bluuebunny/crossref_metadata_2025 huggingface dataset:
Prediction of the heat capacity for compounds based on the conjugate gradient and support vector machine methods
Authors: Shi Jingjie , Chen Liping , Chen Wanghua
Published: September 2013

A quantitative structure–property relationship model for prediction of the heat capacity was developed from molecular structures. By using DRAGON 2.1, various kinds of molecular structure descriptors were calculated to represent the molecular structures of compounds, which contain 18 categories of descriptors in total. The novel variable selection method of ant colony optimization (ACO) algorithm was employed to select an optimal subset of descriptors that have significant contribution to the property from a large pool of calculated descriptors. As a result, five descriptors were screened out as input parameters. With the same five descriptors, ACO coupled with the conjugate gradient (CG) method and support vector machine (SVM) method was employed to construct the linear model (ACO‐CG) and the nonlinear model (ACO‐SVM), respectively. The results showed robust models and small prediction error, and the built models were very satisfying. In addition, the fitting and predicting performances of the ACO‐SVM model (squared correlation coefficient, , ) are both better than that of the ACO‐CG model (, ). The traditional validation parameters of (internal validation) and (external validation) have been supplemented with two novel parameters and for a stricter test of validation. The developed models could achieve the required values for the novel parameters (, ) and (). From the preceding analysis, it can be concluded that the proposed methods can be successfully used to predict the heat capacity with preselected theoretical descriptors, which can be directly calculated solely from the molecular structure. The applicability domain of the model was assessed by the Williams plot. Copyright © 2013 John Wiley & Sons, Ltd.
Impacts of nutrient competition on microalgae biomass production
Authors: White Lauren H. , Martin David W. , Witt Khendl K. , Vogt Frank
Published: September 2013

Marine microalgae cells are key environmental players as they transform inorganic nutrients dissolved in oceans into biomass. Most prominent among these inorganic compounds is bicarbonate, which originates in considerable quantities from atmospheric CO2, a potent greenhouse gas. Because microalgae cells act as a sink of anthropogenic CO2, understanding phytoplankton's carbon sequestration is a crucial link between environmental chemistry and ecology.

The impact of ambient chemical and physical parameters onto phytoplankton and their chemical composition have been investigated in some detail. However, species↔species interactions, namely their nutrient competition, require in‐depth investigations of the impact of competing species on the dynamics of biomass production as well as the amount of biomass produced. Experimental studies presented here have been based on two marine microalgae species, that is, Nannochloropsis oculata and Dunaliella parva. For investigating dynamic aspects of biomass production, the species growth rates have been measured, under otherwise identical conditions, in single‐species cultures as well as in competition situations. Depending on the species and nutrient type the cells compete for, growth rates in species mixtures were found to change from 50% to 200% of the corresponding single‐species cultures. Competition impacts regarding the maximum cell concentration in a culture were even more drastic as the cell production was reduced, in some cases, down to 11% of the corresponding single‐cell culture's growth rate. Furthermore, a slight but significant shift in cell size distributions toward smaller cell sizes was found in competition situations. This study demonstrates that biomass production is also driven by the cells' biological environment. Copyright © 2013 John Wiley & Sons, Ltd.
Zwitterionic Base‐Stabilized Digermadistannacyclobutadiene and Tetragermacyclobutadiene
Authors: Yeong Hui‐Xian , Xi Hong‐Wei , Li Yongxin , Kunnappilly Sophy Bhasi , Chen Bozhen , Lau Kai‐Chung , Hirao Hajime , Lim Kok Hwa , So Cheuk‐Wai
Published: September 2013

