bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mononuclear Manganese–Peroxo and Bis(μ‐oxo)dimanganese Complexes Bearing a Common N‐Methylated Macrocyclic Ligand
Authors: Kang Hyeona , Cho Jaeheung , Cho Kyung‐Bin , Nomura Takashi , Ogura Takashi , Nam Wonwoo 
Published: September 2013

AbstractMononuclear MnIII–peroxo and dinuclear bis(μ‐oxo)MnIII2 complexes that bear a common macrocyclic ligand were synthesized by controlling the concentration of the starting MnII complex in the reaction of H2O2 (i.e., a MnIII–peroxo complex at a low concentration (≤1 mM) and a bis(μ‐oxo)MnIII2 complex at a high concentration (≥30 mM)). These intermediates were successfully characterized by various physicochemical methods such as UV–visible spectroscopy, ESI‐MS, resonance Raman, and X‐ray analysis. The structural and spectroscopic characterization combined with density functional theory (DFT) calculations demonstrated unambiguously that the peroxo ligand is bound in a side‐on fashion in the MnIII–peroxo complex and the Mn2O2 diamond core is in the bis(μ‐oxo)MnIII2 complex. The reactivity of these intermediates was investigated in electrophilic and nucleophilic reactions, in which only the MnIII–peroxo complex showed a nucleophilic reactivity in the deformylation of aldehydes.
Synthesis and Morphology Control of AM‐6 Nanofibers with Tailored ‐V‐O‐V‐ Intermediates
Authors: Guo Meiling , Feng Zhaochi , Hofmann Jan P. , Weckhuysen Bert M. , Fan Fengtao , Li Can 
Published: September 2013

AbstractMicroporous vanadosilicates with octahedral VO6 and tetrahedral SiO4 units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO3− intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of VO terminals, and thus improve the catalytic performance.
Conversion of trans‐Diboran(4)yl Platinum Complexes into Their cis‐Bisboryl Analogues
Authors: Braunschweig Holger , Damme Alexander , Kupfer Thomas 
Published: September 2013

AbstractThe diboran(4)yl trans‐[(iPr3P)2Pt(Br){B(NMe2)B(NMe2)Br}] (1) is readily converted into its cis‐bisboryl analogues 2 and 3 by reaction with the chelating bisphosphines 1,2‐bis(dicyclohexylphosphino)ethane (dcpe) and 1,1‐bis(dicyclohexylphosphino)methane (dcpm), respectively. A plausible mechanism of this transformation consists of a sequence of reductive diborane(4) elimination and subsequent reoxidative addition of its BB bond to the low‐valent platinum centers. Thus, the forced cis configuration of the phosphine ligands induces a change in the preferred reaction site of the diborane(4) with respect to oxidative addition. The reactions proceed with high selectivities, and the cis‐bisboryl complexes 2 and 3 were isolated in moderate yields (55 and 46 %). Moreover, their identity was clearly verified by NMR spectroscopy and X‐ray diffraction studies.
Tuning Redox Chemistry and Photophysics in Core‐Substituted Tetraazaperopyrenes (TAPPs)
Authors: Geib Sonja , Martens Susanne C. , Märken Michaela , Rybina Arina , Wadepohl Hubert , Gade Lutz H. 
Published: September 2013

AbstractCore substitution of tetraazaperopyrenes (TAPPs) has been achieved, and with it, considerable variation of their photo‐ and redox‐chemical properties. Through Suzuki cross coupling starting from the fourfold core‐brominated tetraazaperopyrene, aryl‐substituted TAPPs were synthesized, which displayed very high fluorescence quantum yields (up to 100 %) in solution. Besides the Suzuki reactions, Stille and Sonogashira cross‐couplings were also found to be suitable methods for core derivatization, as demonstrated in the syntheses of alkynyl‐substituted tetraazaperopyrene congeners. Furthermore, TAPPs incorporating intramolecular donor–acceptor combinations of aromatic units (8, 9) were accessible by coupling the electron‐poor peropyrene core with electron‐rich aromatic units, which act as strong electron donors. Finally, C‐heteroatom coupling (O, S, N) gave rise to novel TAPP derivatives with strongly modified redox‐chemical behaviour and photophysics in the solid state as well in solution. In particular, TAPP derivatives displaying red fluorescence were obtained for the first time.
A 1,3‐Phenylene‐Bridged Hexameric Porphyrin Wheel and Efficient Excitation Energy Transfer along the Wheel
Authors: Jiang Hua‐Wei , Ham Sujin , Aratani Naoki , Kim Dongho , Osuka Atsuhiro 
Published: September 2013

