bluuebunny/crossref_metadata_2025_split huggingface dataset:
Molecular Origin of the Hydrolytic Activity and Fixed Regioselectivity of a ZrIV‐Substituted Polyoxotungstate as Artificial Protease
Authors: Stroobants Karen , Goovaerts Vincent , Absillis Gregory , Bruylants Gilles , Moelants Eva , Proost Paul , Parac‐Vogt Tatjana N. 
Published: June 2014

AbstractA multitechnique approach has been applied in order to identify the thermodynamic and kinetic parameters related to the regioselective hydrolysis of human serum albumin (HSA) promoted by the Wells–Dawson polyoxometalate (POM), K15H[Zr(α2‐P2W17O61)2]. Isothermal titration calorimetry (ITC) studies indicate that up to four POM molecules interact with HSA. While the first interaction site is characterized by a 1:1 binding and an affinity constant of 2×108 M−1, the three remaining sites are characterized by a lower global affinity constant of 7×105 M−1. The higher affinity constant at the first site is in accordance with a high quenching constant of 2.2×108 M−1 obtained for fluorescence quenching of the Trp214 residue located in the only positively charged cleft of HSA, in the presence of K15H[Zr(α2‐P2W17O61)2]. In addition, EuIII luminescence experiments with an EuIII‐substituted POM analogue have shown the replacement of water molecules in the first coordination sphere of EuIII due to binding of the metal ion to amino acid side chain residues of HSA. All three interaction studies are in accordance with a stronger POM dominated binding at the positive cleft on the one hand, and interaction mainly governed by metal anchoring at the three remaining positions, on the other hand. Hydrolysis experiments in the presence of K15H[Zr(α2‐P2W17O61)2] have demonstrated regioselective cleavage of HSA at the Arg114Leu115, Ala257Asp258, Lys313Asp314 or Cys392Glu393 peptide bonds. This is in agreement with the interaction studies as the Arg114Leu115 peptide bond is located in the positive cleft of HSA and the three remaining peptide bonds are each located near an upstream acidic residue, which can be expected to coordinate to the metal ion. A detailed kinetic study has evidenced the formation of additional fragments upon prolonged reaction times. Edman degradation of the additional reaction products has shown that these fragments result from further hydrolysis at the initially observed cleavage positions, indicating a fixed selectivity for K15H[Zr(α2‐P2W17O61)2].
Homogeneous Pd‐Catalyzed Transformation of Terminal Alkenes into Primary Allylic Alcohols and Derivatives
Authors: Tomita Ren , Mantani Kohei , Hamasaki Akiyuki , Ishida Tamao , Tokunaga Makoto 
Published: June 2014

AbstractSynthesis of primary alcohols from terminal alkenes is an important process in both bulk and fine chemical syntheses. Herein, a homogeneous Pd‐complex‐catalyzed transformation of terminal alkenes into primary allylic alcohols, by using 5 mol % [Pd(PPh3)4] as a catalyst, and H2O, CO2, and quinone derivatives as reagents, is reported. When alcohols were used instead of H2O, allylic ethers were obtained. A proposed mechanism includes the addition of oxygen nucleophiles at the less‐hindered terminal position of π–allyl Pd intermediates.
Calculation of Powder Particle Adhesion on Structured Surfaces
Authors: Hartmüller Jürgen , Ripperger Siegfried 
Published: June 2014