The syntheses of a zwitterionic base‐stabilized digermadistannacyclobutadiene and tetragermacyclobutadiene supported by amidinates and low‐valent germanium amidinate substituents are described. The reaction of the amidinate GeI dimer, [LGe:]2 (1, L=PhC(NtBu)2), with two equivalents of the amidinate tin(II) chloride, [LSnCl] (2), and KC8 in tetrahydrofuran (THF) at room temperature afforded a mixture of the zwitterionic base‐stabilized digermadistannacyclobutadiene, [L2Ge2Sn2L′2] (3; L′=LGe:), and the bis(amidinate) tin(II) compound, [L2Sn:] (4). Compound 3 can also be prepared by the reaction of 1 with [LArSnCl] (5, LAr=tBuC(NAr)2, Ar=2,6‐iPr2C6H3) in THF at room temperature. Moreover, the reaction of 1 with the “onio‐substituent transfer” reagent [4‐NMe2‐C5H4NSiMe3]OTf (8) in THF and 4‐(N,N‐dimethylamino)pyridine (DMAP) at room temperature afforded a mixture of the zwitterionic base‐stabilized tetragermacyclobutadiene, [L4Ge6] (9), the amidinium triflate, [PhC(NHtBu)2]OTf (10), and Me3SiSiMe3 (11). X‐ray structural data and theoretical studies show conclusively that compounds 3 and 9 have a planar and rhombic charge‐separated structure. They are also nonaromatic.
From Nongelating to Gelating: Synthesis and Structural Self‐Assembling Property Relationships of a Homologous Series of Oligo(amide–triazole)s
Authors: Zhang Juntao , Chow Hak‐Fun , Chan Man‐Chor , Chow Gary Ka‐Wai , Kuck Dietmar
Published: September 2013

A homologous series of oligo(amide–triazole)s (OAT) [OAT‐CO2H‐2 n and OAT‐COPrg‐(2 n+1)] with an increasing number of primary amide (CONH) and triazole hydrogen‐bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self‐assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen‐bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non‐organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the Tgel value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole CH groups were involved in the hydrogen‐bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths (OAT‐CO2H‐6 and OAT‐CO2H‐12) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen‐bonding units exhibited self‐sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state.
Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with RuII or PdII
Authors: Seidel Wolfram W. , Dachtler Woldemar , Semmler Julia , Tänzler Marco , Folk Manuel , Villinger Alexander
Published: September 2013

A series of heterodinuclear complexes with acetylene dithiolate (acdt2−) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C2S2)Pd(dppe)] and [Tp′W(CO)2(C2S2)Pd(dppe)][PF6] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η2‐κ2‐C2S2)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me3Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)][PF6]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt2− linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt2− in [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] relative to [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)]+. In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL2(C2S2)Pd(dppe)] (L=(CN−)(CO) or (CO)2). The central [W(C2S2)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.
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

Mononuclear 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

Microporous 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

The 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

Core 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

A 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

We 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

A 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

In 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

This 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

Over 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

This 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

Volume 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

A 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

BACKGROUND

The impact of somatostatin receptor type 2 (SSTR‐2a) expression levels on outcomes in patients with pancreatic neuroendocrine tumors (PNETs) has not been evaluated.

METHODS

Correlations between clinicopathologic characteristics, including SSTR‐2a expression and outcomes, were retrospectively studied in 79 patients with pancreatic neuroendocrine tumors (PNETs).

RESULTS

The 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.

CONCLUSIONS

The 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

Aqueous‐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

This 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

We 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
Detection of Machine Failure by Using Information on Higher‐Order Correlations Between Sound and Vibration
Authors: Ikuta Akira , Orimoto Hisako , Ogawa Hitoshi
Published: September 2013

In this study, a method for stochastic detection of the failure of machines based on changes in information not only on linear correlations but also on higher‐order nonlinear correlations is proposed in a form suitable for on‐line signal processing in the time domain on a personal computer, especially in order to find in detail the mutual relationship between sound and vibration emitted from rotational machines. More specifically, a conditional probability hierarchically reflecting various types of correlation information is theoretically derived by introducing an expression for the multidimensional probability distribution in orthogonal expansion series form. The effectiveness of the proposed theory is experimentally confirmed by applying it to observed data emitted from a rotational machine driven by an electric motor. © 2013 Wiley Periodicals, Inc. Electron Comm Jpn, 96(10): 50–59, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ecj.11386
Copper(II)–imida‐salen Complexes Encapsulated into NaY Zeolite for Oxidations Reactions
Authors: Kuźniarska‐Biernacka Iwona , Carvalho M. Alice , Rasmussen Soren B. , Bañares Miguel A. , Biernacki Krzysztof , Magalhães Alexandre L. , Rolo Anabela G. , Fonseca António M. , Neves Isabel C.
Published: September 2013