AbstractA 1,3‐phenylene‐bridged hexameric ZnII porphyrin wheel was synthesized by a Suzuki–Miyaura coupling reaction through a one‐pot or a stepwise route. The hexameric wheel structure was revealed by using X‐ray diffraction analysis. The porphyrin wheel exhibits a split Soret band due to effective exciton coupling and displays efficient excitation energy transfer along the wheel. Measurements of fluorescence anisotropy decay and pump‐power‐dependent decay reveal a rapid excitation energy hopping along the wheel with a rate of 1.4 ps.
Regioselective Hydroxylation of C12–C15 Fatty Acids with Fluorinated Substituents by Cytochrome P450 BM3
Authors: Chiang Chih‐Hsiang , Ramu Ravirala , Tu Yi‐Jung , Yang Chung‐Ling , Ng Kok Yaoh , Luo Wen‐I , Chen Charles H. , Lu Yu‐Ying , Liu Chen‐Lun , Yu Steve S.‐F. 
Published: September 2013

AbstractWe demonstrate herein that wild‐type cytochrome P450 BM3 can recognize non‐natural substrates, such as fluorinated C12–C15 chain‐length fatty acids, and show better catalysis for their efficient conversion. Although the binding affinities for fluorinated substrates in the P450 BM3 pocket are marginally lower than those for non‐fluorinated substrates, spin‐shift measurements suggest that fluoro substituents at the ω‐position can facilitate rearrangement of the dynamic structure of the bulk‐water network within the hydrophobic pocket through a micro desolvation process to expel the water ligand of the heme iron that is present in the resting state. A lowering of the Michaelis–Menten constant (Km), however, indicates that fluorinated fatty acids are indeed better substrates compared with their non‐fluorinated counterparts. An enhancement of the turnover frequencies (kcat) for electron transfer from NADPH to the heme iron and for CH bond oxidation by compound I (Cpd I) to yield the product suggests that the activation energies associated with going from the enzyme–substrate (ES state) to the corresponding transition state (ES≠ state) are significantly lowered for both steps in the case of the fluorinated substrates. Delicate control of the regioselectivity by the fluorinated terminal methyl groups of the C12–C15 fatty acids has been noted. Despite the fact that residues Arg47/Tyr51/Ser72 exert significant control over the hydroxylation of the subterminal carbon atoms toward the hydrocarbon tail, the fluorine substituent(s) at the ω‐position affects the regioselective hydroxylation. For substrate hydroxylation, we have found that fluorinated lauric acids probably give a better structural fit for the heme pocket than fluorinated pentadecanoic acid, even though pentadecanoic acid is by far the best substrate among the reported fatty acids. Interestingly, 12‐fluorododecanoic acid, with only one fluorine atom at the terminal methyl group, exhibits a comparable turnover frequency to that of pentadecanoic acid. Thus, fluorination of the terminal methyl group introduces additional interactions of the substrate within the hydrophobic pocket, which influence the electron transfers for both dioxygen activation and the controlled oxidation of aliphatics mediated by high‐valent oxoferryl species.
Site‐Specifically Arraying Small Molecules or Proteins on DNA Using An Expanded Genetic Alphabet
Authors: Li Zhengtao , Lavergne Thomas , Malyshev Denis A. , Zimmermann Jörg , Adhikary Ramkrishna , Dhami Kirandeep , Ordoukhanian Phillip , Sun Zhelin , Xiang Jie , Romesberg Floyd E. 
Published: September 2013

