bluuebunny/crossref_metadata_2025_split huggingface dataset:
Well‐Designed Hierarchical Co3O4 Architecture as a Long‐Life and Ultrahigh Rate Capacity Anode for Advanced Lithium‐Ion Batteries
Authors: Liu Mengting , Deng Xia , Ma Yaodong , Xie Wenhe , Hou Xiaoyi , Fu Yujun , He Deyan 
Published: July 2017

AbstractIn a simple strategy of mild heat‐assistant precipitation followed by annealing in air, hierarchical Co3O4 flower‐like microspheres self‐constructed by porous nanosheets are synthesized in bulk and tested as an anode material for advanced lithium‐ion batteries (LIBs). Benefited from its high porosity and specific surface area as well as a necessary short activation, the as‐prepared architecture shows an enhanced lithium storage performance of high capacity, long‐life cycle, and ultrahigh rate capacity compared with the great majority of reported and commercial Co3O4 materials. Especially, it delivers a reversible capacity of 715 mAh g−1 after 1000 cycles under a current density of 1000 mA g−1 with a coulombic efficiency of more than 99%. When the electrode is laid aside for 5 d and recycled again, it can reach upward of 680 mAh g−1 for another 150 cycles. Such an impressive electrochemical performance indicates that the hierarchical Co3O4 flower‐like microspheres can be a promising electrode material of advanced LIBs in future.
Annulated 1,3,4‐Azadiphospholides: Heterocycles with Widely Tunable Optical Properties
Authors: Suter Riccardo , Benkő Zoltán , Bispinghoff Mark , Grützmacher Hansjörg 
Published: July 2017

AbstractPhosphorus heterocycles find applications in the synthesis of π‐conjugated compounds and as precursors for optoelectronic materials such as organic light‐emitting diodes (OLEDs), electronic switches, and transistors. A high‐yield, one‐pot synthesis of anionic annulated 1,3,4‐azadiphospholides from Na(OCP) and 2‐chloropyridines is presented. The synthesis proceeds without the use of transition metals and tolerates a wide range of substrates. Cyano‐substituted compounds are especially deeply colored and have absorption maxima which range from λmax=525 to 596 nm. The optical properties are dominated by the spatial separation of an electron acceptor and donor unit within one molecule (push–pull chromophore). The anionic 1,3,4‐azadiphospholides are silylated to neutral siloxy compounds with a strong blue‐shifted absorption. This reaction can be reversed by addition of fluoride ions, which allows fluoride ions to be detected in optically low concentrations.
Bioinspired, Size‐Tunable Self‐Assembly of Polymer–Lipid Bilayer Nanodiscs
Authors: Ravula Thirupathi , Ramadugu Sudheer Kumar , Di Mauro Giacomo , Ramamoorthy Ayyalusamy 
Published: July 2017

AbstractPolymer‐based nanodiscs are valuable tools in biomedical research that can offer a detergent‐free solubilization of membrane proteins maintaining their native lipid environment. Herein, we introduce a novel ca. 1.6 kDa SMA‐based polymer with styrene:maleic acid moieties that can form nanodiscs containing a planar lipid bilayer which are useful to reconstitute membrane proteins for structural and functional studies. The physicochemical properties and the mechanism of formation of polymer‐based nanodiscs are characterized by light scattering, NMR, FT‐IR, and TEM. A remarkable feature is that nanodiscs of different sizes, from nanometer to sub‐micrometer diameter, can be produced by varying the lipid‐to‐polymer ratio. The small‐size nanodiscs (up to ca. 30 nm diameter) can be used for solution NMR spectroscopy studies whereas the magnetic‐alignment of macro‐nanodiscs (diameter of > ca. 40 nm) can be exploited for solid‐state NMR studies on membrane proteins.
Eigenschaften von Wasser in den Poren von periodisch mesoporösen Organosilicas – Nanoabprägung der lokalen Struktur
Authors: Mietner J. Benedikt , Brieler Felix J. , Lee Young Joo , Fröba Michael 
Published: July 2017

