bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reversible Selectivity Modulation of Gasoline and Diesel by a Facile Metal‐Salt‐Modified Fischer–Tropsch Synthesis Strategy
Authors: Wang Hao , Xu Ke , Cheng Yi , Pei Yan , Yan Shirun , Qiao Minghua , Li Zhen Hua , Zong Baoning 
Published: September 2016

AbstractIt has long been known that inorganic additives enhance the product selectivity in organic catalytic transformations. However, the potential of this facile approach in the industrially significant Fischer–Tropsch synthesis (FTS) has not been well explored. Herein, after examining the promotion effects of a diversified range of metal sulfates on product distribution over an active and recyclable Ru/P25 catalyst in the aqueous‐phase, low‐temperature FTS, we show that whereas enhancing the selectivity to diesel is a general feature for most metal sulfates, nickel sulfate is unique in enhancing the selectivity to gasoline. Moreover, this strategy enables the reversible boosting of the selectivity to gasoline or diesel with ease and thus provides access to a FTS process with unprecedented versatility. Probe reactions and theoretical studies point to the scenario that metal sulfates modify the reaction pathway by affecting the stability of the endogenous α‐olefins, which hence alters the probability of chain growth and product distribution.
Redox‐Assisted Self‐Assembly of a Water‐Soluble Cyanido‐Bridged Mixed Valence {CoIII/FeII}2 Square
Authors: Alcázar Laura , Aullón Gabriel , Ferrer Montserrat , Martínez Manuel 
Published: September 2016

AbstractThe facile redox‐assisted assembly of a water‐soluble, extremely robust, cyanide‐bridged mixed‐valence [{CoIII{(Me)2(μ‐ET)cyclen}}2{(μ‐NC)2FeII(CN)4}2]2− square is reported. The preparation process involved the use of the enhanced lability of inert CoIII synthons triggered by outer‐sphere redox processes. Characterization of the final compounds has been carried out by NMR, UV/Vis, electrochemistry, and ICP analyses. DFT calculations have been conducted to optimize a structure that has the same hydrodynamic radius as that obtained from DOSY experiments. The new compound is extremely robust, surviving in aqueous solution within the 0–12 pH range for months. The species shows a high affinity for both protons and hydroxo ions in aqueous medium.
Nickel‐Catalyzed [2+2+2] Cycloaddition of Alkyne‐Nitriles with Alkynes Assisted by Lewis Acids: Efficient Synthesis of Fused Pyridines
Authors: You Xu , Xie Xin , Wang Gaonan , Xiong Meijun , Sun Renhong , Chen Haoyi , Liu Yuanhong 
Published: September 2016

AbstractA Ni/BPh3 catalyzed [2+2+2] cycloaddition of alkyne‐nitriles with alkynes has been developed, which provides an efficient route to fused pyridines under mild reaction conditions. Mechanistic studies indicate that an azanickelacycle via heterocoupling of an alkyne with a nitrile moiety is possibly formed as a key reaction intermediate. The Lewis acid catalyst is crucial to the successful transformation, which is suggested to promote the oxidative cyclization process.
Bridging C−H Activation: Mild and Versatile Cleavage of the 8‐Aminoquinoline Directing Group
Authors: Berger Martin , Chauhan Rajan , Rodrigues Catarina A. B. , Maulide Nuno 
Published: September 2016

Abstract8‐Aminoquinoline has emerged as one of the most powerful bidentate directing groups in history of C−H activation within the last decade. However, cleavage of its robust amide bond has shown to be challenging in several cases, thus jeopardizing the general synthetic utility of the method. To overcome this limitation, we herein report a simple oxidative deprotection protocol. This transformation rapidly converts the robust amide to a labile imide, allowing subsequent cleavage in a simple one‐pot fashion to rapidly access carboxylic acids or amides as final products.
A review of personalized blood glucose prediction strategies for T1DM patients
Authors: Oviedo Silvia , Vehí Josep , Calm Remei , Armengol Joaquim 
Published: September 2016

AbstractThis paper presents a methodological review of models for predicting blood glucose (BG) concentration, risks and BG events. The surveyed models are classified into three categories, and they are presented in summary tables containing the most relevant data regarding the experimental setup for fitting and testing each model as well as the input signals and the performance metrics. Each category exhibits trends that are presented and discussed. This document aims to be a compact guide to determine the modeling options that are currently being exploited for personalized BG prediction.
The Reaction Pathway of Cellulose Pyrolysis to a Multifunctional Chiral Building Block: The Role of Water Unveiled by a DFT Computational Investigation
Authors: Marforio Tainah Dorina , Bottoni Andrea , Calvaresi Matteo , Fabbri Daniele , Giacinto Pietro , Zerbetto Francesco 
Published: September 2016