AbstractA class of replicable unnatural DNA base pairs formed between d5SICS and either dMMO2, dDMO, or dNaM were developed. To explore the use of these pairs to produce site‐specifically labeled DNA, the synthesis of a variety of derivatives bearing propynyl groups, an analysis of their polymerase‐mediated replication, and subsequent site‐specific modification of the amplified DNA by Click chemistry is reported. With the d5SICS scaffold a propynyl ether linker is accommodated better than its aliphatic analogue, but not as well as the protected propargyl amine linker explored previously. It was also found that with the dMMO2 and dDMO analogues, the dMMO2 position para to the glycosidic linkage is best suited for linker attachment and that although aliphatic and ether‐based linkers are similarly accommodated, the direct attachment of an ethynyl group to the nucleobase core is most well tolerated. To demonstrate the utility of these analogues, a variety of them were used to site‐selectively attach a biotin tag to the amplified DNA. Finally, we use d5SICSCO–dNaM to couple one or two proteins to amplified DNA, with the double labeled product visualized by atomic force microscopy. The ability to encode the spatial relationships of arrayed molecules in PCR amplifiable DNA should have important applications, ranging from SELEX with functionalities not naturally present in DNA to the production, and perhaps “evolution” of nanomaterials.
Cleavage of PO in the Presence of P–N: Aminophosphine Oxide Reduction with In Situ Boronation of the PIII Product
Authors: Kenny Niall P. , Rajendran Kamalraj V. , Jennings Elizabeth V. , Gilheany Declan G. 
Published: September 2013

AbstractIn contrast to tertiary phosphine oxides, the deoxygenation of aminophosphine oxides is effectively impossible due to the need to break the immensely strong and inert PO bond in the presence of a relatively weak and more reactive PN bond. This long‐standing problem in organophosphorus synthesis is solved by use of oxalyl chloride, which chemoselectively cleaves the PO bond forming a chlorophosphonium salt, leaving the PN bond(s) intact. Subsequent reduction of the chlorophosphonium salt with sodium borohydride forms the PIII aminophosphine borane adduct. This simple one‐pot procedure was applied with good yields for a wide range of PN‐containing phosphoryl compounds. The borane product can be easily deprotected to produce the free PIII aminophosphine. Along with no observed PN bond cleavage, the use of sodium borohydride also permits the presence of ester functional groups in the substrate. The availability of this methodology opens up previously unavailable synthetic options in organophosphorus chemistry, two of which are exemplified.
The relational benefits of personalized communications in an online environment
Authors: Dantas Danilo C. , Carrillat François 
Published: September 2013

AbstractThis research investigates how personalized communications enhance customer‐company relationships, which ultimately produce favourable marketing outcomes. Two factors were manipulated in an online experiment: the perceived effort made by customers to obtain a personalized newsletter (high vs. low) and the level of relevance of the message (high vs. low). The results indicate that perceived effort positively affects calculative commitment (even more so for highly involved customers), while the level of relevance of the message increases affective commitment. In addition, the interaction between perceived effort and message relevance has significant effects on calculative and affective commitment. Finally, affective commitment partially mediates the relationships between relevance and both loyalty and word‐of‐mouth intentions. Managerial implications regarding the best usage of personalized communications are discussed. Copyright © 2013 ASAC. Published by John Wiley & Sons, Ltd.
The impact of AACSB accreditation: A multiple case study of Canadian university business schools
Authors: Elliott Catherine 
Published: September 2013

AbstractOver the last two decades there has been a significant increase in the number of university business schools seeking accreditation from the Association to Advance Collegiate Schools of Business (AACSB International). Despite this remarkable growth there has been limited empirical research on this phenomenon. Using a qualitative multiple case study approach, this research explores the impact of accreditation on four Canadian university business schools. Participants reported seven main effects, with the most important being enhanced reputation, leverage for change, increased management efficiencies, and focus on research. These impacts were influenced by the context in which accreditation took place. Environmental uncertainty as a contextual dimension is discussed. Copyright © 2013 ASAC. Published by John Wiley & Sons, Ltd.
Capacités d'innovation technologique, stratégie produit et performance des entreprises: Le cas de l'industrie électronique en Chine
Authors: Shan Juan , Jolly Dominique R. 
Published: September 2013

AbstractThis research was conducted with a sample of 215 Chinese companies from the electronics industry. It shows that the different technological innovation capabilities have a positive impact on product innovation, beginning with the linkage capability, and then moving to the production capability, and ending with the investment capability. The research also shows that product innovation has a mediating effect on the relationship between different technological innovation capabilities and firm performance. Copyright © 2013 ASAC. Published by John Wiley & Sons, Ltd.
Numerical approaches and analysis of spray characteristics for pressuriser nozzles
Authors: Lan Zhike , Zhu Dahuan , Tian Wenxi , Su Guanghui , Qiu Suizheng 
Published: September 2013

