bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modeling early in situ wetting of a compacted bentonite buffer installed in low permeable crystalline bedrock
Authors: Dessirier B. , Frampton A. , Fransson Å. , Jarsjö J. 
Published: August 2016

AbstractThe repository concept for geological disposal of spent nuclear fuel in Sweden and Finland is planned to be constructed in sparsely fractured crystalline bedrock and with an engineered bentonite buffer to embed the waste canisters. An important stage in such a deep repository is the postclosure phase following the deposition and the backfilling operations when the initially unsaturated buffer material gets hydrated by the groundwater delivered by the natural bedrock. We use numerical simulations to interpret observations on buffer wetting gathered during an in situ campaign, the Bentonite Rock Interaction Experiment, in which unsaturated bentonite columns were introduced into deposition holes in the floor of a 417 m deep tunnel at the Äspö Hard Rock Laboratory in Sweden. Our objectives are to assess the performance of state‐of‐the‐art flow models in reproducing the buffer wetting process and to investigate to which extent dependable predictions of buffer wetting times and saturation patterns can be made based on information collected prior to buffer insertion. This would be important for preventing insertion into unsuitable bedrock environments. Field data and modeling results indicate the development of a de‐saturated zone in the rock and show that in most cases, the presence or absence of fractures and flow heterogeneity are more important factors for correct wetting predictions than the total inflow. For instance, for an equal open‐hole inflow value, homogeneous inflow yields much more rapid buffer wetting than cases where fractures are represented explicitly thus creating heterogeneous inflow distributions.
A Novel Imaging Marker for Small Vessel Disease Based on Skeletonization of White Matter Tracts and Diffusion Histograms
Authors: Baykara Ebru , Gesierich Benno , Adam Ruth , Tuladhar Anil Man , Biesbroek J. Matthijs , Koek Huiberdina L. , Ropele Stefan , Jouvent Eric ,   Alzheimer's Disease Neuroimaging Initiative, Chabriat Hugues , Ertl‐Wagner Birgit , Ewers Michael , Schmidt Reinhold , de Leeuw Frank‐Erik , Biessels Geert Jan , Dichgans Martin , Duering Marco 
Published: August 2016

ObjectiveTo establish a fully automated, robust imaging marker for cerebral small vessel disease (SVD) and related cognitive impairment that is easy to implement, reflects disease burden, and is strongly associated with processing speed, the predominantly affected cognitive domain in SVD.MethodsWe developed a novel magnetic resonance imaging marker based on diffusion tensor imaging, skeletonization of white matter tracts, and histogram analysis. The marker (peak width of skeletonized mean diffusivity [PSMD]) was assessed along with conventional SVD imaging markers. We first evaluated associations with processing speed in patients with genetically defined SVD (n = 113). Next, we validated our findings in independent samples of inherited SVD (n = 57), sporadic SVD (n = 444), and memory clinic patients with SVD (n = 105). The new marker was further applied to healthy controls (n = 241) and to patients with Alzheimer's disease (n = 153). We further conducted a longitudinal analysis and interscanner reproducibility study.ResultsPSMD was associated with processing speed in all study samples with SVD (p‐values between 2.8 × 10−3 and 1.8 × 10−10). PSMD explained most of the variance in processing speed (R2 ranging from 8.8% to 46%) and consistently outperformed conventional imaging markers (white matter hyperintensity volume, lacune volume, and brain volume) in multiple regression analyses. Increases in PSMD were linked to vascular but not to neurodegenerative disease. In longitudinal analysis, PSMD captured SVD progression better than other imaging markers.InterpretationPSMD is a new, fully automated, and robust imaging marker for SVD. PSMD can easily be applied to large samples and may be of great utility for both research studies and clinical use. Ann Neurol 2016;80:581–592.
Influence of the introduction of flexible alkyl chains on the thermal behavior and mechanical properties of mesogenic epoxy thermosets
Authors: Harada Miyuki , Okamoto Naoki , Ochi Mitsukazu 
Published: August 2016