AbstractLAC (hydroxylactone (1R,5S)‐1‐hydroxy‐3,6‐dioxabicyclo[3.2.1]octan‐2‐one) is one of the most interesting products of the pyrolysis of cellulose and represents a useful chiral building block in organic synthesis. A computational investigation at the DFT level on the mechanism of formation of LAC shows that this species can be obtained following two reaction paths, path A and path B, starting from a well‐known pyrolysis product (ascopyrone P). A series of internal rearrangements involving in all cases a proton transfer leads directly to LAC (path B). An alternative path (path A) can be also followed. From this path, via a “gate” connecting the two reaction channels, it is possible to reach path B and form LAC. In both cases, the rate‐determining step of the process is the initial keto‐enol isomerization. We found that water, which is present in the reaction mixture, “catalyzes” the reaction by assisting the proton transfers present in all the steps of the process. In particular, water lowers the barrier of the rate‐determining step that becomes 40.9 kcal mol−1 (79.4 kcal mol−1 in the absence of water). The corresponding computed rate constant is 4.3×10 s−1 at 500 °C, a value which is consistent with the presence of LAC in the absence of metal catalysts. The results of this study on the non‐catalyzed process underpin the important role played by water in the formation of pyrolysis products of cellulose where proton transfer is a key mechanistic step.
14N Solid‐State NMR Spectroscopy of Amino Acids
Authors: Veinberg Stanislav L. , Friedl Zachary W. , Lindquist Austin W. , Kispal Brianna , Harris Kristopher J. , O'Dell Luke A. , Schurko Robert W. 
Published: September 2016

Abstract14N ultra‐wideline solid‐state NMR (SSNMR) spectra were obtained for 16 naturally occurring amino acids and four related derivatives by using the WURST–CPMG (wideband, uniform rate, and smooth truncation Carr–Purcell–Meiboom–Gill) pulse sequence and frequency‐stepped techniques. The 14N quadrupolar parameters were measured for the sp3 nitrogen moieties (quadrupolar coupling constant, CQ, values ranged from 0.8 to 1.5 MHz). With the aid of plane‐wave DFT calculations of the 14N electric‐field gradient tensor parameters and orientations, the moieties were grouped into three categories according to the values of the quadrupolar asymmetry parameter, ηQ: low (≤0.3), intermediate (0.31–0.7), and high (≥0.71). For RNH3+ moieties, greater variation in N−H bond lengths was observed for systems with intermediate ηQ values than for those with low ηQ values (this variation arose from different intermolecular hydrogen‐bonding arrangements). Strategies for increasing the efficiency of 14N SSNMR spectroscopy experiments were discussed, including the use of sample deuteration, high‐power 1H decoupling, processing strategies, high magnetic fields, and broadband cross‐polarization (BRAIN‐CP). The temperature‐dependent rotations of the NH3 groups and their influence on 14N transverse relaxation rates were examined. Finally, 14N SSNMR spectroscopy was used to differentiate two polymorphs of l‐histidine through their quadrupolar parameters and transverse relaxation time constants. The strategies outlined herein permitted the rapid acquisition of directly detected 14N SSNMR spectra that to date was not matched by other proposed methods.
Theoretical Study of the Substituent Effects on the Nonlinear Optical Properties of a Room‐Temperature‐Stable Organic Electride
Authors: Sun Wei‐Ming , Li Xiang‐Hui , Li Ying , Ni Bi‐Lian , Chen Jing‐Hua , Li Chun‐Yan , Wu Di , Li Zhi‐Ru 
Published: September 2016

AbstractExcess‐electron compounds can be considered as novel candidates for nonlinear optical (NLO) materials because of their large static first hyperpolarizabilities (β0). A room‐temperature‐stable, excess‐electron compound, that is, the organic electride Na@(TriPip222), was successfully synthesized by the Dye group (J. Am. Chem. Soc. 2005, 127, 12416). In this work, the β0 of this electride was first evaluated to be 1.13×106 au, which revealed its potential as a high‐performance NLO material. In particular, the substituent effects of different substituents on the structure, electride character, and NLO response of this electride were systemically studied for the first time by density functional theory calculations. The results revealed that the β0 of Na@(TriPip222) could be further increased to 8.30×106 au by introducing a fluoro substituent, whereas its NLO response completely disappeared if one nitryl group was introduced because the nitro‐group substitution deprived the material of its electride identity. Moreover, herein the dependence of the NLO properties on the number of substituents and their relative positions was also detected in multifluoro‐substituted Na@(TriPip222) compounds.
Solvation Structure of Uracil in Ionic Liquids
Authors: Norman Sarah E. , Turner Adam H. , Holbrey John D. , Youngs Tristan G. A. 
Published: September 2016