The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff‐base salen ligand, 1,5‐bis[(E)‐5‐chloro‐2‐hydroxybenzylideneamino]‐1H‐imidazole‐4‐carbonitrile, and encapsulated into NaY zeolite by using two different methods. The new heterogeneous catalysts were characterized by SEM, XRD, FTIR, EPR and Raman spectroscopy as well as by chemical analysis. The structures of the copper(II) complexes were proposed on the basis of theoretical studies (DFT). The catalytic activities of the encapsulated copper(II) complexes in NaY were compared with their homogeneous counterparts. The results show higher or similar substrate conversion when compared with the free complex in all the reactions tested. After their use in catalytic reaction, these catalysts were found to be reusable without loss of activity.
Preparation and Properties of a Series of [Cr2Ln2] Oximato‐Bridged Complexes
Authors: Hołyńska Małgorzata , Korabik Maria
Published: September 2013

A series of new [Cr2Ln2] (Ln = La, Ce, Pr, Nd, Sm, Eu) complexes 1–6 is reported with phenyl 2‐pyridyl ketoxime (ppkoH) acting as a ligand and with a new oximato‐bridged butterfly‐like complex core. Compounds 1–6 were characterized mainly by X‐ray diffraction studies, EDX, elemental analyses, IR spectroscopy and studies of magnetic properties, the latter showing negligible coupling of the Cr3+ ions in 1.
Carbohydrate‐Based Ferrocenyl Boronate Esters: Synthesis, Characterization, Crystal Structures, and Antibacterial Activity
Authors: Rami Reddy E. , Trivedi Rajiv , Giribabu L. , Sridhar B. , Pranay kumar K. , Srinivasa Rao M. , Sarma A. V. S.
Published: September 2013

A set of ferrocenyl boronate esters based on carbohydrate scaffolds was designed and synthesized efficiently by the reaction of ferroceneboronic acid with protected sugar diols derived from D‐xylose, L‐sorbose, and D‐mannitol in good yield. These compounds identified as 1,2‐O‐isopropylidene‐α‐D‐xylofuranose‐3,5‐ferrocenyl boronate (3a), 1,2‐O‐cyclohexylidene‐α‐D‐xylofuranose‐3,5‐ferrocenyl boronate (3b), 1‐O‐benzyl‐2,3‐O‐isopropylidene‐α‐L‐sorbofuranose‐4,6‐ferrocenyl boronate (3c), 1,2:5,6‐di‐O‐isopropylidene‐D‐mannitol‐3,4‐ferrocenyl boronate (3d), and 1,2:5,6‐di‐O‐cyclohexylidene‐D‐mannitol‐3,4‐ferrocenyl boronate (3e), were isolated as air‐ and moisture‐stable orange/yellow crystalline solids. All of the six‐membered (3a, 3b, and 3c) and five‐membered (3d and 3e) cyclic boronate esters were fully characterized by IR, multinuclear NMR (1H, 13C and 11B), and UV/Vis spectroscopy, and also elemental analysis. The electrochemical behavior of the synthesized ferrocenyl boronate esters containing carbohydrates was investigated. Furthermore, the structures of 3a and 3c were unambiguously established by single‐crystal X‐ray diffraction analysis. The compounds have been screened for in vitro antibacterial activity against various Gram‐positive and Gram‐negative bacteria. They exhibited moderate to good inhibitory activity against the tested bacterial strains in comparison with standard drugs.
Facile One‐Pot Palladium‐Catalyzed Sequential Coupling to Diarylmethanes by Using Aryl Methyl Ketones as the Methylene Donors
Authors: Wang Xing , Liu Lian‐Hua , Shi Jin‐Hua , Peng Ji , Tu Hai‐Yang , Zhang Ai‐Dong
Published: September 2013