ABSTRACTA mesogenic epoxy resin (DGETAM) was cured with a series of curing agents having different lengths of long alkyl chain (nBAB, n = 4, 8, 12). Properties of the curings were compared with those of the DGEBA cured with the same curing agents revealing the achievement of a balance between certain levels of thermal properties and excellent mechanical properties. Moreover, some curing systems were prepared with twin mesogenic type epoxy resins (DGEnMA, n = 4, 6, 8, 10, 12) having different lengths of alkyl chain as a flexible spacer and the same curing agents (n′BABs). Combinations of the same concentrations of chemical structures in the basic units of the network structure were applied, and the thermal and mechanical properties of their curing systems were investigated. The fracture energy of each system increased considerably with the increase of the alkyl chain length that adjoins the two mesogenic groups in the epoxy resins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44244.
Facile fabrication of superhydrophobic polyaniline structures and their anticorrosive properties
Authors: Xu Hui , Liu Jiayue , Chen Yong , Tang Jing , Zhao Zeting 
Published: August 2016

ABSTRACTWe report a simple approach for the preparation of superhydrophobic polyaniline (PANI) and its application for the corrosion protection coatings. First, PANI was synthesized conventionally by oxidative polymerization with APS. Subsequently, PANI with different wettability was obtained by modification with different surfactants. The surface modification of PANI with three different surfactants (sodium dodecylbenzenesulfonate, polyethylene glycol, and cetyltrimethylammonium bromide) provided excellent surface superhydrophobicity (water contact angle >150°). The structure and morphology of as‐prepared PANI were characterized with Fourier transform infrared, Energy dispersive X‐ray spectroscopy, and Scanning electron microscopy. Corrosion protection performance of PANI with different wettability was evaluated in 3.5% NaCl electrolyte using Tafel polarization curves and electrochemical impedance spectroscopy. The results indicated that various superhydrophobic PANI coatings have better anticorrosion performance as compared to the hydrophilic PANI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44248.
Cost-effectiveness of same-admission versus interval cholecystectomy after mild gallstone pancreatitis in the PONCHO trial
Authors: da Costa D W , Dijksman L M , Bouwense S A , Schepers N J , Besselink M G , van Santvoort H C , Boerma D , Gooszen H G , Dijkgraaf M G W 
Published: August 2016

Abstract

Background
Same-admission cholecystectomy is indicated after gallstone pancreatitis to reduce the risk of recurrent disease or other gallstone-related complications, but its impact on overall costs is unclear. This study analysed the cost-effectiveness of same-admission versus interval cholecystectomy after mild gallstone pancreatitis.

Methods
In a multicentre RCT (Pancreatitis of biliary Origin: optimal timiNg of CHOlecystectomy; PONCHO) patients with mild gallstone pancreatitis were randomized before discharge to either cholecystectomy within 72 h (same-admission cholecystectomy) or cholecystectomy after 25–30 days (interval cholecystectomy). Healthcare use of all patients was recorded prospectively using clinical report forms. Unit costs of resources used were determined, and patients completed multiple Health and Labour Questionnaires to record pancreatitis-related absence from work. Cost-effectiveness analyses were performed from societal and healthcare perspectives, with the costs per readmission prevented as primary outcome with a time horizon of 6 months.

Results
All 264 trial participants were included in the present analysis, 128 randomized to same-admission cholecystectomy and 136 to interval cholecystectomy. Same-admission cholecystectomy reduced the risk of acute readmission for recurrent gallstone-related complications from 16·9 to 4·7 per cent (P = 0·002). Mean total costs from a societal perspective were €234 (95 per cent c.i. –1249 to 738) less per patient in the same-admission cholecystectomy group. Same-admission cholecystectomy was superior to interval cholecystectomy, with a societal incremental cost-effectiveness ratio of –€1918 to prevent one readmission for gallstone-related complications.

Conclusion
In mild biliary pancreatitis, same-admission cholecystectomy was more effective and less costly than interval cholecystectomy.
Assessment of sites of marrow and extramedullary hematopoiesis by hybrid imaging in primary myelofibrosis patients
Authors: Ojeda‐Uribe Mario , Morel Olivier , Ungureanu Constantin , Desterke Christophe , Le Bousse‐Kerdilès Marie‐Caroline , Boulahdour Hatem 
Published: August 2016

