practical graphene‐based spintronic applications.
Fluorination of Isotopically Labeled Turbostratic and Bernal Stacked Bilayer Graphene
Authors: Ek Weis Johan , Costa Sara D. , Frank Otakar , Bastl Zdenek , Kalbac Martin 
Published: November 2014

AbstractFluorination of graphene opens up a bandgap, which creates opportunities for optoelectronics, and also paves the way for the creation of extremely thin insulating layers, which can be important for applications in devices. However, in spite of many interesting features offered by, for example, unequally doped layers in multilayered systems, most of the work has concerned the fluorination of graphene monolayers. Here, the fluorination process of graphene bilayers is investigated through high‐resolution Raman mapping followed by analysis of more than 10 000 spectra of bilayer graphene. Isotopically labeled bilayers are used, allowing each individual layer in bilayer graphene to be addressed unambiguously. The fluorinated graphene is prepared through exposure to XeF2. Monolayer graphene is found to be significantly more sensitive to fluorination than bilayer graphene. Through comparison of the D/G area ratio and the position of the G band for turbostratic and Bernal stacked (AB) bilayers, it is found that the fluorination process is more effective for turbostratic than for AB‐stacked bilayer graphene. The fluorination changes the electronic structure similarly for the top and bottom layers in turbostratic bilayers. However, the top layer is more sensitive than the bottom layer in AB‐stacked bilayers.
ChemInform Abstract: High‐Throughput ab initio Screening for Two‐Dimensional Electride Materials.
Authors: Tada Tomofumi , Takemoto Seiji , Matsuishi Satoru , Hosono Hideo 
Published: November 2014

AbstractHigh‐throughput ab initio electronic structure calculations of about 34000 materials in a screening platform are performed to identify two‐dimensional electride materials, which are composed of cationic layers and anionic electrons confined in a two‐dimensional empty space.
ChemInform Abstract: mP‐BaP3: A New Phase from an Old Binary System.
Authors: Dolyniuk Juli‐Anna , Kaseman Derrick C. , Sen Sabyasachi , Zhao Jing , Osterloh Frank E. , Kovnir Kirill 
Published: November 2014

AbstractThe new title phase is synthesized by solid state reaction of a stoichiometric mixture of the elements (carbonized silica ampule, 1073 K, 140 h) and characterized by single crystal XRD, UV/VIS diffuse reflectance spectroscopy, 31P solid state MAS NMR, surface photovoltage spectroscopy, and DFT band structure calculations.