AbstractDie Haftung von Partikeln an Feststoffoberflächen ist von vielen Einflussfaktoren abhängig. Unter diesen sind die van‐der‐Waals‐Kräfte und die Kräfte aufgrund von Flüssigkeitsbrücken infolge der relativen Luftfeuchte von besonderer Bedeutung. Da viele herkömmliche Haftkraftmodelle maßgebliche Parameter vernachlässigen, werden in diesem Beitrag verschiedene Möglichkeiten vorgestellt, die wirkenden Haftkräfte einer Berechnung zugänglich zu machen. Die berechneten Werte erlauben eine Interpretation von Haftkraftverteilungen und die Zuordnung von Haftkräften zu Haftkraftmechanismen.
Children of cancer patients: Prevalence and predictors of emotional and behavioral problems
Authors: Möller Birgit , Barkmann Claus , Krattenmacher Thomas , Kühne Franziska , Bergelt Corinna , Beierlein Volker , Ernst Johanna , Brähler Elmar , Flechtner Hans‐Henning , Herzog Wolfgang , von Klitzing Kai , Führer Daniel , Resch Franz , Romer Georg 
Published: June 2014

BACKGROUNDChildren of patients with cancer are at increased risk for developing emotional and behavioral problems. This study explored the prevalence and predictors of emotional and behavioral problems in Children of cancer patients in a multisite research project.METHODSA cross‐sectional sample of N = 235 families was recruited simultaneously in 5 university medical centers. The participants, including parents (N = 402) and children (N = 324; ages 11‐21 years) completed standardized questionnaires. Emotional and behavioral problems in children were measured by the Strengths and Difficulties Questionnaire (SDQ). On the basis of previous research and using a mixed‐model approach, child‐, parent‐, family‐ and cancer‐related variables were examined in addition to socioeconomic status as potential predictors. Descriptive statistics and a multiple random coefficient model were used in the analyses.RESULTSCompared to norms, Children of cancer patients show increased mean levels of emotional and behavioral symptoms. The best predictor of emotional and behavioral problems from the perspectives of the child, the healthy parent, and the ill parent was general family dysfunction. Although family dysfunction was identified as the main predictor, the analysis revealed that the main part of variance was related to the individual child's level.CONCLUSIONSThe results indicate that screening for child mental health problems and family dysfunction in oncological and psychosocial treatment units can identify the families most in need of psychosocial support. Psychological services need to be both family‐oriented and child‐centered and focus on family dysfunction to prevent mental health problems in children. Cancer 2014;120:2361–2370. © 2014 American Cancer Society.
Genomic testing in cancer: Patient knowledge, attitudes, and expectations
Authors: Blanchette Phillip S. , Spreafico Anna , Miller Fiona A. , Chan Kelvin , Bytautas Jessica , Kang Steve , Bedard Philippe L. , Eisen Andrea , Potanina Larissa , Holland Jack , Kamel‐Reid Suzanne , McPherson John D. , Razak Albiruni R. , Siu Lillian L. 
Published: June 2014

BACKGROUNDGenomic testing in cancer (GTC) characterizes genes that play an important role in the development and growth of a patient's cancer. This form of DNA testing is currently being studied for its ability to guide cancer therapy. The objective of the current study was to describe patients' knowledge, attitudes, and expectations toward GTC.METHODSA 42‐item self‐administered GTC questionnaire was developed by a multidisciplinary group and patient pretesting. The questionnaire was distributed to patients with advanced cancer who were referred to the Princess Margaret Cancer Center for a phase 1 clinical trial or GTC testing.RESULTSResults were reported from 98 patients with advanced cancer, representing 66% of the patients surveyed. Seventy‐six percent of patients were interested in learning more about GTC, and 64% reported that GTC would significantly improve their cancer care. The median score on a 12‐item questionnaire to assess knowledge of cancer genomics was 8 of 12 items correct (67%; interquartile range, 7‐9 of 12 items correct [58%‐75%]). Scores were associated significantly with patients' education level (P < .0001). Sixty‐six percent of patients would consent to a needle biopsy, and 39% would consent to an invasive surgical biopsy if required for GTC. Only 48% of patients reported having sufficient knowledge to make an informed decision to pursue GTC whereas 34% of patients indicated a need for formal genetic counseling.CONCLUSIONSPatients with advanced cancer are motivated to participate in GTC. Patients require further education to understand the difference between somatic and germline mutations in the context of GTC. Educational programs are needed to support patients interested in pursuing GTC. Cancer 2014;120:3066–3073. © 2014 American Cancer Society.
Racial disparities in urologist visits among elderly men with prostate cancer: A cohort analysis of patient‐related and county of residence‐related factors
Authors: Onukwugha Eberechukwu , Osteen Phillip , Jayasekera Jinani , Mullins C. Daniel , Mair Christine A. , Hussain Arif 
Published: June 2014