AbstractVolume of fluid (VOF) method combined with primary breakup model (PBM) is developed to model large flow rate pressure‐swirl nozzle used in pressuriser of the pressurised water reactor (PWR) power plant system. For the VOF model, the renormalisation‐group (RNG) K–ϵ model is selected to ensure the accuracy of simulation for swirling flows. The 3‐D transient flow is simulated and the dynamic stability of the injection pattern is analysed for the nozzle. Based on the growth rate of the disturbance at the interface of the two phases, PBM is embedded in the VOF model in the form of user defined functions (UDF) to investigate the further breakup from sheet to spray drop and predict the spray drop size spectrum. In addition, experimental studies, considering the characteristics of mass flow rate, spray cone angle, spray flux distribution and drop size spectrum, were conducted to verify accuracy of the numerical results. The result of comparison shows that there is good agreement between the simulated results and the experimental data. Especially, the distribution tendency of the spray drop size simulated by PBM fits the experimental value well and the drop size corresponding to the maximum probability is predicted successfully. The present investigation shows that the VOF–PBM methodology can be applied to simulate the pressure‐swirl nozzle and optimise design of spraying systems.
Prediction of minimum spouting velocity by CFD–TFM: Approach development
Authors: Liu Xuejiao , Shao Yingjuan , Zhong Wenqi , Grace John R. , Epstein Norman , Jin Baosheng 
Published: September 2013

AbstractA three‐dimensional (3D) Eulerian–Eulerian multiphase model (two‐fluid model, TFM) was developed to predict the minimum spouting velocity (ums) of spouted beds, with the aid of UBC experiments in a 152‐mm conical–cylindrical vessel. The gas motion was simulated by the k–ϵ two‐equation turbulent model, while the particle phase motion was estimated from the kinetic theory of granular flow. The inlet minimum spouting velocity, ums, was numerically predicted by visual observations and analysis of simulated distributions of the solid volume fraction and particle vector field for decreasing gas flow. The effects of particle diameter, static bed height and fluid inlet diameter on ums were checked, in order to confirm the validity of the present developed method. In addition, numerical predictions are compared with the predicted values from several empirical correlations reported in the open literature. Best congruence is with the popular Mathur–Gishler equation.
Clinicopathologic characteristics of pancreatic neuroendocrine tumors and relation of somatostatin receptor type 2A to outcomes
Authors: Okuwaki Kosuke , Kida Mitsuhiro , Mikami Tetuo , Yamauchi Hiroshi , Imaizumi Hiroshi , Miyazawa Shiro , Iwai Tomohisa , Takezawa Miyoko , Saegusa Makoto , Watanabe Masahiko , Koizumi Wasaburo 
Published: September 2013

BACKGROUNDThe impact of somatostatin receptor type 2 (SSTR‐2a) expression levels on outcomes in patients with pancreatic neuroendocrine tumors (PNETs) has not been evaluated.METHODSCorrelations between clinicopathologic characteristics, including SSTR‐2a expression and outcomes, were retrospectively studied in 79 patients with pancreatic neuroendocrine tumors (PNETs).RESULTSThe SSTR‐2a score was 0 in 27% of patients, 1 in 24% of patients, 3 in 30% of patients, and 4 in 18% of patients. The overall survival rate was 87% at 1 year, 77% at 3 years, and 71% at 5 years. On univariate analysis, a pancreatic tumor that measured ≥20 mm in greatest dimension, stage IV disease, vascular invasion, neuroendocrine carcinoma (NEC), and an SSTR‐2a score of 0 were associated significantly with poor outcomes. On multivariate analysis, NEC (P = .000; hazard ratio, 28.8; 95% confidence interval, 7.502‐111.240) and an SSTR‐2a score of 0 (P = .001; hazard ratio, 3.611; 95% confidence interval, 1.344‐9.702) were related independently to poor outcomes.CONCLUSIONSThe current analysis of prognostic factors in patients with PNETs demonstrated that NEC and an SSTR‐2a score of 0 both were significant independent predictors of poor outcomes. The results suggest that the assessment of SSTR‐2a may facilitate the selection of treatment regimens and the prediction of outcomes. Because a considerable proportion of patients with NEC have SSTR‐2a‐positive tumors, further analyses of the usefulness of somatostatin analogues are warranted in patients who have SSTR‐2a‐positive NEC. Cancer 2013. © 2013 American Cancer Society.
Towards Stable Catalysts for Aqueous Phase Conversion of Ethylene Glycol for Renewable Hydrogen
Authors: Koichumanova Kamila , Vikla Anna Kaisa K. , de Vlieger Dennis J. M. , Seshan K. , Mojet Barbara L. , Lefferts Leon 
Published: September 2013