AbstractDie Eigenschaften von Gastmolekülen in den Poren poröser Materialien sind sowohl aus wissenschaftlicher wie auch aus technologischer Perspektive hochinteressant. Entscheidenden Einfluss auf die durch eine geometrische Beschränkung hervorgerufenen Effekte haben insbesondere die Topologie, Größe und Oberflächenpolarität der Poren. Allerdings ist über die Kontaktfläche zwischen Gastmolekül und Porenwand noch zu wenig bekannt. Hier wird gezeigt, dass die Mobilität von Wassermolekülen in den Poren von periodisch mesoporösen Organosilicas (PMOs) stark von der Polarität der organischen Einheit abhängt. Mithilfe mehrdimensionaler Festkörper‐NMR‐Spektroskopie wurde die räumliche Anordnung von Wasser im Inneren von Poren bestimmt. Wassermoleküle interagieren, abhängig von der alternierenden Oberflächenpolarität, entweder nur mit den anorganischen Silicatschichten oder auch mit den organischen Schichten. Als Ergebnis wird in Abhängigkeit von den PMO‐Typen entweder eine modulierte oder eine gleichmäßige Porenfüllung mit Wasser vorgeschlagen.
Cyclodextrin Cavity‐Induced Mechanistic Switch in Copper‐Catalyzed Hydroboration
Authors: Zhang Pinglu , Meijide Suárez Jorge , Driant Thomas , Derat Etienne , Zhang Yongmin , Ménand Mickaël , Roland Sylvain , Sollogoub Matthieu 
Published: July 2017

AbstractN‐heterocyclic carbene‐capped cyclodextrin (ICyD) ligands, α‐ICyD and β‐ICyD derived from α‐ and β‐cyclodextrin, respectively give opposite regioselectivities in a copper‐catalyzed hydroboration. The site‐selectivity results from two different mechanisms: the conventional parallel one and a new orthogonal mechanism. The shape of the cavity was shown not only to induce a regioselectivity switch but also a mechanistic switch. The scope of interest of the encapsulation of a reactive center is therefore broadened by this study.
Intermediate Product Regulation in Tandem Solid Catalysts with Multimodal Porosity for High‐Yield Synthetic Fuel Production
Authors: Duyckaerts Nicolas , Bartsch Mathias , Trotuş Ioan‐Teodor , Pfänder Norbert , Lorke Axel , Schüth Ferdi , Prieto Gonzalo 
Published: July 2017

AbstractTandem catalysis is an attractive strategy to intensify chemical technologies. However, simultaneous control over the individual and concerted catalyst performances poses a challenge. We demonstrate that enhanced pore transport within a Co/Al2O3 Fischer–Tropsch (FT) catalyst with hierarchical porosity enables its tandem integration with a Pt/ZSM‐5 zeolitic hydrotreating catalyst in a spatially distant fashion that allows for catalyst‐specific temperature adjustment. Nevertheless, this system resembles the case of close active‐site proximity by mitigating secondary reactions of primary FT α‐olefin products. This approach enables the combination of in situ dewaxing with a minimum production of gaseous hydrocarbons (18 wt %) and an up to twofold higher (50 wt %) selectivity to middle distillates compared to tandem pairs based on benchmark mesoporous FT catalysts. An overall 80 % selectivity to liquid hydrocarbons from syngas is attained in one step, attesting to the potential of this strategy for increasing the carbon efficiency in intensified gas‐to‐liquid technologies.
Polyladderane Constructed from a Gemini Monomer through Photoreaction
Authors: Wang Zhihan , Miller Benjamin , Butz Jonathan , Randazzo Katelyn , Wang Zijun D. , Chu Qianli R. 
Published: July 2017

AbstractPolyladderane, the first polymer to contain the ladderane functional group, was synthesized from a gemini monomer through photoreaction in the solid state. The modular design of the gemini monomers used to create polyladderane allowed specific structural modification, resulting in the formation of two distinct polymer products. Monomers were synthesized by connecting two photoreactive units, either sorbic acids (monomer I) or 2‐furanacrylic acids (monomer II), with a 1,4‐butanediol linker. Single‐crystal X‐ray diffraction analysis of the monomers confirmed that they packed in the desired head‐to‐tail orientation and within a viable distance for photoreaction by electronically complementary interaction. Pre‐organized gemini monomers were irradiated with UV light and monitored by FT‐IR. Two polyladderanes with cis,anti,cis‐[3]‐ladderane as a characteristic functional group were constructed stereospecifically in 24–36 hours.
Selectivity in the Cyclization of Citronellal Introduced by Squalene Hopene Cyclase Variants
Authors: Bastian Silke A. , Hammer Stephan C. , Kreß Nico , Nestl Bettina M. , Hauer Bernhard 
Published: July 2017