AbstractWe investigated noninvasive procedures by hybrid imaging to assess the sites of active or inactive hematopoiesis in patients with primary myelofibrosis (PMF). To this end, we used two radionuclides, technetium 99m (99mTc) and indium 111‐chloride (111In‐Cl3), coupled with single‐photon emission tomography/computed tomography (SPECT/CT). We studied five patients with PMF and one with secondary myelofibrosis (MF). The classical pattern of lower fixation of both tracers at the axial skeleton where the myelofibrotic process occurs and the reactivation of sites of active hematopoiesis at the distal skeleton were confirmed. Coupling both radionuclides to SPECT/CT imaging allowed for more precise visualization of the sites of extramedullary hematopoiesis as those observed in the spleen and liver. Splenic high uptake of 111In‐Cl3 coupled with SPECT/CT represents a pathognomonic feature of PMF. We conclude that, the hybrid imaging procedures that we studied might constitute an alternative noninvasive method for the screening of the whole‐body marrow and, by this way, to assess the impact of targeted therapies in PMF patients in whom it is well known that the distribution of the hematopoietic active areas is disturbed. Hybrid imaging could also be useful for diagnostic purposes in cases of early PMF or in suspected cases of myelofibrosis secondary to polycythemia vera or essential thrombocythemia.
Impact of overlapping on 1‐year clinical outcomes in patients undergoing everolimus‐eluting bioresorbable scaffolds implantation in routine clinical practice: Insights from the European multicenter GHOST‐EU registry
Authors: Ortega‐Paz Luis , Capodanno Davide , Giacchi Giuseppe , Gori Tommaso , Nef Holger , Latib Azeem , Caramanno Giuseppe , Di Mario Carlo , Naber Christoph , Lesiak Maciej , Capranzano Piera , Wiebe Jens , Mehilli Julinda , Araszkiewicz Aleksander , Pyxaras Stelios , Mattesini Alessio , Geraci Salvatore , Naganuma Toru , Colombo Antonio , Münzel Thomas , Sabaté Manel , Tamburino Corrado , Brugaletta Salvatore 
Published: August 2016

BackgroundOverlapping implantation of bioresorbable scaffolds (BRSs) are frequent in long coronary lesions. Its impact on clinical outcomes is unknown. Objective: To compare the clinical outcomes of patients treated with overlapping BRS with those patients treated with no‐overlap BRS. Methods: We analyzed the 1‐year clinical outcomes of 1,477 patients treated with BRS in the GHOST‐EU registry, according to the implantation of overlapping BRS. Primary endpoint was patient oriented composite endpoint (PoCE) of: all‐cause death, any myocardial infarction (MI) and any repeated revascularization. Scaffold thrombosis, according to Academic Research Consortium definition, was also analyzed. Results: A total of 320 (21.7%) patients were treated with overlapping BRS (overlap group), whereas the remaining 1,157 (78.3%) received no‐overlap BRS (no‐overlap group). The overlap group had significantly higher frequency of male sex, diabetes mellitus, stable angina, B2/C lesion type, SYNTAX score ≥22, lesion length >34 mm, use of intracoronary imaging guidance, pre‐ and postdilatation. At 1‐year, there were no differences in PoCE between the overlap versus no‐overlap group (18.4% vs. 18.2%; HR 1.07, [0.80–1.44]; P = 0.636), even after adjustment (HR 1.05, [0.48–2.20]; P = 0.904). Scaffold thrombosis rate did not differ either at one‐month (1.3% vs. 1.5%, P = 0.769) or at 1‐year (1.9% vs. 2.1%, P = 0.823). Conclusions: In “Real‐world” clinical practice, overlapping BRS does not appear to have an impact on clinical outcomes as compared to no‐overlapping BRS. These preliminary data should be confirmed. © 2016 Wiley Periodicals, Inc.
Transapical tricuspid valve‐in‐ring implantation: An alternative approach to a challenging clinical scenario
Authors: Girdauskas Evaldas , Lauer Bernward , Kuntze Thomas 
Published: August 2016

We report on a transapical tricuspid valve‐in‐ring implantation performed via right ventricular apex using the Sapien‐XT‐prosthesis. A 57‐year‐old woman with recurrent episodes of right heart failure and three previous sternotomies, including tricuspid valve repair with a 32 mm Carpentier–Edwards–Classic annuloplasty ring was admitted due to recurrent severe tricuspid regurgitation. Given the excessive surgical risk, a 29 mm Sapien‐XT‐prosthesis was selected for valve‐in‐ring implantation. Transapical valve‐in‐ring implantation procedure was uneventful. Predischarge echocardiography showed only trace paravalvular tricuspid regurgitation in the septal region. Transapical approach via right ventricular apex is a viable alternative for tricuspid valve‐in‐ring implantation in selected high‐risk patients. © 2016 Wiley Periodicals, Inc.
From Oleo Chemicals to Polymer: Bis‐hydroaminomethylation as a Tool for the Preparation of a Synthetic Polymer from Renewables
Authors: Seidensticker Thomas , Busch Hanna , Diederichs Christopher , von Dincklage Jork Jonas , Vorholt Andreas J. 
Published: August 2016