A novel palladium‐catalyzed coupling reaction of an aryl methyl ketone with two molecules of an aryl halide to yield symmetric diarylmethanes is described. In the facile one‐pot reaction, the aryl methyl ketone acts as a formal methylene donor. The experimental facts, including TLC monitoring, speculated intermediates as the raw materials, analysis of the cesium benzoate coproduct by ex situ IR spectroscopy, and the cross‐coupling reactions of two different aryl halides, indicate a mechanism involving a palladium‐catalyzed sequential two‐step coupling process, in which the presence of a trace amount of H2O is indispensable. The reaction is applicable to a broad spectrum of substrates and delivers the products in good to excellent yields. Access to unsymmetrical diarylmethanes with this method is also explored and various factors are discussed.
Synthesis of 2,6‐Dialkyl(aryl)purine Nucleosides by Exploiting the Reactivity of Nebularine N1‐Oxide towards Grignard Reagents
Authors: D'Errico Stefano , Oliviero Giorgia , Borbone Nicola , Piccialli Vincenzo , D'Atri Valentina , Mayol Laura , Piccialli Gennaro
Published: September 2013

The synthesis of 2,6‐dialkyl(aryl)purine nucleosides by application of a double addition of Grignard reagents to N1‐oxide purine nucleosides is described. The synthetic protocol exploits the reactivity of both the C6–N1–O– and C2–N1–O– moieties of the purine base. The overall process consists of initial Grignard reagent addition to the C6 of nebularine N1‐oxide followed by aromatization to give a C6‐substituted nucleoside. Regeneration of the N1‐oxide is then followed by a second Grignard addition at C2 causing the opening of the pyrimidine ring. Cyclization of the transiently opened pyrimidine is then driven by aromatization of the system to afford the final purine system.
Synthesis of Highly Functionalised Dihydrobenzofurans and Indolines by Palladium‐Catalysed Mizoroki–Heck–Heteroannulation Cascade Reactions of Alkoxy‐1,3‐dienes
Authors: Toppino Antonio , Arru Paolo , Bianco Niccolò , Prandi Cristina , Venturello Paolo , Deagostino Annamaria
Published: September 2013

A Mizoroki–Heck–heteroannulation cascade reaction has been used to prepare substituted dihydrobenzofurans and indolines in good yields by the reaction between functionalised alkoxy‐1,3‐dienes and several o‐iodophenols or protected o‐iodoanilines.
Multifunctional activated carbon/chitosan composite preparation and its simultaneous adsorption of phenol and Cr(VI) from aqueous solutions
Authors: Huang Ruihua , Yang Bingchao , Liu Qian , Liu Yanping
Published: September 2013

The simultaneous adsorption of phenol and Cr(VI) from aqueous solution onto this activated carbon/chitosan composite was investigated. This composite almost removes phenol and Cr(VI) simultaneously in a pH range of 2–5. The removals of phenol and Cr(VI) reached up to 95% when phenol and Cr(VI) concentrations were less than 50 mg/L and 200 mg/L, respectively. The presence of phenol reduced Cr(VI) adsorption, while the presence of Cr(VI) had no evident effect on phenol adsorption. The adsorption for both Cr(VI) and phenol followed pseudo‐second‐order kinetics in single or mixedsystems. © 2013 American Institute of Chemical Engineers Environ Prog, 33: 814–823, 2014
Application of poly(acrlymide‐co‐sodium methacrylate) hydrogels in copper and cadmium removal from aqueous solution
Authors: Milosavljević N. , Debeljković A. , Krušić M. Kalagasidis , Milašinović N. , Üzüm Ö.B. , Karadağ E.
Published: September 2013