AbstractAqueous‐phase reforming of ethylene glycol over alumina‐supported Pt‐based catalysts is reported. Performance of the catalysts is investigated by conducting kinetics and in situ attenuated total reflectance (ATR)‐IR spectroscopic analysis. Pt/γ‐Al2O3 is unstable under APR conditions (270 °C, 90 bar) and undergoes phase transformation to boehmite [AlO(OH)]. This conversion of alumina is studied in situ by using ATR‐IR spectroscopy; transition into boehmite proceeds even at milder conditions (210 °C, 40 bar). Pt/γ‐Al2O3 deactivates irreversibly because the Pt surface area decreases owing to an increasing metal particle size and coverage with boehmite. However, Pt supported on boehmite itself shows stable activity. Surprisingly, the rate of formation of hydrogen per Pt surface atom is significantly higher on boehmite compared to an alumina‐supported catalyst. This observation seems correlated to both increased concentration of surface OH groups as well as to enhanced oxidation of Pt when comparing Pt/γ‐Al2O3 with Pt/AlO(OH).
Dyadic concordance in mother and preschooler resting cardiovascular function varies by risk status
Authors: Creaven Ann‐Marie , Skowron Elizabeth A. , Hughes Brian M. , Howard Siobhán , Loken Eric 
Published: September 2013

AbstractThis study examined concordance in heart rate (HR) and respiratory sinus arrhythmia (RSA) in a sample of 104 child‐maltreating (CM) and nonCM mother–preschooler dyads (208 individuals). In a laboratory setting, mother and child cardiac physiology was simultaneously monitored via ECG in a 5‐min resting period. Mothers ranged in age from 20 to 49 years; children ranged in age from 3 to 5 years. Significant within‐dyad (WD) and between‐dyad (BD) associations were observed for mother HR and both child HR and RSA, and the associations were moderated by CM status. Only CM dyads exhibited BD associations: Higher average maternal HR was associated with higher child HR and lower child RSA. By contrast, when the time interval was divided into 30 s epochs, nonCM dyads exhibited positive WD (dynamic) associations in mother and child HR, and both CM and nonCM dyads showed negative WD associations in mother HR and child RSA. Further, mothers' mean HR levels moderated the extent of epoch‐by‐epoch WD concordance observed in mother and child, such that elevated average maternal HR was associated with lower levels of WD (dynamic) concordance. No BD or WD concordance in maternal and child RSA was observed. The findings suggest that measures of intraindividual variation provide useful, alternate perspectives in the study of dyadic processes in at‐risk families. © 2013 Wiley Periodicals, Inc. Dev Psychobiol 56: 142–152, 2014.
Sub‐Micron‐Wide Surficial Trench Frames to Define the Coating Areas of Sensitive Layers on Silicon MEMS Resonant Chemical Sensors
Authors: Murakami Sunao , Ikehara Tsuyoshi , Konno Mitsuo , Maeda Ryutaro , Fukawa Tadashi , Kimura Mutsumi , Mihara Takashi 
Published: September 2013

SUMMARYWe propose a new processing method to form thin films on the predefined micro‐areas of movable parts of microdevices by using trench frames on the device surfaces in the coating of solutions containing the membrane materials. We fabricated 500‐nm‐wide surficial trench frames additively on silicon microcantilevers to define the areas coated with the thin films by increasing the tolerance to protrusion of a liquid droplet from the edge in the coating process. The trench frames were fabricated on the silicon surfaces by deep‐reactive ion etching with the resist mask patterned by electron beam lithography. We also fabricated the same trench frames on planar silicon substrates, and we examined the proper conditions for the formation of polybutadiene (PBD) thin films on the framed surfaces by coating PBD solution using a microdispenser system. When the n‐dodecane solution of PBD was applied to the micro‐area framed by the trenches, PBD film was successfully defined within the framed area. The trench frames fabricated on the cantilevers indicated the practical effectiveness to define the PBD thin films within the framed micro‐areas. © 2013 Wiley Periodicals, Inc. Electron Comm Jpn, 96(10): 60–66, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ecj.11379