BACKGROUNDFactors contributing to the lower likelihood of urologist follow‐up among African American (AA) men diagnosed with prostate cancer may not be strictly related to patient factors. The authors investigated the relationship between crime, poverty, and poor housing, among others, and postdiagnosis urologist visits among AA and white men.METHODSThe authors used linked cancer registry and Medicare claims data from 1999 through 2007 for men diagnosed with American Joint Committee on Cancer stage I to III prostate cancer. The USA Counties and County Business Patterns data sets provided county‐level data. Variance components models reported the percentage of variation attributed to county of residence. Postdiagnosis urologist visits for AA and white men were investigated using logistic and modified Poisson regression models.RESULTSA total of 65,635 patients were identified; 87% of whom were non‐Hispanic white and 9.3% of whom were non‐Hispanic AA. Approximately 16% of men diagnosed with stage I to III prostate cancer did not visit a urologist within 1 year after diagnosis (22% of AA men and 15% of white men). County of residence accounted for 10% of the variation in the visit outcome (13% for AA men and 10% for white men). AA men were more likely to live in counties ranked highest in terms of poverty, occupied housing units with no telephone, and crime. AA men were less likely to see a urologist (odds ratio, 0.65 [95% confidence interval, 0.6‐0.71]; rate ratio, 0.94 [95% confidence interval, 0.92‐0.95]). The sign and magnitude of the coefficients for the county‐level measures differed across race‐specific regression models of urologist visits.CONCLUSIONSAmong older men diagnosed with stage I to III prostate cancer, the social environment appears to contribute to some of the disparities in postdiagnosis urologist visits between AA and white men. Cancer 2014;120:3385–3392. © 2014 American Cancer Society.
Synthesis of Au‐BiVO4 Nanocomposite through Anodic Electrodeposition Followed by Galvanic Replacement and Its Application to the Photocatalytic Decomposition of Methyl Orange
Authors: Myung Noseung , Lee Wooju , Lee Changhyun , Jeong Seonghan , Rajeshwar Krishnan 
Published: June 2014

AbstractA Au‐BiVO4 nanocomposite is synthesized by a two‐step strategy involving anodic electrodeposition combined with in situ galvanic replacement. First, a BiVO4 layer is prepared by the anodic oxidation of pre‐electrodeposited Bi film in a VO43− containing electrolyte. Thus‐prepared BiVO4 film contains excess metallic Bi, which is then galvanically replaced with Au from an aqueous HAuCl4 solution, resulting in the Au‐BiVO4 composite in the second step. Optical, photoelectrochemical and photocatalytic properties are investigated by using X‐ray diffraction, energy‐dispersive X‐ray analysis, diffuse reflectance spectrometry, and photoelectrochemical analyses. The visible‐light photocatalytic activity of the Au‐BiVO4 composite is evaluated using the decomposition of methyl orange dye and is superior to the bare BiVO4 film counterpart.
Environmental‐Confinement‐Induced Stability Enhancement of Chiral Molecules
Authors: Meng Yan , Dai Xing , Xin Minsi , Tian Chuanjin , Liu Hang , Jin Mingxing , Wang Zhigang , Zhang Rui‐Qin 
Published: June 2014

