bluuebunny/crossref_metadata_2025_split huggingface dataset:
Incidence and outcome of infective endocarditis following percutaneous versus surgical pulmonary valve replacement
Authors: Lluri Gentian , Levi Daniel S. , Miller Emily , Hageman Abbie , Sinha Sanjay , Sadeghi Soraya , Reemtsen Brian , Laks Hillel , Biniwale Reshma , Salem Morris , Fishbein Gregory A. , Aboulhosn Jamil 
Published: September 2017

AbstractObjectivesTo provide a comparison of the outcome of infective endocarditis (IE) in patients undergoing transcatheter pulmonary valve replacement (TPVR) versus surgical pulmonary valve replacement (SPVR).BackgroundAlthough TPVR is thought to be associated with a higher risk of IE than SPVR, there is paucity of data to support this.MethodsPatients who underwent TPVR or SPVR at UCLA between October 2010 and September 2016 were included and retrospectively analyzed.ResultsThree hundred forty‐two patients underwent PVR at UCLA including 134 SPVR and 208 TPVR. Patients undergoing TPVR were more likely to have had a history of endocarditis than those undergoing SPVR (5.3% vs. 0.7%, P = 0.03) and a right ventricle to pulmonary artery (RV to PA) conduit (37% vs. 17%, P = 0.0001). Two SPVR and seven TPVR patients developed IE with a 4‐year freedom from endocarditis of 94.0% in the SPVR versus 84% in the TPVR group (P = 0.13). In patients who underwent TPVR and developed endocarditis, the mean gradient across the RVOT prior to intervention was higher (28.1 ± 4.5 vs. 17.4 ± 0.6 mmHg, P = 0.02) and were more likely to have a conduit (71% vs. 36%, P = 0.049).ConclusionsIn this study, patients undergoing TPVR were not at a higher risk of IE than patients undergoing SPVR. TPVR patients were more likely to have had a prior history of IE and RV‐PA conduit. The patients at highest risk were those with stenotic RV to PA conduits who were treated with TPVR.
Organosilica Nanotube Templates: One‐Pot Synthesis of Carbon‐Modified Polymeric Carbon Nitride Nanorods for Photocatalysis
Authors: Li Mei , Wang Hua , Li Xiaobo , Zhang Shengbo , Han Jinyu , Masters Anthony F. , Maschmeyer Thomas , Liu Xiao 
Published: September 2017

AbstractPolymeric carbon nitride (PCN) nanorods with surface carbon modifications were prepared in a one‐step procedure by using phenylene‐bridged organosilica nanotubes as structure‐directing templates. The carbon‐modified PCN nanorods demonstrated enhanced activity in photocatalytic hydrogen production and the degradation of methyl orange relative to conventional bulk PCN and PCN nanorod templated from pure silica nanotube. The enhancement is attributed to the nanorod structure and the formation of carbon nitride carbon heterojunctions, which facilitate photogenerated charge separation and migration.
Functionalized Ultrasmall Fluorinated Graphene with High NIR Absorbance for Controlled Delivery of Mixed Anticancer Drugs
Authors: Gong Peiwei , Zhao Qiao , Dai Dujuan , Zhang Shumiao , Tian Zhenzhen , Sun Lu , Ren Jiashuo , Liu Zhe 
Published: September 2017

AbstractFluorinated graphene (FG) possess distinctively novel properties different from graphene and is suitable for many biomedical applications. However, the hydrophobic nature and inert properties of FG limit its further application as a biological material. Here we show the preparation of nano‐sized FG (ca. 60 nm) that exhibits high NIR absorbance for photothermal therapy. In order to make it stable in physiological solutions, the FG is enriched with oxygen and followed by covalent binding with chitosan as a novel pH‐responsive nanocarrier. Furthermore, controlled loading of two anticancer drugs, doxorubicin (DOX) and camptothecin (CPT) has been realized and the functionalized ultrasmall FG shows remarkably high cytotoxicity toward Hela cancer cells compared to that loaded with either CPT or DOX only. This work established nano‐sized FG as a novel photothermal agent due to its small size and can be used a stimulus‐responsive nanocarrier for mixed drug delivery and combined therapy.
Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
Authors: Rebreyend Christophe , Gloaguen Yann , Lutz Martin , van der Vlugt Jarl Ivar , Siewert Inke , Schneider Sven , de Bruin Bas 
Published: September 2017