The application of poly(acrylamide‐co‐sodium methacrylate) hydrogel for the removal of Cu2+ and Cd2+ ions from aqueous solutions has been investigated as a function of pH, adsorbent dose and temperature. FTIR spectra showed that –NH2 and –COOH groups are involved in both metal ions adsorption which followed pseudo‐first order kinetics. Non‐linear regression analysis of six isotherms, Langmuir, Freundlich, Redlich‐Peterson, Toth, Dubinin‐Radushkevich and Sips, have been applied to the sorption data, while the best interpretation was given by Redlich‐Peterson. Based on the separation factor, RL, the Cu2+ and Cd2+ ions adsorption is favorable. The maximum adsorption of 24.05 mg/g (48%) for Cu2+ ions and 32.99 mg/g (66%) for Cd2+ ions has been obtained at pH 5.0 and sorbent dosage of 300 mg. © 2013 American Institute of Chemical Engineers Environ Prog, 33: 824–834, 2014
ASI: Dunaliella marine microalgae to drop‐in replacement liquid transportation fuel
Authors: Wang Wei‐Cheng , Allen Elle , Campos Andrew A. , Cade Rushyannah Killens , Dean Lisa , Dvora Mia , Immer Jeremy G. , Mixson Stephanie , Srirangan Soundarya , Sauer Marie‐Laure , Schreck Steven , Sun Keyi , Thapaliya Nirajan , Wilson Cameron , Burkholder JoAnn , Grunden Amy M. , Lamb H. Henry , Sederoff Heike , Stikeleather Larry F. , Roberts William L.
Published: September 2013

Microalgae are a promising biofuels feedstock, theoretically yielding concentrations of triacylglycerides (TAGs) per unit area that are far higher than traditional feedstocks due to their rapid growth. Dunaliella is particularly advantageous as a feedstock because it is currently commercially mass cultured, thrives in salt water, and has no cell wall. Fourteen strains of Dunaliella have been investigated for growth rates and lipid production in mass culture and tested for enhanced lipid production under a range of environmental stressors including salinity, pH, nitrogen and phosphorus limitation, and light regime. The nuclear genome has been sequenced for four of these strains, with the objective of increasing carbon flux through genetic engineering. Electroflocculation followed by osmotic membrane rupturing may be a very energy and cost efficient means of harvesting the lipid bodies from Dunaliella. A technically feasible and scalable thermo‐catalytic process to convert the lipids into replacements for liquid transportation fuels has been developed. The lipids were converted into long‐chain alkanes through continuous thermal hydrolysis followed by fed‐batch thermo‐catalytic decarboxylation. These alkanes can be reformed into renewable diesel via conventional catalytic hydrocarbon isomerization reactions to improve cold flow properties, if desired. © 2013 American Institute of Chemical Engineers Environ Prog, 32: 916–925, 2013
Effects of Frame Materials and Structures on Stress Concentration of Membrane Electrode Assembly of PEMFCs
Authors: Ye D. H. , Zhan Z. G. , Lee Y. J. , Tu Z. K. , Zhang Y. , Pan M.
Published: September 2013

A membrane electrode assembly (MEA) is one of the core components of proton exchange membrane fuel cells (PEMFCs) comprising a catalyst coated membrane, gas diffusion electrodes, frames, and seals. By employing a 2D finite element model the mechanical stresses in membrane caused during the cell assembly procedure are analyzed for different MEA frame materials, frame structures and contact behaviors. The stress distributions in the membrane are presented and quantified. A zone with strong nonuniform stresses in the membrane under the end edge of frame/membrane is observed. The stepped frames assembly (SFA) and the bonded contact behaviors have more uniform stress distributions than the aligned frames assembly (AFA) does. The frame materials are not the main factors affecting the stress concentration in membrane for the SFA, while for the AFA the mechanical properties of frame materials should be close to those of the membrane. The results are expected to be helpful for people to select the frame materials and to design frame structures, and can be applied to guide the assembly of PEMFCs.
Characterization of Sr1–xDyxCoO3–δ (x = 0.1, 0.2, 0.3) Cathode Materials for IT‐SOFCs
Authors: Liu T.
Published: September 2013