AbstractThe local solvation environment of uracil dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute (ionic liquid:uracil) ratios of 3:1 and 2:1, little perturbation of the ion–ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia‐Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109–4120). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favourable uracil–uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution.
Alternative fluorescent labeling strategies for characterizing gram‐positive pathogenic bacteria: Flow cytometry supported counting, sorting, and proteome analysis of Staphylococcus aureus retrieved from infected host cells
Authors: Hildebrandt Petra , Surmann Kristin , Salazar Manuela Gesell , Normann Nicole , Völker Uwe , Schmidt Frank 
Published: September 2016

AbstractStaphylococcus aureus is a Gram‐positive opportunistic pathogen that is able to cause a broad range of infectious diseases in humans. Furthermore, S. aureus is able to survive inside nonprofessional phagocytic host cell which serve as a niche for the pathogen to hide from the immune system and antibiotics therapies. Modern OMICs technologies provide valuable tools to investigate host‐pathogen interactions upon internalization. However, these experiments are often hampered by limited capabilities to retrieve bacteria from such an experimental setting. Thus, the aim of this study was to develop a labeling strategy allowing fast detection and quantitation of S. aureus in cell lysates or infected cell lines by flow cytometry for subsequent proteome analyses. Therefore, S. aureus cells were labeled with the DNA stain SYTO® 9, or Vancomycin BODIPY® FL (VMB), a glycopeptide antibiotic binding to most Gram‐positive bacteria which was conjugated to a fluorescent dye. Staining of S. aureus HG001 with SYTO 9 allowed counting of bacteria from pure cultures but not in cell lysates from infection experiments. In contrast, with VMB it was feasible to stain bacteria from pure cultures as well as from samples of infection experiments. VMB can also be applied for histocytochemistry analysis of formaldehyde fixed cell layers grown on coverslips. Proteome analyses of S. aureus labeled with VMB revealed that the labeling procedure provoked only minor changes on proteome level and allowed cell sorting and analysis of S. aureus from infection settings with sensitivity similar to continuous gfp expression. Furthermore, VMB labeling allowed precise counting of internalized bacteria and can be employed for downstream analyses, e.g., proteomics, of strains not easily amendable to genetic manipulation such as clinical isolates. © 2016 International Society for Advancement of Cytometry
Carbon Nanotube Modified V2O5 Porous Microspheres as Cathodes for High‐Performance Lithium‐Ion Batteries
Authors: Li Qian , Chen Yuanfu , He Jiarui , Fu Fei , Qi Fei , Lin Jie , Zhang Wanli 
Published: September 2016

AbstractFor the first time, V2O5/carbon nanotube (CNT) porous microspheres (VCMs) constructed from V2O5 particles homogenously wrapped in highly conductive CNTs have been synthesized through a facile spray‐drying route by using commercial V2O5 and CNTs as starting materials. Compared with bare commercial V2O5 particles, the electrochemical performance of VCM is significantly enhanced: it exhibits a large specific capacity of 242.3 mAh g−1, which is about 69 % higher than that of bare commercial V2O5 (145.4 mAh g−1); the capacity remains 223.8 mAh g−1 at 0.2 C (1 C=294 mAh g−1) after 80 cycles with a high capacity retention of 92.3 %. The C‐rate capacities at 1, 2, 5, and 10 C are 180.8, 154.1, 134.8, and 109.3 mAh g−1, respectively; these values indicate excellent rate performance. The remarkable performance enhancement is attributed to the interconnected network of conductive CNTs, which guarantees high conductivity and enables fast electron transport between CNTs and V2O5 of the uniformly dispersed VCM. Moreover, VCM provides a hierarchical template to accommodate the structural degradation and delamination of V2O5 particles during electrochemical cycling. The proposed spray‐drying strategy is facile, effective, and easy to realize on a large scale for the low‐cost industrial production of V2O5/CNT composite cathodes, which can be extended to produce other high‐capacity electrode materials with large volume variations and low electrical conductivities.
Mortality and survival patterns of childhood lymphomas: geographic and age‐specific patterns in Southern‐Eastern European and SEER/US registration data
Authors: Karalexi Maria A. , Georgakis Marios K. , Dessypris Nick , Ryzhov Anton , Zborovskaya Anna , Dimitrova Nadya , Zivkovic Snezana , Eser Sultan , Antunes Luis , Sekerija Mario , Zagar Tina , Bastos Joana , Demetriou Anna , Agius Domenic , Florea Margareta , Coza Daniela , Bouka Evdoxia , Dana Helen , Hatzipantelis Emmanuel , Kourti Maria , Moschovi Maria , Polychronopoulou Sophia , Stiakaki Eftichia , Pourtsidis Apostolos , Petridou Eleni Th. 
Published: September 2016