AbstractOne‐electron oxidation of the rhodium(I) azido complex [Rh(N3)(PNP)] (5), bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N2)(PNP)]+ (9+). Interestingly, complex 5 also acts as a catalyst for electrochemical N3− oxidation (Ep≈−0.23 V vs. Fc+/0) in the presence of excess azide. This is of potential relevance for the design of azide‐based and direct ammonia fuel cells, expelling only harmless dinitrogen as an exhaust gas.
Different and Often Opposing Forces Drive the Encapsulation and Multiple Exterior Binding of Charged Guests to a M4L6 Supramolecular Vessel in Water
Authors: Sgarlata Carmelo , Mugridge Jeffrey S. , Pluth Michael D. , Zito Valeria , Arena Giuseppe , Raymond Kenneth N. 
Published: September 2017

AbstractThe supramolecular assembly [Ga4L6]12− acts as a nanoscale flask to mediate the reactivity of encapsulated reactive guests and also functions as a catalyst to carry out enzyme‐like chemical transformations. The guest binding to the interior cavity and exterior of this host is difficult to untangle because multiple equilibria occur in solution, and only when refining simultaneously data obtained from different techniques, such as NMR, UV/Vis, and calorimetry, can the accurate solution thermodynamics of these host–guest systems be determined. This study reports the driving forces for the inclusion and stepwise exterior guest binding of different aliphatic quaternary ammonium guests to the [Ga4L6]12− assembly. Encapsulation into the host cavity was found to be an entropy‐driven process, whereas exterior ion association is driven either by enthalpically favorable attractive forces or by the entropy gain due to desolvation, depending on guest size and character. The analysis of the energetics of reaction may help predicting and understanding the intimate role and contribution of the transition state in those rate‐accelerated reactions involving this supramolecular assembly as an enzyme‐like molecular flask.
Functionalization of 3‐Iridacyclopentenes
Authors: Gómez Margarita , Rendón Nuria , Álvarez Eleuterio , Mereiter Kurt , Poveda Manuel L. , Paneque Margarita 
Published: September 2017

AbstractMembers of a series of iridacyclopentenes of composition [TpMe2Ir(k2‐C,C‐CH2CR′=CRCH2)(CO)] (TpMe2=hydrotris(3,5‐dimethylpyrazolyl)borate; R=R′=H,1; R=Me, R′=H,2; R=R′=Me,3) have been subjected to common organic chemistry procedures for hydrogenation, cyclopropanation, epoxidation, water addition through hydroboration,cis‐dihydroxylation, and ozonolysis. The stability of metallacycles1–3, imparted by the presence of the co‐ligands TpMe2and CO, directs the reactivity towards the C=C double bonds, and furthermore the stereochemistry of the products formed is strongly dictated by the steric demands of the TpMe2ligand. While the products obtained in some of the above‐mentioned reactions are the expected ones from an organic chemistry point of view, in other cases the results differ from the outcomes of similar reactions carried out with the all‐carbon counterparts.
Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox‐Switchable 20π, 19π, and 18π 5,10,15,20‐Tetraaryl‐5,15‐diazaporphyrinoids
Authors: Sudoh Keisuke , Satoh Takaharu , Amaya Toru , Furukawa Ko , Minoura Mao , Nakano Haruyuki , Matano Yoshihiro 
Published: September 2017

AbstractIn spite of significant advances in redox‐active porphyrin‐based materials and catalysts, little attention has been paid to 20π and 19π porphyrins because of their instability in air. Here we report the meso‐modification of 5,10,15,20‐tetraarylporphyrin with two nitrogen atoms, which led to redox‐switchable 20π, 19π, and 18π 5,10,15,20‐tetraaryl‐5,15‐diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal‐templated annulation of the corresponding metal‐bis(dipyrrin) complexes. The inductive and resonance effects of the meso‐nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP π‐systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and π–π* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the π‐systems. In contrast to the isoelectronic 5,10,15,20‐tetraarylporphyrin derivatives, the 20π and 19π TADAPs were chemically stable under air. In particular, the 19π TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low‐lying singly occupied molecular orbitals of their π‐systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19π/20π redox cycle.
Highly K+‐Selective Fluorescent Probes for Lifetime Sensing of K+ in Living Cells
Authors: Schwarze Thomas , Mertens Monique , Müller Peter , Riemer Janine , Wessig Pablo , Holdt Hans‐Jürgen 
Published: September 2017