AbstractWe computationally study the transition process of a chiral difluorobenzo[c]phenanthrene (DFBcPh) molecule within non‐polar fullerene C260 to explore the confinement effect. We find blue‐shifts in the infrared and Raman spectra of the molecule inside the fullerene relative to those of isolated systems. Six types of spectrum features of the molecule appear in the 0–60 cm−1 band. Interestingly, the energy barrier of the chiral transformation of the molecule is elevated by 15.88 kcal mol−1 upon the confinement by the fullerene, indicating improvement in the stability of the enantiomers. The protection by C260 lowers the highest occupied molecular orbital energy level and lifts the lowest unoccupied molecular orbital energy level of the chiral molecule such that the chiral molecule is further chemically stabilized. We concluded that the confinement environment has an impact at the nanoscale on the enantiomer transformation process of the chiral molecule.
Photocatalytic Application of 4f–5f Inorganic–Organic Frameworks: Influence of Lanthanide Contraction on the Structure and Functional Properties of a Series of Uranyl–Lanthanide Complexes
Authors: Hou Ya‐Nan , Xu Xue‐Ting , Xing Na , Bai Feng‐Ying , Duan Shi‐Bo , Sun Qiao , Wei Si‐Yue , Shi Zhan , Zhang Huan‐Zhi , Xing Yong‐Heng 
Published: June 2014

AbstractA series of 4f–5f heteronuclear metallic complexes were synthesized by a hydrothermal route from mixtures of uranyl acetate, lanthanide nitrate, and 1,2,4,5‐benzenetetracarboxylic acid (H4BTA) in an aqueous system. Single‐crystal X‐ray analysis revealed that the thirteen UO2‐Ln‐BTA complexes ([(UO2)1.5Ln(C10O8H2)1.5(H2O)x]⋅y H2O; Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13); x=6 for 1–4, x=5 for 5–13; y=0 for 4, y=1 for 3, y=2 for 2, y=3 for 5, 9, 10, 12, 13, y=4 for 1, 6, 7, 8, 11) are isomorphous with three‐dimensional structures. For the purpose of developing potential applications of the UO2‐Ln‐BTA complexes, we investigated their surface photovoltage and photocatalytic properties. In addition, the thermogravimetric analysis and photoluminescent properties of these complexes were also studied in detail.
Structure in the Edge Plasma Profiles in Tokamaks
Authors: Stacey W. M. 
Published: June 2014

AbstractIt is argued that the structure observed in radial profiles in the tokamak edge plasma is determined by the requirements of ion particle, momentum and energy conservation and the underlying transport mechanisms in the presence of sources and losses of particles, energy and momentum. The intent of this paper is to define a systematic formalism that can be employed for evaluating these transport coefficients from experimental inference and comparison with theory. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Long‐Term Hydrogen Outgassing from Plasma Facing Components
Authors: Guterl J. , Smirnov R. D. , Krasheninnikov S. I. 
Published: June 2014

AbstractThe time evolution of hydrogen outgassing fluxes from plasma facing components (PFCs) in tokamaks at room temperature is investigated using a diffusion‐reaction model with a single trap in the bulk of PFCs material. The release of hydrogen is surface‐limited or diffusion‐limited depending on properties of material and surface processes. In both surface and diffusion‐limited regimes, the long‐term decrease of the hydrogen outgassing flux follows a time power‐law ∼t–κ, for which κ depends on the concentration of hydrogen in the material and on surface desorption processes. In surface‐limited regime, reaction‐diffusion models of hydrogen outgassing from wall material(with hydrogen diffusion in the material bulk) are shown to be equivalent to models of outgassing from wall surfaces. Experimental results showing power‐law decays of hydrogen outgassing fluxes from PFCs during long off‐plasma events (κ = 0.7 for graphite and κ = 0.8 for ITER‐like JET configuration) can be then reproduced using a diffusion‐reaction model in surface‐limited regime. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Modeling of Stark‐Broadened Lines in a Fluctuating Edge Plasma
Authors: Rosato J. , Marandet Y. , Peiffer A. , Capes H. , Godbert‐Mouret L. , Koubiti M. , Stamm R. 
Published: June 2014