AbstractResource‐efficient bis‐hydroaminomethylation of the castor oil derived renewables methyl 10‐undecenoate and 10‐undecene‐1‐ol with piperazine furnished linear, bifunctional molecules. A structured and sustainable path towards a novel polyester from these monomers was developed. Key to success was the selective crystallization of the linear product directly from the crude reaction mixture in >98 % purity. Additionally, with this methodology, the homogeneous Rh catalyst was retained in the supernatant and was successfully recycled. Finally, polycondensation yielded a novel piperazine‐linked polyester.
Local pH Gradient Initiated by Light on TiO2 for Light‐Triggered Modulation of Polyhistidine‐Tagged Proteins
Authors: Andreeva Daria V. , Melnyk Inga , Baidukova Olga , Skorb Ekaterina V. 
Published: August 2016

AbstractA new principle of photo‐assisted spatial desorption of (poly)histidine‐tagged (His‐Tag) proteins on a TiO2 surface is suggested. A semiconductor TiO2 surface is decorated by layer‐by‐layer (LbL) assembly of a strong polyelectrolyte, namely, polystyrene sulfonate (PSS), and nickel–nitrilotriacetic acid (NTA). The PSS/NTA multilayer architecture provides n‐fold (n×NTA) binding efficiency for more precise protein recognition in comparison to existing molecular His‐Tag protein recognition with one‐ and threefold multiplication (1×NTA, 3×NTA). Spatially resolved desorption of proteins is regulated by non‐ photodestructive short‐term low‐intensity light irradiation (<5 mW cm−2). The local pH shift on irradiated TiO2 selectively affects the pH‐sensitive NTA/protein complex, but not the LbL assembly of PSS and NTA, which is stable in a broad pH range.
Tuning Optical and Electron Donor Properties by Peripheral Thio–Aryl Substitution of Subphthalocyanine: A New Series of Donor–Acceptor Hybrids for Photoinduced Charge Separation
Authors: KC Chandra B. , Lim Gary N. , D'Souza Francis 
Published: August 2016

AbstractSubphthalocyanine (SubPc), a unique ring‐reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light‐energy‐harvesting applications. In the present study, by peripheral thio–aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near‐IR region. Additionally, for α‐ring‐substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor–acceptor dyads containing the well‐known electron acceptor C60 connected to the central boron atom of SubPc was accomplished by making use of the 1,3‐dipolar cycloaddition reaction. Control experiments and free‐energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light‐to‐electricity or light‐to‐fuel production devices.
Multiple Condensation Reactions Involving PtII/PdII−OH2, Pt−NH3, and Cytosine−NH2 Groups: New Twists in Cisplatin−Nucleobase Chemistry
Authors: Yin‐Bandur Lu , Sanz Miguel Pablo J. , Rodríguez‐Santiago Luis , Sodupe Mariona , Berghaus Melanie , Lippert Bernhard 
Published: August 2016

AbstractThe coordination chemistry of the antitumor agent cisplatin and related complexes with DNA and its constituents, that is, the nucleobases, appears to be dominated by 1:1 and 1:2 adducts of the types cis‐[Pta2(nucleobase)X] and cis‐[Pta2(nucleobase)2] (a=NH3 or amine; a2=diamine or diimine; X=Cl, OH or OH2). Here, we have studied the interactions of the putative 1:1 adducts cis‐[Pta2(1‐MeC‐N3)(OH2)]2+ (with a=NH3, a2=2,2′‐bpy (2,2′‐bipyridine), 1‐MeC=model nucleobase 1‐methylcytosine) with additional cis‐[Pt(NH3)2(OH2)2]2+ or its kinetically superior analogues [Pd(en)(OH2)2]2+ (en=ethylenediamine) and [Pd(2,2′‐bpy)(OH2)2]2+. Depending upon the conditions applied different compounds of different nuclearity are formed. Without exception they represent condensation products of the components, containing μ‐1‐MeC‐H, μ‐OH−, as well as μ‐NH2− bridges. In the presence of Ag+ ions, the isolated products in several cases display additionally Pt→Ag dative bonds. On the basis of the cytosine‐containing structures established by X‐ray crystallography, it is proposed that any of the feasible initial 1:1 nucleobase adducts of cisplatin could form dinuclear Pt complexes upon reaction with additional hydrolyzed cisplatin, thereby generating nucleobase adducts other than the presently established ones. Two findings appear to be of particular significance: First, hydrolyzed cisplatin can have a moderately accelerating effect on the formation of a secondary nucleobase product. Second, NH3 ligands of the cisplatin moiety can be converted into bridging amido ligands following condensation with the diaqua species of cisplatin.
Twisted Polycyclic Aromatic Systems Prepared by Annulation of Bis(arylethynyl)arenes with Biphenylboronic Acids
Authors: Tokoro Yuichiro , Oishi Anna , Fukuzawa Shin‐ichi 
Published: August 2016