AbstractThe new K+‐selective fluorescent probes 1 and 2 were obtained by CuI‐catalyzed 1,3‐dipolar azide alkyne cycloaddition (CuAAC) reactions of an alkyne‐substituted [1,3]dioxolo[4,5‐f][1,3]benzodioxole (DBD) ester fluorophore with azido‐functionalized N‐phenylaza‐18‐crown‐6 ether and N‐(o‐isopropoxy) phenylaza‐18‐crown‐6 ether, respectively. Probes 1 and 2 allow the detection of K+ in the presence of Na+ in water by fluorescence enhancement (2.2 for 1 at 2000 mm K+ and 2.5 for 2 at 160 mm K+). Fluorescence lifetime measurements in the absence and presence of K+ revealed bi‐exponential decay kinetics with similar lifetimes, however with different proportions changing the averaged fluorescence decay times (τf(av)). For 1 a decrease of τf(av) from 12.4 to 9.3 ns and for 2 an increase from 17.8 to 21.8 ns was observed. Variation of the substituent in ortho position of the aniline unit of the N‐phenylaza‐18‐crown‐6 host permits the modulation of the Kd value for a certain K+ concentration. For example, substitution of H in 1 by the isopropoxy group (2) decreased the Kd value from >300 mm to 10 mm. 2 was chosen for studying the efflux of K+ from human red blood cells (RBC). Upon addition of the Ca2+ ionophor ionomycin to a RBC suspension in a buffer containing Ca2+, the fluorescence of 2 slightly rose within 10 min, however, after 120 min a significant increase was observed.
Dichloro‐Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry
Authors: Bresien Jonas , Hinz Alexander , Schulz Axel , Suhrbier Tim , Thomas Max , Villinger Alexander 
Published: September 2017

AbstractA dichloro‐cycloazatriphosphane that incorporates a cyclic NP3 backbone could be synthesized using knowledge gained from the chemistry of N2P2 and P4 ring systems. It fills the gap between the congeneric compounds [ClP(μ‐NR)]2 and [ClP(μ‐PR)]2 (R=sterically demanding substituent), and thus contributes to the systematic development of nitrogen–phosphorus chemistry in general. The title compound was studied with respect to its formation via a labile aminodiphosphene, which readily underwent different rearrangement reactions depending on the solvent. All compounds were fully characterized by experimental and computational methods.
Evaluating the networking characteristics of the Cray XC‐40 Intel Knights Landing‐based Cori supercomputer at NERSC
Authors: Doerfler Douglas , Austin Brian , Cook Brandon , Deslippe Jack , Kandalla Krishna , Mendygral Peter 
Published: September 2017

SummaryThere are many potential issues associated with deploying the Intel Xeon PhiTM (code named Knights Landing [KNL]) manycore processor in a large‐scale supercomputer. One in particular is the ability to fully utilize the high‐speed communications network, given that the serial performance of a Xeon PhiTM core is a fraction of a Xeon®core. In this paper, we take a look at the trade‐offs associated with allocating enough cores to fully utilize the Aries high‐speed network versus cores dedicated to computation, eg, the trade‐off between MPI and OpenMP. In addition, we evaluate new features of Cray MPI in support of KNL, such as internode optimizations. We also evaluate one‐sided programming models such as Unified Parallel C. We quantify the impact of the above trade‐offs and features using a suite of National Energy Research Scientific Computing Center applications.
Interaction of Ester‐Functionalized Ionic Liquids with Atomically‐Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability
Authors: Xu Tao , Waehler Tobias , Vecchietti Julia , Bonivardi Adrian , Bauer Tanja , Schwegler Johannes , Schulz Peter S. , Wasserscheid Peter , Libuda Joerg 
Published: September 2017

AbstractHybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester‐functionalized ILs with atomically defined Co3O4(111) and CoO(100) surfaces. Both supports are prepared under ultra‐high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3‐butyl‐1‐methyl imidazolium bis(trifluoromethyl‐sulfonyl) imide ([BMIM][NTf2]), 3‐(4‐methoxyl‐4‐oxobutyl)‐1‐methylimidazolium bis(trifluoromethyl‐sulfonyl) imide ([MBMIM][NTf2]), and 3‐(4‐isopropoxy‐4‐oxobutyl)‐1‐methylimidazolium bis(trifluoromethyl‐sulfonyl) imide ([IPBMIM][NTf2]), were deposited on these surfaces by physical vapor deposition (PVD). Time‐resolved and temperature‐programmed infrared reflection absorption spectroscopy (TR‐IRAS, TP‐IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP‐IRAS, we determined the multilayer desorption temperature of [BMIM][NTf2] (360±5 K), [MBMIM][NTf2] (380 K) and [IPBMIM][NTf2] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf2]− ion interacts with the surface through the SO2 groups and the CF3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM]+ and [IPBMIM]+ interact with the surface Co2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf2] and [MBMIM][NTf2] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf2] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL‐derived species in the monolayer desorb at temperatures around 500 to 550 K.
Rational Development of Neutral Aqueous Electrolytes for Zinc–Air Batteries
Authors: Clark Simon , Latz Arnulf , Horstmann Birger 
Published: September 2017

AbstractNeutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc–air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders‐of‐magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell‐level performance of pH‐buffered aqueous electrolytes. We apply our model to conduct the first continuum‐scale simulation of secondary ZABs using aqueous ZnCl2–NH4Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine‐containing solids may precipitate in addition to ZnO.
Pulmonary blastoma in a child: Report of a case with cytological findings
Authors: Das Mou , Maity Chaudhuri Priyanka , Bandyopadhyay Anis , Chatterjee Uttara 
Published: September 2017

AbstractPulmonary blastoma is an uncommon tumour. It constitutes <0.1% of all resected lung cancers. It is even more rare in children with only a few case reports describing this entity in them. Pulmonary blastoma should not be confused with pleuropulmonary blastoma which is a paediatric lung tumour with different morphology and better outcome. Here we take the opportunity of describing pulmonary blastoma in a 3 years old child along with its cytological findings.
Regulation of fibroblast growth factor 8 (FGF8) in chicken embryonic stem cells differentiation into spermatogonial stem cells
Authors: Wang Man , Zhang Chen , Huang Chuanli , Cheng Shaoze , He Nana , Wang Yilin , Ahmed Mahmoud F. , Zhao Ruifeng , Jin Jing , Zuo Qisheng , Zhang Yani , Li Bichun 
Published: September 2017

AbstractFibroblast growth factors (FGFs) are essential in regulating the formation of spermatogonial stem cells (SSCs). Here, we explored the effect of FGF8 on chicken SSCs formation by knockdown or overexpression of FGF8 in chicken embryonic stem cells (ESCs) both in vitro and in vivo. Our results showed that knockdown of FGF8 could facilitate the differentiation of ESCs into SSCs, overexpression of FGF8 could promote PGCs self‐renewal, inhibit SSCs formation. This study further revealed the positive correlation between the expression level of FGF8 and MAPK/ERK signal. In the absence of FGF8, the expression of downstream genes such as FGFR2, GRB2, RAS, BRAF, RAF1, and MEK2 was not maintained, while overexpressing FGF8 enhances them. Thus, our study demonstrated that FGF8 can regulate germ cell fate by modulating the dynamic equilibrium between differentiation and self‐renewal, which provides a new idea for the study of germ cell regulatory network.
Enhanced heterologous expression of Trichoderma reesei Cel5A/Cel6A in Pichia pastoris with extracellular co‐expression of Vitreoscilla hemoglobin
Authors: Sun Fubao Fuelbiol , Yang Huimin , Bai Renhui , Fang Xu , Wang Fei , He Jing , Tu Maobing 
Published: September 2017

