bluuebunny/crossref_metadata_2025_split huggingface dataset:
Signal‐Amplified Analysis of Molecular Layers Prepared through Bipolar Electrochemistry
Authors: Shida Naoki , Kitamura Fusao , Fuchigami Toshio , Tomita Ikuyoshi , Inagi Shinsuke 
Published: September 2015

AbstractIn this article, we investigate the surface modification of an indium tin oxide (ITO) plate as a bipolar electrode (BPE) by bipolar electrolysis with the well‐established electrochemistry of aryl diazonium salts. To study in detail the formation behavior of a molecular layer of the aryl groups, we employ two different approaches, namely, the direct analysis of the layer and the indirect analysis based on the idea of signal amplification by the surface‐initiated polymerization (SIP) technique. For the direct analysis, we made X‐ray photoelectron spectroscopy (XPS) measurements of the molecular layer and find that the amount of the aryl group introduced is in a gradient manner, reflecting the potential slope generated on the BPE. After the SIP process, signals amplified by the grafting polymers can be detected by infrared reflection absorption spectroscopy (IR–RAS) and film thickness measurement with a stylus‐type tester. Atomic force microscopy (AFM) measurement of the surface of the polymer brush was also carried out. These indirect methods afford detailed information on the modification behavior of the original molecular layer prepared through the bipolar electrolysis process.
Mechanistic Aspects of Aryl–Halide Oxidative Addition, Coordination Chemistry, and Ring‐Walking by Palladium
Authors: Zenkina Olena V. , Gidron Ori , Shimon Linda J. W. , Iron Mark A. , van der Boom Milko E. 
Published: September 2015

AbstractThis contribution describes the reactivity of a zero‐valent palladium phosphine complex with substrates that contain both an aryl halide moiety and an unsaturated carbon–carbon bond. Although η2‐coordination of the metal center to a CC or CC unit is kinetically favored, aryl halide bond activation is favored thermodynamically. These quantitative transformations proceed under mild reaction conditions in solution or in the solid state. Kinetic measurements indicate that formation of η2‐coordination complexes are not nonproductive side‐equilibria, but observable (and in several cases even isolated) intermediates en route to aryl halide bond cleavage. At the same time, DFT calculations show that the reaction with palladium may proceed through a dissociation–oxidative addition mechanism rather than through a haptotropic intramolecular process (i.e., ring walking). Furthermore, the transition state involves coordination of a third phosphine to the palladium center, which is lost during the oxidative addition as the Chalide bond is being broken. Interestingly, selective activation of aryl halides has been demonstrated by adding reactive aryl halides to the η2‐coordination complexes. The product distribution can be controlled by the concentration of the reactants and/or the presence of excess phosphine.
Versatile Tailoring of Paddle‐Wheel ZnII Metal–Organic Frameworks through Single‐Crystal‐to‐Single‐Crystal Transformations
Authors: Pal Tapan K. , Neogi Subhadip , Bharadwaj Parimal K. 
Published: September 2015

AbstractA new tetracarboxylate ligand having short and long arms formed 2D layer ZnII coordination polymer 1 with paddle‐wheel secondary building units under solvothermal conditions. The framework undergoes solvent‐specific single crystal‐to‐single crystal (SC‐SC) transmetalation to produce 1Cu. With a sterically encumbered dipyridyl linker, the same ligand forms non‐interpenetrated, 3D, pillared‐layer ZnII metal–organic framework (MOF) 2, which takes part in SC‐SC linker‐exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker‐exchange experiments. All the 3D MOFs undergo complete SC‐SC transmetalation with CuII, whereby metal exchange in different solvents and monitoring of X‐ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis.
Separation of Ofloxacin and Its Six Related Substances Enantiomers by Chiral Ligand‐Exchange Chromatography
Authors: Liang Xinlei , Zhao Longshan , Deng Miaoduo , Liu Lijie , Ma Yongfu , Guo Xingjie 
Published: September 2015