AbstractChildhood (0‐14 years) lymphomas, nowadays, present a highly curable malignancy compared with other types of cancer. We used readily available cancer registration data to assess mortality and survival disparities among children residing in Southern‐Eastern European (SEE) countries and those in the United States. Average age‐standardized mortality rates and time trends of Hodgkin (HL) and non‐Hodgkin (NHL; including Burkitt [BL]) lymphomas in 14 SEE cancer registries (1990‐2014) and the Surveillance, Epidemiology, and End Results Program (SEER, United States; 1990‐2012) were calculated. Survival patterns in a total of 8918 cases distinguishing also BL were assessed through Kaplan‐Meier curves and multivariate Cox regression models. Variable, rather decreasing, mortality trends were noted among SEE. Rates were overall higher than that in SEER (1.02/106), which presented a sizeable (−4.8%, P = .0001) annual change. Additionally, remarkable survival improvements were manifested in SEER (10 years: 96%, 86%, and 90% for HL, NHL, and BL, respectively), whereas diverse, still lower, rates were noted in SEE. Non‐HL was associated with a poorer outcome and an amphi‐directional age‐specific pattern; specifically, prognosis was inferior in children younger than 5 years than in those who are 10 to 14 years old from SEE (hazard ratio 1.58, 95% confidence interval 1.28‐1.96) and superior in children who are 5 to 9 years old from SEER/United States (hazard ratio 0.63, 95% confidence interval 0.46‐0.88) than in those who are 10 to 14 years old. In conclusion, higher SEE lymphoma mortality rates than those in SEER, but overall decreasing trends, were found. Despite significant survival gains among developed countries, there are still substantial geographic, disease subtype‐specific, and age‐specific outcome disparities pointing to persisting gaps in the implementation of new treatment modalities and indicating further research needs.
Application of an Algal Bloom Control Technique using Large Zooplankton Predators in An Eutrophic Agricultural Reservoir: A Preliminary Study
Authors: Nam Gui‐Sook , Lee Eui‐Haeng , Chang Kwang‐Hyeon 
Published: September 2016

AbstractMassive nuisance algal blooms are a primary concern for the management of eutrophic reservoirs. The effects of biomanipulation using trophic cascade effects in the aquatic food chain vary with the conditions of applied water bodies and are controversial. However, this mode of biomanipulation has long been considered an ecosystem‐friendly approach for the management of algal blooms. In the present study, herbivorous Daphnia similoides were artificially proliferated using a large culture system and were used to control algal blooms in a eutrophic agricultural reservoir. Introduced predators proliferated rapidly in the culture tanks, and high densities were subsequently sustained. Predators were then released into the reservoir at 1‐week intervals during early summer and autumn, and 84.4% algal removal efficiency was observed and mean values of chlorophyll a concentration decreased from 219 to 34.2 mg m−3 during the algal bloom period in autumn. However, no apparent effects were observed during early summer when fish predation and water temperatures were high. These data suggest that continuous release of predators from our culture facility efficiently facilitates early expansion of zooplankton populations and maintenance of their populations in the reservoir. The effects of introduced zooplankton may be maximized with concurrent management of resident zooplanktivorous fish. Copyright © 2016 John Wiley & Sons, Ltd.
Effects of Flow Path Geometrical Parameters on Flow Characteristics and Hydraulic Performance of Drip Irrigation Emitters
Authors: Zhangzhong Lili , Yang Peiling , Li Yunkai , Ren Shumei 
Published: September 2016