The cobaltate perovskites Sr1–xDyxCoO3–δ (SDCO, x = 0.1, 0.2, 0.3) materials were synthesized and evaluated as cathode for La0.8Sr0.2Ga0.8Mg0.2O3–δ solid electrolyte supported intermediate‐temperature‐solid oxide fuel cells (IT‐SOFCs). The crystal structure of Sr0.9Dy0.1CoO3–δ was defined in the cubic Pm–3m space group (No. 221), Sr0.8Dy0.2CoO3–δ and Sr0.7Dy0.3CoO3–δ had a tetragonal I4/mmm structure. The electrical conductivities were all higher than 100 S cm–1 in the temperature of 170–800 °C. The polarization resistance (Rp) and its activation energy (Ea) increased with increasing x. SEM analysis confirmed the porous microstructure of the SDCO cathodes and good LSGM|LDC|SDCO adherence. Sr0.9Dy0.1CoO3–δ exhibited the best cathode characteristics with a maximum test‐cell power density of 841 mW cm–2, being a high potential candidate of cathode material for IT‐SOFCs.
Residual Stress Assessment for Thin 8YSZ Electrolytes Using Focused Ion Beam Milling and Digital Image Correlation
Authors: Malzbender J. , Van Gestel T.
Published: September 2013

With respect to solid oxide fuel cell power density it has been verified that 1–2 μm thick 8YSZ electrolytes have significant advantages, offering the potential to operate stacks at temperatures of 600 °C. However, reliability of the component depends on integrity and hence residual stress state. In this work, an advanced method is used to determine the electrolyte residual stress locally using stress relaxation tests by a combination of focused ion beam milling and digital image correlation.
The influence of water vapor absorption in the 290–350 nm region on solar radiance: Laboratory studies and model simulation
Authors: Du Juan , Huang Li , Min Qilong , Zhu Lei
Published: September 2013

Water vapor is an important greenhouse gas in the Earth's atmosphere. Absorption of solar radiation by water vapor in the near‐UV region may partially account for up to 30% discrepancy between the modeled and the observed solar energy absorbed by the atmosphere. But the magnitude of water vapor absorption in the near‐UV region at wavelengths shorter than 384 nm is not known. We have determined absorption cross sections of water vapor at 5 nm intervals in the 290–350 nm region, by using cavity ring‐down spectroscopy. Water vapor cross‐section values range from 2.94 × 10−24 to 2.13 × 10−25 cm2/molecule in the wavelength region studied. The effect of the water vapor absorption in the 290–350 nm region on the modeled radiation flux at the ground level has been evaluated using radiative transfer model.
Along‐strike structural changes controlled by dehydration‐related fluids within the Philippine Sea plate around the segment boundary of a megathrust earthquake beneath the Kii peninsula, southwest Japan
Authors: Kurashimo Eiji , Iwasaki Takaya , Iidaka Takashi , Kato Aitaro , Yamazaki Fumihito , Miyashita Kaoru , Shibutani Takuo , Ito Kiyoshi , Takeda Tetsuya , Obara Kazushige , Hirata Naoshi
Published: September 2013

Active and passive seismic experiments in the Kii Peninsula, southwest Japan, revealed prominent structural features around the segment boundary of a megathrust earthquake associated with the subduction of the Philippine Sea Plate (PHS). A distinct reflection band in the uppermost part of the PHS shows significant lateral variation along its strike. The thicker reflection band, which corresponds to the deeper extension of the fault area of the 1944 Tonankai Earthquake, is interpreted to be a zone of high pore fluid pressure, causing a state of conditionally stable slip on the plate boundary by the reduction in effective normal stress. A thinner reflective band corresponds to the deepest part of the rupture area of the 1946 Nankai earthquake, where plate coupling is stronger due to less effect of fluids. This along‐strike structural variation controls the differences in frictional properties and the lateral limit of rupturing along the plate boundary.