AbstractA chiral ligand‐exchange high‐performance liquid chromatography method was developed for the enantioseparation of ofloxacin and its six related substances termed impurities A, B, C, D, E, and F. The separation was performed on a conventional C18 column. Different organic modifiers, copper salts, amino acids, the ratio of Cu2+ to amino acid, pH of aqueous phase, and column temperature were optimized. The optimal mobile phase conditions were methanol‐water systems consisting of 5 mmol/L copper sulfate and 10 mmol/L L‐isoleucine (L‐Ile). Under such conditions, good enantioseparation of ofloxacin and impurities A, C, E, and F could be observed with resolutions (RS) of 3.54, 1.97, 3.21, 3.50, and 2.12, respectively. On the relationship between the thermodynamic parameters and structures of analytes, the mechanism of chiral recognition was investigated. It was concluded that ofloxacin and impurities A, C, E, and F were all enthalpically driven enantioseparation and that low column temperature was beneficial to enantioseparation. Furthermore, the structure–separation relationship of these analytes is also discussed. Chirality 27:843–849, 2015. © 2015 Wiley Periodicals, Inc.
Discovery of Inhibitors of Trypanosoma brucei by Phenotypic Screening of a Focused Protein Kinase Library
Authors: Woodland Andrew , Thompson Stephen , Cleghorn Laura A. T. , Norcross Neil , De Rycker Manu , Grimaldi Raffaella , Hallyburton Irene , Rao Bhavya , Norval Suzanne , Stojanovski Laste , Brun Reto , Kaiser Marcel , Frearson Julie A. , Gray David W. , Wyatt Paul G. , Read Kevin D. , Gilbert Ian H. 
Published: September 2015

AbstractA screen of a focused kinase inhibitor library against Trypanosoma brucei rhodesiense led to the identification of seven series, totaling 121 compounds, which showed >50 % inhibition at 5 μm. Screening of these hits in a T. b. brucei proliferation assay highlighted three compounds with a 1H‐imidazo[4,5‐b]pyrazin‐2(3H)‐one scaffold that showed sub‐micromolar activity and excellent selectivity against the MRC5 cell line. Subsequent rounds of optimisation led to the identification of compounds that exhibited good in vitro drug metabolism and pharmacokinetics (DMPK) properties, although in general this series suffered from poor solubility. A scaffold‐hopping exercise led to the identification of a 1H‐pyrazolo[3,4‐b]pyridine scaffold, which retained potency. A number of examples were assessed in a T. b. brucei growth assay, which could differentiate static and cidal action. Compounds from the 1H‐imidazo[4,5‐b]pyrazin‐2(3H)‐one series were found to be either static or growth‐slowing and not cidal. Compounds with the 1H‐pyrazolo[3,4‐b]pyridine scaffold were found to be cidal and showed an unusual biphasic nature in this assay, suggesting they act by at least two mechanisms.
Imidazotriazines: Spleen Tyrosine Kinase (Syk) Inhibitors Identified by Free‐Energy Perturbation (FEP)
Authors: Lovering Frank , Aevazelis Cristina , Chang Jeanne , Dehnhardt Christoph , Fitz Lori , Han Seungil , Janz Kristin , Lee Julie , Kaila Neelu , McDonald Joseph , Moore William , Moretto Alessandro , Papaioannou Nikolaos , Richard David , Ryan Mark S. , Wan Zhao‐Kui , Thorarensen Atli 
Published: September 2015

AbstractThere has been significant interest in spleen tyrosine kinase (Syk) owing to its role in a number of disease states, including autoimmunity, inflammation, and cancer. Ongoing therapeutic programs have resulted in several compounds that are now in clinical use. Herein we report our optimization of the imidazopyrazine core scaffold of Syk inhibitors through the use of empirical and computational approaches. Free‐energy perturbation (FEP) methods with MCPRO+ were undertaken to calculate the relative binding free energies for several alternate scaffolds. FEP was first applied retrospectively to determine if there is any predictive value; this resulted in 12 of 13 transformations being predicted in a directionally correct manner. FEP was then applied in a prospective manner to evaluate 17 potential targets, resulting in the realization of imidazotriazine 17 (3‐(4‐(3,4‐dimethoxyphenylamino)imidazo[1,2‐f][1,2,4]triazin‐2‐yl)benzamide), which shows a tenfold improvement in activity relative to the parent compound and no increase in atom count. Optimization of 17 led to compounds with nanomolar cellular activity.
Discovery of Novel Allosteric Non‐Bisphosphonate Inhibitors of Farnesyl Pyrophosphate Synthase by Integrated Lead Finding
Authors: Marzinzik Andreas L. , Amstutz René , Bold Guido , Bourgier Emmanuelle , Cotesta Simona , Glickman J. Fraser , Götte Marjo , Henry Christelle , Lehmann Sylvie , Hartwieg J. Constanze D. , Ofner Silvio , Pellé Xavier , Roddy Thomas P. , Rondeau Jean‐Michel , Stauffer Frédéric , Stout Steven J. , Widmer Armin , Zimmermann Johann , Zoller Thomas , Jahnke Wolfgang 
Published: September 2015