AbstractIn this paper, 13 fractal flow paths were designed and the effects of flow path geometric parameters on the internal flow characteristics and hydraulic performance explored. The results showed as the flow path width increased from 0.9 to 1.3 mm, the flow velocity followed from 1.83 to 2.43 m s−1. There was significant difference in the turbulence intensity. The flow velocity (about 2.14 m s−1) and turbulence intensity distribution (5.6–48.1%) in flow paths with different depths were approximately the same. Different flow path lengths would obviously affect the values of the flow characteristics, while the distributions were similar. The length increased from 128 to 256 mm, the flow velocity decreased from 2.52 to 1.84 m s−1 and the maximum turbulence intensity dropped from 55.6 to 40.1%. As for hydraulic performance, the flow regime indexes were all about 0.49. The flow coefficient was obviously positively related to flow path width and depth, but very negatively correlated with flow path length and a prediction model of flow coefficient was constructed (R2 = 0.94). After comprehensive consideration, the optimized flow path width was about 1.0 mm, the length should be less than 224 mm, and a series of emitters with different flow rates could be developed by changing the depth. Copyright © 2016 John Wiley & Sons, Ltd.
Exacerbation of innate immune response in mouse primary cultured sertoli cells caused by nanoparticulate TiO2 involves the TAM/TLR3 signal pathway
Authors: Wu Nan , Hong Fashui , Zhou Yingjun , Wang Yajing 
Published: September 2016

AbstractSertoli cells provide appropriate mitogens, differentiation factors and sources of energy for developing germ cells throughout the lifetime of males, and protect these germ cells from harmful agents and from the host's own immune system. Therefore, reductions in the rate and quality of spermatogenesis caused by nanoparticulate titanium dioxide (nano‐TiO2) may be closely involved in the immunoregulation of Sertoli cells. However, the underlying mechanism of this response is still unclear. To address this issue, we used mouse primary cultured Sertoli cells to examine the toxic effects of nano‐TiO2 via alterations in morphology, cell viability, and activation of the TAM/TLR3 signal pathway. The results demonstrated that nano‐TiO2 could cross the cytomembrane into the cytoplasm or nucleus, decrease Sertoli cell viability, damage morphology (such as elongated fusiform, cellular and nuclear shrinkage) and induce the expression of various immune mediators and inflammatory cytokines, including TLR3(+0.31‐fold to +0.81‐fold), IL‐lβ(+0.33‐fold to +5.0‐fold), NF‐κB(+0.22‐fold to +3.65‐fold), IL‐6(+0.47‐fold to +3.53‐fold), TNF‐α(+0.14‐fold to +2.44‐fold), IFN‐α(+0.17‐fold to +2.27‐fold), and IFN‐β(+0.09‐fold to +2.29‐fold), and suppress the expression of Tyro3(−9.33% to −61.93%), Axl(−19.03% to −60.67%), Mer(−8.04% to −59.16%), and IκB(−34.35% to −86.59%) in primary cultured Sertoli cells. These results suggest that testicular innate immune responses to pathogens caused by nano‐TiO2 may be involved in the regulatory mechanisms of TAM/TLR3 signaling in testicular Sertoli cells. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 198–208, 2017.
Morphological examination of highly porous polylactic acid/Bioglass® scaffolds produced via nonsolvent induced phase separation
Authors: Rezabeigi Ehsan , Wood‐Adams Paula M. , Drew Robin A. L. 
Published: September 2016

AbstractIn this study, we produce highly porous (up to ∼91%) composite scaffolds of polylactic acid (PLA) containing 2 wt % sol‐gel‐derived 45S5 Bioglass® particles via nonsolvent induced phase separation at −23°C with no sacrificial phases involved. Before the incorporation of the bioglass with PLA, the particles are surface modified with a silane coupling agent which effectively diminishes agglomeration between them leading to a better dispersion of bioactive particles throughout the scaffold. Interestingly, the incorporation route (via solvent dichloromethane or nonsolvent hexane) of the surface modified particles in the foaming process has the greatest impact on porosity, crystallinity, and morphology of the scaffolds. The composite scaffolds with a morphology consisting of both mesopores and large macropores, which is potentially beneficial for bone regeneration applications, are examined further. SEM images show that the surface modified bioglass particles take‐up a unique configuration within the mesoporous structure of these scaffolds ensuring that the particles are well interlocked but not completely covered by PLA such that they can be in contact with physiological fluids. The results of preliminary in vitro tests confirm that this PLA/bioglass configuration promotes the interaction of the bioactive phase with physiological fluids. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2433–2442, 2017.