AbstractA line shape model that accounts for low‐frequency fluctuations is applied to the Balmer series of the hydrogen isotopes (atomic transitions n → 2). The plasma fluid parameters (density, temperature, etc.) are described as random variables characterized by a prescribed joint probability density function. A special emphasis is devoted to Stark broadened lines, which are sensitive to the plasma density. It is shown that fluctuations can lead to a significant increase of the line width if the fluctuation level ΔNe/〈Ne〉 (with 〈Ne〉 and ΔNe being respectively the density averaged along the line‐of‐sight and its RMS value) is large. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Integrated Core‐SOL Simulations of ITER H‐Mode Scenarios with Different Pedestal Density
Authors: Ivanova‐Stanik I. , Koechl F. , Voitsekhovitch I. , Telesca G. , Zagörski R. , EU‐ITM ITER Scenario Modelling group  
Published: June 2014

AbstractFusion performance of ITER H‐mode plasmas in presence of intrinsic (He, Be and W) and seeded (Ne) im purities is investigated in self‐consistent core‐pedestal‐SOL simulations for two values of pedestal density npede = 6.12 × 1019m–3 (reference case) and 9 × 1019m–3 using the JETTO and COREDIV codes iteratively. The theory‐based GLF23 transport model which predicts a relatively high density peaking (ne0/〈ne〉 = 1.37 ÷ 1.39) has been used for this study. For medium density case the H‐mode operation with a power across the separatrix well above the L‐H power threshold has been obtained, but the divertor heat loads exceed 10 MW/m2. Neon gas puff strongly reduces the power to divertor plate in this scenario, increasing at the same time the tungsten sputtering by Ne that leads to even larger core radiation and dilution, than in the case without Ne. As a result, the medium density H‐mode operation with Ne seeding and low divertor heat loads is barely above the L‐H power threshold. This operational point is weakly sensitive to tungsten inward pinch due to a strong coupling between W transport, radiation and sputtering. At high density with much larger core radiation (90 MW), the possibility of H‐mode operation strongly depends on the choice transport model, with the power through the separatrix well below (above) the L‐H power threshold in simulations with the GLF23 (H98y scaling‐based) transport model. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Performance modeling of FEC‐based unequal error protection for H.264/AVC video streaming over burst‐loss channels
Authors: Kuo Chun‐I , Shieh Ce‐Kuen , Hwang Wen‐Shyang , Ke Chih‐Heng 
Published: June 2014

SummaryUnequal error protection systems are a popular technique for video streaming. Forward error correction (FEC) is one of error control techniques to improve the quality of video streaming over lossy channels. Moreover, frame‐level FEC techniques have been proposed for video streaming because of different priority video frames within the transmission rate constraint on a Bernoulli channel. However, various communication and storage systems are likely corrupted by bursts of noise in the current wireless behavior. If the burst losses go beyond the protection capacity of FEC, the efficacy of FEC can be degraded. Therefore, our proposed model allows an assessment of the perceived quality of H.264/AVC video streaming over bursty channels, and is validated by simulation experiments on the NS‐2 network simulator at a given estimate of the packet loss ratio and average burst length. The results suggest a useful reference in designing the FEC scheme for video applications, and as the video coding and channel parameters are given, the proposed model can provide a more accurate evaluation tool for video streaming over bursty channels and help to evaluate the impact of FEC performance on different burst‐loss parameters. Copyright © 2014 John Wiley & Sons, Ltd.
Spinal cord stimulation is safe and feasible in patients with advanced heart failure: early clinical experience
Authors: Torre‐Amione Guillermo , Alo Kenneth , Estep Jerry D. , Valderrabano Miguel , Khalil Nashwa , Farazi Taraneh G. , Rosenberg Stuart P. , Ness Lanitia , Gill John 
Published: June 2014