AbstractFarnesyl pyrophosphate synthase (FPPS) is an established target for the treatment of bone diseases, but also shows promise as an anticancer and anti‐infective drug target. Currently available anti‐FPPS drugs are active‐site‐directed bisphosphonate inhibitors, the peculiar pharmacological profile of which is inadequate for therapeutic indications beyond bone diseases. The recent discovery of an allosteric binding site has paved the way toward the development of novel non‐bisphosphonate FPPS inhibitors with broader therapeutic potential, notably as immunomodulators in oncology. Herein we report the discovery, by an integrated lead finding approach, of two new chemical classes of allosteric FPPS inhibitors that belong to the salicylic acid and quinoline chemotypes. We present their synthesis, biochemical and cellular activities, structure–activity relationships, and provide X‐ray structures of several representative FPPS complexes. These novel allosteric FPPS inhibitors are devoid of any affinity for bone mineral and could serve as leads to evaluate their potential in none‐bone diseases.
Control over Water Adhesion on Nanostructured Parahydrophobic Films Using Mesh Substrates
Authors: Darmanin Thierry , Diouf Alioune , El‐Maiss Janwa , Yandé Dieng Samba , Guittard Frédéric 
Published: September 2015

AbstractControl over water adhesion is extremely necessary for many applications in water harvesting, liquid transportation, and water/oil separation, for example. Inspired by natural species such as rose petals and gecko feet, these properties can be controlled with the topography of surface structures. Here, we report for the first time the electrodeposition of sticking conducting polymers forming nanofilaments or nanosheets on textured mesh substrates. We show that the presence of mesh textures can reduce the water adhesion, although the adhesion still remains relatively high. This is probably due to a high amount of air between the mesh wires and a low amount of air on them. Moreover, it is also possible to control the water adhesion with the mesh opening or by modifying the shape of the nanostructures. This work opens new strategies for the control of water adhesion.
Photo‐electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation
Authors: Reichert Robert , Zambrzycki Christian , Jusys Zenonas , Behm R. Jürgen 
Published: September 2015

AbstractTo better understand organic‐molecule‐assisted photo‐electrochemical water splitting, photo‐electrochemistry and on‐line mass spectrometry measurements are used to investigate the photo‐electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2+ and CO2+ ion currents show that water oxidation is strongly suppressed by the organic species. Photo‐electro‐oxidation of formic acid is dominated by formation of CO2, whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo‐electro‐oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed.
The conservation value of elevation data accuracy and model sophistication in reserve design under sea‐level rise
Authors: Zhu Mingjian , Hoctor Tom , Volk Mike , Frank Kathryn , Linhoss Anna 
Published: September 2015

AbstractMany studies have explored the value of using more sophisticated coastal impact models and higher resolution elevation data in sea‐level rise (SLR) adaptation planning. However, we know little about to what extent the improved models and data could actually lead to better conservation outcomes underSLR. This is important to know because high‐resolution data are likely to not be available in some data‐poor coastal areas in the world and running more complicated coastal impact models is relatively time‐consuming, expensive, and requires assistance by qualified experts and technicians. We address this research question in the context of identifying conservation priorities in response toSLR. Specifically, we investigated the conservation value of using more accurate light detection and ranging (Lidar)‐based digital elevation data and process‐based coastal land‐cover change models (Sea Level Affecting Marshes Model,SLAMM) to identify conservation priorities versus simple “bathtub” models based on the relatively coarse National Elevation Dataset (NED) in a coastal region of northeast Florida. We compared conservation outcomes identified by reserve design software (Zonation) using three different model dataset combinations (Bathtub–NED, Bathtub–Lidar, andSLAMM–Lidar). The comparisons show that the conservation priorities are significantly different with different combinations of coastal impact models and elevation dataset inputs. The research suggests that it is valuable to invest in more accurate coastal impact models and elevation datasets inSLRadaptive conservation planning because this model–dataset combination could improve conservation outcomes underSLR. Less accurate coastal impact models, including ones created using coarser Digital Elevation Model (DEM) data can still be useful when better data and models are not available or feasible, but results need to be appropriately assessed and communicated. A future research priority is to investigate how conservation priorities may vary among differentSLRscenarios when different combinations of model‐data inputs are used.
Carbocation Catalysis: Oxa‐Diels–Alder Reactions of Unactivated Aldehydes and Simple Dienes
Authors: El Remaily Mahmoud Abd El Aleem Ali Ali , Naidu Veluru Ramesh , Ni Shengjun , Franzén Johan 
Published: September 2015