AbstractBACKGROUNDThe deficiency of family 5 endoglucanase (Cel5A) and family 6 cellobiohydrolase (Cel6A) has become a key limiting factor on cellulase enzymatic hydrolysis in bioprocessing of cellulosic biomass. To improve the production of Trichoderma reesei Cel5A / Cel6A, a Vitreoscilla hemoglobin (VHb) gene was tried to co‐express extracellularly for the first time with Cel5A / Cel6A in Pichia pastoris GS115.RESULTSNewly constructed recombinant of co‐expressing Cel5A / Cel6A extracellularly with VHb was consistent with the single expression at some key variables of culture condition, i.e. inoculum size, initial pH, culture temperature and methanol concentration. Comparing their single expression, the CMCase activity of co‐expressed Cel5A and Cel6A enzymes enhanced by 40% and 30%, respectively. With high‐cell‐density fed‐batch (HCDFB) fermentation, the co‐expressed Cel5A enzyme activity was 366.8 U mL‐1 with 4.3 g L‐1 protein content and the Cel6A enzyme activity reached 1.3 U mL‐1 with 2.23 g L‐1 protein content. The two co‐expressed enzyme activities were enhanced by 35% and 20%, respectively, compared with the single expression.CONCLUSIONVHb protein capable of binding oxygen can be successfully co‐expressed extracellularly with other target proteins. The co‐expression of VHb with recombinant Cel5A / Cel6A is efficient at improving oxygen‐limited condition and thus enzyme production in both shake‐flask and HCDFB fermentation. © 2017 Society of Chemical Industry
An Euler‐genus approach to the calculation of the crosscap‐number polynomial
Authors: Chen Yichao , Gross Jonathan L. 
Published: September 2017

AbstractIn 1994, J. Chen, J. Gross, and R. Rieper demonstrated how to use the rank of Mohar's overlap matrix to calculate the crosscap‐number distribution, that is, the distribution of the embeddings of a graph in the nonorientable surfaces. That has ever since been by far the most frequent way that these distributions have been calculated. This article introduces a way to calculate the Euler‐genus polynomial of a graph, which combines the orientable and the nonorientable embeddings, without using the overlap matrix. The crosscap‐number polynomial for the nonorientable embeddings is then easily calculated from the Euler‐genus polynomial and the genus polynomial.
The Effect of Child's School Entry on Maternal Employment: Regression Discontinuity Evidence from South Korea
Authors: Choi Jaehee , Jung Haeil 
Published: September 2017

AbstractPublic school is a form of highly subsidized, universal childcare and thus an important aspect of childcare policies. We examine the impact of a child's school entry on maternal employment in South Korea where mothers have been inactive in the labour force. We utilize a natural experiment where the school‐age eligibility requirement in South Korea generates an exogenous variation in the cost of childcare and lends itself to a regression discontinuity design. Our findings suggest that for women with low levels of own or spouse's education, enrolling their children in school leads to a sizeable increase in labour force participation. Copyright © 2017 John Wiley & Sons, Ltd.
Protein surface roughness accounts for binding free energy of Plasmepsin II‐ligand complexes
Authors: Valdés‐Tresanco Mario E. , Valdés‐Tresanco Mario S. , Valiente Pedro A. , Cocho Germinal , Mansilla Ricardo , Nieto‐Villar J.M. 
Published: September 2017

AbstractThe calculation of absolute binding affinities for protein‐inhibitor complexes remains as one of the main challenges in computational structure‐based ligand design. The present work explored the calculations of surface fractal dimension (as a measure of surface roughness) and the relationship with experimental binding free energies of Plasmepsin II complexes. Plasmepsin II is an attractive target for novel therapeutic compounds to treat malaria. However, the structural flexibility of this enzyme is a drawback when searching for specific inhibitors. Concerning that, we performed separate explicitly solvated molecular dynamics simulations using the available high‐resolution crystal structures of different Plasmepsin II complexes. Molecular dynamics simulations allowed a better approximation to systems dynamics and, therefore, a more reliable estimation of surface roughness. This constitutes a novel approximation in order to obtain more realistic values of fractal dimension, because previous works considered only x‐ray structures. Binding site fractal dimension was calculated considering the ensemble of structures generated at different simulation times. A linear relationship between binding site fractal dimension and experimental binding free energies of the complexes was observed within 20 ns. Previous studies of the subject did not uncover this relationship. Regression model, coined FD model, was built to estimate binding free energies from binding site fractal dimension values. Leave‐one‐out cross‐validation showed that our model reproduced accurately the absolute binding free energies for our training set (R2 = 0.76; 
 =0.55 kcal/mol; SDerror = 0.19 kcal/mol). The fact that such a simple model may be applied raises some questions that are addressed in the article.