AbstractThe squalene hopene cyclase from Alicyclobacillus acidocaldarius (AacSHC) is a highly efficient enzyme catalyst for stereoselective Brønsted acid catalysis. We engineered AacSHC to catalyze the selective Prins cyclization of citronellal. Four active site variants were identified for the diastereoselective cyclization of (S)‐citronellal to stereoisomers (−)‐iso‐isopulegol, (+)‐isopulegol and (−)‐neo‐isopulegol, respectively. The replacement of active site residues resulted in two triple variants that catalyzed the transformation of (R)‐citronellal to give the isomers (+)‐neo‐isopulegol and (−)‐isopulegol with up to >99 % de, respectively. The newly designed library of functionally diverse active site geometries exhibits high selective control during citronellal cyclization, leading exclusively to a single diastereomer of the desired isopulegol. Whereas the cyclization of citronellal with chemical catalysts was observed to produce the isopulegol isomer with the lowest energy, the reaction with AacSHC variants proceeded with higher product selectivity. The results of this study show that variants of AacSHC are excellent catalysts for the highly selective formation of isopulegol stereoisomers.
Embedding Reduced Graphene Oxide in Bacterial Cellulose‐Derived Carbon Nanofibril Networks for Supercapacitors
Authors: Chang Yanhong , Zhou Lu , Xiao Zhichang , Liang Jiaxu , Kong Debin , Li Zihao , Zhang Xinghao , Li Xianglong , Zhi Linjie 
Published: July 2017

AbstractA simple, effective, eco‐friendly, and scalable reduced graphene oxide embedding strategy is developed to construct self‐supported carbon electrode material networks for supercapacitors from a naturally occurring biomaterial−bacterial cellulose. The thus‐engineered self‐supported carbon nanofibril networks exhibit superior supercapacitive performance compared to their counterparts, thus opening up an avenue to design self‐supported high‐capacitance carbon electrode materials toward high‐class supercapacitors.
Magnetic Shielding Studies of C2 and C2H2 Support Higher than Triple Bond Multiplicity in C2
Authors: Karadakov Peter B. , Kirsopp Josh 
Published: July 2017

AbstractThe carbon–carbon bonds in the ground states of C2 and C2H2, at their equilibrium geometries, are compared by analysing the changes in the off‐nucleus magnetic shielding tensor within the space surrounding each of these molecules. A wide range of quantum‐chemical approaches, including full‐valence CASSCF‐GIAO, CCSD(T)‐GIAO and CCSDT‐GIAO, all with the cc‐pVQZ basis set, as well as HF‐GIAO and MP2‐GIAO, with the cc‐pVQZ, cc‐pV5Z and cc‐pV6Z basis sets, show that the surroundings of the carbon–carbon bond in C2 are more shielded than those of the carbon–carbon bond in C2H2. The additional shielding of the carbon–carbon bond in C2 is found to be due to a larger paramagnetic contribution to the component of the shielding tensor which is perpendicular to the molecular axis. The analysis of the off‐nucleus shielding data indicates that the carbon–carbon bond in C2 is “bulkier” and, therefore, of a higher multiplicity, but weaker than the corresponding bond in C2H2. According to the results of the shielding calculations, the carbon nuclei in C2 should be much more shielded than those in C2H2, with 13C isotropic magnetic shieldings in the ranges of around 224–227 ppm and around 123–125 ppm for C2 and C2H2, respectively.
MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold‐Diverse Macrocyclic Libraries
Authors: Saupe Jörn , Kunz Oliver , Haustedt Lars Ole , Jakupovic Sven , Mang Christian 
Published: July 2017

AbstractMacrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide‐based scaffolds is reported. The process, named here as “MacroEvoLution”, is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character.
Asymmetric Alkynylation of β‐Ketoesters and Naphthols Promoted by New Chiral Biphenylic Iodanes
Authors: Companys Simon , Peixoto Philippe A. , Bosset Cyril , Chassaing Stefan , Miqueu Karinne , Sotiropoulos Jean‐Marc , Pouységu Laurent , Quideau Stéphane 
Published: July 2017