AbstractThe versatility of the trityl cation (TrBF4) as a highly efficient Lewis acid organocatalyst is demonstrated in the oxa‐Diels–Alder reaction of various unactivated aromatic and aliphatic aldehydes and simple unactivated dienes, such as isoprene and 2,3‐dimethylbutadiene. The transformation proceeds smoothly to give 3,6‐dihydropyrane adducts in high to moderate yields with catalyst loadings down to 1.0 mol‐% under mild reaction conditions. In contrast to most previously reported strategies, this protocol does not require substrate functional group activation, neither by electron‐deficient aldehydes (2‐oxo aldehydes) or electron‐rich dienes (methoxy or amino‐butadiene).
Using magnetic resonance imaging to quantify the inflammatory response following allergen challenge in allergic rhinitis
Authors: Leaker Brian R. , Scadding Glenis , Jones C. Richard , Barnes Peter J. 
Published: September 2015

AbstractCurrent rhinometric and flow assessments measure nasal patency and are often poorly correlated with rhinitis symptoms. To evaluate magnetic resonance imaging (MRI) as a new method to measure inflammatory changes in nasal and sinus mucosa following nasal allergen challenge. A pilot study (n = 6) determined the optimal technical settings for MRI to measure inflammatory change which were then adopted for the main study. This study was a single blind, placebo‐controlled, three‐way crossover trial in 14 subjects with seasonal allergic rhinitis. Effects of cetirizine, cetirizine and pseudoephedrine (Cet+PE), or placebo on total nasal symptom scores (TNSS), peak nasal inspiratory flow (PNIF), nasal nitric oxide (nNO), acoustic rhinometry, and MRI end points following nasal intranasal allergen challenge were measured. There were significant changes in all parameters after allergen challenge (P < 0.01), except for nNO. MRI end points were less variable and more consistent than PNIF and acoustic rhinometry in detecting changes after allergen challenge. Total nasal airspace volume was the most sensitive and reproducible MRI measurement, with a mean reduction from −5.37 cm3 (95%CI −7.35, −3.38; P < 0.001), which was maximal 60 min after allergen challenge. A change of one in TNSS corresponded to a change in MRI volume of −0.57 cm3. There was an improvement in all parameters (except nNO) in subjects taking Cet+PE compared with placebo, however this did not achieve significance probably because of the small study size (overall analysis P > 0.07; comparison of active versus placebo P > 0.09). MRI provides novel insights into the anatomical inflammatory changes post allergen challenge and provides a new method for assessment of nasal patency and objective measurement of inflammatory responses.
Physicochemical and Redox Characteristics of Fe Ion‐doped CeO2 Nanoparticles
Authors: Ansari Anees A. , Labis J. , Alam Manawwer , Ramay Shahid M. , Ahmad Naushad , Mahmood Asif 
Published: September 2015

AbstractWe report the structural, thermal, optical, and redox properties of Fe‐doped cerium oxide (CeO2) nanoparticles, obtained using the polyol‐co‐precipitation process. X‐ray diffraction data reveal the formation of single‐phase structurally isomorphous CeO2. The presence of Fe3+ may act as electron acceptor and/or hole donor, facilitating longer lived charge carrier separation in Fe‐doped CeO2 nanoparticles as confirmed by optical band gap energy. The increased content of localized defect states in the ceria gap and corresponding shift of the optical absorption edge towards visible range in Fe‐doped samples can significantly improve the optical activity of nanocrystalline ceria. The better‐quality redox performances of the Fe‐doped CeO2 nanoparticles, compared with undoped CeO2 nanoparticles, were ascribed mainly to a decrease in band gap energy and an increase in specific surface area of the material. As observed from TPR studies all Fe ‐doped CeO2 nanoparticles, particularly the 10 mol % Fe doped CeO2 nanoproduct, exhibit excellent reduction performance.
Quantum Mechanical Study of Substituent Dependence on the Structure, Spectroscopic (13C, 1H NMR and UV), NBO, Hyperpolarizability and HOMOLUMO Analysis of Ru(NHC)2Cl2(CH‐p‐C6H4X) Complexes
Authors: Ghiasi Reza , Abdolmohammadi Shahrzad , Moslemizadeh Sara 
Published: September 2015