AbstractTwisted polycyclic aromatic hydrocarbons (PAHs) were prepared by the successive rhodium‐catalyzed annulation and dehydrogenative cyclization of bis(arylethynyl)arenes with di‐tert‐butylbiphenyl‐2‐ylboronic acid. The molecular structures of the PAHs were determined by single‐crystal XRD analysis. The PAHs showed up to four fjord regions, and the twisting angle was 46.7°. The nonplanarity (NP) and harmonic oscillator model of aromaticity (HOMA) were calculated by using the structural data obtained from XRD analysis. The PAHs derived from dialkynyl naphthalenes showed low planarity and HOMA of the central ring. The optical properties of the PAHs were investigated by UV/Vis absorption and fluorescence spectroscopy analyses. The absorption and emission maxima of the PAHs with a larger planar region appeared at a longer wavelength. DFT calculations support that the absorption band at λ≈450 nm can be mainly attributed to the HOMO–LUMO transition.
Duality of Orbital‐Symmetry‐Allowed Transition States for Thermal Sigmatropic Hydrogen Shifts in Transition Metal Compounds
Authors: Mauksch Michael , Tsogoeva Svetlana B. 
Published: August 2016

AbstractHerein, the Zimmerman Möbius/Hückel concept is extended to pericyclic reactions involving transition metals. While sigmatropic hydrogen shifts in parent hydrocarbons are either uniquely antarafacial or suprafacial, we have shown by theoretical orbital topology considerations and quantum chemical computations at DFT level that both modes of stereoselectivity must become allowed in the same system as a consequence of Craig–Möbius‐type orbital arrays, in which a transition metal d orbital induces a phase dislocation in metallacycles. This may have fundamental implications for the understanding of reactivity and bonding in organometallic chemistry.
Designing, Describing and Disseminating New Materials by using the Network Topology Approach
Authors: Öhrström Lars 
Published: August 2016

AbstractThis Concept article describes how network topology analysis is applied to different fields of solid‐state chemistry. Its usefulness is demonstrated by examples from metal–organic frameworks, group 14 allotropes and related compounds, ice polymorphs, zeolites, supramolecular (organic) solid‐state chemistry, Zintl phases, and cathode materials for Li‐ion batteries.
Cu/Cu2O Electrodes and CO2 Reduction to Formic Acid: Effects of Organic Additives on Surface Morphology and Activity
Authors: Huan Tran Ngoc , Simon Philippe , Benayad Anass , Guetaz Laure , Artero Vincent , Fontecave Marc 
Published: August 2016

AbstractCopper/copper oxide (Cu/Cu2O) electrodes are known to display interesting electrocatalytic performances for the reduction of CO2, and thus, deserve further investigation for optimization. Here, we show that the addition of nitrogen‐based organic additives greatly improves the activity of these electrodes (higher current densities, greater selectivity, and higher faradaic yields). The best effector is found to be tetramethyl cyclam. For example, electrolysis at −2.0 V versus Fc+/Fc in CO2‐saturated DMF/H2O (99:1, v/v) in the presence of this effector results in formic acid with almost 90 % faradaic yield. SEM and XPS analysis of the electrode surface reveals that the organic additive promotes the formation of active Cu0 nanoparticles from Cu2O during electrolysis. This simple approach provides a straightforward strategy toward the optimization of Cu/Cu2O electrodes.