AbstractThe preparation of new chiral biphenylic λ3‐iodane reagents bearing transferable alkynyl ligands is described. These reagents transfer their carbon‐based ligands onto β‐ketoesters with an enantiomeric excess (ee) up to 68 %, and most remarkably, enable the dearomative alkynylation of naphthols in good to high yields up to 84 % ee.
Cesium Removal from Human Blood by Poly(ethylene glycol)‐Decorated Prussian Blue Magnetic Nanoparticles
Authors: Qian Jun , Xu Jiaying , Kuang Liangju , Hua Daoben 
Published: July 2017

AbstractThe current oral administration of drugs for cesium (Cs) decorporation treatment are often subject to side effects and low efficiency. Therefore, it is of great significance, yet challenging, to develop novel materials and techniques for efficient removal of Cs from the human body. We report herein a new method for directly removing cesium from blood by poly(ethylene glycol)‐decorated Prussian blue magnetic nanoparticles (PEG‐PB MNs). The nanoparticles have been successfully synthesized by one‐pot hydrothermal reaction. The adsorption of cesium in aqueous solution is a highly selective process and kinetically follows a pseudo‐second‐order model, which can reach equilibrium with a large capacity of 274.7 mg Cs g−1 within one hour at 298.15 K. PEG‐PB MNs were also efficiently regenerated and reused with high adsorption efficiency after five cycles. The nanoparticles successfully removed cesium ions from human blood with improved biocompatibility. The removal efficiency achieved 64 % in the blood with an initial Cs concentration of 168.4 ppb. This study provides a new approach to directly remove cesium ions from the human body by utilizing biocompatible Prussian blue magnetic nanoparticles.
In‐Situ Observation of Nanoparticle Formation Under Different Power of Microwave Irradiation
Authors: Asakuma Yusuke , Matsumura Shungo , Saptoro Agus 
Published: July 2017

AbstractMicrowave technology has emerged as one of the useful methods for nanoparticle synthesis. Despite many studies on this area, its underlying mechanism has not been clearly understood. In this study, in‐situ observation of nanoparticle growth was carried out and the profiles and behaviors of produced bubbles and particles under microwave effect were reported. Sizes of bubble and nanoparticle particle were measured during and after microwave irradiation using a DLS apparatus and behavior of particle growth and superheating effect were observed. From the experimental data, it is apparent that the maximum bubble sizes were greatly influenced by the irradiation power and solute concentration. Particle number density, which is related to the initial solute concentration, is also an important factor for the bubble size produced during the irradiation. Finally, through in‐situ observation of superheating effect, the behavior was frequently caused by the irradiation at higher power. To prevent superheating effect, influencing factors such as the irradiation power and number density should be controlled to ensure a stable operation of particle formation process.
A Multiobjective Optimization Including Results of Life Cycle Assessment in Developing Biorenewables‐Based Processes
Authors: Helmdach Daniel , Yaseneva Polina , Heer Parminder K. , Schweidtmann Artur M. , Lapkin Alexei A. 
Published: July 2017

AbstractA decision support tool has been developed that uses global multiobjective optimization based on 1) the environmental impacts, evaluated within the framework of full life cycle assessment; and 2) process costs, evaluated by using rigorous process models. This approach is particularly useful in developing biorenewable‐based energy solutions and chemicals manufacturing, for which multiple criteria must be evaluated and optimization‐based decision‐making processes are particularly attractive. The framework is demonstrated by using a case study of the conversion of terpenes derived from biowaste feedstocks into reactive intermediates. A two‐step chemical conversion/separation sequence was implemented as a rigorous process model and combined with a life cycle model. A life cycle inventory for crude sulfate turpentine was developed, as well as a conceptual process of its separation into pure terpene feedstocks. The performed single‐ and multiobjective optimizations demonstrate the functionality of the optimization‐based process development and illustrate the approach. The most significant advance is the ability to perform multiobjective global optimization, resulting in identification of a region of Pareto‐optimal solutions.
Pressure‐based alkaline lysis with immunocapture, a method for enhanced recovery in differential extraction
Authors: Martinez Vanessa , Nori Deepthi , Dimsoski Pero , McCord Bruce 
Published: July 2017