AbstractIn this work, we have explored the structural, electronic properties, 13C and 1H NMR parameters and first hyperpolarizability of Ru(NHC)2Cl2(CH‐p‐C6H4X) complexes (XH, F, Cl, Me, NH2, OH, CN, NO2, CHO, COOH) by mpw1pw91 quantum method. The X‐substituent effect on structural parameters, frontier orbital energies, spectroscopic (1H and 13C NMR, UV) of complex was carried out. The results indicate that the substituent has played a significant role on the structures and properties of complex. 1H and 13C NMR chemical shifts were calculated by using the gauge‐invariant atomic orbital (GIAO) method. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (OPDOS) diagrams analysis were exhibited. In analyzing the bonding characteristics of this structure, Ru‐Ccarbene and Ru‐CNHC bonds were identified and characterized in details by Natural bond orbital (NBO) analysis.
Changes in annual, seasonal and monthly precipitation events and their link with elevation in Sichuan province, China
Authors: Zeng Wei , Yu Zhen , Wu Shihu , Qin Jianbo 
Published: September 2015

ABSTRACTThis study performs the spatial and temporal trend analysis of the annual, seasonal and monthly time series of a set of uniformly distributed 36 stations precipitation data in Sichuan Province during 1960–2013. The result indicates that the annual precipitation amount and precipitation days across the region have decreasing trends, but the last is significant. The annual precipitation intensity and maximum 1‐day precipitation have slightly increasing trends. Although annual precipitation amount and precipitation days decline, annual precipitation intensity and maximum 1‐day precipitation rise. This reflects that droughts and floods increase in Sichuan Province in recent years. Seasonally, precipitation amount has decreased in all seasons, while autumn precipitation amount is statistically significant. Regionally average trends in precipitation days also show large differences in all seasons. The temporal variability in regional precipitation intensity increases except for autumn, but significant increases are found in spring and summer. Regional maximum 1‐day precipitation has significantly increasing trends in spring and summer, but slightly decreasing trend in autumn and winter. On a monthly basis, trends of precipitation amount show tremendous differences. Spatial changes in annual, seasonal and monthly precipitation events are not the same, and they are not clustered, either. Additionally, the correlations between elevation and the magnitudes of the trends in annual precipitation amount and precipitation days are statistically significant whereas the correlations are not perfect in precipitation intensity and maximum 1‐day precipitation. As can be seen from the seasonal and monthly precipitation amount, the correlations between elevation and the magnitudes of the trends in precipitation amount are higher in spring and autumn, but not perfect in summer and winter. April, October and December precipitation amount shows the strongest positive correlations with elevation. On the whole, the increasing trend of precipitation is relatively prominent at higher elevations, while the decrease trend is more significant at low elevation stations.
The Phenomenon of Later‐Life Recareering by Well‐Educated Baby Boomers
Authors: Rice Candy K. 
Published: September 2015

As well‐educated Boomer professionals reach later life they are engaging in activities such as recareering that defy the normal expectation for older workers in the late adulthood life stage of adult development. Recareering is embarking on a new career in a new industry later in life, after leaving a long‐term primary career. Growing numbers of Boomers are redefining normal work activities as they reach traditional retirement age.A qualitative phenomenological analysis explored the experience of well‐educated Baby Boomer professionals who have recareered. From the dominant thematic findings emerged seven essences of the shared experience of recareering for this population. Results strikingly defied much of common knowledge of the older worker experience.Implications suggested a critical need to embrace a new paradigm of work activities in positive aging. Insights from these Baby Boomer professionals have the potential to redefine adult development theory. Findings have wide benefits for practitioners, academicians, organizations, and governments in terms of the development and implementation of new products, services, and policies for older workers. Future recommendations and limitations are outlined.