AbstractAimsPre‐clinical work suggests that upper thoracic spinal cord stimulation (SCS) may have therapeutic effects in the treatment of heart failure (HF). We therefore aim to assess the safety and feasibility of SCS in HF patients.Methods and resultsA prospective, randomized, double‐blind, crossover pilot study was conducted in symptomatic HF patients receiving optimal medical therapy. Patients were implanted with an SCS system and randomized to an SCS‐ACTIVE, delivered at 90% paraesthesia threshold, or an SCS‐INACTIVE phase for 3 months, followed by a 1‐month washout period and crossover to the alternative phase. The safety of SCS therapy was assessed by death and cardiac events. Implantable cardioverter defibrillator (ICD) function in the presence of SCS was tested by defibrillation testing during SCS system implant and review of real‐time and stored electrograms during follow‐up. The efficacy of SCS therapy was assessed by changes in patient symptoms, LV function, and BNP level. Nine patients were investigated. In all cases, ICD sensing, detection, and therapy delivery were unaffected by SCS. During follow‐up, one patient died and one was hospitalized for HF while in the SCS‐INACTIVE phase, and two patients had HF hospitalizations during the SCS‐ACTIVE phase. Symptoms were improved in the majority of patients with SCS, while markers of cardiac structure and function were, in aggregate, unchanged.ConclusionThis study shows that an SCS system can be safely implanted in patients with advanced HF and that the SCS system does not interfere with ICD function.
Aqueous Crystallization Strategy for Metastable h‐MoO3 Crystals with Polyvinylpyrrolidone Induction
Authors: Guo Jingnan , Zhao Yan , Zhao Jingzhe , Wu Jiajing , Song Yuehong , Tan Yixin , Wang Fangping , Hao Xinli , Lu Yan , Bao Fengxia 
Published: June 2014

AbstractMicro‐sized hexagonal‐phase MoO3 (h‐MoO3) crystals were successfully prepared by a polyvinylpyrrolidone (PVP) induced aqueous route with (NH4)6Mo7O24·4H2O and HCl as raw materials. The linear structure of the PVP molecules matches the tunnel structure of the metastable h‐MoO3 crystals and, thus, enables the induced crystallization in an aqueous solution even at near‐ambient temperatures (40–50 °C). The achieved h‐MoO3 crystals have good monodispersity with a one‐dimensional (1D) outline and hexagonal cross‐section. The H+/Mo ratio is another key factor for the synthesis of h‐MoO3 crystals. The photochromic properties of PVP‐dependent samples of h‐MoO3 crystals were studied under natural sunlight irradiation.
Vanadium Sandwich Complexes with Boroxine and Boronyl Boroxine Ligands
Authors: Li Da‐Zhi , Zhang Shi‐Guo , Liu Jun‐jie , Tang Cui 
Published: June 2014

AbstractA DFT investigation on half‐sandwich‐type C3v B3O3X3V, full‐sandwich‐type D3d [B3O3X3]2V, and triple‐decker complexes [B3O3X3]3V2 (X = H, BO) containing B3O3H3 or B3O3(BO)3 ligands were performed. Both B3O3H3 and B3O3(BO)3 units serve as robust inorganic ligands in B3O3X3V, [B3O3X3]2V, and [B3O3X3]3V2 complex series. Effective d–π coordination interactions between the partially filled 3d orbitals of the transition‐metal center and the delocalized π orbitals of the B3O3X3 ligands maintain the stabilities of the complexes. The largest contributions to the orbital interactions in the B3O3X3V, [B3O3X3]2V, and [B3O3X3]3V2 complexes come from the V → B3O3X3 δ back donation. The thermodynamic stabilities and magnetic properties of these complexes were also investigated. These magnetic complexes were found to be particularly stable with respect to their reaction energy. The sandwich structural pattern developed in this work expands the structural domain of transition‐metal complexes by introducing inorganic B3O3H3 and B3O3(BO)3 into traditional sandwich‐type structures, and this pattern may be extended to [B3O3X3]nVn–1 sandwiches (n ≥ 4), which could act as linear magnetic wires.