AbstractA pressure‐based protocol for differential extraction has been optimized to provide a rapid and selective alternative to conventional differential extraction techniques with the advantage of an increased recovery of genomic DNA. The protocol involves treating cotton swabs containing mixtures of sperm and vaginal epithelial cells with two sets of pressure treatment using a Barocycler® NEP 2320 in alkaline conditions. This first step quantitatively and selectively removes female epithelial cells. The cotton swab is removed and further treated with alkali at 95°C for the removal of sperm cell DNA. The resultant solution provides a clean male profile at a 20:1 cell ratio. Furthermore, the inclusion of a pretreatment step involving immunomagnetic cell capture of the female cells, permits nearly complete isolation of male sperm cells at cell ratios of up to 200:1 female to male cells.
Bicistronic expression strategy for high‐level expression of recombinant proteins in Corynebacterium glutamicum
Authors: Liu Xiuxia , Zhao Zihao , Zhang Wei , Sun Yang , Yang Yankun , Bai Zhonghu 
Published: July 2017

AbstractDirectly using the promoter associated with 5′‐untranslated region of a high‐protein‐abundance gene from the genome may cause low expression activity of an expression system. A bicistronic expression part containing the short 5′ coding sequence of the source gene and an embedded Shine–Dalgarno sequence can cause higher expression levels of the recombinant gene in a bicistronic cassette. Here, we evaluated two methods to construct expression parts and exploited genomic sequence sources to provide specific functional sequences to complete the expression system. The architecture of the bicistronic part increased the expression levels of target genes and performed more reliably than conventional expression parts with the same promoter and 5′ untranslated region. For Corynebacterium glutamicum, the strongest bicistronic part, HP‐BEP4, was obtained from a heterologous sequence source, leading to a 2.24‐fold increase in the expression level of fluorescent protein over constitutively expressed pXMJ19 or the production of more than 100 mg/L single‐chain variable fragment (scFv). It could meet the needs of overexpressing key genes in C. glutamicum.
Assessing visibility and geomorphological biases in regional field surveys: The case of Roman Aesernia
Authors: Casarotto Anita , Stek Tesse D. , Pelgrom Jeremia , van Otterloo Ruud H. , Sevink Jan 
Published: July 2017

AbstractArchaeological field survey data can be biased by many factors, such as ground visibility conditions (e.g. vegetation, plowing) and geomorphological processes (erosion, deposition). Both visibility and geomorphological factors need, therefore, to be assessed when patterns of settlement and location preferences are inferred from survey data. Although both factors have been taken into account in a variety of fieldwork projects and studies, their combined effects remain hard to predict. In this paper, we aim to address this issue by presenting a visualization method that helps in evaluating in combination the possible visibility and geomorphological effects in regional, site‐oriented field surveys. Capitalizing on first‐hand data on both archaeology and soil types produced by the recent Leiden University field survey project in the area of Isernia (Roman Aesernia, Central‐Southern Italy), we propose a combined application of statistical tests and geo‐pedological analysis to assess the extent and scale of the main biases possibly affecting the interpretation of the ancient settlement organization. Translating both sets of biases into GIS maps, we indicate the likelihood that negative field survey observations (absence of sites), in specific parts of the landscape, are genuine or rather distorted by biasing factors. The resulting “archaeological detectability” maps allow researchers to formally highlight critical surveyed zones where the recording of evidence is likely unreliable, and thus provide a filter through which archaeologists can calibrate their interpretations of field survey datasets.
Adaptive testing for association between two random vectors in moderate to high dimensions
Authors: Xu Zhiyuan , Xu Gongjun , Pan Wei ,   For the Alzheimer's Disease Neuroimaging Initiative
Published: July 2017

ABSTRACTTesting for association between two random vectors is a common and important task in many fields, however, existing tests, such as Escoufier's RV test, are suitable only for low‐dimensional data, not for high‐dimensional data. In moderate to high dimensions, it is necessary to consider sparse signals, which are often expected with only a few, but not many, variables associated with each other. We generalize the RV test to moderate‐to‐high dimensions. The key idea is to data adaptively weight each variable pair based on its empirical association. As the consequence, the proposed test is adaptive, alleviating the effects of noise accumulation in high‐dimensional data, and thus maintaining the power for both dense and sparse alternative hypotheses. We show the connections between the proposed test with several existing tests, such as a generalized estimating equations‐based adaptive test, multivariate kernel machine regression (KMR), and kernel distance methods. Furthermore, we modify the proposed adaptive test so that it can be powerful for nonlinear or nonmonotonic associations. We use both real data and simulated data to demonstrate the advantages and usefulness of the proposed new test. The new test is freely available in R package aSPC on CRAN at https://cran.r-project.org/web/packages/aSPC/index.html and https://github.com/jasonzyx/aSPC.